HK1188233B - Gate insulator layer for electronic devices - Google Patents

Description

Gate insulator layer for electronic devices

Technical Field

The present invention relates generally to the use of polycycloolefins in electronic devices and more particularly to the use of norbornene-based polymers to form gate insulating layers in the preparation of electronic devices, including organic electronic devices (OE), devices including such norbornene-based polymer gate insulating layers and methods for preparing such devices incorporating norbornene-based polymer gate insulating layers.

Background and Prior Art

Electronic devices, such as Field Effect Transistors (FETs), are used in display devices and circuits with logic capability. Conventional FETs typically include a source electrode, a drain electrode, and a gate electrode, a semiconductor layer made of a Semiconductor (SC) material, and an insulator layer (also referred to as a "dielectric" or "gate dielectric") made of a dielectric material and located between the SC layer and the gate electrode. Also known are organic electronic devices, such as Organic Field Effect Transistors (OFETs) used in display devices and circuits with logic capabilities. Conventional OFETs also include source, drain and gate electrodes rather than an inorganic semiconducting layer, and include a semiconducting layer made of an Organic Semiconducting (OSC) material and an insulator layer made of an organic dielectric material, typically located between the OSC layer and the gate electrode.

WO 03/052841 a1 discloses embodiments of Organic Field Effect Transistors (OFETs) in which the gate insulating layer is made of a dielectric material having a dielectric constant () (also known as the relative dielectric constant or permittivity (k)) of less than 3.0. Regardless of whether the organic semiconductor layer is disordered or quasi-ordered, such materials, commonly referred to as "low-k materials," are reported to provide good mobility. WO 03/052841A 1 further reports on commercially available fluoropolymers, such as Cytop^TM(from Asahi Glass) or Teflon AF^TM(from DuPont) is an exemplary low-k material.

Fluoropolymers such as Cytop are disclosed in WO 05/055248^TMAs gate insulator material due to its advantageous solution processed OFET devices, wherein the OSC material is selected from soluble, substituted oligoacenes, such as pentacene, tetracene or anthracene, or heterocyclic derivatives thereof. These OSC materials are soluble in most common organic solvents. Thus, when preparing a top gate OFET, the solvent for the gate insulator composition must be carefully selected to avoid dissolution of the OSC material by the solvent of the gate dielectric composition when deposited in adjacent layers. Such a solvent is usually referred to as an orthogonal (orthogonal) solvent to the material of the OSC layer. Similarly, when preparing a bottom gate device, the solvent used to support the OSC material on the previously formed gate insulating layer is chosen to be orthogonal to the gate dielectric material.

It has been reported that the above fluoropolymers present problems with respect to limited structural integrity and process integration in volume production of OFET devices. For processability, fluoropolymers often do not adhere well to other layers, such as the substrate and OSC layer, and besides they often exhibit poor wettability. Likewise, many fluoropolymers, such as the aforementioned Cytop^TMThose of the series having a low glass transition temperature, T_g100 deg.C and 130 deg.C, which makes it difficult to use standard physical or chemical deposition methods to apply a metalized gate electrode layer over such a fluoropolymer dielectric layer. For structural integrity, if there is a low T_gIn the presence of a fluoropolymerIs heated to or above T during the metallization process_gTemperature, polymer cracking due to intrinsic stress can occur. Even if such cracking can be avoided, differential expansion between the fluoropolymer and any adjacent layers due to heating can result in polymer shrinkage. If it has a higher T_gOf fluoropolymers, e.g. Teflon AF^TMThose of the series (e.g. T)_gTeflon AF 2400 at 240 c) has been used to overcome the aforementioned shrinkage or cracking problems, such materials typically exhibit a lower T than does Teflon AF 2400 (r), which is a low T_gThe materials exhibit more severe wetting and adhesion problems than those exhibited by the prior art.

Thus having good wettability and high T_gThere is a need for polymers that are capable of forming low-k gate dielectric layers.

It is an object of the present invention to provide a gate dielectric layer for an electronic device that has one or more of good wetting, high surface energy, high adhesion, orthogonal solubility with respect to semiconductor materials, and that does not have a significant negative impact on device performance.

Drawings

Embodiments of the present invention are described below with reference to the following drawings.

Fig. 1 depicts a top gate OFET device according to an embodiment of the present invention.

Fig. 2 depicts a bottom gate OFET device according to an embodiment of the present invention.

Fig. 3 through 20 depict transfer curves for top-gate and bottom-gate OFET devices fabricated in accordance with embodiments of the present invention as described in examples C1 through C18.

Fig. 21 is a transfer curve for a bottom gate OFET device prepared as described in example C19.

Fig. 22 is a transfer curve for a bottom gate OFET device prepared as described in example C20.

Fig. 23 depicts the adhesion of organic dielectric layers on glass substrates with or without adhesion promoters as described in examples C19 and C20, respectively.

In fig. 3to 22, the X-axis represents the gate voltage, the Y-axis on the left represents the drain current, and the Y-axis on the right represents the mobility. The upper two curves labeled "c" in the example of fig. 3 represent the current-voltage characteristics of the forward and reverse sweeps, which illustrate the current hysteresis effect of the device. The lower two curves labeled "a" and "b" exemplarily shown in fig. 3 represent mobility-voltage characteristics, in which the curve (a) shows the mobility obtained in a linear state and the curve (b) shows the mobility obtained in a saturation mode.

Summary of The Invention

The present invention relates to the use of a polycycloolefin polymer, or a polymer composition comprising a polycycloolefin polymer, for forming a gate insulating layer in contact with an organic semiconductor layer in an electronic device.

The invention still further relates to a gate insulator in contact with an organic semiconductor layer in an electronic device and comprising a polycycloolefin polymer or a polymer composition comprising a polycycloolefin polymer.

The polycycloolefin polymer is preferably a norbornene-type addition polymer.

The electronic device is preferably an organic electronic device and is, for example, a Field Effect Transistor (FET) with an inorganic semiconductor material or an Organic Field Effect Transistor (OFET) with an organic semiconductor material.

Advantageously, such norbornene-type addition polymers are tailorable in structure to overcome the previously discussed disadvantages observed in known devices. These norbornene-based addition polymers thus allow time, cost and material efficiencies to be made on a large scale for the manufacture of electronic devices, such as OFETs, using organic semiconducting materials and organic dielectric materials, or for the manufacture of FETs using inorganic semiconducting materials and organic dielectric materials. Furthermore, as will be discussed, such norbornene-type addition polymers exhibit orthogonal solubility with respect to organic semiconductor materials. They are readily processable, exhibit structural integrity that generally exceeds that of the aforementioned fluoropolymers, are effective in improving surface energy and provide improved adhesion to adjacent layers. They are therefore particularly suitable for use in gate insulating layers of organic electronic devices, such as FETs and OFETs.

The invention further relates to methods and/or processes for the preparation of electronic or organic electronic devices, such as FETs and OFETs, using such norbornene-type addition polymers or polymer compositions, and to electronic and optoelectronic devices prepared by such methods and/or processes and/or comprising such polymers or polymer compositions.

As described hereinbefore and hereinafter, the present invention also relates to novel polycycloolefin or norbornene-type polymers, or polymer blends or polymer compositions comprising them.

Detailed Description

The terms FET and OFET as used in the present invention will be understood to include a subset of these devices known as Thin Film Transistors (TFTs) and Organic Thin Film Transistors (OTFTs), wherein the FETs or TFTs described in the present invention comprise an organic dielectric material and the OFETs or OTFTs comprise an organic semiconductor material and the aforementioned organic dielectric materials.

It will be understood that the terms "dielectric" and "insulating" are used interchangeably herein. The mentioned insulating layer thus comprises a dielectric layer. Furthermore, the term "organic electronic device" as used in the present invention is to be understood as including the term "organic semiconductor device" and a number of specific embodiments of such devices, such as FETs and OFETs as defined above.

As used herein, the phrase "photoreactive and/or crosslinkable" when used to describe certain pendant groups will be understood to refer to groups that are reactive to actinic radiation and that consequently enter into a crosslinking reaction, or groups that are not reactive to actinic radiation but are nevertheless capable of entering into a crosslinking reaction in the presence of a crosslinking activator.

The term "polymer" as used herein will be understood to mean a molecule comprising a backbone of one or more repeating units of the exact type (the smallest constitutional unit of the molecule), and it includes the commonly known terms "copolymer", "homopolymer" and the like. Furthermore, it will also be understood that, in addition to the polymer itself, the term polymer also includes residues from initiators, catalysts and other elements that occur with the synthesis of such polymers, with the understanding that these residues are not covalently incorporated therein. In addition, these residues and other elements, while usually removed in purification treatments after polymerization, are typically mixed or blended with the polymer as it is transferred between vessels or between solvents or dispersion media so that they generally remain with the polymer.

The term "polymer composition" as used herein means at least one polymer and one or more other materials added to the at least one polymer to provide, or modify, specific properties of the polymer composition and/or at least one polymer therein. It is understood that the polymer composition is the medium used to transport the polymer to the substrate so that a layer or structure can be formed thereon. Exemplary materials include, but are not limited to, solvents, antioxidants, photoinitiators, photosensitizers, crosslinking moieties or agents, reactive diluents, acid scavengers, leveling agents, and adhesion promoters. Further, it is also understood that the polymer composition may include a blend of two or more in addition to the foregoing exemplary materials.

The terms "polycycloolefin" and "norbornene-type" as defined herein are used interchangeably and refer to addition polymerizable monomers, or resulting repeat units, that include at least one norbornene moiety as shown, for example, in structures a1 or a2 below. The simplest norbornene or polycycloolefin monomer bicyclo [2.2.1] hept-2-ene (A1) is usually referred to as norbornene.

However, as used herein, the term "norbornene-type monomer" or "norbornene-type repeat unit" is understood to mean not just norbornene itself, but to mean any substituted norbornene, or substituted and unsubstituted higher cyclic derivatives thereof, such as structures B1 and B2 shown below, wherein Z is selected from the group consisting of-CH₂-or-CH₂-CH₂And m is 0to 3.

By substituting norbornene with pendant groups, the properties of the polymer can be tailored to meet the needs of each application. The methods and processes that have been developed to polymerize functionalized norbornenes exhibit outstanding flexibility and allow for different moieties and groups to be attached to the norbornene ring. In addition to the polymerization of monomers with specific pendant groups, monomers with different functional groups can be randomly polymerized to form the final material, where the type and ratio of monomers used determines the overall properties of the resulting polymer.

The term "hydrocarbyl" as used herein refers to a residue or group comprising a carbon backbone wherein each carbon is suitably substituted with one or more hydrogen atoms. The term "halohydrocarbyl" refers to a hydrocarbyl group in which one or more, but not all, of the hydrogen atoms are replaced with a halogen (F, Cl, Br, I). The term perhalocarbyl refers to a hydrocarbyl group in which each hydrogen is substituted with a halogen. Non-limiting examples of hydrocarbyl groups include, but are not limited to, C₁-C₂₅Alkyl of (C)₂-C₂₄Alkenyl of, C₂-C₂₄Alkynyl of (A), C₅-C₂₅Cycloalkyl of, C₆-C₂₄Aryl or C of₇-C₂₄An aralkyl group of (2). Representative alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl. Representative alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, and hexenyl. Representative alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, and anthracenyl. Representative aralkyl groups include, but are not limited to, benzyl, phenethyl, and phenylbutyl.

The term "halohydrocarbyl" as used herein includes the hydrocarbyl moieties mentioned above, but the degree of halogenation can vary from where at least one hydrogen atom is replaced by a halogen atom (e.g., a fluoromethyl group) to where all hydrogen atoms on the hydrocarbyl group are replaced by halogen atoms (e.g., trifluoromethyl or perfluoromethyl), also referred to as perhalogenation. For example, haloalkyl groups useful in embodiments of the present invention may be partially or fully halogenated of formula C_zX_2z+1Wherein X is independently halogen or hydrogen and z is selected from an integer of 1 to 25. In some embodiments, each X is independently selected from hydrogen, chlorine, fluorine, bromine, and/or iodine. In other embodiments, each X is independently hydrogen or fluorine. Thus, representative examples of halogenated hydrocarbon groups and perhalocarbyl groups are the foregoing exemplary hydrocarbon groups in which an appropriate number of hydrogen atoms are each replaced with a halogen atom.

Further, the definitions of the terms "hydrocarbyl", "halogenated hydrocarbyl" and "perhalogenated hydrocarbyl" include moieties wherein one or more carbon atoms are replaced by a heteroatom selected from O, N, P or Si. These heteroatom-containing moieties may be referred to, for example, as "heteroatom-hydrocarbyl" or "heterohydrocarbyl". Examples of hydrocarbyl groups containing one or more heteroatoms include groups such as ethers, epoxides, glycidyl ethers, alcohols, carboxylic acids, esters, ketones, anhydrides, maleimides, amines, imines, amides, phenols, amino-phenols, silanes, siloxanes, phosphines, phosphine oxides, dialkylphosphinites (phosphinites), phosphonites, phosphites, phosphonates, phosphinates, phosphates and the like.

In a preferred embodiment of the present invention, the polycycloolefin polymer incorporates two or more defined types of repeat units, wherein at least one such repeat unit includes a crosslinkable pendant group or moiety having a degree of latent (latency). By "latent" is meant that such groups do not crosslink under ambient conditions or during the very formation of the polymer, but crosslink when the reaction is specifically initiated, for example, by actinic radiation or heat. Such latent crosslinkable groups are incorporated into the polymer backbone, for example, by providing one or more norbornene-type monomers including such crosslinkable pendent groups (e.g., maleimide-containing pendent groups) to the polymerization reaction mixture and causing polymerization thereof.

One consideration in designing dielectric materials for bottom gate FETs and OFETs is to form layers for the deposited materials that can withstand subsequent solution phase processing steps for depositing or forming the layers after the preceding layers. As discussed above, it has been found advantageous in some embodiments according to the present invention to include crosslinkable side groups or moieties in the repeat units, because including latent crosslinking functional groups on the backbone of the polymer can provide for changing soluble polymer chains to insoluble polymer chains with only a small degree of crosslinking. However, in some embodiments according to the invention, solvent swelling resistance of the dielectric is also desirable and a higher degree of crosslinking may be required to provide insolubility only. Thus, it has been found advantageous to add different crosslinking agents to some embodiments of the invention.

Preferred embodiments of the present invention thus utilize any of a variety of crosslinking methodologies. For example, in a preferred embodiment, acid-catalyzed epoxide ring opening is used for crosslinking, while in another preferred embodiment a photo-induced dimerization (e.g., 2+2) crosslinking reaction is used. In another preferred embodiment heat activated crosslinking is used, wherein heat activated groups are present in the polymer, or a multicomponent mixture (resin) is used, such as trifluorovinyl ether moieties. For the latter, it is possible to use polycycloolefin polymers having reactive sites, such as OH groups, and crosslinking agents, for example latent curing agents, such as isocyanates.

It should be understood that the preferred embodiment according to the present invention is not limited to the crosslinking process described above, as other methods of achieving the desired degree of crosslinking may be used wherein additional photoactivatable crosslinking agents such as bisazide (bisazide) may be used with the appropriate polymer composition. Furthermore, preferred embodiments of the present invention include combinations of the above methods. For example, preferred methods include a basic photopatterning step (to provide patterning of insoluble and dielectric materials), and yet further include an additional high temperature curing step (to increase crosslink density) by other thermally activated crosslinking sites in the polymer, or include the use of a combination of different photoactivating systems, such as maleimides, coumarins, cinnamates and azides to increase the photo-efficacy.

In a preferred embodiment, the polymer composition is a blend of a first polymer having one or more types of repeating units of formula I and a second polymer having one or more types of repeating units of formula II.

In another preferred embodiment, as the polynorbornene polymer, the polymer composition comprises only a first polymer having one or more types of repeating units of formula I, or only a second polymer having one or more types of repeating units of formula II.

In another preferred embodiment, the polymer composition comprises a single norbornene-type polymer having one or more repeat units of formula I and one or more repeat units of formula II:

wherein Z is selected from-CH₂-、-CH₂-CH₂-or-O-, m is an integer from 0to 5, and R¹、R²、R³And R⁴And R⁵、R⁶、R⁷And R⁸Each and all (inclusive) of (a) are independently selected from H, C₁To C₂₅A hydrocarbon group of₁To C₂₅Halogenated hydrocarbon group of or C₁To C₂₅Wherein the groups are as defined above and as exemplified above and below, with the proviso that the first polymer comprises at least one type of repeating unit that is different from the one or more repeating units of the second polymer.

The repeating units of the formulae I and II are formed by corresponding norbornene-type monomers of the formulae Ia and IIa, respectively, in which Z, m, R^1-4And R^5-8As defined above:

in the repeating units and monomers of the formulae I, Ia, II and IIa, Z is-CH in a preferred embodiment of the invention₂And m is 0, 1 or 2, in another preferred embodiment Z is-CH₂And m is 0 or 1, and in yet another preferred embodiment, Z is-CH₂-and m is 0.

Further preferred is where R^1-4Only one of which is not H and R^5-8Only one of which is not H.

To produce the desired properties for a particular application, combinations of norbornene monomers with a variety of different classes of pendant groups can be polymerized to obtain control over the flexibility, adhesion, interface, and solubility of the final polymer. For example, varying the length of the alkyl group attached to the backbone can allow control of the modulus and glass transition temperature (T) of the polymer_g). Further, it is selected from horsePendant groups of the maleimide, cinnamate, coumarin, anhydride, alcohol, ester, and epoxy functional groups can be used to facilitate crosslinking and improve solubility characteristics. Polar functional groups, epoxy groups, and triethoxysilyl groups can be used to provide adhesion to metals, silicon, and oxides in adjacent device layers. For example, fluorinated groups can be used to effectively alter the surface energy and affect the orthogonality of solutions with other materials.

Thus, in other preferred embodiments of the invention, especially for wherein R^1-4Only one of which is not H and in which R is^5-8In an embodiment in which only one is other than H, R^1-4Or R^5-8One or more of which represent a halogenated or perhalogenated aryl or aralkyl group including, but not limited to, those of the formula- (CH)₂)_x-C₆F_yH_5-yAnd- (CH)₂)_x-C₆F_yH_4-y-pC_zF_qH_2z+1-qWherein x, y, q and z are each independently selected from integers of 0to 5, 0to 9 and 1 to 4. In particular, these formulae include, but are not limited to, pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl, pentafluorophenethyl, pentafluorophenylpropyl, and pentafluorophenylbutyl.

Still in a preferred embodiment of the invention, very preferred is where R is^1-4Only one of which is not H and in which R is^5-8Of (a) is not H, at least one group other than H is a polar group having a terminal hydroxy, carboxy or oligoethyleneoxy moiety, such as a terminal hydroxyalkyl, alkylcarbonyloxy (e.g. acetyl), hydroxy-oligoethyleneoxy, alkoxy-oligoethyleneoxy or alkylcarbonyloxy-oligoethyleneoxy moiety, wherein "oligoethyleneoxy" is understood to mean- (CH) is₂CH₂O)_s-, and s is 1, 2 or 3; for example 1- (bicyclo [2.2.1]]Hept-5-en-2-yl) -2, 5,8, 11-tetraoxadodecane (NBTODD) wherein s is 3, and 5- ((2- (2-methoxyethoxy) ethoxy) methyl) bicyclo [2.2.1]Hept-2-ene (NBTON) wherein s is 2.

Still further, among them, R is particularly preferred^1-4Only one of which is not H and in which R is^5-8In a preferred embodiment of the present invention where only one is not H, at least one group other than H is a photoreactive group or a crosslinkable group. Preferably, this type of group comprises a linking moiety L and a functional moiety F. Preferably, L is selected from C₁-C₁₂And F preferably comprises one or more of maleimide, 3-monoalkyl-or 3, 4-dialkylmaleimide, an epoxy group, a vinyl group, an ethynyl group, a cinnamate group, an indenyl group or a coumarin moiety, which is capable of undergoing a crosslinking or 2+2 crosslinking reaction.

Suitable and preferred units of formulae I and II, including, for example, the photoreactive or crosslinkable pendent groups described above, are formed from one or more norbornene-type monomers including, but not limited to, those selected from the group consisting of the following formulae:

wherein n is an integer of 1 to 8, Q¹And Q²Each independently is-H or-CH₃R' is-H or-OCH₃。

Other preferred repeat units of formulae I and II as described above are derived from one or more norbornene-type monomers selected from the group consisting of the following structural formulae 1 to 5:

for formula 1 above, m is an integer from 0to 3, -A-R are those having a linking group, a spacer group, or a bridging groupPendant group, -A-is selected from CZ₂)_n、(CH₂)_n-(CH＝CH)_p-(CH₂)_n、(CH₂)_n-O、(CH₂)_n-O-(CH₂)_n、(CH₂)_n-C₆Q₄-(CH₂)_nAnd C (O) -O; and wherein the end group-R is selected from H, CZ₃、(CZ₂)_nCZ₃、OH、O-(O)CCH₃、(CH₂CH₂O)_nCH₃、(CH₂)_n-C₆Q₅Cinnamate or p-methoxycinnamate, coumarin, phenyl-3-indene, epoxide, CCSi (C)₂H₅)₃Or CCSi (i-C)₂H₅)₃Wherein each n is independently an integer from 0to 12, p is an integer from 1-6, and Q is independently H, F, CH₃、CF₃Or OCH₃Z is independently H or F, and R' is independently H or CH₃. For structural formulas 2-5, -A-is as defined for formula 1.

Preferred monomers according to structural formulae 1-5 include, but are not limited to, those selected from the group consisting of the following chemical names and CAS numbers if available, including 5-butylbicyclo [2.2.1]Hept-2-ene (BuNB) CAS #22094-81-1, 5-hexylbicyclo [2.2.1]Hept-2-ene (HexNB) CAS #22094-83-3, 5-octylbicyclo [2.2.1]Hept-2-ene (OctNB) CAS #22094-84-4, 5-decylbicyclo [2.2.1]]Hept-2-ene (DecNB) CAS #22094-85-5, 5- (2-phenylethyl) bicyclo [2.2.1]Hept-2-ene (PENB) CAS #29415-09-6, 1, 2,3, 4, 4a, 5,8, 8 a-octahydro-1, 4:5, 8-dimethano-naphthalene (TD) CAS #21635-90-5, bicyclo [2.2.1] CAS #21635]Hept-5-en-2-ylmethyl acetate (MeOACNB) CAS #10471-24-6, 2- (bicyclo [2.2.1]]Hept-5-en-2-ylmethoxy) -acetic acid ethyl ester (NBCH)₂GlyOAc), 2- (bicyclo [ 2.2.1)]Hept-5-en-2-ylmethoxy) -ethanol (NBCH)₂GlyOH) CAS #754231-21-5, 5- [ [2- (2-methoxyethoxy) ethoxy]Methyl radical]-bicyclo [2.2.1]Hept-2-ene (NBTON) CAS #544716-19-0, 1-bicyclo [2.2.1]]Hept-5-en-2-yl-2, 5,8, 11-tetraoxadodecane (NBTODD) CAS #307923-40-6, 5- (perfluorobutyl) -bicyclo [2.2.1]]Hept-2-ene (NBC)₄F₉) CAS #118777-97-2, 5- ((Total)Fluorophenyl) methyl) -bicyclo [2.2.1]Hept-2-ene (NBMeC)₆F₅) CAS #848781-71-5, 5- (perfluorophenyl) bicyclo [2.2.1]Hept-2-ene (NBC)₆F₅) 5- (3, 4-difluorobenzyl) bicyclo [2.2.1]Hept-2-ene (NBCH)₂C₆H₃F₂) 5- (4- (trifluoromethyl) phenyl) bicyclo [2.2.1]Hept-2-ene (NBCH)₂C₆H₄CF₃) 2, 2,3, 3, 3-Pentafluoropropylbicyclo [2.2.1]]Hept-5-ene-2-carboxylic acid ester (FPCNB) CAS #908372-02-1, 3, 3,4, 4,5, 5, 6,6, 6-nonafluorohexylbicyclo [ 2.2.1%]Hept-5-ene-2-carboxylic acid ester (FHCNB) CAS #944462-77-5, 2, 2,3, 3,4, 4,5, 5-octafluoropentyl-bicyclo [2.2.1]]Hept-5-ene-2-carboxylic acid ester (FOCHNB) CAS #99807-26-8, 2, 2,3, 3-tetrafluoropropyl-bicyclo [2.2.1]]Hept-5-ene-2-carboxylic acid ester (FPCHNB), bicyclo [2.2.1]Hept-5-en-2-ylmethyl perfluorooctanoic acid ester (C)₈PFAcNB) CAS #908372-04-3, 5- ((1, 1, 2-trifluoro-2- (perfluoropropoxy) -ethoxy) methyl) bicyclo [2.2.1]Hept-2-ene (PPVENB), 2- (6-bicyclo [2.2.1]]Hept-5-en-2-ylhexyl) -oxirane (EONB) CAS #950896-95-4, 2- [ (bicyclo [2.2.1]]Hept-5-en-2-ylmethoxy) methyl]-ethylene oxide (MGENB) CAS #3188-75-8, (4- (bicyclo [2.2.1] s]Hept-5-en-2-yl) but-1-yn-1-yl) triethylsilane (AkSiNB) ((4- (2- (bicyclo [2.2.1 ]))]Hept-5-en-2-yl) ethyl) phenyl) ethynyl) triethylsilane (ArSiNB), (E) -1- (4- (bicyclo [ 2.2.1)]Hept-5-en-2-ylmethoxy) phenyl) -3- (4-methoxyphenyl) prop-2-en-1-one (MCHMNB), (E) -1- (4- (bicyclo [ 2.2.1)]Hept-5-en-2-ylmethoxy) phenyl) -3- (naphthalen-2-yl) prop-2-en-1-one (NPCHMMNB), 1- (bicyclo [2.2.1]]Hept-5-en-2-ylmethyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (DMMIMeNB) CAS #1031898-89-1, 1- (2- (bicyclo [2.2.1]]Hept-5-en-2-yl) ethyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (DMMIEtNB) CAS #1031898-91-5, 1- (4- (bicyclo [2.2.1]]Hept-5-en-2-yl) butyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (DMMIBuNB), 1- (bicyclo [2.2.1] n]Hept-5-en-2-ylmethyl) -3-methyl-1H-pyrrole-2, 5-dione (MMIMMENB), 1- (bicyclo [2.2.1]]Hept-5-en-2-ylmethyl) -1H-pyrrole-2, 5-dione (MIMeNB) CAS #442665-16-9, 1- (2- (bicyclo [ 2.2.1)]Hept-5-en-2-yl) ethyl) -1H-pyrrole-2, 5-dione (MIEtNB), 1- (6- (bicyclo [2.2.1]]Hept-5-en-2-yl) hexyl) -3,4-dimethyl-1H-pyrrole-2, 5-dione (DMMIHxNB), 1- (4- (2- (bicyclo [2.2.1] ring)]Hept-5-en-2-yl) ethyl) phenyl) -3, 4-dimethyl-1H-pyrrole-2, 5-dione (EtPhDMMIiNB), 2- (bicyclo [2.2.1] n]Hept-5-en-2-ylmethyl) -4, 5-dihydro-1H-benzo [ e]Isoindole-1, 3(2H) -Dione (DHNMINB), (E) -bicyclo [2.2.1]Hept-5-en-2-ylmethyl 3- (4-methoxyphenyl) acrylate (MeOSinnNB) CAS #1059706-16-8, bicyclo [2.2.1]Hept-5-en-2-ylmethyl cinnamate (cinnnNB) CAS #185827-76-3, (E) -2- (bicyclo [2.2.1] methyl cinnamate]Hept-5-en-2-yl) ethyl 3- (4-methoxyphenyl) acrylate (EtMeOCinnNB), 7- (bicyclo [2.2.1]]Hept-5-en-2-ylmethoxy) -2H-chromen-2-one (MeCoumNB) CAS #192633-28-6, 7- (2- (bicyclo [ 2.2.1)]Hept-5-en-2-yl) ethoxy) -2H-chromen-2-one (EtCoumNB), 7- (4- (bicyclo [2.2.1] c]Hept-5-en-2-yl) butoxy) -2H-chromen-2-one (BuCoumNB), 2- (4- (2- (bicyclo [2.2.1]]Hept-5-en-2-yl) ethyl) phenyl) -1H-indene (EtPhIndNB), 2- (4- (bicyclo [2.2.1] n]Hept-5-en-2-yl) phenyl) -1H-indene (PhIndNB). It should be noted that as an acronym for each of the chemicals given the above names, it is indicated below by using the acronym for chemical if any of these chemicals is to be referred to.

Particularly suitable and preferred repeating units such as those of formulas I and II above are formed from one or more norbornene-type monomers including, but not limited to, those selected from the group consisting of the following formulas:

wherein "Me" represents a methyl group, "Et" represents an ethyl group, "OMe-p" represents a p-methoxy group, "Ph" and "C₆H₅"represents a phenyl group," C₆H₄"represents a phenylene group," C₆F₅"represents pentafluorophenyl group," OAc "in subformulae 9 and 11 represents acetate group," PFAc "in subformulae 25 represents-OC (O) -C₇F₁₅And for the above CH having a methylene bridge (covalently attached to both the norbornene ring and the functional group)₂) For each of the subformulae (including but not limited to 11-14, 16, 18, 19 and 54), it is understood that the methylene bridge group may be covalently bonded or- (CH)₂)_p-is substituted, and p is an integer from 1 to 6.

It is further understood that while 54 specific examples are provided above, other monomers according to preferred embodiments of the present invention are also included in the monomers represented by formulas Ia and IIa, where R is¹、R²、R³And R⁴Or R⁵、R⁶、R⁷And R⁸At least one of which is a hydrocarbyl, halohydrocarbyl and perhalocarbyl group, including heteroatoms, which include- (CH)₂)_n-C(CF₃)₂-OH，-(CH₂)_n-C(CF₃)(CH₃)-OH，(CH₂)_n-C(O)NHR^*，(CH₂)_n-C(O)Cl，-(CH₂)_n-C(O)OR^*，(CH₂)_n-OR^*，-(CH₂)_n-OC(O)R^*And- (CH)₂)_n-C(O)R^*Wherein n independently representsAn integer of 0to 10 and R^*Independently represent hydrogen, C₁-C₁₁Alkyl of (C)₁-C₁₁Halogenated or perhalogenated alkyl, C₂-C₁₀Alkenyl of, C₂-C₁₀Alkynyl of (A), C₅-C₁₂Cycloalkyl of, C₆-C₁₄Aryl of (C)₆-C₁₄Halogenated or perhalogenated aryl, C₇-C₁₄Aralkyl or halo or perhalo C of₇-C₁₄An aralkyl group of (2). Suitable and preferred perhaloalkyl groups include, but are not limited to, trifluoromethyl, trichloromethyl, -C₂F₅、-C₃F₇、-C₄F₉、-C₇F₁₅and-C₁₁F₂₃. Other suitable and preferred halogenated or perhalogenated aryl and aralkyl groups include, but are not limited to, those having the formula- (CH)₂)_x-C₆F_yH_5-yAnd- (CH)₂)_x-C₆F_yH_4-y-pC_zF_qH_2z+1-qWherein x, y, q and z are independently selected from integers of 0to 5, 0to 9 and 1 to 4, respectively. Highly preferred perhaloaryl groups include, but are not limited to, pentachlorophenyl, pentafluorophenyl, pentafluorobenzyl, 4-trifluoromethylbenzyl, pentafluorophenethyl, pentafluorophenylpropyl, and pentafluorophenylbutyl.

Although no stereochemical description is given for each of formulas I, Ia, II and IIa and each of the structural formulae provided above, it should be noted that unless indicated to the contrary, each of the monomers is typically obtained as a mixture of diastereomers which retains their configuration when converted into repeating units. Since the outer and inner (racemic) isomers of such diastereomeric mixtures may have slightly different properties, it will further be appreciated that these differences are exploited by using monomers which are themselves enriched in the outer or inner (racemic) isomer mixture or in the substantially pure advantageous isomer mixture to obtain the preferred embodiment of the invention.

In another preferred embodiment of the present inventionIn one embodiment, the polycycloolefin polymer has repeating units derived from a monomer according to formula Ia, wherein R^1-4Of (1), e.g. R¹Is a fluoro or perfluoroalkyl, aryl or aralkyl radical as described above and R^1-4The other group in (1) is H. A very preferred monomer is NBC₄F₉、NBCH₂C₆F₅、NBC₆F₅、NBCH₂C₆H₃F₂、NBCH₂C₆H₄CF₃、FPCNB、FHCNB、FHCNB、FPCHNB、C₈One of PFAcNB or PPVENB.

In another preferred embodiment of the invention, the polycycloolefin polymer has repeat units derived from a monomer according to formula Ia, wherein R^1-4Of (1), e.g. R¹Is a photoreactive or crosslinkable group as described above and R^1-4The other group in (1) is H. Very preferred monomers are one of DCPD, EONB, MGENB, AkSiNB, ArSiNB, MCHMNB, NPCHMMNB, DMMIMeNB, DMMIEtNB, DMMIBuNB, MMMIMeNB, MIMeNB, MIEtNB, DMMIHxNB, EtPhDMMIiNB, DHNMINB, MeOCinnNB, CinnNB, EtMeOCinnNB, MeCoumNB, EtCoumNB, BuCoumNB, EtPhIndNB or PhIndNB.

In another preferred embodiment of the invention, the polycycloolefin polymer has repeat units derived from a monomer according to formula Ia, wherein R^1-4Of (1), e.g. R¹Is an alkyl group as described above and R^1-4The other group in (a) represents H. A very preferred monomer is one of BuNB, HexNB, OctNB and DecNB.

In another preferred embodiment of the invention, the polycycloolefin polymer has repeat units derived from a monomer according to formula Ia, wherein R^1-4Of (1), e.g. R¹Is a polar group having a hydroxyl, carboxyl, acetoxy or oligoethyleneoxy moiety as described above and R^1-4The other group in (a) represents H. Very preferred monomers are MeOAc NB, NBXOH, NBCH₂GlyOAc、NBCH₂GlyOH, NBTON or NBTODD.

An exemplary preferred embodiment of the present invention includes polymers having a first type of repeating unit derived from a fluorinated monomer as described above and a second type of repeating unit derived from a crosslinkable monomer also as described above. A very preferred example of such a preferred embodiment is a compound having a chemical formula derived from NBCH₂C₆F₅And further having a polymer derived from repeat units of a monomer selected from DMMIMeNB, DMMIEtNB, DMMIBuNB and DMMIHxNB.

Another preferred example of such a preferred embodiment is a polymer having repeating units derived from monomers according to BuNB, HexNB, OctNB, DecNB and MeOAcNB, and furthermore having repeating units derived from monomers selected from the group consisting of EONB, MGENB, DMMIMeNB, DMMIEtNB, DMMIBuNB and DMMIHxNB.

Another preferred embodiment of the present invention relates to polymers having more than three different types of repeating units according to formula I or formula II. Another preferred embodiment of the present invention relates to a polymer blend of a first polymer having a first type of repeating unit according to formula I and a second polymer having at least a first type of repeating unit and a second type of repeating unit according to formula II. Another preferred embodiment of the present invention relates to a polymer blend comprising the aforementioned second polymer and an alternative first polymer having two or more types of repeating units according to formula I. Another preferred embodiment of the present invention relates to a polymer blend comprising an alternative second polymer having three types of repeat units according to formula II mixed with the aforementioned alternative first polymer.

Another preferred embodiment of the present invention comprises polymers having at least one recurring unit according to formula I and at least one recurring unit according to formula II, wherein the ratio of recurring units of formulae I and II is from 95: 5to 5: 95. In another preferred embodiment, the ratio of the recurring units of the formulae I and II is from 80: 20 to 20: 80. In another still preferred embodiment, the ratio of the recurring units of formula I and formula II is from 60: 40 to 40: 60. In another further preferred embodiment, the ratio of the recurring units of the formulae I and II is from 55: 45 to 45: 55.

Another preferred embodiment of the present invention comprises a polymer blend of one or more polymers each having at least one type of repeating unit according to formula I and one or more polymers having a repeating unit different from a norbornene-type repeating unit. These other polymers are preferably selected from polymers including, but not limited to, poly (methyl methacrylate) (PMMA), Polystyrene (PS), poly-4-vinylphenol, polyvinylpyrrolidone, or combinations thereof, such as PMMA-PS and PS-polyacrylonitrile.

Examples of suitable norbornene monomers, polymers and methods for their synthesis are provided by the present invention and may also be found in US 5,468,819, US 6,538,087, US 2006/0020068 a1, US 2007/0066775 a1 and US 2008/0194740 a1, which are incorporated herein by reference. For example, an exemplary polymerization process using a group VIII transition metal catalyst is described in the aforementioned US 2006/0020068 a1.

Embodiments of the polymers formed in the present invention have a weight average molecular weight (M) suitable for their use_w). Typically, M is found to be 5,000 to 500,000_wAre suitable for some embodiments, while other M's are suitable for other embodiments_wMay be advantageous. For example, in a preferred embodiment, the polymer has an M of at least 30000_wAnd in another preferred embodiment, the polymer has an M of at least 60000_w. In another preferred embodiment, M of the polymer_wIs up to 400000, while in another preferred embodiment, M of the polymer_wUp to 250000. It will be appreciated that this is due to the appropriate M_wIs a function of the desired physical properties in the cured polymer, film, layer or structure derived therefrom, and thus this is a design choice and thus any M within the ranges provided above_wAre within the scope of the invention.

A preferred embodiment according to the present invention comprises the use of the polymer composition for forming a gate insulating layer in an organic electronic device. Such compositions comprise, in addition to one or more polycycloolefin polymer components, a casting solvent, optionally having orthogonal solubility properties with respect to the OSC layer material, and optionally one or more additives selected from the group consisting of cross-linking agents, reactive solvents, stabilizers, UV sensitizers, adhesion promoters and heat sensitizers.

Sensitizers and other additives are typically added to the composition before it is used to form the aforementioned gate insulating layer. Thus, preferred embodiments according to the present invention include electronic or optoelectronic devices having such polymer compositions or obtained by using such polymer compositions.

Such electronic devices include, inter alia, Field Effect Transistors (FETs) and Organic Field Effect Transistors (OFETs), Thin Film Transistors (TFTs) and Organic Thin Film Transistors (OTFTs), which may be top or bottom gate transistors, Integrated Circuits (ICs) and devices such as Radio Frequency Identification (RFID) tags. A transistor prepared by using such a polymer composition as a gate insulator or dielectric layer is schematically depicted in, for example, fig. 1 and 2.

When using polynorbornenes that include pendent maleimide groups as crosslinkable groups, preferred embodiments of the present invention use commercially available UV sensitizers, such as 1-chloro-4-propoxythioxanthone (CPTX), other commercially available UV sensitizers that absorb at a wavelength different from that of the maleimide groups, thereby increasing the amount of absorption of incident light and undergoing triplet-triplet energy transfer to the maleimide excited state. The sensitizer may be incorporated into the polymer chain or added to the above-mentioned polymer composition. It is also possible to use a first compound of formula Ia or IIa having better absorption properties at a given wavelength, incorporated into a polymer formed from a second compound of formula Ia or IIa having the same potentially reactive groups as the first compound. This can be achieved by adding a lower amount, for example 20%, of the first compound to a larger amount, for example 80%, of the second compound and allowing curing to occur at a given wavelength. For example, compound DHNMINB (43) absorbs well at 365nm, which is not the case with compound DMMIMeNB (34), thus allowing curing to occur at 365nm without the addition of other UV sensitizers by adding, for example, 20% DHNMINB to DMMIMeNB. DMMIMeNB may undergo a reaction with DHNMINB or, alternatively, if the second component does not involve crosslinking, it may be insoluble through the surrounding DHNMINB polymer network.

Epoxide crosslinking is preferably achieved using a combination of epoxy side functional groups and acid catalysts. Such acid catalysts are typically onium salts, which undergo decomposition upon exposure to UV radiation or heat. In the case of a photoacid generator (PAG), initiation typically requires a low UV dose of appropriate wavelength, followed by a thermal anneal between 80 and 180 ℃. Generally, a temperature at the lower end of the aforementioned range is more preferred, as higher temperatures may require a nitrogen atmosphere to prevent oxidation of the polymer. Alternatively, the crosslinking may be thermally initiated and cured by baking at 180 ℃ for 30 minutes in a nitrogen atmosphere. After the crosslinking treatment, the polymer network may contain residual acid from the PAG. To prevent undesired effects due to such residual acids in organic transistor devices comprising dielectrics, the crosslinked polymer may be subjected to a swelling solvent in which water or a base dissolves. In this way, this residual acid can be captured, neutralized and/or dissolved and then removed from the polymer by further washing with fresh swelling solvent.

In another preferred embodiment of the present invention, in addition to the addition of components directly involved in photocrosslinking, a multi-component formulation may be added to the norbornene-type addition polymer to improve specific other properties. These additional components are preferably selected from the group consisting of antioxidants, radical scavengers, adhesion promoting components, surface modifying components and morphology controlling components. In particular, suitable and preferred adhesion promoting compounds include silanes or sulfur containing compounds.

In still other preferred embodiments of the present invention, in the method for preparing a gate insulating layer, a separate formulation, such as a formulation comprising an adhesion promoter or a purging reactive washing solution, is used in addition to the gate insulator polymer composition described in the present invention.

The invention also relates to an electronic device having such a polymer composition or obtained by using such a polymer composition. Such electronic devices include, inter alia, Organic Field Effect Transistors (OFETs), Thin Film Transistors (TFTs), Integrated Circuits (ICs) and Radio Frequency Identification (RFID) tags. If such an electronic device embodiment comprises a transistor prepared by using such a polymer composition for forming a gate insulating layer, such a transistor may advantageously comprise both top-gate and bottom-gate transistors.

Turning now to the discussion of the drawings, fig. 1 and 2 depict top-gate and bottom-gate organic field effect transistors, respectively, according to preferred embodiments of the present invention.

The top gate OFET device of fig. 1 comprises a substrate (1), source and drain electrodes (2), an OSC layer (3), a gate insulating layer (4), a gate electrode (5) and optionally a second insulator or protective layer (6) in order to shield the gate electrode from other layers or devices that may be subsequently provided.

Another object of the invention is a method for the preparation of a device, e.g. as shown in fig. 1, wherein a) source and drain electrodes (2) are formed on a substrate (1), b) a layer of an Organic Semiconductor (OSC) material (3) is formed over a portion of the substrate (1) and the source and drain electrodes (2), c) a gate insulating layer (4) is formed over the OSC material (3), d) a gate electrode (5) is formed over at least a portion of the insulator layer (4), and e) optionally a further layer (6), e.g. an insulating and/or protective and/or stabilizing and/or adhesive layer, is formed over the gate electrode (5) and the gate insulating layer (4).

In a preferred embodiment of the invention, a device such as that shown in figure 1 is prepared by the above method, but wherein the OSC layer (3) is formed on the substrate (1) before the source and drain electrodes (2) are formed.

The bottom gate OFET device of fig. 2 comprises a substrate (1), source and drain electrodes (2), an OSC layer (3), a gate insulating layer (4), a gate electrode (5) and optionally a second insulator or protective layer (6) to shield the source and drain electrodes from other layers and devices provided on top of the OFET.

Another object of the invention is a method for manufacturing a device, as illustrated schematically in fig. 2, wherein: a) forming a gate electrode (5) on a substrate (1), b) forming a gate insulating layer (4) over the gate electrode (5) and portions of the substrate (1), c) forming a layer of an Organic Semiconducting (OSC) material (3) over the gate insulating layer (4), d) forming source and drain electrodes (2) over at least a portion of the organic semiconducting layer (3) and e) optionally forming a further layer (6), such as an insulating and/or protective and/or stabilizing and/or adhesive layer, over portions of the source and drain electrodes (2) and the OSC layer (3).

In a preferred embodiment of the invention, a device such as that shown in figure 2, is prepared by a method as described above, but wherein the source and drain electrodes (2) are located above the gate insulating layer (4) prior to formation of the organic semiconductor layer (3).

In the method of the present invention, the formation of some or all of the layers is preferably carried out using solution processing techniques, as described above in connection with fig. 1 and 2. This can be achieved, for example, by applying a formulation or composition, usually a solution, for example comprising, for example, the OSC or gate dielectric material, respectively, and at least one solvent, onto or over the previously deposited layer, followed by evaporation of the solvent. To form a gate dielectric or insulating layer, the polymer composition embodiments of the present invention described above are used. Highly preferred deposition techniques include, but are not limited to, dip coating, spin coating, ink jet printing, letterpress printing, screen printing, doctor blade coating, roll printing, reverse roll printing, offset printing, flexographic printing, web printing, spray coating, brush coating, or pad printing. More preferably, spin coating, flexographic printing or inkjet printing techniques are used.

It will of course also be appreciated that the particular parameters in any of the above solution deposition techniques may be tailored to the ultimate desired characteristics of the particular layers used to form them and the devices of which they are a part. For example, if a gate insulator layer having a thickness of 0.5 micrometers (μm) is desired in some preferred OFETs, such a layer may form the desired thickness of 1.0 μm in other preferred OFETs. The specific parameters required to form a 1.0 μm layer must therefore be different from those required to form a 0.5 μm layer. That is, when spin-on deposition techniques are used, a suitable amount of the polymer composition of the embodiments of the present invention is applied to a substrate and spun, for example between 500 and 2000rpm, for example for a period of 20 to 50 seconds, to form a layer having a desired thickness, for example between 0.2 and 1.5 μm. After casting the layer on the substrate, the substrate and layer are typically heated to remove residual volatile solvent. This heating can be accomplished in an oven or by placing the substrate on a heated surface set at a temperature of 70 to 130 c, for example for a period of 1 to 30 minutes. It should be noted that if a spin coating technique is used it is generally desirable to use a solvent that can evaporate off for the most part after the spin coating is completed, whereas when inkjet or flexographic printing techniques are used, organic ketone solvents with high boiling points are generally used to extend the processing time associated with the equipment.

A preferred embodiment of the present invention relates to a composition comprising one or more polyolefin polymers or polymer blends as described above and below and one or more solvents, preferably selected from organic solvents including but not limited to hydrocarbon solvents, aromatic solvents, alicyclic cyclic ethers, esters, lactones, ketones, amides, cyclic carbonates, fluorinated or perfluorinated solvents or mixtures of the above. Exemplary solvents include cyclohexanone, mesitylene, xylene, toluene, tetrahydrofuran, Methyl Ethyl Ketone (MEK), methyl n-amyl ketone (MAK), cyclohexanone, 4-methyl anisole, butyl phenyl ether, cyclohexylbenzene, Propylene Glycol Methyl Ether Acetate (PGMEA), HFE7500, perfluoromethyldecalin, and perfluorophenanthrene.

The concentration of the polycycloolefin polymer or polymer blend in the composition is preferably from 0.1 to 30 wt%, very preferably from 1 to 20 wt% and most preferably from 2to 12 wt%.

As mentioned above, in order to improve one or more properties of the resulting film, preferred polymer compositions of the present invention comprise a crosslinkable or crosslinked polycycloolefin polymer to form the gate insulating layer or a component therein. The properties of these films include, inter alia, structural integrity, durability, mechanical resistance, and solvent resistance. Suitable and preferred crosslinkable polymers are, for example, those having one or more repeating units derived from monomers of the formula Ia, where R is^1-4One or more of which represent a crosslinkable group as described above, for example one of the DMMI-type monomers or one of the EONB or MGENB.

For crosslinking, the polymer forming the gate insulator is typically exposed to electron beam or electromagnetic (actinic) radiation, such as X-ray, UV or visible light radiation or IR radiation, e.g. concentrated IR for local thermal crosslinking (e.g. using a laser). For example, actinic radiation may be used to image (image) the polymer using wavelengths from 11nm to 700nm, for example 200 to 700 nm. The dose of actinic radiation used for the exposure is generally from 25 to 5000mJ/cm²Although higher energies may be used if appropriate. Suitable sources of actinic radiation include mercury, mercury/xenon, mercury/halogen and xenon lamps, argon or xenon laser sources, X-ray or electron beam sources. The exposure to actinic radiation results in crosslinking in the exposed areas.

In a preferred embodiment, the gate insulating layer is baked at a temperature of 70 ℃ to 300 ℃ for a period of time, for example, 1 to 10 minutes, after exposure. Post-exposure bake may be used to further promote crosslinking of other crosslinkable moieties in the exposed portions of the polymer, where the increased temperature of such bake is used to further crosslink the degree in these exposed regions.

In a preferred embodiment, a crosslinkable polymer composition is used to form a gate insulating layer, which comprises one or more crosslinkable polycycloolefin polymers comprising repeat units of formula I or II, wherein at least one of these repeat units comprises a crosslinkable pendent group.

Very preferred are polymer compositions comprising a sensitizer, such as CPTX, and a solvent, such as MAK, cyclohexanone, or cyclopentanone.

In another preferred embodiment, the crosslinkable polymeric composition includes a stabilizer material or moiety to prevent self-crosslinking and to increase the shelf life of the polymeric composition. Suitable stabilizers are antioxidants, such as catechol or phenol derivatives, which optionally comprise one or more large alkyl groups, such as tert-butyl groups, in ortho position to the phenolic OH group.

The physical integrity of electronic devices is a key factor in the fabrication of more complex structures, such as the active matrix backplane of flat panel electro-optic displays. The bond between the substrate and the overlying stack of layers should be strong enough to withstand further processing, such as air curtain drying or wet processing using organic solvents. If the bond is not strong enough, it is possible that the overlying layer may peel off, for example in the case of air curtain drying, or that the layer may migrate from the substrate, for example when solvent reaches between the substrate and the layer by capillary forces in the case of wet processing. This is even more important when using plastic substrates, since the surface energy of untreated plastics is generally so low that the adhesion is not high. Possible solutions suggested in the prior art to overcome these problems include methods of chemically modifying the surface of these substrates, such as oxygen plasma treatment, or the use of substrates previously coated with additional layers, such as metal oxide layers for plastic substrates. However, methods of chemical modification of, for example, dielectric polymers are limited because these can have a negative impact on their properties, such as their solubility, or can have a negative impact on device performance.

In a preferred embodiment of the present invention, therefore, a reactive adhesion promoter is used in addition to the crosslinkable polymer composition comprising the crosslinkable polycycloolefin used to form the gate insulating layer. The reactive adhesion promoter includes a first crosslinking functional group capable of crosslinking with the crosslinkable pendent groups in the crosslinkable polycycloolefin polymer, and a second functional group that is a surface active group capable of interacting, e.g., chemically linking, with an adjacent device layer. Such adjacent device layers are for example underlying functional device layers on which a substrate or gate insulating layer is deposited, or functional layers deposited on the gate insulating layer.

In a first class of such preferred embodiments, the adhesion promoter is deposited on the substrate or a layer on which the gate insulator is subsequently formed, prior to the deposition of the crosslinkable polycycloolefin polymer composition which is to form the insulator layer. The adhesion promoter is deposited on the substrate, for example, by soaking the substrate with a solution of the adhesion promoter in a suitable solvent and then removing the solvent. The adhesion promoter forms a thin layer on the surface of the substrate, optionally in the case of forming a chemical bond to the substrate. Thereafter, a crosslinkable polymer composition is deposited on the substrate surface covered with the adhesion promoter layer. After removal of any solvent, the adhesion promoter and the crosslinkable groups of the crosslinkable polycycloolefinic polymer are crosslinked, for example by UV exposure.

The gate insulating layer according to the first class of preferred embodiments may thus be prepared by a method comprising the steps of: a) depositing an adhesion promoter as described above and below, optionally dissolved or dispersed in one or more organic solvents, on a substrate or on a device layer, for example a semiconductor layer or an electrode, b) removing the solvent, if present, thereby forming an adhesion promoter layer on the surface of the substrate, c) depositing a layer of a crosslinkable polycycloolefin polymer composition comprising a crosslinkable polycycloolefin polymer as described above and below and optionally a solvent, d) removing the solvent, if present, and e) exposing the polycycloolefin polymer layer to heat or actinic radiation which causes crosslinking of the crosslinkable groups of the adhesion promoter and the crosslinkable groups of the polycycloolefin polymer, thereby forming a gate insulating layer, on the surface of the substrate comprising the adhesion promoter layer.

In a second class of such preferred embodiments, the gate insulating layer is formed from a crosslinkable polymer composition comprising a crosslinkable polycycloolefin polymer and an adhesion promoter additive comprising a surface-active functional group and a crosslinkable functional group capable of crosslinking with the crosslinkable group of the crosslinkable polycycloolefin polymer.

The gate insulating layer according to the second preferred embodiment may be prepared by a method comprising the steps of: a) depositing a layer of a crosslinkable polymer composition comprising an adhesion promoter, a crosslinkable polycycloolefin polymer and a solvent on a substrate or a device layer, such as a gate insulating layer, a semiconductor layer or an electrode, b) removing the solvent, and c) exposing the layer of the polymer composition to heat or actinic radiation which results in crosslinking of the crosslinkable groups of the adhesion promoter with the crosslinkable groups of the polyolefin-based polymer, thereby forming the gate insulating layer.

The use of these reactive adhesion promoters in the crosslinkable polymer compositions of the invention can advantageously improve the adhesion of the layer formed therefrom to the underlying layer.

Thus, the adhesion of the gate insulating layer can be improved without changing the polymer used to form the layer and without potentially negatively affecting the performance of the layer.

The surface-active group of the reactive adhesion promoter is preferably a silane or silazane group. Preferably the surface active group is of the formula-SiR¹²R¹³R¹⁴Or a silane group of the formula-NH-SiR¹²R¹³R¹⁴A silazane group of (2), wherein R¹²、R¹³And R¹⁴Each independently selected from halogen, silazane, C₁-C₁₂-alkoxy, C₁-C₁₂-alkylamino, optionally substituted C₅-C₂₀Aryloxy and optionally substituted C₂-C₂₀-heteroaryloxy, and wherein R¹²、R¹³And R¹⁴One or both of which may also represent C₁-C₁₂-alkyl, optionally substituted C₅-C₂₀-aryl or optionally substituted C₂-C₂₀-a heteroaryl group.

The crosslinkable group of the reactive adhesion promoter is preferably selected from the group consisting of maleimide, 3-monoalkylmaleimide, 3, 4-dialkylmaleimide, epoxy, vinyl, acetyl, indenyl, cinnamate or coumarin groups, or comprises a substituted or unsubstituted maleimide, epoxide, vinyl, cinnamate or coumarin moiety.

Very preferably, the adhesion promoter is selected from formula III:

G-A′-P III

wherein G is a surface-active group, preferably as defined above and below, a' is a single bond or a linking, spacer or bridging group, and P is a crosslinkable group, preferably as defined above and below.

G is preferably of the formula-SiR¹²R¹³R¹⁴Or a group of the formula-NH-SiR¹²R¹³R¹⁴Wherein R is¹²、R¹³And R¹⁴Each independently selected from halogen, silazane, C₁-C₁₂-alkoxy, C₁-C₁₂-alkylamino, optionally substituted C₅-C₂₀Aryloxy and optionally substituted C₂-C₂₀-heteroaryloxy, and wherein R¹²、R¹³And R¹⁴One or both of which may also represent C₁-C₁₂-alkyl, optionally substituted C₅-C₂₀-aryl or optionally substituted C₂-C₂₀-a heteroaryl group.

P is preferably selected from the group consisting of maleimide, 3-monoalkylmaleimide, 3, 4-dialkylmaleimide, epoxy, vinyl, acetyl, indenyl, cinnamate or coumarin groups, or comprises a substituted or unsubstituted maleimide moiety, epoxide moiety, vinyl moiety, cinnamate moiety or coumarin moiety.

Preferably A' is selected from (CZ)₂)_n、(CH₂)_n-(CH＝CH)_p-(CH₂)_n、(CH₂)_n-O、 (CH₂)_n-O-(CH₂)_n、(CH₂)_n-C₆Q₄-(CH₂)_n、(CH₂)_n-C₆Q₁₀-(CH₂)_nAnd C (O) -O, wherein each n is independently an integer of 0to 12, p is an integer of 1 to 6, Z is independently H or F, C₆Q₄Is phenyl substituted by Q, C₆Q₁₀Is cyclohexyl substituted by Q, Q is independently H, F, CH₃、CF₃Or OCH₃。

Suitable and preferred compounds are selected from formula a 1:

wherein SiR¹²R¹³R¹⁴Is a silane group as defined above, A' is as defined above and below, and R¹⁰And R¹¹Each independently is H or C₁-C₆An alkyl group. Particularly preferred is DMMI-propyl- (Si (OEt)₃DMMI-butyl- (Si (OEt)₃DMMI-butyl- (Si (OMe)₃DMMI-hexyl- (Si (OMe)₃。

The terms "spacer group", "linker group" and "bridging group" as used herein are known to those skilled in the art (see, e.g., Pure appl. chem.73(5), 888 (2001)).

The radical A' preferably represents a linear C₁To C₃₀Alkylene or branched C₃To C₃₀Alkylene or cyclic C of₅To C₃₀Alkylene, each of which is unsubstituted or mono-or polysubstituted with F, Cl, Br, I or CN, wherein optionally one or more non-adjacent CH₂The radicals being, independently of one another in each case, substituted by-O-, -S-, -NH-, -NR-in such a way that O and/or S atoms are not linked directly to one another¹⁸-、-SiR¹⁸R¹⁹-, -C (O) -, -C (O) O-, -OC (O) -, -OC (O) -O-, -S-C (O) -, -C (O) -S-, -CH ≡ CH-or-C ≡ C-substitution.

R¹⁸And R¹⁹Each of which isIndependently is H, methyl, ethyl or C₃To C₁₂Linear or branched alkyl groups of (a).

Preferred groups A' are- (CH)₂)_p-、-(CH₂CH₂O)_q-CH₂CH₂-、-CH₂CH₂-S-CH₂CH₂-or-CH₂CH₂-NH-CH₂CH₂-or- (SiR)¹⁸R¹⁹-O)_p-, and p is an integer from 2to 12, q is an integer from 1 to 3, and R¹⁸And R¹⁹Having the meaning given above.

Other preferred groups A' are selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

The synthesis of adhesion promoters similar to those of formula a1 is disclosed in example AD1 and in US 4,565,873.

In another preferred embodiment the gate insulating layer comprises a polymer or polymer composition comprising one or more repeating units, preferably of formula I or formula II, having a repeating unit of a crosslinkable group and the gate insulating layer further comprises a crosslinking agent which is a compound comprising two or more crosslinkable functional groups capable of reacting with the crosslinkable groups of said repeating units of the polymer or polymer composition.

In order to improve the processing of functional layers and the integrity of electronic devices, it is desirable to reduce the time required for processing while maintaining or improving the physical properties of the layers formed. This can be maintained if subsequent layers and the solvent used to form these layers are orthogonal and therefore do not dissolve in each other. If such orthogonality makes it difficult to obtain cross-linking, typically UV cross-linking, the first functional layer renders such first layer insoluble in relation to the polymer composition of the second functional layer, which will prevent any influence on the properties of any of the other layers.

Reducing the time required for processing can be carried out, for example, by adjusting the coating method, while reducing the time required for UV crosslinking can be achieved by chemical adjustment of the dielectric polymer or by changes in the method.

However, chemical modification of dielectric polymers is limited because UV sensitivity involves certain properties of the polymer dielectric and, for example, changes toward increasing UV sensitivity can reduce solubility. Modifying the process, for example by using higher energy UV, can increase the likelihood of producing an ozone atmosphere and thus lead to undesirable modifications on the surface of the polymer dielectric.

Thus, in a preferred embodiment of the present invention, the polymer composition comprises one or more crosslinking additives. Such additives include two or more functional groups capable of reacting with the crosslinkable pendent group of the polycycloolefin polymer used to form the gate insulating layer. It will also be appreciated that the use of such crosslinking additives will also enhance the crosslinking of the aforementioned polymers.

Crosslinking by exposure to UV radiation is preferred.

The use of a cross-linking agent enhances the ability to pattern the gate insulating layer through the use of imagewise exposure to a suitable wavelength and dose of UV radiation.

The crosslinkable group of the crosslinker is preferably selected from a maleimide, 3-monoalkylmaleimide, 3, 4-dialkylmaleimide, epoxy, vinyl, acetyl, indenyl, cinnamate or coumarin group, or a group comprising a substituted or unsubstituted maleimide moiety, epoxide moiety, vinyl moiety, cinnamate moiety or coumarin moiety.

Very preferred crosslinkers are selected from the formulae IV1 or IV 2:

P-X-P IV1

H_4-mC(A″-P)_mIV2

wherein X is A ' -X ' -A ', X ' is O, S, NH or a single bond, A ' is a single bond or a linking, spacer or bridging group, which is preferably selected from (CZ)₂)_n、(CH₂)_n-(CH＝CH)_p-(CH₂)_n、(CH₂)_n-O、(CH₂)_n-O-(CH₂)_n、(CH₂)_n-C₆Q₁₀-(CH₂)_nAnd C (O) -O, wherein each n is independently an integer of 0to 12, p is an integer of 1 to 6, Z is independently H or F, C₆Q₁₀Is cyclohexyl substituted by Q, Q is independently H, F, CH₃、CF₃Or OCH₃And P has the meaning of formula III or one of the preferred meanings given above and below, m is 2,3 or 4.

Suitable and preferred compounds are selected from the formula C1:

wherein R is¹⁰And R¹¹Each independently is H or C₁-C₆Alkyl group of (1). A' is as defined in formula (I), and n is an integer from 1 to 10. Particularly preferred are DMMI-butyl-DMMI, DMMI-pentyl-DMMI and DMMI-hexyl-DMMI.

The spacer group A' preferably represents a linear chain C₁To C₃₀Alkylene or branched C of₃To C₃₀Alkylene or cyclic C₅To C₃₀Alkylene, each of which is unsubstituted or mono-or polysubstituted with F, Cl, Br, I or CN, wherein optionally one or more non-adjacent CH' s₂The radicals being, independently of one another in each case, substituted by-O-, -S-, -NH-, -NR-in such a way that O and/or S atoms are not linked directly to one another¹⁸-、-SiR¹⁸R¹⁹-、-C(O)-、 -C(O)O-、-OC(O)--OC (O) -, -O-, -S-C (O) -, -S-, -CH ═ CH-or-C.ident.C-substitution, R¹⁸And R¹⁹Each independently of the other being H, methyl, ethyl or C₃To C₁₂Linear or branched alkyl groups of (a).

A preferred group A' is- (CH)₂)_p-、-(CH₂CH₂O)_q-CH₂CH₂-、-CH₂CH₂-S-CH₂CH₂-or-CH₂CH₂-NH-CH₂CH₂-or- (SiR)¹⁸R¹⁹-O)_p-, and p is an integer from 2to 12, q is an integer from 1 to 3, and R¹⁸And R¹⁹Having the meaning given above.

Other preferred groups A' are selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene-thioethylene, ethylene-N-methyl-iminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

The synthesis of crosslinkers similar to those of formula C1 is disclosed, for example, in examples AD2 and AD3 and in US 3,622,321.

In another preferred embodiment of the present invention, in the aforementioned method for preparing a gate insulating layer or an electronic device, the gate insulating layer is formed of a polymer composition comprising a crosslinkable polycycloolefin polymer and a crosslinking agent as described above and below, and the method for forming the gate insulating layer comprises the step of crosslinking the crosslinking agent and the crosslinkable group of the crosslinkable polymer, preferably by UV exposure.

Other components or functional layers of the electronic device, such as the substrate, electrodes and OSC layers, may be selected from standard materials and may be fabricated and applied to the device by standard methods. Suitable materials and manufacturing methods for these components and layers are known to those skilled in the art and described in the literature.

While different substrates may be used to fabricate organic electronic devices, such as glass or plastic substrates, these plastic substrates are generally more common. Preferred plastic materials include, but are not limited to, alkyds, allyl esters, benzocyclobutene, butadiene-styrene, cellulose acetate, epoxies, epoxy polymers, ethylene-chlorotrifluoroethylene copolymers, ethylene-tetrafluoroethylene copolymers, glass fiber reinforced plastics, fluorocarbon polymers, hexafluoropropylene vinylidene fluoride copolymers, high density polyethylene, parylene, polyamides, polyimides, polyaramides, polydimethylsiloxane, polyethersulfone, polyethylene naphthalate, polyethylene terephthalate, polyketones, polymethylmethacrylate, polypropylene, polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyvinylchloride, silicone, and silicone. While polyethylene terephthalate, polyimide, and polyethylene naphthalate are commonly used substrate materials, useful substrates may also include metal or glass components coated with any of the above-described plastic materials. Furthermore, it should not be surprising that the use of a substrate having a uniform, uniform surface generally results in good pattern definition. For top gate embodiments, the substrate may also be uniformly pre-aligned by extrusion, stretching, or rubbing in order to affect the orientation of the organic semiconductor to improve carrier mobility.

The electrode may be deposited by liquid coating, such as spray coating, dip coating, roll coating or spin coating, or by vacuum deposition or chemical vapor deposition. Suitable electrode materials and deposition methods are known to those skilled in the art. Suitable electrode materials include, but are not limited to, inorganic or organic materials, or a combination of both.

Examples of suitable conductor or electrode materials include polyaniline, polypyrrole, PEDOT or doped conjugated polymers, but also dispersions or pastes of graphite or metal particles, such as Au, Ag, Cu, Al, Ni or mixtures thereof, and sputter-coated or evaporated metals, such as Cu, Cr, Pt/Pd or metal oxides, such as Indium Tin Oxide (ITO). Organometallic precursors resulting from liquid phase deposition may also be used.

The OSC materials and methods for applying the OSC layer may be selected from standard materials and methods known to the person skilled in the art and described in the literature.

In the case of an OFET device in which the OFET layer is an OSC, it may be an n-or p-type OSC, which may be deposited by vacuum or chemical vapour, or from solution. The desired OSC has more than 1x10^-5cm²V^-1s^-1The FET mobility of (1).

The OSC is used, for example, as an active channel material in OFETs or as a layer element of organic rectifying diodes. The OSC is typically deposited by liquid coating to allow environmental processing. Exemplary liquid coating methods include, but are not limited to, spray coating, dip coating, roll coating, or spin coating. In some embodiments according to the invention, deposition by inkjet is used. Furthermore, in some embodiments, the OSC may be vacuum or chemical vapor deposited.

The semiconductor channel may also be a composite of two or more semiconductors of the same type. Furthermore, the p-type channel material may be mixed with the n-type material for example for the effect of doping the layer. Multiple semiconductor layers may also be used. For example, the semiconductor may be intrinsic near the insulator interface and the highly doped region may additionally be coated adjacent to the intrinsic layer.

The OSC material may be any conjugated molecule, such as an aromatic molecule comprising at least three aromatic rings. In some preferred embodiments of the invention, the OSC comprises an aromatic ring selected from a 5-, 6-or 7-membered aromatic ring, while in other preferred embodiments the OSC comprises an aromatic ring selected from a 5-or 6-membered aromatic ring. The OSC material may be a monomer, oligomer or polymer, including mixtures, dispersions and blends of one or more monomers, oligomers or polymers.

Each aromatic ring of the OSC optionally contains one or more heteroatoms selected from Se, Te, P, Si, B, As, N, O or S, wherein the heteroatoms are typically selected from N, O or S.

Furthermore, the aromatic rings may be optionally substituted by alkyl, alkoxy, polyalkoxy, thioalkyl, acyl, aryl or substituted aryl groups, halogens, in particular fluorine, cyano, nitro or optionally substituted via-N (R)¹⁵)(R¹⁶) A secondary or tertiary alkylamine or arylamine of formula (I), wherein R¹⁵And R¹⁶No more than one of which is H, and one or both are independently substituted alkyl or optionally substituted aryl, alkoxy or polyalkoxy groups, and if R is¹⁵Or R¹⁶Are alkyl or aryl, those may be fluorinated or perfluorinated.

The rings may also be fused or linked to a covalent linking group, e.g. -C (T)¹)＝C(T²)-，-C≡C-，-N(R′)₂-，-N＝N-，-N＝C(R’)-。T¹And T²Each independently represents H, Cl, F, -C ≡ N or lower alkyl, especially C_1-4An alkyl group; r' represents H, optionally substituted alkyl or optionally substituted aryl. If R' is alkyl or aryl, those may also optionally be fluorinated.

Other preferred OSC materials that may be used in the present invention include compounds, oligomers and derivatives of compounds selected from the group consisting of conjugated hydrocarbon polymers, such as polyacenes, polyphenylenes, poly (phenylenevinylenes), polyfluorenes, including oligomers of these conjugated hydrocarbon polymers; condensed aromatic hydrocarbons, e.g. tetracenes,(chrysene), pentacene, pyrene, perylene, coronene, or soluble, substituted derivatives of these; oligomeric para-substituted phenylenes, such as para-tetraphenyl (P-4P), para-pentaphenyl (P-5P), para-hexaphenyl (P-6P), or soluble substituted derivatives of these; conjugated heterocyclic polymers, e.g. poly (3-substituted thiophenes), poly (3, 4-disubstituted thiophenes), optionally substituted polythieno [2, 3-b]Thiophene(s)Optionally substituted polythieno [3, 2-b ]]Thiophene, poly (3-substituted selenophene), polybenzothiophene, polyisothianaphthene, poly (N-substituted pyrrole), poly (3, 4-disubstituted pyrrole), polyfuran, polypyridine, poly-1, 3, 4-oxadiazole, polyisothianaphthene, poly (N-substituted aniline), poly (2-substituted aniline), poly (3-substituted aniline), poly (2, 3-disubstituted aniline), polyazulene, polypyrene, pyrazoline compounds; polyselenophenes, polybenzofurans; a polybenzazole; poly-pyridazine; a polytriarylamine; a biphenylamine compound; a stilbene compound; a triazine; substituted metal-containing or metal-free porphyrins, phthalocyanines, fluorophthalocyanines, naphthalocyanines or fluoronaphthalocyanines; c₆₀And C₇₀Fullerene, N, N ' -dialkyl-substituted dialkyl, diaryl or substituted diaryl-1, 4,5, 8-naphthalenetetracarboxylic diimide and fluoro derivatives, N, N ' -dialkyl-, substituted dialkyl-, diaryl or substituted diaryl-3, 4, 9, 10-perylenetetracarboxylic diimide, bathophenanthroline, diphenoquinone, 1, 3, 4-oxadiazole, 11, 11, 12, 12-tetracyanonaphthalene-2, 6-quinodimethane, α ' -bis (dithieno [3, 2-b2 ', 3 ' -d)]Thiophene); 2, 8-dialkyl, substituted dialkyl, diaryl, or substituted diaryl bisthiophene anthracene; 2, 2 '-dibenzo [1, 2-b:4, 5-b']A dithiophene. In some preferred embodiments, the above OSC compounds and their derivatives are soluble in orthogonal solvents.

In some preferred embodiments according to the invention, the OSC material is a polymer or copolymer comprising one or more repeating units selected from thiophene-2, 5-diyl, 3-substituted thiophene-2, 5-diyl, optionally substituted thieno [2, 3-b ] thiophene-2, 5-diyl, optionally substituted thieno [3, 2-b ] thiophene-2, 5-diyl, selenophene-2, 5-diyl or 3-substituted selenophene-2, 5-diyl.

In other very preferred embodiments of the invention, the OSC material is a substituted oligocene, such as pentacene, tetracene or anthracene, or a heterocyclic derivative thereof. For example bis (trialkylsilylethynyl) oligoacenes or bis (trialkylsilylethynyl) heteroacenes as disclosed in US 6,690,029 or WO 2005/055248 a1 or US 7,385,221.

In another preferred embodiment of the invention, the OSC layer comprises one or more organic binders to adjust the rheological properties as described in, for example, WO 2005/055248 a1.

As used herein, the plural forms of terms herein are to be construed to include the singular forms and vice versa, unless the context clearly dictates otherwise.

It will be apparent that variations of the foregoing embodiments of the invention may be made while remaining within the scope of the invention. Each feature disclosed in this specification may, unless stated otherwise, be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

It is also apparent that features disclosed in this specification may be combined to produce embodiments in accordance with the invention, except where the combination includes mutually exclusive features and/or steps. It should be apparent that many of the features described above are inventive in their own right and not just as part of an embodiment of the invention.

The present invention will now be described in more detail by reference to the following examples, which are illustrative only and do not limit the scope of the present invention.

Unless otherwise indicated, percentages are by weight and temperatures are given in degrees celsius.

In the following examples, synthetic routes to some exemplary monomers and methods for polymerizing these monomers are exemplified. These examples do not limit the scope or spirit of embodiments according to the invention. Furthermore, it should also be noted that for each of the synthetic routes and the polymerization, anhydrous conditions are generally used unless otherwise indicated. That is, if the examples teach injecting a solvent into the reaction vessel, the solvent is anhydrous and/or sparged with an inert gas, such as nitrogen, to remove any dissolved oxygen.

A: synthesis of monomers

Example A1 Synthesis of DMMIMeNB

Dimethyl maleic anhydride (679g, 5.39mol) and 6L of toluene were charged to a 12L flask equipped with a mechanical stirrer, Dean-Stark trap (trap), condenser and thermocouple. The mixture was cooled to 16 ℃ as the dimethylmaleic anhydride dissolved in toluene. To the mechanically stirred mixture were added 663g of 99% aminomethylnorbornene (5.39mol) and 600ml of toluene wash. An exotherm to 34 ℃ was immediately observed and the mixture was slowly heated (to avoid excessive foaming) until reflux was observed. At 109 ℃, the solution cleared within about 1.5 hours from the start of heating. 98ml of water (> 100% of theory) was collected in the Dean Stark trap indicating that the reaction was complete, which can be determined by GC analysis. The mixture was then cooled to room temperature, filtered and the filtrate was rotary evaporated to obtain 1656g (> 100%) of a light brown liquid, 98.9% pure (GC). To this 128g of the remainder of the previous batch of crude material was added and then both batches were vacuum distilled. 132g of preliminary distillate was collected and found to contain 96.8% pure product and unreacted dimethylmaleic anhydride. Furthermore, 281g of a first fraction of 99.4% pure product was collected at 149 ℃ C. (0.78-1.15Torr) and 920g of a second fraction of 99.8% pure product was collected at 149 ℃ C. (1.15-1.55 Torr). The first and second fractions were combined to produce > 99% pure product, 1201g, 87% yield.

Example A2. Synthesis of MIEtNB

Maleic anhydride (389g, 3.96mol), triturated in a mortar, and 6300ml of xylene were charged to a reaction vessel equipped with a mechanical stirrer, condenser, Dean Stark trap, and thermocouple. The temperature drop to 19 ℃ was observed when a turbid solution was obtained. Aminoethylnorbornene (90.1% purity, 600g, 3.94mol) was added dropwise to the stirred mixture over a period of 20 minutes, the temperature was raised to 49 ℃ and a dark amber solution was obtained. The solution was heated to reflux and after 5 hours 40 minutes the process of extracting water in the Dean-Stark trap was seen to substantially stop; 49ml (68% of theory) of water were collected. Proton NMR analysis of the reaction mixture showed very weak amide-acid signals at 6.3-6.45ppm and GC analysis showed 86.8% of the desired product. The reaction was cooled to room temperature and filtered to remove 72g of white solid. Half of the reaction mixture, 3500ml, was loaded directly onto a silica gel (1280g) column and the reaction solvent was eluted from the silica column. The initial 1000ml of eluent showed no product (by TLC using 2.5% methanol/dichloromethane), but the second 1000ml, mainly xylene, showed a point on the TLC and after rotary evaporation thereof, 61g of product was obtained (a 2). The silica gel was washed with dichloromethane to give three successive 1000ml fractions containing 150g of impure product (A3, a4 and a5 respectively). 3500ml of the reactant solution in the remaining xylene was loaded on 1273g of silica and rinsed with recovered xylene. The first three 1000ml xylene fractions (B1-B3) each showed a point on TLC. The next 1000ml fraction B4 obtained with toluene as eluent gave one point on TLC, but the next two 1000ml toluene fractions (B5 and B6) showed weak levels of product in the presence of other by-products. Fractions a2, B1, B2, B3 and B4 were combined and rotary evaporated to obtain 223g of oil, which crystallized on standing. It was found to be 97.4% pure by GC. It was recrystallized from 150ml hot heptane to obtain 124g of product of 99.9% purity. The second harvest yielded 22g of product with 99.7% purity.

Example A3 Synthesis of MIMeNB

Maleic anhydride (117g, 1.19mol) was charged to a reaction vessel equipped with a mechanical stirrer, Dean Stark trap, condenser and thermocouple, which was mixed with 860ml o-xylene, resulting in a temperature drop to 17 ℃ while obtaining a cloudy solution. Aminomethyl norbornene (98% purity, 1.17mol) was dissolved in 144ml o-xylene and added dropwise to the stirred mixture over a period of 15 minutes, resulting in a temperature increase to 64 ℃ and a white slurry. The mixture was mechanically stirred during which time it was heated to reflux for 5 hours. The water withdrawal in the Dean Stark trap was stopped at 13.5ml (64% of theory) after 4.5 hours. TLC (2.5% methanol/dichloromethane) and NMR confirmed the presence of the product and absence of non-cyclic amic acid. The reaction was allowed to cool to room temperature, filtered to remove the precipitated white solid, and it was divided into two 600ml portions. Each fraction was independently loaded on 1000-1100g of silica and rinsed with 6000ml of dichloromethane. The combined eluates were rotary evaporated to give 89g of crystalline product, which was recrystallized from 40ml of hot heptane to obtain 81g of 99.4% pure product. NMR analysis showed the product to contain up to 5.7 mol% o-xylene. The crystals were rotary evaporated at 45 ℃ under high vacuum to remove ortho-xylene, but subsequent NMR analysis showed the presence of 1.8% maleic anhydride (which is believed to be masked by previous analysis of ortho-xylene). The crystals were again rotary evaporated at 65-75 ℃ under high vacuum to obtain a product showing < 0.6 wt% maleic anhydride by NMR. GC analysis showed 99.4% purity and no detectable maleic anhydride. The yield was 77g (33% yield), mp 69.1-71.3 deg.C (glassy at 66.1-68.6 deg.C).

Example A4 Synthesis of Exo-DMMIEtNB

Dimethyl maleic anhydride (18.75g, 0.149mol) was charged to a reaction vessel equipped with a mechanical stirrer, Dean Stark trap, condenser and thermocouple and dissolved in 120ml of toluene, resulting in a cooling of the solution to 18 ℃. A toluene slurry of solid exo- (aminoethyl) norbornene (20.4g, 0.149mol) was added to a solution of dimethylmaleic anhydride, giving a white solid precipitate immediately. The reaction mixture was mechanically stirred while the reaction was heated to reflux. At 102 ℃, reflux started and the solution was clear. After 17 minutes of reflux, the theoretical amount of water was collected in a Dean Stark trap. The reaction was heated at reflux for an additional 2 hours and then cooled to 9 ℃. The mixture was then filtered to remove solids and the filtrate was rotary evaporated to yield 43.7 g. It was distilled in a Kugelrohr oven to collect 17.9g (46% yield) of product at 175 ℃ and 185 ℃ (< 1 mbar). GC analysis showed 99.0% purity.

Example A5 Synthesis of MMIMMeNB

Citraconic anhydride (352g, 3.15mol) and 1500ml of toluene were charged to a 5L flask with mechanical stirrer, Dean-Stark separator, condenser and thermocouple. The mixture was observed to cool to 16 ℃ as the citraconic anhydride dissolved in toluene. To the mechanically stirred mixture was added 99% aminomethyl norbornene (387g, 3.15mol) and 600ml toluene wash. The mixture immediately became a solid material and showed an exotherm of 39 ℃. The mixture was carefully heated to reflux (to avoid excessive foaming). At 110 ℃ approximately 1.5h after the start of heating, the solution was clear and 56ml of water (> 100% of theory) were collected in a Dean-Stark separator. GC analysis showed the reaction was complete. The mixture was cooled to room temperature and filtered. The filtrate was then rotary evaporated to give 672g (98.2%) of a light brown liquid (97.9% purity by GC). The crude product was vacuum distilled at 125 ℃ and 128 ℃ (1.15-1.2Torr) to obtain 624g of product of 99.1% purity.

Example A6 Synthesis of DMMIBuNB

200mL of toluene was charged to a 1L 4-neck RBF equipped with a thermowell, condenser with nitrogen inlet, addition funnel and mechanical stirrer, followed by addition of DMMI potassium (35g, 0.21mol) and 18-crown-6 (5.7g, 0.021mol, 10 mol%) with stirring. To the addition funnel was added endo-/exo-NBBuBr (45g, 0.20mol) in 200mL of toluene and added over 5 minutes. The mixture was heated to 100 ℃ and a whitish slurry was observed. The mixture was continuously stirred at 100 ℃ for an additional 6.5 hours, the color changing from the first observed whitish to dark green and then to reddish brown. The reaction was monitored by GC, which showed 73.6% ofThe reaction was complete with 15.6% unreacted endo-/exo-NBBuBr. The reaction mixture was then cooled to room temperature and then quenched by the addition of 250mL of water and then diluted with 150mL of toluene. With (2x200mL) CH₂Cl₂The aqueous layer was extracted and the organic layer was washed with brine, Na₂SO₄Dried, filtered and evaporated to give 55g of crude product as a brown oil. At 55g SiO₂Adsorbing the crude product and at 330g of SiO₂Chromatography was performed eluting with pentane (3L), 2% EtOAc in pentane (5L), 3% EtOAc in heptane (3L) and 4% EtOAc in heptane (2L). The purified fractions were concentrated to give 31g of product (58% yield) with 99.3% purity by HPLC and another fraction (13.1% yield) of 7.0g of product with 99.09% purity by HPLC as a colorless viscous oil. The combined yield of the reaction was 71%.¹H NMR and MS were consistent with the structure of DMMIBuNB.

Example A7 Synthesis of MeOCinnNB

4-methoxy cinnamoyl chloride:the first 3L, 4-neck Round Bottom Flask (RBF) was equipped with a mechanical stirrer, a thermowell and a condenser with nitrogen adapter. To the RBF was charged 4-methoxycinnamic acid (175g, 982mmol) and 0.1mL dry pyridine in 2L dry toluene. 107.2mL (1.473mol) of SOCl was charged to the addition funnel₂After which it is slowly added to the reaction mixture at room temperature. The reaction mixture was heated to reflux and monitored by GC analysis (aliquots were withdrawn periodically, quenched with MeOH, and analyzed). After 5 hours GC analysis indicated the reaction was complete and the reaction mixture was cooled to room temperature. Excess SOCl₂And toluene were removed by rotary evaporation and the crude product was purified by distillation to obtain 182g of 4-methoxycinnamoyl chloride with 98.9% purity by GC (94% yield).

NBCH ₂ O ₂ CCH＝CHC ₆ H ₄ Ome (meocinnnb): equipped with thermowell, toolCold with nitrogen adapterSecond 3L 4-necked RBF of the condenser, addition funnel and mechanical stirrer was charged with NBCH₂OH (100g, 805mmol), Dimethylaminopyridine (DMAP) (4.9g, 40mmol, 5 mol%), 563mL of triethylamine (4.03mol) and 1.2L of dichloromethane. The mixture was stirred at room temperature for 45 minutes, during which time 4-methoxycinnamoyl chloride (174g, 0.885mol) dissolved in 400mL of methylene chloride, obtained as above, was added to the addition funnel. After the addition of 4-methoxycinnamoyl chloride was completed at room temperature, the mixture was stirred at 25 ℃ overnight. After confirmation of completion of the reaction by GC, the reaction product was diluted with 1L dichloromethane and (2 × 2L) NaHCO₃Solution, (2x1L) NH₄Cl solution, wash the resulting solution with (2 × 2L) brine, then Na₂SO₄Dried, filtered and the filtrate evaporated, and finally 208g of crude product was collected. It was then adsorbed onto 200g silica and chromatographed on 600g silica gel eluting with 0% to 30% EtOAc in cyclohexane. The purified fractions were concentrated to give 133g of a colorless viscous oily product with 98.1% purity by GC (58% yield). The other fractions were combined to obtain another 72g product with > 96% purity by GC, giving an overall yield of 88% (205 g).

Example A8. Synthesis of MeCoumNB

NBCH ₂ OTs: to a condenser equipped with a mechanical stirrer, thermowell, addition funnel and nitrogen adapterThe first 3L of 4-necked RBF of the vessel was charged with tosyl chloride (377g, 1.93mol) and NBCH in 800mL of dry methylene chloride₂OH (200g, 1.61 mol). 270mL (1.93mol) of triethylamine was added to the addition funnel and the batch was slowly added to the reaction mixture at 0 ℃. The reaction mixture was stirred at room temperature, during which time the reaction was monitored by TLC/GC. TLC monitoring indicated that the reaction was complete after 48 hours. The reaction mixture was diluted with 1L of dichloromethane, followed by 1L of water, (2X1L) NaHCO₃Solution, (2 × 1L) brine wash, Na₂SO₄Dried and filtered. Then evaporating the filtrate463g of crude product are obtained, which is then chromatographed by adsorption onto 450g of silica and elution on 1600g of silica gel with 0% to 10% EtOAc in cyclohexane. The concentrated purified fractions of the chromatographic analysis gave 427g of product as a colorless viscous oil with 95.3% purity by GC (95% yield). Proton NMR is consistent with this structure.

MeCoumNB: to a second 3L 4-necked RBF equipped with a thermowell, condenser with nitrogen adapter, and mechanical stirrer was charged 7-hydroxycoumarin (168g, 1.04mol), potassium carbonate (179g, 1.29mol), NBCH₂OTs (300g, 1.08mol) and washing with 1.5L of dry NMP. The mixture is heated to 100 ℃ and stirred, during which time it is TLC @¹HNMR monitors the response. Proton NMR indicated that the reaction was complete after 54h and then the reaction mixture was cooled to room temperature. The reaction mixture was then quenched with 24L1N HCl, and the resulting slightly white solid precipitated was filtered, washed with 4L water and dried to obtain 268g of crude product. This product was charged to 5L RBF, dissolved in 2L (3: 1 ratio) heptane to toluene and refluxed with 26.8g charcoal and filtered through a silica pad. The filtrate was concentrated and added to an excess of heptane to toluene (3: 1 ratio) to obtain 158g (57% yield) of pure white crystalline product having 98.2% purity by HPLC.

Example A9. Synthesis of EtMeOCinnNB

5-norbornene-2-ethanol (NBCH) ₂ CH ₂ OH): a19 liter Parr reactor was charged with 611g (4.6mol) of bisCyclopentadiene and 2000g (27.7mol) of 3-buten-1-ol. With stirring, the reactor was purged three times with nitrogen and then sealed under a nitrogen pressure of 10 psi. The reactor was brought to 220 ℃ over a period of 2 hours and 17 minutes, and a maximum pressure of 185psi was observed. The reaction was stirred at 220 ℃ for 4 hours and the pressure was reduced to 130 psi. The reaction mixture was then allowed to cool to room temperature and discharged, collecting 2603g of the reaction mixture. GC analysis indicated product mix packageContains 65.6% NBEtOH isomer as determined by GC (3-buten-1-ol is still present, but not counted as it is in the solvent front). Excess 3-buten-1-ol, 1260g, was removed by rotary evaporation at 50 ℃. The final concentrate was purified by distillation under high vacuum through a14 "column with a glass spiral wrap. Fractions 4 and 5 were found to be 96.1% and 95.6% pure and were collected. In each fraction, DCPD, F4-3.4% and F53.5% of trimers were also found. The total product had a purity of > 95% (F4+ F5) 722 g.% yield 56%.

NBCH ₂ CH ₂ O ₂ CCH＝CHC ₆ H ₄ Ome (etmeocinnnb): equipped with thermowell, charging hopper and machine100mL of 3-necked RBF on a blender was charged with NBCH₂OH (2g, 14.47mmol), DMAP (88.4mg, 0.72mmol, 5 mol%), 10.1mL triethylamine (72.4mmol) and 25mL dichloromethane. The mixture was stirred at room temperature for 45 minutes before starting the addition of 4-methoxycinnamoyl chloride (3.1g, 15.9mmol) in 5mL of dichloromethane from the addition funnel. After the addition was complete, the mixture was stirred at 25 ℃ overnight. After completion of the reaction as determined by GC, the reaction mixture was diluted with 20mL dichloromethane, followed by (2 × 25mL) NaHCO₃Solution, (2x15mL) NH₄Cl solution, (2 × 25mL) brine, Na₂SO₄Dried and filtered. The filtrate was concentrated to give 3.9g of a crude colorless viscous oil product having a crude purity of 96% by GC (93% crude yield).

Example A10. Synthesis of EtCoumNB

NBCH ₂ CH ₂ OTs: to a cold press equipped with a mechanical stirrer, thermowell, addition funnel and nitrogen adapter5L of 4-necked RBF from the condenser was charged with tosyl Chloride (CH)₃C₆H₄SO₂TsCl ═ TsCl) (745g, 3.9mol) and NBCH₂CH₂OH (450g, 3.26mol) and 2l dryDried dichloromethane. 547mL (3.9mol) of triethylamine was added to the addition funnel and slowly added to the reaction mixture which had been cooled to 0 ℃ beforehand. Stirring is continued at room temperature while simultaneously taking the mark by TLC¹H NMR monitored the reaction. After 24 hours, proton NMR analysis indicated the reaction was complete. The reaction mixture was then diluted with 4L dichloromethane, followed by 2L water, (2 × 1L) NaHCO₃Solution, (2 × 1L) brine wash, Na₂SO₄Drying, filtering and rotary evaporating the filtrate to obtain 1064g of filtrate with a clear solution¹Crude product was a colorless viscous oil with > 95% purity as determined by H NMR (consistent with structure) (110% crude yield). The crude product was used for the next reaction without further purification.

EtCoumNB: to a 12L 4-necked RBF equipped with a thermowell, condenser with nitrogen adapter and mechanical stirrer was charged 7-hydroxycoumarin (450g, 2.77mol), 3.5L dry NMP, potassium carbonate (498.6g, 3.6mol), NBCH₂CH₂OTs (932.6g, 3.19mol) and 1L of dried NMP. The mixture was heated to 100 ℃ with stirring and monitored by TLC/NMR. TLC-¹H NMR monitoring indicated completion of the reaction after 24 hours and the reaction mixture was allowed to cool to room temperature. The reaction was then quenched with 50L 1N HCl, resulting in the product precipitating as a slightly white solid, which was filtered, washed with (5x4L) water and dried to give 1394g of crude product. 1394g of the crude product are dissolved in 4L of dichloromethane. About 500mL of water was separated and removed; then using Na₂SO₄The remaining dichloromethane solution was dried, filtered and evaporated to obtain 864g of crude product. The 864g of crude product was combined with 60g of crude product of the pilot reaction and dissolved in dichloromethane, adsorbed on 1000g of silica and chromatographed on 4kg of silica gel for elution with 0% to 25% EtOAc in cyclohexane. The purified fractions were concentrated to obtain 508g of product as a fluffy pale yellow solid with > 97% purity by HPLC. The product was then recrystallized from 1.6L of refluxing heptane: toluene (ratio 4: 1) to obtain 480g (57% yield) of pure white crystalline powdery product with 99.3% purity by HPLC;¹h NMR was consistent with the structure.

Example A11 Synthesis of AkSiNB

NBCH ₂ CH ₂ OMs: to 12L of 4 equipped with thermowell, nitrogen adapter, addition funnel and mechanical stirrerTo the neck RBF was added 5- (2-hydroxyethyl) norbornene (420g, 3.03mol), 4L of methylene chloride and methanesulfonyl Chloride (CH)₃SO₂Cl or MsCl) (369g, 3.22 mol). An additional 500ml of methylene chloride was added for the reaction in CH₃SO₂Washed in Cl. The stirred mixture was cooled to-16 ℃ and triethylamine (371g, 3.64mol) was added dropwise over a period of 1.5 hours, the temperature rising to 0 ℃ being observed during the addition. The final slurry was allowed to warm continuously to 189 ℃ over a period of 4 hours and then 2L of water was added with continuous stirring. After the addition of water was complete, the phases were separated and the aqueous phase was extracted with 2L of dichloromethane. With (2X2L) NaHCO₃The solution was then washed with 1600mL of 1N HCl and then with 2000mL portions of brine until a wash pH of 6 was observed. The dichloromethane solution was then dried over sodium sulfate, filtered and rotary evaporated to obtain 613g of red liquid. NMR was consistent with the structure. GC analysis gave a content of 93.2% of methanesulfonyl ester. No other purification was attempted because the material showed instability during distillation.

NBCH ₂ CH ₂ Br: to a 22L reaction equipped with a thermowell, nitrogen adapter, addition funnel and mechanical stirrerLithium bromide (369g, 4.25mol) and 4L of 2-pentanone were charged to the vessel and stirred until LiBr dissolved, after which the solution was warmed to 30 ℃. Norbornene ethyl methanesulfonate (613g, 2.83mol) dissolved in 2L 2-pentanone was added to the LiBr solution with stirring and then further diluted with additional 2L 2-pentanone (total volume of 2-pentanone ═ 8L). The solution was then heated to reflux and observed to turn to a white slurry. Once 92 ℃ was reached, GC analysis showed that < 0.8% of the starting material remained and over 1 hourAfter refluxing, GC analysis showed no remaining starting material. The mixture was cooled to 27 ℃ and 4L of distilled water was added to clarify the mixture. The phases were separated and the aqueous phase was extracted with (2 × 2L) ethyl acetate. The organic fractions were combined and rotary evaporated at < 30 ℃. The residue was transferred to a separatory funnel using 4L of dichloromethane as the rinse solvent. The product was washed with (2 × 1L) saturated sodium bicarbonate followed by 1L of brine until the final wash pH 7. The product was dried over sodium sulfate, filtered and the filtrate was rotary evaporated to obtain 440g of crude product (93.6% purity by GC). The crude product was then vacuum distilled using a 14-inch Vigreux column, in which the following fractions were collected: 1.17 deg.C (10Torr) -43 deg.C (1.15Torr), 20.6g, by GC to determine 97.5%, by NMR determination of no 2-pentanone; 2.42 deg.C (0.83Torr) -44 deg.C (0.33Torr), 334.2g, 98.0% by GC; 3.32 deg.C (0.3Torr) -44 deg.C (0.32Torr), 53g, 93.5% by GC, 3.5% CPD trimer. The overall yield of product > 93% purity was 408g (71.6% yield).

NBCH ₂ CH ₂ C≡CSiEt ₃ (AkSiNB): A3L 4-necked RBF was equipped with a thermowell, nitrogen adapter, and feed funnelA hopper and a mechanical stirrer. To the RBF was charged triethylethynylsilane (128.4g, 915mmol) in 800mL dry THF. The reaction mixture was cooled to-78 ℃ and 359mL of n-BuLi (2.5M in hexanes, 899mmol) were added slowly and stirred at-78 ℃ for 1 hour. The reaction mixture was then warmed to 0 ℃ and charged to the addition funnel with NBCH in 640mL of dry DMSO₂CH₂Br (160g, 795.6 mmol). Slowly add NBCH₂CH₂After the Br solution, the reaction mixture was warmed to room temperature and stirred for 2 h. The reaction was complete after 2h stirring at room temperature by GC analysis. The reaction mixture was quenched with 4L water and diluted with 8L heptane, then washed with (3x8L) water, (2x4L) brine, washed with Na₂SO₄Dried, filtered and evaporated. GC analysis showed the crude product to contain 62% product and 27% by-product (Et)₃SiCCSiEt₃). Steaming at high vacuum through 14' column with glass spiral package178g of crude product are distilled off to separate triethylsilylacetylene and Et₃SiCCSiEt₃By-products. The product was obtained in > 99% purity (88.8g, 43% yield), boiling point 93-97 ℃ at 0.20-0.21 mmHg.

Example A12. Synthesis of EtPhDMMINB

Bromophenyl-2, 3-dimethylmaleimide (BrC) ₆ H ₄ DMMI): 1L of RBF equipped with magnetic stir bar, with nitrogenCondenser of the gas adapter. To the RBF were charged 4-bromoaniline (150.1g, 872mmol) and dimethylmaleic anhydride (DMMA) (100g, 792mmol) in 600mL of glacial acetic acid. The reaction mixture was refluxed for 6h and checked by TLC in 30% EtOAc in heptane. The reaction was complete as determined by TLC and the reaction mixture was allowed to cool overnight. The product solidified as slightly white crystals, which were filtered and washed with MeOH. The crystals were dissolved in EtOAc and washed with NaHCO₃And (4) washing the solution. The organic layer was washed with Na₂SO₄Drying and, after concentration, gives bromophenyl-2, 3-dimethylmaleimide (BrC) with a purity of 99.7% as determined by GC₆H₄DMMI, 170g, 76.5% yield).

NBCH ₂ CH ₂ C ₆ H ₄ Dmmi (etphdmminb): A3L 4-neck RBF equipped with thermowell, with nitrogen adapterA condenser, an addition funnel and a mechanical stirrer. To the RBF were charged Zn (82.0g, 1.26mol), iodine (10.6g, 0.04mol) and 800mL degassed N-methylpyrrolidone (NMP). The mixture was stirred at room temperature until the red color of iodine disappeared (about 2 minutes). NBCH in 100mL degassed NMP was added to the addition funnel₂CH₂Br (169g, 0.84 mol). The NBCH₂CH₂The Br solution was added dropwise and the mixture was stirred at 80 ℃ for 3 h. GC analysis of the reaction mixture by hydrolysis indicated complete zinc insertion. The mixture was cooled to 60 ℃ and BrC was added continuously at 60 ℃₆H₄DMMI (157g, 0.56mol) and Pd (PPh)₃)₄(51.8g, 0.045 mol). The reaction mixture was then heated at 80 ℃ for 2 hours and 30 minutes. The reaction was monitored by quenching aliquots with 1N HCl and extracted with EtOAc followed by GC analysis. After 2 hours and 30 minutes, only 38.8% of the product was found by GC, so a further 2 mol% of Pd (PPh) was added₃)₄And stirred at 80 ℃ for another 1 hour, but no significant change was observed in the product. The reaction mixture was cooled to room temperature and quenched with 2L 1N HCl for extraction with (2 × 4L) 50% EtOAc in cyclohexane. The combined organic phase is treated with NaHCO₃Washed with brine and washed over Na₂SO₄Dried, filtered and evaporated. 200g of the crude product were absorbed onto 200g of silica and chromatographed on 800g of silica gel with elution of 0% to 20% EtOAc in cyclohexane. The concentrated purified fraction yielded 30.4g of a slightly white product with > 94% purity as determined by GC (17% yield).

Example A13 Synthesis of Exo-ArSiNB

Exo-norbornenylbenzenes: in a 5-neck 3-liter glass-jacketed reactor purged with nitrogen, 1-bromo-4-iodobenzene (250 g, 884mmol) and PdCl in 400mL of anhydrous DMF₂(PPh₃)₂(6.20 g, 8.84mmol) norbornadiene (360mL, 3.54mmol) and triethylamine (Et)₃N) (398mL, 2.85 mol). The reactor was heated by a hot water bath with a set point of 50 ℃. Fumaric acid (88%, 80mL, 1.86mmol) was added dropwise through an addition funnel at an internal reactor temperature of 50 ℃ to prevent an exothermic reaction from occurring. The solution was heated and stirred at 50 ℃ for 1.25 hours, and samples were monitored by GC every 15 minutes to ensure that all 1-bromo-4-iodobenzene reacted. The reaction mixture was cooled, transferred to a separatory funnel and extracted with 500mL 10% HCl and 470mL heptane. The combined aqueous layers were discarded. The combined organic layers were washed with 5g MgSO₄Dried and stirred for 30 minutes. The mixture was filtered through a column eluted with heptane over silica gel (200-425 mesh). The crude exo-norbornenylbenzene product (169g, 77% yield) was purified by short path distillation set at 90 ℃ and 0.2 Torr. The distillation fraction contained 62 g (> 80%), 80g (> 99%) and was a colorless liquid. By passing¹H NMR samples of pure (> 99%) exo-norbornenylbenzene were analyzed and consistent with the proposed structure and literature values.

Exo-NBCH ₂ CH ₂ C ₆ H ₄ C≡CSiEt ₃ (exo-ArSiNB): in a three-necked 1l glass jacketed reaction with nitrogen purgeTo exo-norbornenylbenzene (103.8g, 0.417mol) and triethylsilylacetylene (70.2 g, 0.5 mol) in 750mL dry DMF was added dibutylamine (Bu2NH) (77.5 g, 0.6mol), PdCl₂(PPh₃)₂(10.53 g, 0.015mol) and copper (I) iodide (2.86 g, 0.015 mol). The reactor was heated by a hot water bath with a set point of 65 ℃. The solution was heated continuously and stirred every 3 hours at 65 ℃ for 27 hours under GC monitoring to ensure that all exo-norbornenylbromide reacted. The reaction mixture was cooled and extracted with 200mL 10% HCl and 410 g heptane. The combined aqueous layers were discarded. The combined organic layers were filtered through a silica bed (200-425 mesh) through a chromatography column and eluted with heptane. The crude material contained 122 grams of exo-norbornenylphenylethynyl triethylsilane. The main impurities in the sample are reaction by-products, which are confirmed to be acetylene dimer and Et by GCMS₃SiC≡C-C≡CSiEt₃. Since the crude material cannot be purified by distillation. The column was treated again with silica gel and eluted once more with heptane. The final material (43 g, 35% yield) was a light yellow oil (> 98% purity).¹H NMR confirmed the identity of the final product as exo-norbornenylphenylethynyltriethylsilane.

Example A14 Synthesis of EONB

1, 2-epoxy-9-decene (EPD) (. gtoreq.96% (31.5Kg)) was fed to a jacketed reactor equipped with a dedicated hot oil unit, a device providing a zoned pressure control mode, and a feed weight tank equipped with metering pumps. A premix (4.32kg) of dicyclopentadiene (DCPD) (. gtoreq.98%) and EPD (9: 1 molar ratio) was prepared and fed to a feed weight tank. Oxygen was removed from the headspace of the reactor using (3) a pressure/vacuum swing with nitrogen and then pressurized to 5psig with nitrogen. The reactor contents were heated to 210 ℃ and the premix was metered into the reactor at a constant rate over a period of 6 hours while at that temperature. After the metering in was complete, the reactor contents were rapidly cooled to 25 ℃.

Reference is made to table a below: the crude reaction mixture of known weight of Epoxyoctylnorbornene (EONB) was then fed to a vacuum distillation apparatus consisting of a still having a heating mantle, a compression distillation column (3 theoretical plates), a reflux splitter, a water cooled condenser, a condensate receiver and a vacuum pump. The vacuum of the distillation system was adjusted to the desired set point and the still pot was heated using an oil bath to establish reflux conditions within the distillation column. Once these conditions are established, the liquid fraction is then removed from the overhead receiver by timing, and the reflux splitter is started with the desired reflux ratio and distillation of the fraction. The overhead liquid fraction composition was determined using GC analysis. The distillation reflux ratio is adjusted as necessary to affect the composition of the overhead vapor. The initial overhead fraction is rich in "light" components, which are primarily Cyclopentadiene (CPD), dicyclopentadiene (DCPD), and Epoxydecene (EPD). After removal of the "light" components, a medium-purity EONB (. gtoreq.92%) is then separated from the remaining cyclopentadiene trimer (CPDT) and the Epoxyoctyltetracyclododecene (EOTD). The EOTD and other heavies remain in the still. Once most of the EONB was removed from the still bottoms, the distillation process was complete.

Reference is made to table B below: the second (second-pass) distillation of the medium-purity EONB obtained from the first distillation was used to obtain a high-purity EONB (. gtoreq.98%) product.

TABLE A first distillation

TABLE B second path distillation

Example A15 Synthesis of DHNMINB

Norbornene methylamine (60.0mL, 0.49mol) in 57.5g of toluene was added dropwise with vigorous stirring to 3, 4-dihydronaphthalene dianhydride (80.1g, 0.40mol) dissolved in about 290g of toluene. A light brown solid formed. The mixture is heated. The solid was dissolved between 65-95 ℃ to give a clear, dark brown solution. The solution was heated to reflux and water was removed over the course of 6 hours using a Dean-Stark trap (8.6 g). The reaction mixture was cooled and then concentrated using a rotary evaporator to obtain a very viscous brown oil (170 g). A portion of the oil (80g) was purified by column chromatography on silica gel using 5: 1 hexane and ethyl acetate as eluent. Fractions of 25, 125mL were collected. Fractions 4-12 were combined and concentrated to dryness using a rotary evaporator to give a viscous yellow oil (19.7 g).¹H NMR confirmed the product identity to be DHNMINB.

Example A16.NBCH₂Synthesis of GlyOAc

An initial charge of 5.51kg allyloxyethyl acetate was weighed into the reactor and heated to 210 ℃. 0.07kg of allyloxyethyl acetate and 0.32kg of dicyclopentadiene were premixed and fed to a metering vessel and then metered into the reactor at a constant flow rate over a period of 5 hours once the reaction temperature was reached. At the end of the metering period, the batch was allowed to cool to room temperature and analysis by GC showed 29% norbornene methoxyethyl acetate with about 0.6% cyclopentadiene trimer and 0.9% tetracyclododecene methoxyethyl acetate; the remainder was predominantly allyloxyethyl acetate (all results are GC area%). Purification of norbornene methoxyethyl acetate was achieved by vacuum fractional distillation on a compression column. The high purity distillation is carried out under vacuum of 150 to 200mTorr with an overhead distillate temperature of 65 to 67 c. About 80% of the norbornene contained is recovered, with a purity of more than 99% (based on GC area%).

Example A17 Synthesis of MCHMNB

4' -hydroxy-4-methoxychalcones: to a solution of sodium hydroxide (100g, 2.50mol) in 1.8L of a 10: 8 mixture of water and methanol was added 4-hydroxyacetophenone (136g, 1.00 mol). After stirring at room temperature for 30 minutes, 4-methoxybenzaldehyde (136g, 1.00mol) was added to the mixture. The reaction mixture was stirred under an oil bath at 50 ℃ for 16 hours. The resulting clear yellow solution was stirred at room temperature for 30 minutes. 1N HCl aq (500mL) and 600mL of a 1: 1 mixture of dichloromethane and THF were added to the two layers. By saturated NaHCO₃aq (300mL x 2) and water (300mL x 3) the organic layer was washed and evaporated to give an orange solid. The solid was washed twice with 300mL EtOAc. The resulting yellow solid was dried in vacuo. Yield 133g (52%).¹H NMR(CDCl₃)：3.85(s，3H)，6.93(m，4H)，7.47(d，1H)，7.50(d，2H)，7.75(d，1H)，7.96(d，2H)。

1- (4-bicyclo [2.2.1]]Hept-5-en-2-methoxyphenyl) -3- (4-methoxyphenyl) -2-propen-1-one (MCHMNB): k in 200mL DMF₂CO₃To the solution (18.0g, 0.130mol) were added 4' -hydroxy-4-methoxychalcone (25.4g, 0.100mol) and bicyclo [ 2.2.1%]Hept-5-ene-2-methyltrifluoromethane sulfonate (23.3g, 0.115 mol). The reaction mixture was stirred in an oil bath at 100 ℃ for 24 hours. The resulting orange suspension was stirred at room temperature for 1 hour. 300mL of methylene chloride and300mL of 1N HCl aq was added to the resulting two layers. With saturated NaHCO₃The organic layer was washed with aq (200mL) and water (200mL x 5) and then evaporated to give an orange solid. The solid was washed twice with 300mL EtOAc. The resulting pale yellow solid was dried in vacuo. Yield 16.0g (44%). By passing¹HNMR(CDCl₃) The structure is determined.

Example A18. Synthesis of DMMIEtNB

Cyanomethyl norbornene: a 1L 4-neck RBF was equipped with a thermowell, condenser with nitrogen inlet, stopper and mechanical stirrer. To the RBF was added chloromethyl norbornene (120g, 0.84mol, 95.6% pure), 400mL DMSO and solid NaCN (74.2g, 1.51 mol). An additional 20mL of DMSO was added to wash in NaCN. The reaction mixture was stirred at 90 ℃ for 72 hours. GC analysis of an aliquot indicated that all of the starting material had been consumed and the reaction was complete. The reaction mixture was cooled to room temperature. Approximately 200mL of water was poured into the flask and diluted with 200mL of MTBE. The organic phase was separated and the aqueous layer was re-extracted with (3x300mL) MTBE. The organic phases were combined and washed with (3x500mL) tap water until the aqueous wash reached pH 6. MTBE was dried over anhydrous sodium sulfate overnight, filtered and rotary evaporated, and dried in high vacuum (0.94torr) at a bath temperature of 50 ℃ for 3 hours to obtain 112g (100% yield) of product with 95.8% purity by GC. Proton NMR analysis indicated that the material contained 1% MTBE. The dark brown crude product was used in the next reaction without further purification. Data: GC analysis on DB5 column, 30 meters, 0.32mm ID, 0.25 μm membrane, 75 ℃ to 300 ℃ at 25 ℃/min, hold at 300 ℃ for 2 min, injector temperature: 275 ℃, detector temperature: at 350 ℃.

NBCH ₂ CH ₂ DMMI: 3L 4-necked RBF equipped with thermowell connected to condenser with nitrogen inletDean Stark trap, addition funnel and mechanical stirrer. To the RBF was charged 600mL of toluene with stirring, followed by dimethyl maleic anhydride (DMMA, 92g, 0.73 mol).The mixture was cooled to 14 ℃ as the dimethylmaleic anhydride dissolved in toluene. The mixture was warmed to 25 ℃ to clarify the solution. Aminoethylnorbornene in 100mL of toluene (104g, 0.73mol, 96.4% purity) was charged to the addition funnel and added dropwise over 15 minutes. An additional 130mL of toluene was added to rinse in the aminoethylnorbornene and the addition funnel was replaced with a stopper. The mixture immediately exothermed to 50 ℃ and a white thick precipitate was observed. The mixture was carefully heated to reflux (to avoid excessive foaming) over 30 minutes and refluxed for 2 hours. A clear solution was observed and 13.1mL of water (99.5% of theoretical) were collected in the Dean Stark trap. GC analysis showed the reaction to be complete (94.9% product with 1.8% DCPD and 1.7% unknown impurities at 7.8 minutes). The reaction mixture was cooled to room temperature and transferred to a 5L flask, which was concentrated in a rotary evaporator. The crude product was further dried at a bath temperature of 75 ℃ in a rotary evaporator under high vacuum (0.94torr) for 5 hours and 179g of crude product was obtained as a dark orange viscous oil. GC analysis showed the purity of the crude product after drying under high vacuum to be 97.4% with 0.3% DCPD and 1.8% unknown impurities. 179g of the crude product are adsorbed in 179g of silica gel and chromatographed on 500g of silica gel eluting with heptane (8L), 2% EtOAc in heptane (2L), 2.5% EtOAc in heptane (2L), 3% EtOAc in heptane (4L) and 5% EtOAc in heptane (1L). The concentrated purified fraction yielded 164g of product as a colorless viscous oil with 99.8% purity by GC (91% yield).¹H NMR and mass spectra were consistent with the structure. Data: GC analysis made on DB5 column, 30 meters, 0.32mm ID, 0.25 μm membrane, 75 ℃ to 300 ℃ at 15 ℃/min, hold at 300 ℃ for 2 min, injector temperature: 275 ℃, detector temperature: 350 ℃, retention time: 11.893 minutes.

Example a 19: synthesis of DMMIPrNB

Cyanoethyl norbornene: a 1L 4-neck RBF was equipped with a thermowell, condenser with nitrogen inlet, stopper and mechanical stirrer.To the RBF was added chloroethyl norbornene (100g, 0.64mol), 300mL DMSO and solid NaCN (43.8g, 0.89 mol). An additional 20mL of DMSO was added to wash in NaCN. The reaction mixture was stirred at-80 ℃ for 2 hours. GC analysis of an aliquot indicated that all of the starting material was consumed and the reaction was complete. The reaction mixture was cooled to room temperature. Approximately 200mL of water was poured into the flask and diluted with 100mL of MTBE. The organic phase was separated and the aqueous layer was re-extracted with (3 × 200mL) MTBE. The organic phases were combined and washed with (3x500mL) tap water until the aqueous wash reached pH 6. MTBE was dried over anhydrous sodium sulfate overnight, filtered and rotary evaporated to obtain 93.5g (99.5% yield) product with 99.3% purity by GC. NMR analysis showed that the material contained 1% MTBE. The crude product was used in the next reaction without further purification. Data: GC analysis made on DB5 column, 30 meters, 0.32mm ID, 0.25 μm membrane, 75 ℃ to 300 ℃ at 25 ℃/min, hold at 300 ℃ for 2 min, injector temperature: 275 ℃, detector temperature: at 350 ℃.

Aminopropyl norbornene: a 3L 4-neck RBF was equipped with a thermowell, condenser with nitrogen inlet, addition funnel and mechanical stirrer. To the RBF, LAH pellets (50.6g, 1.33mol) were added and mechanically stirred with 800mL MTBE overnight. A thick paste resulted from some solvent loss. An additional 200mL of MTBE was added and the resulting dispersion was chilled to-6 ℃ with a methanol-ice bath. Cyanoethyl norbornene in 500mL of MTBE (93.5g, 0.635mol) was charged to the addition funnel and added dropwise at a rate that maintained the reaction temperature below-2 ℃ but above-5 ℃. The addition of cyanoethyl norbornene takes place over a period of 1 hour. The cooling bath was removed when GC analysis indicated no residual starting material, the mixture was heated to 35 ℃ over a period of 1.5 hours and stirred at 35 ℃ for an additional 30 minutes. The mixture was cooled to-15 ℃ (methanol/ice bath) and 150ml distilled water was added slowly over 3 hours and 30 minutes, keeping the temperature below 0 ℃. The mixture was then diluted with 250mL MTBE and a second 250mL portion of water was added to precipitate the lithium and aluminum by-products as a free flowing white solid. After stirring for 10 minutes, lithium and aluminum by-products were precipitatedAnd the MTBE phase decanted. The lithium and aluminum residues were covered with an additional 500mL MTBE, then mixed, precipitated, and the MTBE decanted. The MTBE pours were combined, dried over sodium sulfate, then filtered, and rotary evaporated to give 92g (95.8% yield) of a colorless viscous oil. GC analysis indicated 99.7% purity.¹H NMR analysis showed the material to contain 1% MTBE. Crude NB (CH)₂)₃NH₂The product was used in the next reaction without further purification. Data: GC analysis made on DB5 column, 30 meters, 0.32mm ID, 0.25 μm membrane, 75 ℃ to 300 ℃ at 15 ℃/min, injector temperature: 275 ℃, detector temperature: 350 ℃, retention time: 6.225 minutes.

NBCH ₂ CH ₂ CH ₂ DMMI: A3L 4-necked RBF equipped with a thermowell was connected to a condenser with nitrogen inletDean Stark trap, addition funnel and mechanical stirrer. To the RBF was added 500mL of toluene with stirring, followed by dimethyl maleic anhydride (DMMA, 76.7g, 0.60 mol). As the dimethylmaleic anhydride dissolved in toluene, the mixture self-cooled to about 14 ℃. The mixture was warmed to 25 ℃ to clarify the solution. Aminopropylnorbornene in 100mL of toluene (92g, 0.60mol) was charged to the addition funnel and added dropwise over 15 minutes. An additional 100mL of toluene was added to wash in aminopropylnorbornene and the addition funnel was replaced with a stopper. The mixture immediately exothermed to 53 ℃ and a white precipitate was observed. The mixture was carefully heated to reflux (to avoid excessive foaming) over 20 minutes and refluxed for 3 hours. A clear solution was observed and 10.7mL of water (98.2% of theoretical) were collected in the Dean Stark trap. GC analysis showed the reaction was complete (98.2% product and 0.95% DMMA). The reaction mixture was cooled to room temperature and transferred to a 5L flask and concentrated in a rotary evaporator. The crude product was further dried overnight on a rotary evaporator under high vacuum (0.94torr) at a bath temperature of 50 ℃ and 122g of crude product was obtained as a pale yellow viscous oil. GC analysis indicated the crude product was 98.8% pure and it had DMMA as the major impurity of 0.68%. At 122g122g of the crude product was adsorbed in silica gel and chromatographed on 360g of silica gel eluting with heptane (4L), 2% EtOAc in heptane (4L), 2.5% EtOAc in heptane (4L) and 3% EtOAc in heptane (4L). The concentrated purified fraction yielded 115g of product as a colorless viscous oil with 100% purity by GC (73.2% yield).¹H NMR and mass spectra were consistent with the structure. Data: GC analysis made on DB5 column, 30 meters, 0.32mm ID, 0.25 μm membrane, 75 ℃ to 300 ℃ at 15 ℃/min, hold at 300 ℃ for 2 min, injector temperature: 275 ℃, detector temperature: 325 ℃, retention time: 12.634 minutes.

Example A20 Synthesis of DiOxotcN

Norbornadiene (77g, 0.84mol) and perfluoro (5-methyl-3, 6-dioxanon-1-ene) or 3- (perfluorophenyl) pentafluoroprop-1-ene (93g, 0.21mol) were pre-mixed in a 250mL glass vial and transferred to a 0.5L stainless steel reactor. The reactor was sealed and heated under a nitrogen blanket with stirring for 24 hours to 190 ℃. The reactor was cooled to ambient temperature and the reaction mixture (169g) was concentrated by rotary evaporation to obtain 140g of crude product. The crude product was fractionated to obtain 65g (57% yield) of the desired product in excess of 87% purity as measured by GC area percentage.

Example A21 Synthesis of PFBTCN

Norbornadiene (1.2g, 0.013mol) and 3- (perfluorophenyl) pentafluoroprop-1-ene (0.99g, 0.0033mol) were pre-mixed in a glass vial and transferred to a stainless steel reactor equipped with a glass stopper. The reactor was sealed and heated at 190 ℃ for 24 hours. The reactor was cooled to ambient temperature and the reaction mixture was analyzed by Gas Chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) for product confirmation. The desired product in the reaction mixture constituted 45.6% of the reaction mixture as measured by GC area percent.

Example A22. Synthesis of NBTODD

To an 8 liter stainless steel autoclave reactor was charged 3.75kg (18.4mol) of allyl triethylene glycol methyl ether. Agitation was started and the reactor vented and blanketed with 5psig of nitrogen. Heating to 200 ℃ was started and once 200 ℃ was reached, the reactor was held at this temperature for 3.75 hours. During this time, a mixture of 0.06kg (0.3mol) of allyl triethylene glycol methyl ether and 0.21kg (1.6mol) of dicyclopentadiene is added to the reactor at a constant rate of 1.19g/min, and at the end of the addition, the reactor is cooled to ambient temperature and discharged. The major identified components in the feed, as measured by GC area, were: 75% of allyl triethylene glycol methyl ether and 23% of norbornenyl tetraoxatetradecane. The batch was distilled and yielded approximately 0.4kg of norbornenyltetraoxatetradecane with an analytical content of more than 98% (GC area).

Example A23. Synthesis of NBTON

To an 8 liter stainless steel autoclave reactor was charged 3.4kg (21.2mol) of allyl diethylene glycol methyl ether. Agitation was started and the reactor vented and blanketed with 5psig of nitrogen. Heating to 200 ℃ was started and once 200 ℃ was reached, the reactor was held at this temperature for 4.25 hours. During this time, a mixture of 0.06kg (0.4mol) of allyl diglycol methyl ether and 0.24kg (1.8mol) of dicyclopentadiene was fed into the reactor at a constant rate of 1.17 g/min. At the end of the addition, the reactor was cooled to ambient temperature and discharged. The major identified components in the feed, as measured by GC area, were: 72% of allyl diethylene glycol methyl ether, and 26% of norbornenyl trioxonane. The batch distilled and produced over 99% (GC area) after analysis about 0.5kg of norbornenyl trioxonane.

B: synthesis of polymers

In each of the tables provided below, catalysts and each report, unless specifically indicated otherwiseMonomers are present in grams (g); yields are reported in percent (%) and molecular weight (M)_w) PDI (polydispersity index) is M_w/M_nAnd the molar composition (A/B or A/B/C) of the polymer is determined by¹H NMR measurement.

For each of examples B1-B5, the indicated amount of the particular monomer was dissolved in a mixture of toluene and methyl ethyl ketone contained in a vial equipped with a stir bar (72.9 mL and 12.8mL, respectively.) for B6, both the monomer and catalyst were dissolved in anhydrous ααα -trifluorotoluene (98.4 mL and 6.3mL, respectively.) the vial was purged with nitrogen to remove residual oxygen and sealed the amount of catalyst (η 6-toluene) Ni (C.) as indicated in Table 1₆F₅)₂(hereinafter referred to as NiAr)^f) Dissolved in toluene (5mL) in a nitrogen purged glove box.

Example B1 copolymerization of MeOAcNB and DMMIMeNB

The monomer solution was heated to 45 ℃ and the above catalyst mixture was injected into the heated vial. The solution was held at this temperature for 17 hours with stirring, after which it was cooled to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the reaction mixture into an excess of ethanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 60 ℃.

Example B2 copolymerization of BuNB and DMMIMeNB

The monomer solution was heated to 45 ℃ and the above catalyst mixture was injected into the heated vial. The solution was held at this temperature for 1.5 hours with stirring, after which it was allowed to cool to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the reaction mixture into excess 75/25 of acetone/methanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 65 ℃.

Example B3 copolymerization of DecNB and DMMIMeNB

The monomer solution was heated to 45 ℃ and the above catalyst mixture was injected into the heated vial. The solution was held at this temperature for 1.5 hours with stirring, after which it was allowed to cool to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the reaction mixture into excess 75/25 of acetone/methanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 65 ℃.

Example B4 homopolymerization of DMMIMeNB

The monomer solution was heated to 45 ℃ and the above catalyst mixture was injected into the heated vial. The solution was held at this temperature for 1.5 hours with stirring, after which it was allowed to cool to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the reaction mixture into excess 75/25 of acetone/methanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 65 ℃.

Example B5 homopolymerization of FPCNB

The monomer solution was heated to 45 ℃ and the above catalyst mixture was injected into the heated vial. The solution was held at this temperature for 1.5 hours with stirring, after which it was allowed to cool to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the reaction mixture into excess 75/25 of acetone/methanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 65 ℃.

EXAMPLE B6C 8AcNB homopolymerization

The monomer solution was heated to 45 ℃ and the above catalyst mixture was injected into the heated vial. The solution was held at this temperature for 1.5 hours with stirring, after which it was allowed to cool to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the mixture into excess 75/25 of acetone/methanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 65 ℃.

TABLE 1

^*By passing¹³C NMR measurement

For each of examples B7-B19, NBC in the amounts indicated in Table 2 below₄F₉(NBCH in example B13₂C₆F₅) Dissolved in the indicated amount of anhydrous benzotrifluoride (benzotrifluoride and toluene in examples B8 and B9) contained in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. For examples B11, B12, and B17-B19, the indicated amounts of danaba (dimethylanilinium tetrakis (pentafluorophenyl) borate) and (acetonitrile) bis (tert-butyldicyclohexylphosphine) palladium (acetate) tetrakis (perfluorophenyl) borate (Pd 1394) were added to the vial after purging but before sealing the vial. For examples B7-B10 and B13-B16, the amounts indicated, of catalyst, NiAr^fDissolved in the indicated amount of toluene and injected into a sealed vial. For examples 12 and 17-19, the indicated amount of fumaric acid was injected instead of the catalyst. Table 2 also provides the yield (%) and M for each polymer_wAnd PDI (if available).

Example B7.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at ambient temperature and the catalyst solution was injected into the vial. With stirring, the mixture was held at this temperature for 2 hours, after which 2mL of distilled water was added to the vial. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B8.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at 60 ℃ and the catalyst solution was injected into the vial. With stirring, the mixture was held at this temperature for 1.5 hours, after which 2mL of distilled water was added to the vial. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B9.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at 60 ℃ and the catalyst solution was injected into the vial. With stirring, the mixture was held at this temperature for 1.5 hours, after which 2mL of distilled water was added to the vial. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B10.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at 60 ℃ and the catalyst solution was injected into the vial. With stirring, the mixture was held at this temperature for 1.5 hours, after which 2mL of distilled water was added to the vial. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B11.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at 90 ℃ for 16 hours. After removal of residual catalyst and precipitation of the polymer in methanol/water at 90/10, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B12.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at 90 ℃ for 16 hours. After removal of residual catalyst and precipitation of the polymer in methanol/water at 90/10, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B13.NBCH₂C₆F₅By homopolymerization of

The monomer solution was then stirred at ambient temperature and the catalyst solution was injected into the vial. With stirring, the mixture was held at this temperature for 5 minutes, after which 2mL of distilled water was added to the vial. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Examples B14-16.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at 65 ℃ and the catalyst solution was injected into the vial. The mixture was held at this temperature for 2 hours with stirring. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Examples B17-19.NBC₄F₉By homopolymerization of

The monomer solution was then stirred at 90 ℃ and the catalyst solution was injected into the vial. The mixture was held at this temperature for 16 hours with stirring. After removal of residual catalyst and precipitation of the polymer in methanol/water at 90/10, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

TABLE 2

DANFEBA co-catalystDANFEBA cocatalyst/fumaric acid

For each of examples B20-B41, the amounts of monomers specified in table 3 below were dissolved in the amounts of solvent shown below and charged to a vial equipped with a stir bar (for B31 a glass reactor was used). The vial/reactor was purged with nitrogen to remove residual oxygen and sealed. The specified amount of catalyst NiAr^fDissolved in the indicated amount of toluene in a nitrogen purged glove box and injected into a sealed vial/reactor. Table 3 also provides the yields of the polymers obtained for each synthesis and M_wAnd a PDI.

Examples B20-21.NBC₄F₉Aggregation with DMMIMeNB

The monomer solution (60.0g toluene for B20 and 75.0g for B21) was stirred at ambient temperature and the catalyst solution was injected into the vial. Mixture B20 was held at this temperature for 3 hours with stirring, after which 2mL of distilled water was added to the vial. The B21 reaction mixture was held at this temperature for 16 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B22.NBC₄F₉Aggregation with DMMIMeNB

The monomer solution (toluene (56.3g) and trifluorotoluene (18.8g) were stirred at ambient temperature and the catalyst solution was injected into the vial the mixture was held at this temperature for 16 hours with stirring after removal of residual catalyst and precipitation of the polymer in methanol the polymer was isolated and allowed to dry in a vacuum oven at 70-80 ℃.

Example B23.NBCH₂C₆F₅Aggregation with DMMIMeNB

The monomer solution (60.0g of toluene) was stirred at ambient temperature and the catalyst solution was injected into the vial. The mixture was held at this temperature for 2 hours with stirring. After this 2mL of distilled water was added to the vial. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B24.NBC₄F₉And polymerization of PPVENBB

The monomer solution (trifluorotoluene (40.0g), toluene (32.0g) and methyl ethyl ketone (8.0g)) was stirred at 45 ℃ and the catalyst solution was injected into a vial. The mixture was held at this temperature for 16 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B25.NBC₄F₉And MeCoumNB polymerization

The monomer solution (trifluorotoluene (75g)) was stirred at 55 ℃ and the catalyst solution was injected into a vial. The mixture was held at this temperature for 16 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B26-B29-polymerization of BuNB or DecNB and MeOCinnNB

The monomer solution (toluene (103.8g) and methyl ethyl ketone (18.3g)) was stirred at ambient temperature and the catalyst solution was injected into a vial. The mixture was held at this temperature for 16 hours with stirring. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Example B30 polymerization of DecNB and PhIndNB

The monomer solution (toluene (68.0g) and methyl ethyl ketone (12.0g)) was stirred at 50 ℃ and the catalyst solution was injected into a vial. The mixture was held at this temperature for 16 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70-80 ℃.

Embodiment B31. aggregation of BuNB and DMMIMeNB

The monomer solution (toluene (488g) and methyl ethyl ketone (90.0g)) was stirred at 45 ℃ and the catalyst solution was injected into the reactor. The mixture was held at this temperature for 3 hours. After removal of residual catalyst, the product was divided into two batches, each of 50/50 ethanol/isobutanol mixture, and both were solvent exchanged for 2-heptanone.

Examples B32-33. aggregation of DMMIMeNB with HexNB or OctNB

The monomer solution ((98.0g) and methyl ethyl ketone (18.0g)) was stirred at 45 ℃ and the catalyst solution was injected into a vial. The mixture was held at this temperature for 3 hours. After removal of residual catalyst and precipitation of the polymer in methanol/water at 95/5, the polymer was isolated and dried in a vacuum oven at 60-70 ℃.

Examples B34-37 polymerization of DMMIMeNB, DecNB and AkSiNB

The monomer solution (toluene (76.5g) and methyl ethyl ketone (13.5g)) was stirred at ambient temperature and the catalyst solution was injected into a vial. The mixture was held at this temperature for 45 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 65-70 ℃.

Example B38-39 aggregation of DMMIMeNB, DecNB and NBTODD

The monomer solution (toluene (63.8g) and methyl ethyl ketone (11.3g)) was stirred at 45 ℃ and the catalyst solution was injected into a vial. The mixture was held at this temperature for 3.5 hours for B38 and 16 hours for B39. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70 ℃.

Example B40-41 DMMIMeNB, NBCH₂C₆F₅And MeOAcNB polymerization

The monomer solution (toluene (195g)) was stirred at 45 ℃ and the catalyst solution was injected into the vial. The mixture was held at this temperature for 4.75 hours. After removal of residual catalyst and precipitation of the polymer in methanol/water at 95/5, the polymer was isolated and dried in a vacuum oven at 70 ℃.

TABLE 3

Feeding ratio of onium monomer

By passing¹³Composition determined by C-NMR

For each of examples B42-B47, the amounts of monomers specified in table 4 below were dissolved in the amounts of solvent shown below and charged to a vial equipped with a stir bar. The vial/reactor was purged with nitrogen to remove residual oxygen and sealed. The specified amount of catalyst NiAr^fDissolved in the indicated amount of toluene in a nitrogen purged glove box and injected into a sealed vial/reactor. Table 4 also provides the yields of the polymers obtained for each synthesis and M_wAnd a PDI.

Example B42. polymerization of DMMIMeNB, DecNB and NBXOH

The amounts of monomers specified in table 4 below were dissolved in a mixture of toluene and methyl ethyl ketone (65.02 mL and 12.75mL, respectively) contained in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. The amounts of catalyst NiAr indicated in Table 4^fDissolved in the indicated amount of toluene (2.59mL) in a nitrogen purged glove box. The monomer solution was then heated to 45 ℃ and the catalyst solution was injected into the heated vial. The mixture was held at this temperature for 5 hours with stirring, after which it was allowed to cool to room temperature. After removal of residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 60 ℃.

Example B43. polymerization of DMMIMeNB, DecNB and NBXOH

The amounts of monomers specified in table 4 below were dissolved in a mixture of toluene and methyl ethyl ketone (59.76 mL and 12.03mL, respectively) contained in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. The amounts of catalyst NiAr indicated in Table 4^fDissolved in toluene (4.07mL) in a nitrogen purged glove box. The monomer solution was then heated to 45 ℃ and the catalyst solution was injected into the heated vial. The mixture was held at this temperature for 16 hours with stirring, after which it was allowed to cool to room temperature. After removal of residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 60 ℃.

Example B44. aggregation of PPVENB and DMMIMeNB

The amounts of monomers specified in table 4 below were dissolved in anhydrous benzotrifluoride (49.13mL) contained in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. The amounts of catalyst NiAr indicated in Table 4^fDissolved in anhydrous benzotrifluoride (7.50mL) in a nitrogen purged glove box. The monomer solution was kept at room temperature and the catalyst solution was injected into the vial. The mixture was stirred for 1 hour. After removal of the residual catalyst and precipitation polymerization in methanol

After this time, the polymer was isolated and dried in a vacuum oven at 60 ℃.

Example B45. aggregation of PPVENB and DMMIMeNB

The amounts of monomers specified in table 4 below were dissolved in anhydrous benzotrifluoride (56.15mL) contained in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. The amounts of catalyst NiAr indicated in Table 4^fDissolved in anhydrous benzotrifluoride (7.50mL) in a nitrogen purged glove box. Dissolving the monomerThe solution was kept at room temperature and the catalyst solution was injected into the vial. The mixture was stirred for 1 hour. After removal of residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 60 ℃.

Example B46 polymerization of BuNB and MeOCinnNB

The amounts of monomers specified in table 4 below were dissolved in a mixture comprising toluene (140.7mL) and ethyl acetate (25.3mL) in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. The amounts of catalyst NiAr indicated in Table 4^fDissolved in toluene (9.69mL) in a nitrogen purged glove box. The monomer solution was then heated to 45 ℃. The catalyst solution was then injected into the reaction vessel and the mixture was stirred (45 ℃,3 hours). After removal of the residual catalyst and precipitation of the polymer in a mixture of acetone and methanol (75: 25), the polymer was isolated and dried in a vacuum oven at 60 ℃.

Example B47.EtCoumNB homopolymerization

In a nitrogen purged glove box, the amounts of monomers specified in table 4 below were dissolved in anhydrous dichloromethane (21.9mL) contained in a vial equipped with a stir bar. The amounts of catalyst NiAr indicated in Table 4^fDissolved in toluene (1.61mL) in a nitrogen purged glove box. The monomer solution was heated to 45 ℃. The catalyst solution was injected into the reaction vessel and the mixture was stirred (45 ℃,3 hours).

Table 4.

^*By passing¹H NMR-determined proportion of monomers in the Polymer

For each of examples B48-B55, the amounts of monomers specified in table 5 below were dissolved in the amounts of solvent shown below and charged to a vial equipped with a stir bar. The vial/reactor was purged with nitrogen to remove residual oxygen and sealed. The specified amount of catalyst NiAr^f、(η⁶-toluene) Ni (C)₆F₅)₂Dissolved in the indicated amount of toluene in a nitrogen purged glove box and injected into a sealed vial/reactor. Table 5 also provides the yields of the polymers obtained for each synthesis and M_wAnd a PDI.

Example B48-B53. aggregation of DMMIMeNB with BuNB or DecNB

The amounts of monomers specified in table 5 below were dissolved in toluene (170g) and methyl ethyl ketone (31g) contained in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. The amounts of catalyst NiAr indicated in Table 5^fDissolved in toluene (7-9g) in a nitrogen purged glove box. The monomer solution was then stirred at 45 ℃ and the catalyst solution was injected into the vial. The mixture is kept at this temperature for 1-2 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 70 ℃.

Example B54-B55 polymerization of BuNB and/DCPD

The amounts of monomers specified in table 5 below were dissolved in toluene (30g) contained in a vial equipped with a stir bar. The vial was purged with nitrogen to remove residual oxygen and sealed. In a glove box, [ Li (OEt)₂)_2.5][B(C₆F₅)₄](LiFeABA) (Boulder Scientific, Mead, CO) (0.009g) was added to the vial. Hexene-1 (1.85g) was then added to the vial. The vial was heated to 80 ℃. To the vial was added (allyl) palladium (tris) in 2g of toluene and in the amount shown in table 5Naphthyl phosphine) (trifluoroacetate salt). The mixture was held at this temperature for 17 hours. After cooling the reaction mixtures, they were diluted with THF (150 mL). The polymer precipitated with methanol was isolated and allowed to dry in a vacuum oven at 70 ℃.

TABLE 5

^*13C NMR

For each of examples B56-B63, the amounts of monomers specified in table 6 below were charged to the reaction vial and dissolved in 166g of toluene and 29g of methyl ethyl ketone. The vial was then purged with nitrogen to remove residual oxygen and sealed. For each experiment, the amount of catalyst NiAr indicated in Table 6 was determined^fDissolved in the indicated amount of toluene. Table 6 below also provides the yields of polymer obtained for each synthesis and M_wPDI and repeat unit ratio.

Example B56-B57 polymerization of DecNB and MGENB

The monomer solution was then stirred at 40 ℃ and the catalyst solution was injected into the vial. The mixture was held at this temperature for 3 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 80 ℃.

Example B58-B59 polymerization of BuNB and MGENB

The monomer solution was then stirred at 40 ℃ and the catalyst solution was injected into the vial. Maintaining the mixture at the temperatureFor 3 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 80 ℃. Table 6 below provides the yields of the polymers obtained and M for each of the synthetic reactions_wAnd M_w/M_n。

Example B60-B61. polymerization of DecNB and EONB

The monomer solution was then stirred at 40 ℃ and the catalyst solution was injected into the vial. The mixture was held at this temperature for 3 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 80 ℃.

Example B62-B63 polymerization of BuNB and MGENB

The monomer solution was then stirred at 40 ℃ and the catalyst solution was injected into the vial. The mixture was held at this temperature for 3 hours. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 80 ℃.

Example B64 homopolymerization of DMMIBuNB

DMMIBunB, toluene (68.68g) and MEK (13.04g) were mixed together, purged with nitrogen for 30 minutes, and then heated to 45 ℃. The amounts of catalyst NiArf and solvent (toluene) specified in table 6 were added to the monomer mixture. The mixture was stirred overnight and then cooled to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the mixture into an excess of methanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 50 ℃.

Example B65 homopolymerization of PPVENB

The monomers were dissolved in the indicated amounts of trifluorotoluene. The solution was then stirred at room temperature and the trifluorotoluene catalyst solution was injected into the vial. The mixture was allowed to stand at room temperature overnight. After removal of the residual catalyst and precipitation of the polymer in methanol, the polymer was isolated and dried in a vacuum oven at 80 ℃.

Example B66 homopolymerization of HexNB

HexNB, toluene (81.31g) and MEK (15.98g) were mixed together, purged with nitrogen for 30 minutes and then heated to 45 ℃. The amounts of catalyst NiAr indicated in Table 6^fAnd solvent (toluene) were added to the monomer mixture. The mixture was stirred for 16h and then cooled to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the mixture into an excess of ethanol. After the polymer was isolated by filtration, it was dried in a vacuum oven at 60 ℃.

Example B67 homopolymerization of BuNB

BuNB, toluene and MEK were mixed together, purged with nitrogen, and then heated to 45 ℃. The amounts of catalyst NiAr indicated in Table 6^fAnd solvent (toluene) were added to the monomer mixture. The mixture was stirred for 2h and then cooled to room temperature. The residual catalyst was removed and the polymer was precipitated by pouring the mixture into an excess of methanol. After the polymer was isolated by filtration, it was dried in a vacuum oven.

Table 6.

^*By passing¹H NMR-determined proportion of monomers in the Polymer

AD. preparation of additives

Example AD 1: preparation of adhesion promoter-3, 4-dimethyl-1- [3- (triethoxysilyl) propyl ] -1H-pyrrole-2, 5-dione (DMMIPrTEOS)

To a suitably sized reaction vessel equipped with a thermowell, Dean Stark trap connected to a condenser with nitrogen inlet, addition funnel and mechanical stirrer was charged 2.2L cyclohexane followed by dimethylmaleic anhydride (DMMA, 107.8g, 0.85mol) and pyridine (3.5mL, 0.042mol) with stirring. A slight exotherm (20 to 14 ℃) was observed with the dissolution of dimethylmaleic anhydride in the epoxyhexane. The mixture was warmed to 25 ℃ and a cloudy solution was observed. 3-aminopropyltriethoxysilane (189.2g, 200mL, 0.85mol) was added slowly over 15 minutes to the addition funnel. To 3-aminopropyltriethoxysilane was added an additional 300mL of cyclohexane for rinsing and the addition funnel was replaced with a stopper. The mixture immediately exothermed to 24 ℃ and a white cloudy solution was observed. The mixture was carefully heated (to avoid excessive foaming) to reflux over a period of 30 minutes. A clear solution was observed at 40 ℃ and it turned into a white turbid solution again at 70 ℃. The reaction mixture was refluxed at 70 ℃ for 1h and an aliquot was analyzed, which indicated that the reaction was complete (88% product with 11% DMMA and no 3-aminopropyltriethoxysilane). The reaction mixture was cooled to room temperature and the cyclohexane layer was poured into a 5L flask, leaving a white polymer residue (120 g). The cyclohexane layer was concentrated on a rotary evaporator at a bath temperature of 60 ℃. The residue was transferred to 500ml rbf and dried under high vacuum at a bath temperature of 7 ℃ for 2h to obtain 132g of crude product (crude purity 96.5% with 3.2% DMMA) as a viscous oil. The crude product was further purified by Kugelrohr distillation under vacuum of 0.15-0.2torr at an oven temperature of 150 ℃ and 170 ℃ to obtain 64.4g (23% yield) of the product as a clear liquid with a purity of 99.7% as determined by Gas Chromatography (GC).¹H NMR and mass spectra were consistent with the expected structure. The pot residue was 60.6g and the total polymer residue was 180.1g (64%). Data:GC analysis on a DB-5MS column, 25 meters, 0.32mm ID, 0.52 μm membrane, heated from 75 ℃ to 200 ℃ at 15 ℃/min, then held at 300 ℃ for 2 minutes from 200 ℃ to 300 ℃, syringe temperature: 200 ℃, detector temperature: 350 ℃, retention time: 9.250 minutes.

Example AD2 preparation of the crosslinker 1, 4-bis (dimethylmaleimido) butane

To a suitably sized reaction vessel equipped with a thermowell, septum, condenser with nitrogen inlet, and mechanical stirrer was charged DMMA (28.6g, 0.226mol) in 110mL of glacial acetic acid. The reaction mixture was heated to 35 ℃ and a clear solution was observed. Pure butane-1, 4-diamine (10g, 0.113mol) was then added slowly and rinsed with 30mL of glacial acetic acid. The reaction mixture exothermed to 75 ℃ and was then heated to 118 ℃ and held at this temperature for 3h, during which a pale yellow solution was obtained. The reaction was monitored by GC (aliquots were quenched with ice/water and the precipitate was filtered and dissolved in CH₂Cl₂Medium) and found to be complete after 3h stirring at 118 ℃. The reaction was cooled to room temperature, quenched with 500g of ice, diluted with 500mL of water and stirred for 30 minutes. The white product precipitated was filtered and washed with 1L of water and dried under vacuum. The white precipitate was pulverized with 1L of water in an ultrasonic bath for 1 hour. The white precipitate was filtered again and then dried under vacuum to obtain 29.8g (87% yield) of the product as a white powder with 99.03% purity as determined by GC. MS, MS,¹HNMR and¹³c NMR was consistent with the expected structure. The melting point of the product was 127-130 ℃. Data: GC analysis was performed on a DB-5MS column, 25 meters, 0.32mm ID, 0.52 μm membrane, heated from 75 ℃ to 300 ℃ at 30 ℃/min, held at 300 ℃ for 6 minutes, syringe temperature: 200 ℃, detector temperature: 350 ℃, retention time: 7.745 min.

Example AD3 preparation of crosslinker-1, 6-bis (dimethylmaleimido) hexane

To a suitably sized reaction vessel equipped with a thermowell, septum, condenser with nitrogen inlet, and mechanical stirrer was charged DMMA (26g, 0.206mol) in 100mL of glacial acetic acid. The reaction mixture was heated to 35 ℃ and a clear solution was observed. Pure hexane-1, 6-diamine (12g, 0.103mol) was then added slowly and rinsed with 20mL of glacial acetic acid. The reaction mixture exothermed to 75 ℃ and was then heated to 118 ℃ and held at this temperature for 3h, during which a pale yellow solution was obtained. The reaction was monitored by GC (aliquots were quenched with ice/water and the precipitate was filtered and dissolved in CH₂Cl₂Medium) and found to be complete after 3h stirring at 118 ℃. The reaction was cooled to room temperature, quenched with 500g of ice, diluted with 500mL of water and stirred for 30 minutes. The white product precipitated was filtered and washed with 1L of water and dried under vacuum. The white precipitate was pulverized with 1L of water in an ultrasonic bath for 1 hour. The white precipitate was filtered and then dried under vacuum to obtain 30.4g (88.6% yield) of the product as a white powder with 99.02% purity by GC. MS, MS,¹H NMR and¹³CNMR is consistent with the desired structure. The melting point of the product was 122-125 ℃. Data: GC analysis on a DB-5MS column, 25 meters, 0.32mmID, 0.52 μm membrane, heating from 75 ℃ to 300 ℃ at 30 ℃/min, holding at 300 ℃ for 6 minutes, injector temperature: 200 ℃, detector temperature: 350 ℃, retention time: 8.590 minutes.

C: device fabrication

The top gate OFET was prepared as follows. A Corning 1737 glass substrate was sonicated in 3% Decon90 for 30 minutes at 70 ℃, washed twice with water and sonicated in MeOH, then dried by spin drying on a spin coater. Gold source and drain electrodes having a thickness of 30nm were evaporated on the substrate through a shadow mask, yielding a channel L of 50 μm and W of 1000 μm. With surface-treating composition Lisicon^TMM001 (commercially available from Merck KGaA, Darmstadt (germany)) treated the substrate for 1 minute, washed with isopropanol and spin dried on a spin coater.

After the above treatment, the OSC composition Lisicon^TMS1036 (commercially available from Merck KGaA, Darmstadt (germany)) was spin coated on the substrate and then annealed on a hot plate at 100 ℃ for 1 minute. In the next step, the dielectric layer was spin coated according to the conditions described in example C13-20 below. A 30nm gold layer was thermally evaporated on the dielectric layer through a shadow mask to form a gate electrode.

The bottom gate OFET was prepared as follows. A Corning Eagle XG glass substrate was sonicated in 3% Decon90 for 30 minutes at 70 ℃, washed twice with water and sonicated in MeOH, then dried by spin drying on a spin coater. A 30nm layer of aluminum was then thermally evaporated on the substrate through a shadow mask to form a gate electrode. The dielectric was rotated, annealed and cured according to the conditions described in example C1-12. In the case of potential reactivity provided by EONB or MGENB moieties (example C1-4), it was necessary to use Lisicon after annealing^TMM008 (obtained from Merck KGaA, Darmstadt (Germany)) was subjected to a reactive washing step, in which the dielectric was covered in M008 for 1 minute, rinsed twice with THF and spin-dried. After dielectric deposition, 30nm thick silver source and drain electrodes were evaporated onto the dielectric, yielding a channel with L-50 μm and W-1000 μm. With surface-treating composition Lisicon^TMM001 (obtained from Merck KGaA, Darmstadt (germany)) treated the substrate for 1 minute, washed with isopropanol and dried by spin-drying on a spin coater.

After the above treatment, the OSC composition Lisicon^TMS1200 and S1036 (commercially available from Merck KGaA, Darmstadt (germany)) were spin coated on a substrate and then annealed on a hot plate at 100 ℃ for 30 seconds.

For electrical properties, the samples were placed on a probe station and connected to an Agilent4155C semiconductor analyzer through a Suess PH100 probe head. Linear and saturated mobilities were calculated at VD ═ 5V and VD ═ 60V (or VD ═ 40V), respectively, using the following formulas:

where L and W are the length and width of the channel, Cox ═ dielectric capacitance [ F/cm ═²]ID is the drain current, sqrt ID is the square root of the absolute ID value, VG is the gate voltage, and VD is the drain voltage.

Example c1 OFET comprising the gate insulator of example B56

A50: 50 ratio of DecNB and MGENB copolymer was formulated as a 15% w/w solution in 2-heptanone comprising 0.7% (by weight of polymer) of 365 nmPAG. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and 3 minutes on a hotplate with UV light at 365nm (11 mW/cm) before annealing at 120 ℃ for 3 minutes²) The lower radiation is for 30 seconds. Merck Lisicon S1200 using spin coating in this example^TMA composition is provided. The transfer curve is depicted in fig. 3.

Embodiment C2. OFET comprising the gate insulator of embodiment B56

A50: 50 ratio of DecNB and MGENB copolymer was formulated as a 15% w/w solution in 2-heptanone comprising 0.7% (by weight of polymer) of 365 nmPAG. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and at 365nm UV light (11 mW/cm) 3 minutes before post annealing at 120 ℃ on a hotplate²) The lower radiation is for 30 seconds. Merck Lisicon S1200 using inkjet printing in this example^TMA composition is provided. The transfer curve is depicted in fig. 4.

Embodiment C3. OFET comprising the gate insulator of embodiment B56

A50: 50 ratio of DecNB and MGENB copolymer was formulated as a 15% w/w solution in 2-heptanone comprising 0.7% (by weight of the polymer) of p-isopropylphenyl (p-methylphenyl) iodonium tetrakis (perfluorophenyl) borate. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and UV light at 254nm (1 mW/cm) before annealing at 120 ℃ for 3 minutes on a hotplate²) The lower radiation is for 30 seconds. Merck Lisicon S1200 using spin coating in this example^TMA composition is provided. The transfer curve is depicted in fig. 5.

Example C4 OFET comprising the Gate insulator of example B57

A69: 31 ratio of DecNB and MGENB copolymer was formulated as a 15% w/w solution in 2-heptanone comprising 0.5% (by weight of the polymer) of p-isopropylphenyl (p-methylphenyl) iodonium tetrakis (perfluorophenyl) borate. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and UV light at 254nm (1 mW/cm) before annealing at 120 ℃ for 3 minutes on a hotplate²) The lower radiation is for 30 seconds. In this example, MerckLisicon S1036 spin-coated in toluene was used^TM. The transfer curve is depicted in fig. 6.

Embodiment C5. OFET comprising the gate insulator of embodiment B64

DMMIBuNB homopolymer was formulated as a 17% w/w solution in 2-heptanone comprising 0.7% (by weight of the polymer) of 1-chloro-4-propoxythioxanthone. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and irradiated with UV light at 365nm (11 mW/cm)²) And irradiating for 200 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 7.

Embodiment C6. OFET comprising the gate insulator of embodiment B47

EtCoumNB homopolymer was formulated as a 14% w/w solution in 2-heptanone comprising 0.7% (by weight of the polymer) of 1-chloro-4-propoxythioxanthone. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and irradiated with UV light at 365nm (11 mW/cm)²) And irradiating for 200 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 8.

Embodiment C7. OFET comprising the gate insulator of embodiment B30

A54: 46 ratio of DecNB and PhIndNB copolymer was formulated as a 15% w/w solution in 2-heptanone. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and irradiated with UV light at 365nm (11 mW/cm)²) Lower radiation for 120 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 9.

Embodiment C8. OFET comprising the gate insulator of embodiment B26

BuNB and MeOCinnNB copolymers in a 55: 45 ratio were formulated to include 1.0% by weight of the polymer) Of 1-chloro-4-propoxythioxanthone in 2-heptanone. The solution was spun at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and UV light at 365nm (11 mW/cm)²) And irradiating for 200 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 10.

Example C9. OFET including gate insulator with examples B2 and B26 as sensitizers

A65: 35 ratio copolymer of MeDMMINB and BuNB was combined with a 55: 45 ratio copolymer of BuNB and MeOCinnamateNB in a 4: 1 ratio and formulated as a 13% w/w solution in 2-heptanone. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hot plate and subjected to UVA (320-400nm) UV light (0.35W/cm)²) Lower radiation for 20 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 11.

Example c10 OFET comprising gate insulator of example B4

The MeDMMINB homopolymer was formulated as a 13% w/w solution in 2-heptanone comprising 0.7% (by weight of the polymer) of 1-chloro-4-propoxythioxanthone. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hotplate and under 302nm UV light (7 mW/cm)²) Lower radiation for 120 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 12.

Example c11 OFET comprising the gate insulator of example B2

A35: 65 ratio of BuNB and MeDMMINB copolymer was formulated as a 13% w/w solution in 2-heptanone comprising 0.5% (by weight of the polymer) of 1-chloro-4-propoxythioxanthone. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hot plate and heated atUV light at 302nm (7 mW/cm)²) And irradiating for 300 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 13.

Embodiment c12 OFET comprising gate insulator of embodiment B1

A51: 49 ratio of MeOAcNB and MeDMMINB copolymer was formulated as a 13% w/w solution in 2-heptanone comprising 0.5% (by weight of the polymer) of 1-chloro-4-propoxythioxanthone. The solution was spin coated at 1500rpm for 30 seconds, annealed at 120 ℃ for 2 minutes on a hot plate and subjected to UVA (320-400nm) UV light (0.35W/cm)²) The lower radiation is for 30 seconds. Merck Lisicon S1200 using spin coating in this example^TM. The transfer curve is depicted in fig. 14.

Embodiment c13 OFET comprising gate insulator of embodiment B15

NBC (N-bromosuccinimide)₄F₉The homopolymer was formulated to be 10% solids weight in 80/20 mixture of perfluorophenanthrane and HFE7500 and spin coated at 500rpm for 10 seconds, then 1000rpm for 20 seconds, followed by annealing on a hot plate at 100 ℃ for 2 minutes. Merck Lisicon S1200 was used in this example^TMAn OSC composition. The transfer curve is depicted in fig. 15.

Example c14 OFET comprising the gate insulator of example B65

Will NBCH₂CF₂CHFOC₃F₇(PPVENBB) homopolymer was formulated as 10% solids weight in 80/20 mixture of perfluorophenanthrane and HFE7500 and spin coated at 500rpm for 10 seconds, then 1000rpm for 20 seconds, followed by annealing at 100 ℃ for 2 minutes on a hot plate. Merck Lisicon S1200 was used in this example^TMAn OSC composition. The transfer curve is depicted in fig. 16.

Example c15 OFET comprising gate insulator of example B66

The HexNB homopolymer was formulated at 12.5% solids weight in decane and spin coated at 500rpm for 10 seconds followed by 1500rpm for 30 seconds, followed by annealing on a hot plate at 100 ℃ for 1 minute. Merck Lisicon SP320 was used in this example^TMAn OSC composition. The transfer curve is depicted in fig. 17.

Embodiment c16 OFET comprising gate insulator of embodiment B67

BuNB homopolymer was formulated to be 12.5% solids weight in decane and spin coated at 500rpm for 10 seconds, then at 1500rpm for 30 seconds, followed by annealing on a hot plate at 100 ℃ for 1 minute. MerckLisicon SP320 was used in this example^TMAn OSC composition. The transfer curve is depicted in fig. 18.

Example c17 OFET comprising gate insulator of example B48

The BuNB/DMMIMeNB copolymer was formulated at a 0.9/0.1 ratio to 15% solids weight in decane and spin coated at 500rpm for 10 seconds, then at 1500rpm for 30 seconds, followed by annealing at 100 ℃ for 1 minute on a hot plate. Merck Lisicon SP320 was used in this example^TMAn OSC composition. The transfer curve is depicted in fig. 19.

Embodiment c18 OFET comprising gate insulator of embodiment B61

A 0.7/0.3 ratio of DecNB/EONB copolymer was formulated as 16% solids weight in decane and spin coated at 500rpm for 10 seconds, then at 1500rpm for 30 seconds, followed by annealing at 100 ℃ for 1 minute on a hot plate. MerckLisicon SP320 was used in this example^TMAn OSC composition. The conversion curve is depicted in FIG. 20A wire.

Examples C1-C18 show that the gate insulator according to the invention is suitable for use in organic field effect transistors, where it shows good wettability and orthogonal solubility in relation to organic semiconductor materials and enables good transistor performance.

Example c19 OFET comprising gate insulator with adhesion promoter

The bottom gate OFET was prepared as follows. A Corning Eagle XG glass substrate was sonicated in 3% Decon90 for 30 minutes at 70 ℃, washed twice with water and sonicated in MeOH, then dried by spin-drying on a spin coater. A 30nm layer of aluminum was then thermally evaporated through a shadow mask onto the substrate to form a gate electrode.

The substrate was wetted with 1% DMMI-propyl-triethoxysilane in PGMEA, spun dry and washed with IPA.

A17% DMMIBuNB homopolymer solution (see example B64) containing 0.7% (relative to polymer w/w) sensitizer CPTX in MAK was applied by spin coating and at 11mW/cm²UV curing at 365nm for 4 minutes.

Silver source and drain electrodes 30nm thick were thermally evaporated on the substrate through a shadow mask to yield a channel length L of 50 μm and a channel width W of 1000 μm. Next step application of the surface treatment composition Lisicon^TMM001 (obtained from Merck KGaA, Darmstadt (germany)) for 1 minute, washed with isopropanol and dried by spin-drying on a spin coater. Next step after the above treatment, the OSC composition Lisicon^TMS1200 (obtained from Merck KGaA, Darmstadt (Germany)) was spin-coated on a substrate and annealed at 100 ℃ for 1 minute on a hot plate.

Fig. 21 shows the characteristics of a transistor comprising an organic dielectric pDMMIBuNB and an adhesion promoter DMMI-propyl-triethoxysilane.

Example C20 OFET comprising Gate insulator without adhesion promoter

A bottom gate OFET was prepared as described in example D3, but in which the step of impregnating the substrate with DMMI-propyl-triethoxysilane was omitted.

Fig. 22 shows the characteristics of a transistor including an organic dielectric pDMMIBuNB but without an adhesion promoter. The comparison between fig. 21 and 22 shows that the performance of the transistor is not affected by the use of adhesion promoters.

For mechanical properties, the 1% DMMI-propyl-triethoxysilane solution used in PGMEA impregnated the glass substrate, spin dried and washed with IPA. A solution of 0.7% w/w CPTX in 17% DMMIBuNB homopolymer contained in MAK (see example B64) was applied by spin coating at 11mW/cm²UV curing at 365nm for 4 minutes.

The reference examples were prepared by the method described above, but without the step of impregnating the substrate with a 1% solution of DMMI-propyl-triethoxysilane in PGMEA.

Both samples were mechanically tested in a 180-degree geometric adhesion test using a Mecmesin instrument (Multitest 1-i).

Fig. 23 shows a graph of adhesion versus distance for two samples. It can be seen that there is a significant improvement in adhesion between the glass substrate and the DMMIBuNB polymer layer including the adhesion promoter DMMI-propyl-triethoxysilane as compared to the DMMIBuNB polymer layer without the adhesion promoter.

Example c21 OFET comprising gate insulator with crosslinker

The bottom gate OFET was prepared as follows. A substrate of Corning Eagle XG glass was sonicated in 3% Decon90 for 30 minutes at 70 ℃, washed twice with water and sonicated in MeOH, then dried by spin-drying on a spin coater. A 30nm layer of aluminum was then thermally evaporated through a shadow mask onto the substrate to form a gate electrode.

0.7% CPTX (w/w relative polymer), or 0.5% di-DMMI-butyl (w/w relative polymer), or 17% DMMIBuNB homopolymer solution without additives (see example B64) contained in the MAK was applied by a spin coater at 11mW/cm²UV curing under 365nm radiation for various times.

Silver source and drain electrodes, 30nm thick, were thermally evaporated onto the substrate through a shadow mask, creating channels with L-50 μm and W-1000 μm. Next, a surface treatment composition Lisicon was applied^TMM001 (obtained from Merck KGaA, Darmstadt (germany)) for 1 minute, washed with isopropanol and dried by spin-drying on a spin coater. Next, after the above treatment, the OSC composition Lisicon^TMS1200 (obtained from Merck KGaA, Darmstadt (germany)) was spin coated on a substrate and then annealed at 100 ℃ for 1 minute on a hot plate.

The carrier mobilities obtained from bottom-gate transistors prepared with different UV cure times are shown in table C1 below. The times in table C1 are in seconds and represent the minimum and optimum time (Min and Opt) required for crosslinking the polymer layer and for obtaining a given mobility for each additive.

TABLE C1

Additive agent	Min＞0.8cm2/Vs	Opt＞1cm2/Vs
			Is free of	180s	300s
0.7％CPTX	120s	240s
			0.5% of DiDMMI-butyl	90s	120s

Examples C19 through C21 further demonstrate that device performance is not negatively impacted by the use of adhesion promoters or crosslinkers, but certain advantages such as shorter UV exposure times and improved adhesion are obtained.

Claims (39)

1.A gate insulating layer in contact with an organic semiconductor layer in an organic electronic device, the gate insulating layer comprising a polycycloolefin polymer or a polymer composition comprising a polycycloolefin polymer,

wherein the polycycloolefin polymer comprises one or more types of repeating units of formula I:

wherein Z is selected from-CH₂-、-CH₂-CH₂-or-O-, m is an integer from 0to 5, R¹、

R²、R³And R⁴Is independently selected from H, C₁To C₂₅A hydrocarbon group of₁To C₂₅Halogenated hydrocarbon group of or C₁To C₂₅A perhalocarbon group of (2).

2. The gate insulator layer of claim 1, wherein the polycycloolefin polymer includes a first type of repeat unit having a crosslinkable pendent group.

3. The gate insulator layer of claim 2, wherein the crosslinkable pendent group is a latent crosslinkable group.

4. The gate insulator layer of claim 2 wherein said crosslinkable pendent group is a maleimide, 3-monoalkylmaleimide, 3, 4-dialkylmaleimide, epoxy, vinyl, acetyl, indenyl, cinnamate or coumarin group, or said crosslinkable pendent group comprises a substituted or unsubstituted maleimide, epoxide, vinyl, cinnamate or coumarin moiety.

5. A gate insulator layer according to claim 2, wherein the first type of repeat unit having a crosslinkable pendent group is derived from any one of the following monomers:

wherein n is an integer of 1 to 8, Q¹And Q²Each independently is-H or-CH₃And R' is-H or-OCH₃。

6. The gate insulating layer of claim 1, wherein the polycycloolefin polymer includes a second type of repeating unit different from the first type of repeating unit.

7. The gate insulating layer according to claim 1, wherein the polycycloolefin polymer comprises one or more types of repeating units of formula I and one or more types of repeating units of formula II:

wherein Z is selected from-CH₂-、-CH₂-CH₂-or-O-, m is an integer from 0to 5, R¹、R²、R³And R⁴And R⁵、R⁶、R⁷And R⁸Is independently selected from H, C₁To C₂₅A hydrocarbon group of₁To C₂₅Halogenated hydrocarbon group of or C₁To C₂₅And wherein the repeating unit of formula I is different from the repeating unit of formula II.

8. The gate insulating layer according to claim 1 or 7, wherein the repeating units of formula I and formula II are each independently formed by a norbornene-type monomer selected from the group consisting of the following subformulae:

wherein "Me" represents a methyl group, "Et" represents an ethyl group, "OMe-p" represents a p-methoxy group, "Ph" and "C₆H₅"represents a phenyl group," C₆H₄"represents a phenylene group," C₆F₅"represents a perfluorophenyl group," OAc "represents an acetate, and" PFAc "represents-OC (O) -C₇F₁₅And for each of the above subformulae there is a methylene bridge comprising a covalent bond or- (CH)₂)_p-, and p is an integer of 1 to 6.

9. The gate insulator layer of claim 1 wherein the polymer composition comprises a blend of a first polycycloolefin polymer and a second polycycloolefin polymer.

10. The gate insulating layer according to claim 9, wherein the first polycycloolefin polymer includes one or more types of repeating units of formula I, and the second polycycloolefin polymer includes one or more types of repeating units of formula II:

wherein Z is selected from-CH₂-、-CH₂-CH₂-or-O-, m is an integer from 0to 5, R¹、R²、R³And R⁴And R⁵、R⁶、R⁷And R⁸Is independently selected from H, C₁To C₂₅A hydrocarbon group of₁To C₂₅Halogenated hydrocarbon group of or C₁To C₂₅And wherein the repeating unit of formula I is different from the repeating unit of formula II.

11. The gate insulator layer of claim 1, wherein said polymer or polymer composition further comprises one or more of a solvent, a cross-linking agent, a stabilizer, a UV sensitizer, and a thermal sensitizer.

12. The gate insulator layer of claim 11 wherein said polymer or polymer composition further comprises a reactive solvent.

13. The gate insulating layer of claim 1, wherein the polymer or polymer composition comprises one or more repeating units having a crosslinkable group, and the gate insulating layer further comprises an adhesion promoter which is a compound comprising a surface active functional group and a crosslinkable functional group capable of crosslinking with the crosslinkable group of the repeating units of the polymer or polymer composition.

14. A gate insulator layer according to claim 13, wherein the adhesion promoter is a compound of formula III:

G-A'-P III

wherein G is a surface-active group, A' is a single bond or a spacer, linking or bridging group, and P is a crosslinkable group.

15. A gate insulator layer according to claim 13 or 14, wherein the surface active group of the adhesion promoter is a silane group, or a silazane group.

16. The gate insulator layer of claim 15, wherein saidThe surface-active group of the adhesion promoter is of the formula SiR¹²R¹³R¹⁴In which R is¹²、R¹³And R¹⁴Each independently selected from halogen, silazane, C₁-C₁₂-alkoxy radical, C₁-C₁₂-alkylamino, optionally substituted C₅-C₂₀Aryloxy and optionally substituted C₂-C₂₀-heteroaryloxy, and wherein R¹²、R¹³And R¹⁴One or both of which may also represent C₁-C₁₂-alkyl, optionally substituted C₅-C₂₀-aryl or optionally substituted C₂-C₂₀-a heteroaryl group.

17. The gate insulator layer of claim 15 wherein the surface active group of the adhesion promoter is of the formula-NH-SiR¹²R¹³R¹⁴A silazane group of (2), wherein R¹²、R¹³And R¹⁴Each independently selected from halogen, silazane, C₁-C₁₂-alkoxy radical, C₁-C₁₂-alkylamino, optionally substituted C₅-C₂₀Aryloxy and optionally substituted C₂-C₂₀-heteroaryloxy, and wherein R¹²、R¹³And R¹⁴One or both of which may also represent C₁-C₁₂-alkyl, optionally substituted C₅-C₂₀-aryl or optionally substituted C₂-C₂₀-a heteroaryl group.

18. The gate insulator layer of claim 13 wherein said crosslinkable group of said adhesion promoter is selected from the group consisting of maleimide, 3-monoalkylmaleimide, 3, 4-dialkylmaleimide, epoxy, vinyl, acetyl, indenyl, cinnamate or coumarin groups, or said crosslinkable group comprises a substituted or unsubstituted maleimide moiety, epoxide moiety, vinyl moiety, cinnamate moiety or coumarin moiety.

19. The gate insulator layer of claim 13, wherein said adhesion promoter is a compound having the structure:

wherein SiR¹²R¹³R¹⁴As defined in claim 14, A' is as defined in claim 14 and R¹⁰And R¹¹Each independently is H or C₁-C₆An alkyl group.

20. The gate insulating layer according to claim 1, wherein the polymer or polymer composition comprises one or more repeating units having a crosslinkable group, and the gate insulating layer comprises a crosslinking agent which is a compound comprising two or more crosslinkable functional groups capable of crosslinking with the crosslinkable group of the repeating unit in the polymer or polymer composition.

21. A gate insulator layer according to claim 20, wherein the cross-linking agent is a compound of formula IV1 or IV 2:

P-X-P IV1

H_4-mC(A"-P)_mIV2

wherein X is A ' -X ' -A ', X ' is O, S, NH or a single bond, A ' is a single bond or a spacer, linker or bridge, P has the meaning of claim 14, and m is 2,3 or 4.

22. The gate insulator layer of claim 20 wherein the cross-linkable group of the cross-linker is selected from the group consisting of maleimide, 3-monoalkylmaleimide, 3, 4-dialkylmaleimide, epoxy, vinyl, acetyl, indenyl, cinnamate or coumarin groups, or the cross-linkable group comprises a substituted or unsubstituted maleimide moiety, epoxide moiety, vinyl moiety, cinnamate moiety or coumarin moiety.

23. The gate insulator layer of claim 20 wherein said crosslinker is a compound of the formula:

wherein R is¹⁰And R¹¹Each independently is H or C₁-C₆Alkyl, A' has the meaning of claim 22.

24. The gate insulator layer of claim 23 wherein a "is selected from the group Consisting of (CZ)₂)_n、(CH₂)_n-(CH＝CH)_p-(CH₂)_n、(CH₂)_n-O、(CH₂)_n-O-(CH₂)_n、(CH₂)_n-C₆Q₁₀-(CH₂)_nAnd C (O) -O, wherein each n is independently an integer from 0to 12, p is an integer from 1 to 6, Z is independently H or F, C₆Q₁₀Is cyclohexyl substituted by Q, Q is independently H, F, CH₃、CF₃Or OCH₃。

25. The gate insulator layer of claim 1, wherein the polymer composition further comprises a solvent having orthogonal solubility properties associated with the organic semiconductor layer.

26. The gate insulator layer of claim 1 comprising a solvent, a crosslinkable norbornene-type polymer, and one or more of a crosslinking agent, a UV sensitizer and an adhesion promoter.

27. The gate insulating layer of claim 26, wherein the norbornene-type polymer comprises repeating units derived from a norbornene-type monomer selected from DMMIMeNB, DMMIEtNB, DMMIPrNB or DMMIBuNB.

28. The gate insulating layer of claim 26, wherein the UV sensitizer is CPTX and the solvent is MAK, cyclohexanone or cyclopentanone.

29. A gate insulating layer according to claim 26, wherein the cross-linking agent is DMMI-butyl-DMMI, DMMI-pentyl-DMMI or DMMI-hexyl-DMMI.

30. The gate insulator layer of claim 26 wherein said adhesion promoter is DMMI-propyl-Si (OEt)₃DMMI-butyl-Si (OEt)₃DMMI-butyl-Si (OMe)₃Or DMMI-hexyl-Si (OMe)₃。

31. The gate insulating layer of claim 1, comprising a polycycloolefin polymer comprising a polymer derived from a group selected from BuNB, HexNB, OctNB, DecNB, NBC₄F₉And repeating units of a norbornene-type monomer of PPVENB.

32. The gate insulating layer of claim 1, comprising a polycycloolefin polymer comprising crosslinkable repeat units derived from norbornene-type monomers selected from the group consisting of EONB, MGENB, DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB, and DMMIHxNB.

33. The gate insulating layer of claim 1, comprising a polycycloolefin polymer comprising repeating units derived from a norbornene-type monomer selected from BuNB, HexNB, OctNB, DecNB and repeating units derived from a norbornene-type monomer selected from EONB, MGENB, DMMIMeNB, DMMIEtNB, DMMIPrNB, DMMIBuNB and DMMIHxNB.

34. Use of a polycycloolefin polymer, or a polymer composition comprising a polycycloolefin polymer, as defined in any one of claims 1 to 33, to form an organic gate insulating layer in contact with an organic semiconductor layer in an organic electronic device.

35. An organic electronic device comprising an organic gate insulating layer in contact with an organic semiconducting layer, wherein the gate insulating layer is formed from a polymer or polymer composition as defined in any one of claims 1 to 33.

36. The organic electronic device according to claim 35, which is an Organic Field Effect Transistor (OFET), an Organic Thin Film Transistor (OTFT), an Integrated Circuit (IC) or a Radio Frequency Identification (RFID) tag.

37. An organic electronic device according to claim 36, which is a top gate or bottom gate OFET.

38. A process for preparing a bottom gate OFET according to claim 37, which comprises the steps of: a) depositing a gate electrode (5) on a substrate (1); b) depositing a layer of an organic dielectric material on the gate electrode (5) and the substrate (1) to form a gate insulating layer (4), the dielectric material comprising a polycycloolefin polymer as defined in any one of claims 1 to 33, or comprising a polymer composition comprising a polycycloolefin polymer as defined in any one of claims 1 to 33; c) depositing a layer of organic semiconductor material (3) on the gate insulating layer (4); d) depositing source and drain electrodes (2) on at least a portion of the organic semiconductor layer (3); e) optionally, a further layer (6), for example an insulating and/or protective and/or stabilizing and/or adhesive layer, is deposited on the source and drain electrodes (2) and the organic semiconductor layer (3).

39. A process for preparing the top gate OFET of claim 37, which comprises the steps of: a) depositing a source electrode and a drain electrode (2) on a substrate (1); b) depositing a layer (3) of organic semiconductor material on the substrate (1) and the source and drain electrodes (2); c) depositing a layer of an organic dielectric material on the OSC layer (3) to form the gate insulating layer (4), the dielectric material comprising a polycycloolefin polymer as defined in any one of claims 1 to 33, or comprising a polymer composition comprising a polycycloolefin polymer as defined in any one of claims 1 to 33; d) depositing a gate electrode (5) on at least a portion of the gate insulating layer (4); e) optionally, a further layer (6), for example an insulating and/or protective and/or stabilizing and/or adhesive layer, is deposited on the gate electrode (5) and the gate insulating layer (4).