[go: up one dir, main page]

WO2018060015A1 - Star-shaped styrene polymers with enhanced glass transition temperature - Google Patents

Star-shaped styrene polymers with enhanced glass transition temperature Download PDF

Info

Publication number
WO2018060015A1
WO2018060015A1 PCT/EP2017/073688 EP2017073688W WO2018060015A1 WO 2018060015 A1 WO2018060015 A1 WO 2018060015A1 EP 2017073688 W EP2017073688 W EP 2017073688W WO 2018060015 A1 WO2018060015 A1 WO 2018060015A1
Authority
WO
WIPO (PCT)
Prior art keywords
arylene
alkylene
group
cycloalkylene
linking group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2017/073688
Other languages
French (fr)
Inventor
Emmanuel Martin
Fulvio G. BRUNETTI
Daniel Kaelblein
Konrad Knoll
Jordan Thomas KOPPING
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2018060015A1 publication Critical patent/WO2018060015A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/042—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a polyfunctional initiator
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D30/00—Field-effect transistors [FET]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/791—Starburst compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/471—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising only organic materials

Definitions

  • the present invention relates to star-shaped polymers, to a process for the preparation of a star-shaped polymer, to compositions comprising these polymers and to electronic devices comprising the polymers or a layer formed from the compositions comprising the polymers.
  • FETs Field effect transistors
  • RFID radio-frequency identification
  • Field effect transistors require a dielectric layer formed by a dielectric material.
  • the use of many organic polymers as dielectric material in field effect transistors is known in the art.
  • One common organic polymer for use as dielectric material in field effect transistors is polystyrene.
  • US 2012/0141757 describes dielectric compositions comprising a dielectric material and a low surface tension additive.
  • the dielectric composition may further comprise crosslinking agents. Examples of dielectric material include polystyrene and poly(1 ,3-butadiene).
  • WO 201 1/001007 describes a method for manufacturing electronic components.
  • dielectric materials include polystyrene, poly(4-vinylphenol) and polyvinyl chloride. When used as thermally responsive material, the dielectric material can be used with cross-linking agents.
  • polystyrene as dielectric material suffers from the disadvantage of having a relative low glass temperature (Tg).
  • Tg glass temperature
  • various fabrication steps for example the application of the source/drain electrodes or the gate electrode on top of the dielectric layer by annealing, require high temperatures.
  • Dielectric layers are prone to be altered, for example by solid phase transition, when exposed to temperatures which are higher than the glass temperature of the dielectric material. The exposure of a dielectric layer to temperatures higher than the glass temperature of the dielectric material might result in electrode misplacement or interface defects between the dielectric layer and the semiconducting layer.
  • Copolymers obtainable from styrene and 1 ,1-diphenylethylene monomers, which copolymers have a higher glass temperature than polystyrene are known in the art.
  • US20100010147 describes block copolymers suitable as adhesive or sealant comprising at least one block comprising a mixture of 1 ,1-diphenylethylene and its derivatives with mono alkenyl arenes and at least one block comprising a conjugated diene or conjugated diene containing mixtures from isoprene and/or butadiene.
  • the block copolymers can have the following structures: A-B, (A-B) n , (A-B) n X, (A-B-A) n X, wherein A represents a polymer block of a mixture of one or more mono alkenyl arenes and one or more monomers of 1 ,1 -diphenylethylene and its derivatives, B represents a polymer block of conjugated diene or conjugated diene mixture, n is an integer from 1 to 30, and X represents the residue of a coupling agent.
  • US20100010147 only describes block copolymer with polystyrene end blocks. H. Gausepohl, S. Oepen, K. Knoll, M. Schneider, G. McKee, W.
  • copolymers comprising at least one block A of
  • copolymers can be obtained by anionic polymerization, and block copolymers with at least one block A and at least one, optionally hydrogenated, block B of diene b), which block copolymers can be obtained by sequential anionic polymerization.
  • copolymers of US 5854353 and WO 99/01487 are both thermoplastic polymers, which can be re-shaped upon heating, and which are used for molding.
  • JP59084910 describes copolymers prepared by polymerizing diphenylethylene or a derivative, and divinylbenzene or a derivative, and optionally styrene or a styrene derivative, using an anionic initiator. The final copolymer contains divinylbenzene monomer units still carrying one residual double bond.
  • the organic polymer dielectric material is applied by liquid processing techniques such as spin coating as liquid processing techniques allow the production of low cost field effect transistors.
  • liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and mechanically flexible field effect transistors, which is a requisite for the fabrication of light-weight and flexible displays.
  • the organic polymers used as dielectric material for a field effect transistor should be soluble in organic solvents in order to be compatible with liquid processing techniques.
  • the organic polymers should show good film forming properties, and the films formed from the organic polymers should be elastic in order to allow the production of flexible displays.
  • organic polymers for use as dielectric material in field effect transistors which organic polymers have a higher glass temperature than polystyrene, are compatible with liquid processing techniques, show good film forming properties, and the films formed are elastic.
  • the polymers of the present invention are polymers comprising units of formulae
  • a wavy line represents a valency
  • Ar 1 , Ar 2 and Ar 3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and R 1 is H or Ci-4-alkyl, and at least one n-valent unit X,
  • n is an integer from 3 to 10.
  • the polymers of the present invention are star-shaped polymers.
  • Examples of C6-io-aryl are
  • C6-i4-arylene examples include C6-io-arylene and Ci-4-alkyl, Ci-10-alkyl, Ci-20-alkyl and Ci-30-alkyl can be branched or unbranched.
  • Ci-4-alkyl examples include methyl, ethyl, /7-propyl, isopropyl, /7-butyl, sec-butyl, isobutyl and fe -butyl.
  • Ci-io-alkyl examples include Ci-4-alkyl and /7-pentyl, neopentyl, isopentyl, /7-(1-ethyl)propyl, n- exy ⁇ , /7-heptyl, /7-octyl, /?-(2-ethyl)hexyl, /7-nonyl and n-decy ⁇ .
  • Ci-20-alkyl are Ci-10-alkyl and /7-undecyl, /7-dodecyl, /7-tridecyl, /7-tetradecyl, /7-pentadecyl, /7-hexadecyl, /7-heptadecyl, /7-octadecyl, /7-nonadecyl and /7-icosyl (C20).
  • Ci-30-alkyl are Ci-20-alkyl and
  • Ci-20-alkylene and Ci-30-alkylene can be branched or unbranched. Examples of Ci-20-alkylene are methylene, ethylene, ⁇ propylene, /7-butylene, /7-pentylene, /7-(1 -ethyl)propylene,
  • C1-30- alkylene examples are Ci-20-alkylene and /7-docosylene (C22), /7-tetracosylene (C24), /7-hexacosylene (C26), /7-octacosylene (C28) and /7-triacontylene (C30).
  • C5-6-cycloalkyl examples are cyclopentyl and cyclohexyl.
  • Examples of Cs-s-cycloalkyl are C5-6- cycloalkyl and cycloheptyl and cyclooctyl.
  • Cs-s-cycloalkylene examples include cyclopentylene, cyclohexylene, cycloheptylene and cy- clooctylene.
  • Ar 1 , Ar 2 and Ar 3 are independently from each other C6-io-aryl, which can be substituted with 1 to 7 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-io-aryl and 0-C6-io-aryl.
  • Ar 1 , Ar 2 and Ar 3 are independently from each other phenyl, which can be sub- stituted with 1 to 5 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-30-alkyl, O-Ci-30-alkyl, C6-io-aryl and 0-C6-io-aryl.
  • Ar 1 , Ar 2 and Ar 3 are all phenyl.
  • R 1 is H or methyl.
  • R 1 is H.
  • the n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 and R 6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b , wherein R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • n of the n-valent unit X is an integer from 3 to 10, it is evident that the n-valent unit X only comprises combinations of at least one valency group V and at least one linking group Y, wherein the sum of the wavy lines, each wavy line representing one valency, of all valency groups V in that combination is an integer of 3 to 10.
  • n-valent units X wherein n is an integer from 3 to 10, and which comprise
  • valency-group V each independently selected from the group consisting of V1 to V24, as defined above, and
  • linking group Y each independently selected from the group consisting of Y1 , Y2 or Y3, as defined above,
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H , Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 and R 6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b , wherein R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene, L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
  • a is an integer from 1 to 8
  • b is an integer from 0 to 7
  • c is an integer from 3 to 10
  • d is an integer from 0 to 4,
  • e is an integer from 0 to 2
  • f is an integer from 0 to 6
  • g is an integer from 0 to 3
  • h is an integer from 1 to 8
  • i is an integer from 0 to 4,
  • j is an integer from 1 to 3
  • k is an integer from 0 to 3
  • I is an integer from 1 to 8.
  • n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
  • a wavy line represents one valency of the n-valent
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H , Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 and R 6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b , wherein R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5 cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another lency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 8, and which n-valent unit X comprises
  • valency-group V each independently selected from the group consisting of
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another va- lency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • n-valent unit X is an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
  • valency-group V each independently selected from the group consisting of
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b , wherein R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloal
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • n-valent unit X is an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
  • valency-group V each independently selected from the group consisting of
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H or Ci-30-alkyl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently
  • L 1 is bivalent Ci-30-alkylene or bivalent C6-i4-arylene
  • a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V
  • a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y
  • the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • n-valent units X where n is 4, is
  • Preferred polymers of the present invention are polymers comprising units of formulae
  • a wavy line represents a valency
  • Ar 1 , Ar 2 and Ar 3 are independently from each other Ce-14-aryl, which can be substituted with 1 to 9 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-3o-alkyl, 0-Ci- 3 o-alkyl, C 6 -i4-aryl and 0-C 6 -i4-aryl, and
  • R 1 is H or Ci-4-alkyl, and at least one an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
  • valency-group V each independently selected from the group consisting of
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 and R 6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b , wherein R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another lency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • More preferred polymers of the present invention are polymers comprising units of formulae
  • a wavy line represents a valency
  • Ar 1 , Ar 2 and Ar 3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
  • R 1 is H or Ci-4-alkyl, and at least one an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
  • a wavy line represents one valency of the n-valent unit X, R 2 , R 3 and R 4 are independently from each other at each occurrence H , Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 and R 6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b , wherein R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b)at least one linking group Y each independently selected from the group consisting of
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • a wavy line represents a valency
  • Ar 1 , Ar 2 and Ar 3 are independently from each other C6-io-aryl, which can be substituted with 1 to 7 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, Ce-io-aryl and O-Ce-io-aryl. and
  • R 1 is H or Ci-4-alkyl, and at least one an n-valent unit X, wherein n is an integer from 3 to 8, and which n-valent unit X comprises
  • valency-group V each independently selected from the group consisting of
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another va- lency group V or to a linking group Y, and at least one linking group Y each independently selected from the group consisting of
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • Most preferred polymers of the present invention are polymers comprising units of formulae
  • a wavy line represents a valency
  • Ar 1 , Ar 2 and Ar 3 are independently from each other phenyl, which can be substituted with 1 to 5 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci- 3o-alkyl, O-Ci-30-alkyl, Ce-io-aryl and O-Ce-io-aryl, and
  • R 1 is H or methyl, and at least one an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
  • valency-group V each independently selected from the group consisting of
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another va- lency group V or to a linking group Y, and b) at least one linking group Y each independently
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloal
  • C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents R c ,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • polymers of the present invention are polymers comprising units of formulae
  • a wavy line represents a valency
  • Ar 1 , Ar 2 and Ar 3 are all phenyl
  • R 1 is H
  • n-valent unit X wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
  • valency-group V each independently selected from the group consisting of
  • a wavy line represents one valency of the n-valent unit X
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H or Ci-30-alkyl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently
  • L 1 is bivalent Ci-30-alkylene or bivalent C6-i4-arylene, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V
  • a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y
  • the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
  • the amount of the sum of the units of formulae (1 ) and (2) is at least 70% by weight, preferably 80% by weight, more preferably 85% by weight, most preferably at least 90% by weight, based on the weight of the polymer.
  • the molar ratio of the units of formula (1 ) to the units of formula (2) is in the range of 1 : 1 to 1 : 8, more preferably in the range 1 : 1 to 1 : 6 and most preferably in the range of 1 : 1 to 1 : 4.
  • the molar ratio of the units X to the units of formula (2) is in the range of 0.001 % to 10%, more preferably in the range of 0.01 % to 5%, and most preferably in the range of 0.1 % to 2.5%.
  • the polymers of the present invention may comprise further units.
  • a preferred further unit is a unit S comprising one C-C-double bond.
  • the unit S is selected from the group consisting of
  • a wavy line represents a valency
  • R 10 , R 11 , R 12 and R 13 are independently of each other H or Ci -2 o-alkyl, and s is an integer from 1 to 4.
  • the unit S is selected from the group consisting of:
  • the molar ratio of the sum of the units of formula (1 ) and (2) to the units of formula S is preferably in the range of 8 : 1 to 1 : 1 .
  • the polymers are preferably star-shaped polymers, wherein the units of formula S are present as blocks at the terminal ends of the arms.
  • Preferred polymers of the present invention have a mass average molecular weight Mw of at least 80000 g/mol.
  • Preferred polymers of the present invention have a glass temperature (Tg) of above 120 °C, more preferably in the range of 120 to 180 °C. Also part of the present invention is a process for the preparation of polymers comprising units of formulae
  • a wavy line represents a valency
  • Ar 1 , Ar 2 and Ar 3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
  • R 1 is H or Ci-4-alkyl, and at least one n-valent unit X,
  • n is an integer from 3 to 10, which process comprises the steps of polymerizing a monomer of formula
  • Ar 1 , Ar 2 and Ar 3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents R a , wherein R a is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
  • R 1 is H or Ci-4-alkyl, in the presence of an anion and a precursor PX of the n-valent unit X.
  • the precursor PX of an n-valent unit X is
  • LG 1 represents a leaving group
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 , R 6 and R 10 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b)at least one linking group Y each independently selected from the group consisting of
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV.
  • linking group Y each independently selected from the group consisting of Y1 , Y2 or Y3, as defined above,
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 , R 6 and R 10 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b , wherein R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
  • LG 1 is a leaving group
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a is an integer from 1 to 8,
  • b is an integer from 0 to 7
  • c is an integer from 3 to 10
  • d is an integer from 0 to 4,
  • e is an integer from 0 to 2
  • f is an integer from 0 to 6
  • g is an integer from 0 to 3
  • h is an integer from 1 to 8
  • i is an integer from 0 to 4,
  • j is an integer from 1 to 3
  • k is an integer from 0 to 3
  • I is an integer from 1 to 8.
  • PV1 PV2
  • PV3 PV3
  • LG 1 represents a leaving group
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R 5 and R 6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5 cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
  • a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV
  • a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y
  • a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV.
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • L 3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV.
  • the precursor PX of an n-valent unit X essentially consists of a) at least one groups PV each independently selected from the group consisting of
  • R 2 , R 3 and R 4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents R b ,
  • R b is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b) at least one linking group Y each independently
  • L 1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloal
  • R c is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV.
  • the precursor PX of an n-valent unit X essentially consists of
  • L 1 is bivalent Ci-30-alkylene or bivalent C6-i4-arylene
  • a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV
  • a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y
  • a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV.
  • any suitable anion can be used.
  • the anion is n-butyl anion or sec-butyl anion, more preferably sec-butyl anion.
  • an alkaline metal cation is usually used, preferably a lithium cation.
  • the polymerization is usually performed in the presence of an inert solvent. Examples of inert solvents are cyclohexane or the monomer (M1 ) itself.
  • the monomer (M1 ) is treated with the anion, usually at elevated temperature of 40 to 80 °C, preferably 50 to 70 °C. Then, the monomer (M2) is added, usually in one or more portions.
  • the precursor PX of the n-valent unit X can be added before the addition of monomer (M2), after adding at least one portion of the monomer (M2) or after the addition of all portions of monomer (M2).
  • the temperature is kept at elevated temperatures of 40 to 80 °C, prefer- ably 50 to 70 °C during the polymerization reaction.
  • the polymerization is usually stopped by adding a quenching agent such as acetic acid.
  • the molar ratio of the monomer of formula (M1 ) to the monomer of formula (M2) is in the range of 1 : 1 to 1 : 8, more preferably in the range 1 : 1 to 1 : 6 and most preferably in the range of 1 : 1 to 1 : 4.
  • the molar ratio of the precursors PX of the n- valent units of formula X to the monomers of formula (M2) is in the range of 0.001 % to 10%, more preferably in the range of 0.01 % to 5%, and most preferably in the range of 0.1 % to 2.5%.
  • a preferred further monomer is monomer MS comprising two conjugated C-C-double bonds.
  • the monomer MS is selected from the group consisting of
  • the unit MS is selected from the group consisting of:
  • the unit MS is of formula
  • the monomer of formula (MS) can be added before the first portion of monomer (M2), after at least one portion of monomer (M2) or, preferably, after addition of all portions of monomer (M2).
  • the process comprises a second step of polymerizing monomers of formula (MS) comprising two C-C-double bonds with the polymer intermediate of the first step of the process of the present invention.
  • the amount of the sum of the monomers of formulae (M1 ) and (M2) is at least 70% by weight, preferably 80% by weight, more preferably 85% by weight, most preferably at least 90% by weight, based on the weight of all monomers used in the polymerization reaction. If monomers of formula (MS) are present in the polymerization reaction, the molar ratio of the sum of the monomers of formula (M1 ) and (M2) to the monomers of formula (MS) is preferably in the range of 8 : 1 to 1 : 1.
  • compositions comprising the polymers of the present invention and an organic solvent.
  • the organic solvent can be any suitable organic solvent.
  • the solvent is selected from the group consisting of Ci-6-alkyl-0-Ci-io-alkylene-0-C(0)-Ci-6-alkyl, 5 to 7 membered cyclic ketones and Ci-10-alkyl Ci-10-alkanoate and mixtures thereof.
  • An example of Ci-6-alkyl-0-Ci-6- alkylene-0-C(0)-Ci-6-alkyl is propylene glycol methyl ether acetate (PGMEA).
  • Examples of 5 to 7 membered cyclic ketones are cyclopentanone and cyclohexanone.
  • Ci-10-alkyl Ci- io-alkanoates are ethyl butanoate and butyl acetate. More preferably, the solvent is a Ci-10-alkyl Ci-io-alkanoate or mixtures of Ci-10-alkyl Ci-10-alkanoates with Ci-6-alkyl-0-Ci-6-alkylene-0-C(0)- Ci-6-alkyl or 5 to 7 membered cyclic ketones. Most preferably, the solvent is a mixture of propylene glycol methyl ether acetate (PGMEA) and cyclopentanone.
  • PGMEA propylene glycol methyl ether acetate
  • compositions comprising the polymers of the present invention and a solvent also comprise a crosslinker.
  • the crosslinker can be any suitable crosslinker.
  • the crosslinker is of formula
  • x is O or l
  • R x is at each occurrence selected from the group consisting of H, halogen, SO3M and C1-20- alkyl, which Ci-20-alkyl can be substituted with one or more halogen,
  • M is Na, K or Li
  • L x is a linking group.
  • L x can be any suitable linking group.
  • L x is a linking group of formula
  • ax, bx, cx, dx, ex, fx and gx are independently from each other 0 or 1 , provided that ax, bx, cx, dx, ex, fx and gx are not all at the same time 0,
  • R bx and R cx are independently from each other H or Ci-10-alkyl, or two R bx or R cx groups, which can be from different W 1 , W 2 , W 3 and W 4 , together with the connecting atoms form a 5, 6 or 7 membered ring, which may be substituted with one to three Ci-6-alkyls,
  • Z 1 , Z 2 and Z 3 are independently selected from the group consisting of Ci-10-alkylene, C5-8- cycloalkylene, C6-14- arylene and 5 to 14 membered heteroarylene,
  • Ci-10-alkylene, Cs-s-cycloalkylene, C6-14 membered arylene and 5 to 14 membered het- eroarylene can be substituted with one to five Ci-10-alkyl or phenyl.
  • linking groups L x are 64
  • composition essentially contains
  • composition essentially contains
  • Also part of the present invention is a process for preparing an electronic device which comprises a layer formed from the composition of the present invention, which process comprises the step of applying the composition of the present invention on a pre-cursor of the electronic device in order to form the layer.
  • Also part of the present invention is an electronic device comprising the polymers of the present invention or a layer formed from the composition of the present invention.
  • composition of the present invention can be applied by techniques known in the art.
  • the composition is applied by liquid processing techniques such as spin coating, blading, slot-die coating, drop-casting, spray-coating, ink-jetting or soaking of the precursor of the electronic device in the composition.
  • the composition is applied by spin-coating.
  • the composition comprises a crosslinker of formula (C1 )
  • the composition is preferably treated with light of a suitable wavelength, for example 365 nm, after being applied on the precursor of the electronic device.
  • the composition can be heated, for example at temperatures of 1 10 to 160 °C.
  • the electronic device can be a field-effect transistor, a capacitor, a light emitting diode, a photovoltaic device, a sensing device or a radio-frequency identification (RFID) tag.
  • RFID radio-frequency identification
  • the electronic device is a field-effect transistor, more preferably an organic field ef- feet transistor.
  • An organic field effect transistor is a field effect transistor, where the semiconducting layer comprises an organic semiconducting material.
  • the layer formed from the composition of the present invention can be a dielectric layer, a resist layer, an insulating layer, a passivation layer, a planarization layer, an encapsulation layer or a coating layer.
  • the layer formed from the composition of the present invention is a dielectric layer.
  • the electronic device is an organic field-effect transistor, and the layer formed from the composition of the present invention is the dielectric layer.
  • an organic field effect transistor comprises a dielectric layer, a semiconducting layer, a substrate, a gate electrode and source/drain electrodes.
  • the dielectric layer can have a thickness of 10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800 nm. If the dielectric layer is formed from the composition of the present invention, the dielectric layer usually has a thickness of 100 to 1000 nm, preferably from 200 to 600 nm, more preferably from 300 to 500 nm.
  • the semiconducting layer comprises an organic semiconducting material.
  • organic semiconducting materials are polythiophenes such as poly(3-hexylthiophene) (P3HT), polyfluo- renes, polydiacetylene, poly(2,5-thienylene vinylene), poly(p-phenylene vinylene) (PPV) and polymers comprising repeating units having a diketopyrrolopyrrole group (DPP polymers).
  • the semiconducting material is a polymer comprising units having a diketopyrrolopyrrole group (DPP polymer).
  • the semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.
  • the source/drain electrodes can be made from any suitable organic or inorganic source/drain material.
  • inorganic source/drain materials are gold (Au), silver (Ag), chromium (Cr) or copper (Cu), as well as alloys comprising at least one of these metals.
  • the source/drain electrodes can have a thickness of 1 to 100 nm, preferably from 20 to 70 nm.
  • the gate electrode can be made from any suitable gate material such as highly doped silicon, aluminium (Al), tungsten (W), indium tin oxide or gold (Au), or alloys comprising at least one of these metals.
  • the gate electrode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm.
  • the substrate can be any suitable substrate such as glass, or a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the gate electrode for example highly doped silicon can also function as substrate.
  • the channel width (W) of the organic field effect transistor is typically in the range of 10 to 2000 ⁇ and the channel length (L) of the organic field effect transistor is typically in the range of 5 to 100 ⁇ .
  • the precursor of the electronic device can be any suitable precursor. If the electronic device is an organic field effect transistor, the precursor can be the substrate with the gate, or the substrate with the source/drain electrodes and the semiconducting layer. If the electronic device is an organic field-effect transistor, and the layer formed from the composition of the present invention is the dielectric layer, the organic field effect transistor can be, for example, prepared as follows:
  • the source and drain electrodes can be formed by lithographically patterning a suitable source/drain material, for example gold, on a suitable substrate, for example PET.
  • the source/drain electrodes can then be covered with a semiconducting layer by spin-coating a so- lution of a semiconducting material, for example a DPP polymer, in a suitable solvent, for example toluene, on the substrate.
  • the wet semiconducting layer can be heated.
  • the semiconducting layer can then be covered with a dielectric layer by spin-coating the composition of the present invention on the semiconducting layer.
  • the wet dielectric layer can be heated to 80 to 100 °C, and then, if the composition of the present invention comprises a crosslinker of formula (12), cured by light treatment.
  • the gate electrode can then be deposited on the dielectric layer for example by vapour deposition of a suitable source/drain material, for example gold.
  • Also part of the present invention is the use of the polymers of the present invention or of the composition of the present invention for forming a dielectric layer, a resist layer, an insulating layer, a passivation layer, a planarization layer, an encapsulation layer or a coating layer, preferably a dielectric layer.
  • a passivation layer is an electrically insulating layer on top of the semiconducting layer, which protects the semiconducting layer from damages caused by further processing steps, for exam- pie solvents or plasma used in the deposition of further layers.
  • An encapsulation layer is an electrically insulating layer that is deposited in order to protect the device from damages caused by the environment such as ambient gases, light and mechanical forces.
  • a planarization layer is an electrically insulating layer, which smooth the surface on which the next layer is to be applied, and optionally improves the wetting and adhesion of the subsequently deposited layers.
  • the polymers of the present invention are advantageous as they have a high glass temperature T(g) in the range of 120 to 180 °C, and when used in fabrication of a field effect transistor allow fabrication steps, which require higher temperatures such as applying the source/drain electrodes or the gate electrode on top of the dielectric layer by annealing, without resulting in an electrode misplacement or interface defects between the dielectric layer and the semiconducting layer.
  • the polymers of the present invention are soluble in organic solvents and can be applied by liquid processing techniques such as spin coating, which allow the production of low cost field effect transistors.
  • the polymers of the present invention show good film forming properties, and the films formed from the organic polymers are elastic and allow the production of flexible displays.
  • Figure 1 shows the drain current Ids in relation to the gate voltage V gs (transfer curve) for the top- gate, bottom-contact (TGBC) field effect transistor comprising polymer Pd at a source voltage Vds of -5V (triangle), respectively, -30V (square).
  • Second Step Preparation of a star-shaped polymer from the multifunctional initiator oligomer Styrene (47.9 g, 460.6 mmol) in 135 g cyclohexane was added dropwise within 60 min to the reaction mixture of the first step, the temperature was kept at 60 °C for further 15 min. Then, 0.6 mL (3.75 mmol) p-divinylbenzene (80%) was added and the reaction mixture was stirred for 10 min and then quenched by addition of 1 mL isopropanol and 4 drops of acetic acid. The polymer was precipitated by drop-wise addition of the quenched reaction mixture into ethanol.
  • Second Step Preparation of a star-shaped polymer from the multifunctional initiator oligomer Styrene (47.9 g, 460.6 mmol) in 135 g cyclohexane was added drop-wise within 60 min to the reaction mixture of the first step, the temperature was kept at 60 °C for further 15 min. Then, the reaction mixture was stirred for 10 min and quenched by addition of 1 mL isopropanol and diluted with 400 mL toluene. The polymer was precipitated by drop-wise addition of the quenched and diluted reaction mixture into isopropanol.
  • Second Step Preparation of a star-shaped polymer from the multifunctional initiator oligomer
  • the reaction mixture of the first step was diluted with 962 mL cyclohexane and 261.1 g (251 1 mmol) styrene was added and the reaction mixture was stirred for 30 min. Then, further 321 mL cyclohexane and 90.1 g (866 mmol) styrene were added and the reaction mixture was stirred for further 30 min.
  • the reaction mixture was decolorized by addition of 1.5 mL isopropanol and acidified with 1.5 mL acetic acid.
  • Second Step Preparation of a star-shaped polymer from the multifunctional initiator oligomer 310.8 g (2988 mmol) styrene was added to the reaction mixture of the first step and the reaction mixture was stirred for 30 min. Then, 103.6 g (996 mmol) styrene were added and the reaction mixture was stirred for further 30 min. 172 mL (1 12.5 g, 2009 mmol) butadiene was added to the reaction mixture and the reaction mixture was stirred at 70 °C for 30 min. The reaction mixture was quenched with 1.5 mL isopropanol and acidified with 1 .5 mL acetic acid.
  • the polymer Pd was isolated from the reaction mixture in analogy to the polymer Pc in example 3.
  • the polymer Pd was obtained as white powder.
  • Mn 76000 g/mol.
  • Mw 152000 g/mol.
  • Tg - 102 and 125°C.
  • the polymer Pf was precipitated by dropwise addition of the reaction mixture into ethanol affording 245 g of polymer Pf as a white powder.
  • Mn 142000 g/mol.
  • Mw 257000 g/mol.
  • Tg 145°C.
  • Gold was sputtered onto PET substrate to form approximately 40 nm thick gold source/drain electrodes.
  • a 0.75 % (weight/weight) solution of the diketopyrrolopyrrole semiconducting polymer of example 1 of WO 2013/083506 in toluene was filtered through a 0.45 micrometer polytet- rafluoroethylene (PTFE) filter and then applied by spin coating (1 ,000 rpm, 30 seconds). The wet organic semiconducting layer was dried at 90 °C on a hot plate for 60 seconds.
  • PTFE polytet- rafluoroethylene
  • PGMEA propylene glycol monomethyl ether acetate
  • CP cyclopentanone
  • the wet dielectric layer was pre-baked at 90 °C for 2 minutes and subsequently UV-cured by irradiating at 365 nm with a dosage of ⁇ 100mJ/cm 2 under ambient conditions. Afterwards, the device was wetted with a solution of PGMEA/CP (70/30) for 1 minute to develop the dielectric and spin-coated dry at (2000 rpm, 1 min) followed by a post-bake of 15 minutes at 90°C on a hot plate. Gate electrodes of gold (thickness approximately 80 nm) were evaporated through a shadow mask on the dielectric layer.
  • the top gate, bottom contact (TGBC) field effect transistor was measured by using a Keithley 4200-SCS semiconductor characterization system.
  • the drain current l ds in relation to the gate voltage V gs (transfer curve) for the top-gate, bottom- contact (TGBC) field effect transistor at a source voltage Vd S of -5V (triangle), respectively, -30V (square) is shown in Figure 1.
  • the charge-carrier mobility was extracted in the saturation regime from the slope of the square root drain current Ids 1 ' 2 versus gate-source voltage V gs .
  • the thickness of the dielectric has been measured by a profilometer to 466nm.
  • the average values of the charge carrier mobility ⁇ , the l on /loff ratio and the onset voltage V on for the organic field effect transistor are given in table 1 .
  • ITO indium tin oxide
  • the wet dielectric layer was pre-baked at 90 °C for 2 minutes on a hot plate to obtain a 400 nm thick layer.
  • the polymer dielectric layer was UV-cured using 365 nm (dose of 100 mJ/cm 2 ) under ambient conditions.
  • Development of the dielectric layer was done by immersing the dielectric layer into a mixture of PGEMA and CP for 1 minute followed by heating at 90 °C for 5 minutes.
  • the thickness of the dielectric layer was measured after curing before development (d1 ) and after development (d2) using Veeco Dektak 150 to obtain the film retention ratio (d2/d1 ).
  • the film retention ratio (d2/d1 ) was 80%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides polymers comprising units of formulae (I) and (II) wherein a wavy line represents a valency, Ar1, Ar2 and Ar3 are independently from each other C6-14-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of C1-30-alkyl, O-C1-30-alkyl, C6-14-aryl and O-C6-14-aryl, and R1 is H or C1-4-alkyl, and at least one an n-valent unit X, wherein n is an integer from 3 to 10, as well as electronic devices comprising these polymers.

Description

Star-shaped styrene polymers with enhanced glass transition temperature Description
The present invention relates to star-shaped polymers, to a process for the preparation of a star-shaped polymer, to compositions comprising these polymers and to electronic devices comprising the polymers or a layer formed from the compositions comprising the polymers.
Field effect transistors (FETs) can be used in many applications that require electronic functionalities such as displays, large-area sensors and radio-frequency identification (RFID) tags.
Field effect transistors require a dielectric layer formed by a dielectric material. The use of many organic polymers as dielectric material in field effect transistors is known in the art. One common organic polymer for use as dielectric material in field effect transistors is polystyrene. US 2012/0141757 describes dielectric compositions comprising a dielectric material and a low surface tension additive. The dielectric composition may further comprise crosslinking agents. Examples of dielectric material include polystyrene and poly(1 ,3-butadiene).
WO 201 1/001007 describes a method for manufacturing electronic components. Examples of dielectric materials include polystyrene, poly(4-vinylphenol) and polyvinyl chloride. When used as thermally responsive material, the dielectric material can be used with cross-linking agents.
However, polystyrene as dielectric material suffers from the disadvantage of having a relative low glass temperature (Tg). When fabricating a field effect transistor various fabrication steps, for example the application of the source/drain electrodes or the gate electrode on top of the dielectric layer by annealing, require high temperatures. Dielectric layers are prone to be altered, for example by solid phase transition, when exposed to temperatures which are higher than the glass temperature of the dielectric material. The exposure of a dielectric layer to temperatures higher than the glass temperature of the dielectric material might result in electrode misplacement or interface defects between the dielectric layer and the semiconducting layer.
Copolymers obtainable from styrene and 1 ,1-diphenylethylene monomers, which copolymers have a higher glass temperature than polystyrene, are known in the art. US20100010147 describes block copolymers suitable as adhesive or sealant comprising at least one block comprising a mixture of 1 ,1-diphenylethylene and its derivatives with mono alkenyl arenes and at least one block comprising a conjugated diene or conjugated diene containing mixtures from isoprene and/or butadiene. The block copolymers can have the following structures: A-B, (A-B)n, (A-B)nX, (A-B-A)nX, wherein A represents a polymer block of a mixture of one or more mono alkenyl arenes and one or more monomers of 1 ,1 -diphenylethylene and its derivatives, B represents a polymer block of conjugated diene or conjugated diene mixture, n is an integer from 1 to 30, and X represents the residue of a coupling agent. US20100010147 only describes block copolymer with polystyrene end blocks. H. Gausepohl, S. Oepen, K. Knoll, M. Schneider, G. McKee, W. Loth "Super-Polystyrene" in Designed Monomers and Polymers, 2000, 3, 3, 299-315 describes copolymers, so called "su- per-polystyrene", prepared from styrene and 1 ,1 -diphenylethylene. Gausepohl et al also describes thermoplastic triblock polymers comprising outer blocks formed from styrene and 1 ,1- diphenylethylene and inner blocks of polybutadiene.
US 5854353 describes copolymers comprising styrene and 1 ,1 -diphenylethylene. The copoly- mers are thermoplastics, which are hard and rigid at room temperature.
WO 99/01487 describes
copolymers comprising at least one block A of
- vinyl aromatic monomers a1 ) and
- 1 ,1-diphenyl ethylene or derivatives thereof whose aromatic rings are substituted with al- kyl groups with up to 22 C-atoms a2)
which copolymers can be obtained by anionic polymerization, and block copolymers with at least one block A and at least one, optionally hydrogenated, block B of diene b), which block copolymers can be obtained by sequential anionic polymerization.
The copolymers of US 5854353 and WO 99/01487 are both thermoplastic polymers, which can be re-shaped upon heating, and which are used for molding. JP59084910 describes copolymers prepared by polymerizing diphenylethylene or a derivative, and divinylbenzene or a derivative, and optionally styrene or a styrene derivative, using an anionic initiator. The final copolymer contains divinylbenzene monomer units still carrying one residual double bond. N. Hadjichristidis, S.Pispas, H. latrou and M. Pitsikalis "Linking Chemistry and anionic polymerization" in Current Organic Chemistry, 2002, 6, 155 to 176 reviews various linking agents including 1 ,1-diphenylethylene and divinylstyrene.
When fabricating a field effect transistor, it is desirable that the organic polymer dielectric material is applied by liquid processing techniques such as spin coating as liquid processing techniques allow the production of low cost field effect transistors. In addition, liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and mechanically flexible field effect transistors, which is a requisite for the fabrication of light-weight and flexible displays. Thus, the organic polymers used as dielectric material for a field effect transistor should be soluble in organic solvents in order to be compatible with liquid processing techniques. In addition, the organic polymers should show good film forming properties, and the films formed from the organic polymers should be elastic in order to allow the production of flexible displays.
Thus, there is a need for organic polymers for use as dielectric material in field effect transistors, which organic polymers have a higher glass temperature than polystyrene, are compatible with liquid processing techniques, show good film forming properties, and the films formed are elastic.
This object is solved by the polymers of claim 1 , the process of claim 14, the composition of claim 17 and the electronic device of claim 19.
The polymers of the present invention are polymers comprising units of formulae
Figure imgf000004_0001
(1 ) (2) wherein
a wavy line represents a valency,
Ar1, Ar2 and Ar3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and R1 is H or Ci-4-alkyl, and at least one n-valent unit X,
wherein n is an integer from 3 to 10.
The polymers of the present invention are star-shaped polymers. Examples of C6-io-aryl are
Figure imgf000005_0001
Figure imgf000005_0002
Examples of C6-i4-arylene are C6-io-arylene and
Figure imgf000005_0003
Figure imgf000005_0004
Ci-4-alkyl, Ci-10-alkyl, Ci-20-alkyl and Ci-30-alkyl can be branched or unbranched. Examples of Ci-4-alkyl are methyl, ethyl, /7-propyl, isopropyl, /7-butyl, sec-butyl, isobutyl and fe -butyl. Examples of Ci-io-alkyl are Ci-4-alkyl and /7-pentyl, neopentyl, isopentyl, /7-(1-ethyl)propyl, n- exy\, /7-heptyl, /7-octyl, /?-(2-ethyl)hexyl, /7-nonyl and n-decy\. Examples of Ci-20-alkyl are Ci-10-alkyl and /7-undecyl, /7-dodecyl, /7-tridecyl, /7-tetradecyl, /7-pentadecyl, /7-hexadecyl, /7-heptadecyl, /7-octadecyl, /7-nonadecyl and /7-icosyl (C20). Examples of Ci-30-alkyl are Ci-20-alkyl and
/7-docosyl (C22) , /7-tetracosyl (C24), /7-hexacosyl (C26) , /7-octacosyl (C28) and /7-triacontyl (C30). Ci-20-alkylene and Ci-30-alkylene can be branched or unbranched. Examples of Ci-20-alkylene are methylene, ethylene, ^propylene, /7-butylene, /7-pentylene, /7-(1 -ethyl)propylene,
/7-hexylene, /7-heptylene, /7-octylene, /7-(2-ethyl)hexylene, /7-nonylene, /7-decylene, n- undecylene, /7-dodecylene, /7-tridecylene, /7-tetradecylene, /7-pentadecylene, /7-hexadecylene, /7-heptadecylene, /7-octadecylene, /7-nonadecylene and /?-icosylene(C2o) . Examples of C1-30- alkylene are Ci-20-alkylene and /7-docosylene (C22), /7-tetracosylene (C24), /7-hexacosylene (C26), /7-octacosylene (C28) and /7-triacontylene (C30).
Examples of C5-6-cycloalkyl are cyclopentyl and cyclohexyl. Examples of Cs-s-cycloalkyl are C5-6- cycloalkyl and cycloheptyl and cyclooctyl.
Examples of Cs-s-cycloalkylene are cyclopentylene, cyclohexylene, cycloheptylene and cy- clooctylene.
Preferably, Ar1, Ar2 and Ar3 are independently from each other C6-io-aryl, which can be substituted with 1 to 7 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-io-aryl and 0-C6-io-aryl.
More preferably, Ar1, Ar2 and Ar3 are independently from each other phenyl, which can be sub- stituted with 1 to 5 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-30-alkyl, O-Ci-30-alkyl, C6-io-aryl and 0-C6-io-aryl.
Most preferably, Ar1, Ar2 and Ar3 are all phenyl. Preferably, R1 is H or methyl.
More preferably, R1 is H.
Preferably, the n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
Figure imgf000007_0001
Figure imgf000008_0001
Figure imgf000008_0002
(V14) (V15) (V16)
Figure imgf000008_0003
(V22) (V23) (V24) wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000009_0001
(YD (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
As n of the n-valent unit X is an integer from 3 to 10, it is evident that the n-valent unit X only comprises combinations of at least one valency group V and at least one linking group Y, wherein the sum of the wavy lines, each wavy line representing one valency, of all valency groups V in that combination is an integer of 3 to 10.
Examples of n-valent units X, wherein n is an integer from 3 to 10, and which comprise
a)at least one valency-group V each independently selected from the group consisting of V1 to V24, as defined above, and
b)at least one linking group Y each independently selected from the group consisting of Y1 , Y2 or Y3, as defined above,
are
Figure imgf000010_0001
(X5) (X6)
Figure imgf000011_0001
(X7)
Figure imgf000011_0002
(X8)
Figure imgf000011_0003
(X9)
Figure imgf000012_0001
10
Figure imgf000013_0001
(X14)
5
Figure imgf000013_0002
Figure imgf000013_0003
Figure imgf000013_0004
Figure imgf000014_0001
Figure imgf000014_0002
(X22) wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H , Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylenec an be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
and a is an integer from 1 to 8,
b is an integer from 0 to 7,
c is an integer from 3 to 10,
d is an integer from 0 to 4,
e is an integer from 0 to 2,
f is an integer from 0 to 6,
g is an integer from 0 to 3,
h is an integer from 1 to 8,
i is an integer from 0 to 4,
j is an integer from 1 to 3,
k is an integer from 0 to 3,
I is an integer from 1 to 8.
More preferably,
the n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
Figure imgf000015_0001
(X2) or comprises a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000016_0004
Figure imgf000017_0001
wherein
a wavy line represents one valency of the n-valent
R2, R3 and R4 are independently from each other at each occurrence H , Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5 cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another lency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000017_0002
(Y1 ) (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
Even more preferably,
the n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 8, and which n-valent unit X comprises
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000018_0001
(V1 ) (V2) (V3)
Figure imgf000019_0001
Figure imgf000019_0002
(V8) (V9) wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another va- lency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000019_0003
(Y1 ) (Y2) (Y3) wherein L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
Most preferably,
the n-valent unit X is an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000021_0001
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently
Figure imgf000022_0001
wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
In particular,
the n-valent unit X is an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000023_0001
(V1 ) (V2) (V3)
Figure imgf000023_0002
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H or Ci-30-alkyl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently
Figure imgf000024_0001
(YD wherein
L1 is bivalent Ci-30-alkylene or bivalent C6-i4-arylene, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
A particular preferred example of n-valent units X, where n is 4, is
Figure imgf000024_0002
(X3a) Preferred polymers of the present invention are polymers comprising units of formulae
Figure imgf000025_0001
(1) (2) wherein
a wavy line represents a valency,
Ar1, Ar2 and Ar3 are independently from each other Ce-14-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, 0-Ci-3o-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
R1 is H or Ci-4-alkyl, and at least one an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
Figure imgf000025_0002
(X1) (X2) or comprises
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000025_0003
(V1) (V2) (V3)
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0002
(V22) (V23) (V24) wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another lency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000027_0003
(YD (Y2) (Y3) wherein L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
More preferred polymers of the present invention are polymers comprising units of formulae
Figure imgf000028_0001
(1 ) (2) wherein
a wavy line represents a valency,
Ar1, Ar2 and Ar3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
R1 is H or Ci-4-alkyl, and at least one an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
Figure imgf000029_0001
(X2) or comprises
a)at least one valency-group V each independently selected from the group consisting of
Figure imgf000029_0002
Figure imgf000029_0003
Figure imgf000030_0001
wherein
a wavy line represents one valency of the n-valent unit X, R2, R3 and R4 are independently from each other at each occurrence H , Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b)at least one linking group Y each independently selected from the group consisting of
Figure imgf000031_0001
(YD (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
Even more preferred polymers of the present invention are polymers comprising units of formulae
Figure imgf000032_0001
(1 ) (2) wherein
a wavy line represents a valency,
Ar1, Ar2 and Ar3 are independently from each other C6-io-aryl, which can be substituted with 1 to 7 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, Ce-io-aryl and O-Ce-io-aryl. and
R1 is H or Ci-4-alkyl, and at least one an n-valent unit X, wherein n is an integer from 3 to 8, and which n-valent unit X comprises
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000033_0003
(V8) (V9) wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another va- lency group V or to a linking group Y, and at least one linking group Y each independently selected from the group consisting of
Figure imgf000034_0001
(Y1 ) (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V. Most preferred polymers of the present invention are polymers comprising units of formulae
Figure imgf000035_0001
(1 ) (2) wherein
a wavy line represents a valency,
Ar1, Ar2 and Ar3 are independently from each other phenyl, which can be substituted with 1 to 5 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci- 3o-alkyl, O-Ci-30-alkyl, Ce-io-aryl and O-Ce-io-aryl, and
R1 is H or methyl, and at least one an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000035_0002
(V1 ) (V2) (V3)
Figure imgf000035_0003
(V4) (V5)
Figure imgf000036_0001
(V8) (V9)
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group to another va- lency group V or to a linking group Y, and b) at least one linking group Y each independently
Figure imgf000036_0002
wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene,
C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
In particular preferred polymers of the present invention are polymers comprising units of formulae
Figure imgf000037_0001
(1 ) (2) wherein
a wavy line represents a valency, Ar1, Ar2 and Ar3 are all phenyl, and R1 is H, and at least one an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000037_0002
(V1 ) (V2) (V3)
Figure imgf000038_0001
Figure imgf000038_0002
(V8) (V9)
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H or Ci-30-alkyl, and a line marked with a star represents the connecting side of the valency group to another valency group V or to a linking group Y, and b) at least one linking group Y each independently
Figure imgf000038_0003
wherein
L1 is bivalent Ci-30-alkylene or bivalent C6-i4-arylene, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V. a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
In preferred polymers of the present invention the amount of the sum of the units of formulae (1 ) and (2) is at least 70% by weight, preferably 80% by weight, more preferably 85% by weight, most preferably at least 90% by weight, based on the weight of the polymer.
In preferred polymers of the present invention the molar ratio of the units of formula (1 ) to the units of formula (2) is in the range of 1 : 1 to 1 : 8, more preferably in the range 1 : 1 to 1 : 6 and most preferably in the range of 1 : 1 to 1 : 4.
In preferred polymers of the present invention the molar ratio of the units X to the units of formula (2) is in the range of 0.001 % to 10%, more preferably in the range of 0.01 % to 5%, and most preferably in the range of 0.1 % to 2.5%.
The polymers of the present invention may comprise further units. A preferred further unit is a unit S comprising one C-C-double bond.
Preferably, the unit S is selected from the group consisting of
Figure imgf000039_0001
Figure imgf000040_0001
(SIV) wherein
a wavy line represents a valency, and
R10, R11, R12 and R13 are independently of each other H or Ci-2o-alkyl, and s is an integer from 1 to 4.
More preferably, the unit S is selected from the group
Figure imgf000040_0002
(SII-1 ) (SII-2) (SII-3)
Figure imgf000041_0001
Figure imgf000041_0002
wherein a wavy line represents a valency. Most preferably, the unit S is of formula
Figure imgf000041_0003
(SI-1 )
wherein a wavy line represents a valency.
If units of formula S are present in the polymer, the molar ratio of the sum of the units of formula (1 ) and (2) to the units of formula S is preferably in the range of 8 : 1 to 1 : 1 .
If units of formula S are present, the polymers are preferably star-shaped polymers, wherein the units of formula S are present as blocks at the terminal ends of the arms. Preferred polymers of the present invention have a mass average molecular weight Mw of at least 80000 g/mol.
Preferred polymers of the present invention have a glass temperature (Tg) of above 120 °C, more preferably in the range of 120 to 180 °C. Also part of the present invention is a process for the preparation of polymers comprising units of formulae
Figure imgf000042_0001
(1 ) (2) wherein
a wavy line represents a valency, Ar1, Ar2 and Ar3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
R1 is H or Ci-4-alkyl, and at least one n-valent unit X,
wherein n is an integer from 3 to 10, which process comprises the steps of polymerizing a monomer of formula
Figure imgf000042_0002
(M1 ) with a monomer of formula
Figure imgf000043_0001
(M2)
wherein
Ar1, Ar2 and Ar3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
R1 is H or Ci-4-alkyl, in the presence of an anion and a precursor PX of the n-valent unit X.
Preferably, the precursor PX of an n-valent unit X is
Figure imgf000043_0002
(PX1 ) wherein LG1 is a leaving group, or
a)at least one group PV each independently selected from the group consisting of
Figure imgf000043_0003
(PV1 ) (pv2) (PV3) 43
Figure imgf000044_0001
Figure imgf000045_0001
(PV17) (PV18) (PV19)
Figure imgf000045_0002
(PV22) (PV23) (PV24) wherein
LG1 represents a leaving group,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5, R6 and R10 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b)at least one linking group Y each independently selected from the group consisting of
Figure imgf000046_0001
(YD (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV. Examples of precursors PX of n-valent units X, wherein n is an integer from 3 to 10, and which comprise
c) at least one group PV each independently selected from the group consisting of PV1 to PV24, as defined above, and
d)at least one linking group Y each independently selected from the group consisting of Y1 , Y2 or Y3, as defined above,
are
Figure imgf000047_0001
(PX7)
Figure imgf000048_0001
10
Figure imgf000049_0001
Figure imgf000049_0002
Figure imgf000049_0003
Figure imgf000049_0004
(PX15) (PX16)
Figure imgf000050_0001
Figure imgf000050_0002
Figure imgf000050_0003
Figure imgf000050_0004
wherein R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5, R6 and R10 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
LG1 is a leaving group,
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylenec an be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a is an integer from 1 to 8,
b is an integer from 0 to 7,
c is an integer from 3 to 10,
d is an integer from 0 to 4,
e is an integer from 0 to 2,
f is an integer from 0 to 6,
g is an integer from 0 to 3, h is an integer from 1 to 8,
i is an integer from 0 to 4,
j is an integer from 1 to 3,
k is an integer from 0 to 3,
I is an integer from 1 to 8.
More preferably, precursor PX of an n-valent
Figure imgf000052_0001
(PX2) wherein LG1 is a leaving group,
or
comprises
a) at least one group PV each independently selected from the group consisting of
Figure imgf000052_0002
*
(PV1 ) (PV2) (PV3)
Figure imgf000052_0003
(PV4) (PV5)
Figure imgf000053_0001
(PV8) (PV9)
Figure imgf000053_0002
(PV14) (PV15) (PV16)
Figure imgf000053_0003
(PV18)
(PV17)
wherein
LG1 represents a leaving group,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5 cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000054_0001
(YD (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl,
and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV. Even more preferably, the precursor PX of an n-valent unit X
comprises
a) at least one groups PV each independently selected from the group consisting of
Figure imgf000055_0001
(PV8) (PV9) wherein
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000056_0001
(YD (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV. Most preferably, the precursor PX of an n-valent unit X essentially consists of a) at least one groups PV each independently selected from the group consisting of
Figure imgf000057_0001
(PV8) (PV9)
wherein
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b) at least one linking group Y each independently
Figure imgf000058_0001
wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV.
In particular, the precursor PX of an n-valent unit X essentially consists of
a) at least one groups PV each independently selected from the group consisting of
Figure imgf000059_0001
Figure imgf000059_0002
Figure imgf000059_0003
(PV8) (PV9) wherein R2, R3 and R4 are independently from each other at each occurrence H or Ci-30-alkyl, and a line marked with a star represents the connecting side of the group PV to another group PV or to a linking group Y, and b) at least one linking group Y each independently
Figure imgf000059_0004
(YD wherein
L1 is bivalent Ci-30-alkylene or bivalent C6-i4-arylene, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a group PV, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and another linking group Y, and a connecting side of a linking group Y together with a connecting side of a group PV forms the connecting bond between the linking group Y and the group PV.
Particular preferred examples of the precursor PX of an n-valent unit X are
Figure imgf000060_0001
(PX3a)
Figure imgf000060_0002
Any suitable anion can be used. Preferably, the anion is n-butyl anion or sec-butyl anion, more preferably sec-butyl anion. As a counteraction, an alkaline metal cation is usually used, preferably a lithium cation. The polymerization is usually performed in the presence of an inert solvent. Examples of inert solvents are cyclohexane or the monomer (M1 ) itself.
There are different ways of performing the polymerization. Usually, the monomer (M1 ) is treated with the anion, usually at elevated temperature of 40 to 80 °C, preferably 50 to 70 °C. Then, the monomer (M2) is added, usually in one or more portions. The precursor PX of the n-valent unit X can be added before the addition of monomer (M2), after adding at least one portion of the monomer (M2) or after the addition of all portions of monomer (M2). Usually the temperature is kept at elevated temperatures of 40 to 80 °C, prefer- ably 50 to 70 °C during the polymerization reaction.
The polymerization is usually stopped by adding a quenching agent such as acetic acid.
In a preferred process of the present invention the molar ratio of the monomer of formula (M1 ) to the monomer of formula (M2) is in the range of 1 : 1 to 1 : 8, more preferably in the range 1 : 1 to 1 : 6 and most preferably in the range of 1 : 1 to 1 : 4.
In a preferred process of the present invention the molar ratio of the precursors PX of the n- valent units of formula X to the monomers of formula (M2) is in the range of 0.001 % to 10%, more preferably in the range of 0.01 % to 5%, and most preferably in the range of 0.1 % to 2.5%.
In the polymerization reaction further monomers may be present. A preferred further monomer is monomer MS comprising two conjugated C-C-double bonds.
Preferably, the monomer MS is selected from the group consisting of
Figure imgf000061_0001
(MSI-1 ) (MS 11-1 ) wherein R10, R11, R12 and R13 are independently of each other H or Ci
to 4.
More preferably, the unit MS is selected from the group
Figure imgf000062_0001
(MSI-1) (MSI-2) (MSI-3)
Figure imgf000062_0002
(MSII-1 )
Most preferably, the unit MS is of formula
Figure imgf000062_0003
(MSI-1 )
The monomer of formula (MS) can be added before the first portion of monomer (M2), after at least one portion of monomer (M2) or, preferably, after addition of all portions of monomer (M2).
Preferably, the process comprises a second step of polymerizing monomers of formula (MS) comprising two C-C-double bonds with the polymer intermediate of the first step of the process of the present invention.
Preferably, in polymerization reaction the amount of the sum of the monomers of formulae (M1 ) and (M2) is at least 70% by weight, preferably 80% by weight, more preferably 85% by weight, most preferably at least 90% by weight, based on the weight of all monomers used in the polymerization reaction. If monomers of formula (MS) are present in the polymerization reaction, the molar ratio of the sum of the monomers of formula (M1 ) and (M2) to the monomers of formula (MS) is preferably in the range of 8 : 1 to 1 : 1.
Also part of the present invention are compositions comprising the polymers of the present invention and an organic solvent.
The organic solvent can be any suitable organic solvent. Preferably, the solvent is selected from the group consisting of Ci-6-alkyl-0-Ci-io-alkylene-0-C(0)-Ci-6-alkyl, 5 to 7 membered cyclic ketones and Ci-10-alkyl Ci-10-alkanoate and mixtures thereof. An example of Ci-6-alkyl-0-Ci-6- alkylene-0-C(0)-Ci-6-alkyl is propylene glycol methyl ether acetate (PGMEA). Examples of 5 to 7 membered cyclic ketones are cyclopentanone and cyclohexanone. Examples of Ci-10-alkyl Ci- io-alkanoates are ethyl butanoate and butyl acetate. More preferably, the solvent is a Ci-10-alkyl Ci-io-alkanoate or mixtures of Ci-10-alkyl Ci-10-alkanoates with Ci-6-alkyl-0-Ci-6-alkylene-0-C(0)- Ci-6-alkyl or 5 to 7 membered cyclic ketones. Most preferably, the solvent is a mixture of propylene glycol methyl ether acetate (PGMEA) and cyclopentanone.
Preferably, the compositions comprising the polymers of the present invention and a solvent also comprise a crosslinker.
The crosslinker can be any suitable crosslinker.
Preferably, the crosslinker is of formula
Figure imgf000063_0001
wherein
x is O or l ,
Rx is at each occurrence selected from the group consisting of H, halogen, SO3M and C1-20- alkyl, which Ci-20-alkyl can be substituted with one or more halogen,
wherein M is Na, K or Li, and
Lx is a linking group. Lx can be any suitable linking group. Preferably, Lx is a linking group of formula
Figure imgf000064_0001
wherein
ax, bx, cx, dx, ex, fx and gx are independently from each other 0 or 1 , provided that ax, bx, cx, dx, ex, fx and gx are not all at the same time 0,
W1, W2, W3 and W4 are independently selected from the group consisting of C(O), C(0)0, C(O)- NRbx, S02-NRbx, NRbx, NRbxRbx+, CRCX=CRCX and ethynylene,
wherein
Rbx and Rcx are independently from each other H or Ci-10-alkyl, or two Rbx or Rcx groups, which can be from different W1, W2, W3 and W4, together with the connecting atoms form a 5, 6 or 7 membered ring, which may be substituted with one to three Ci-6-alkyls,
Z1, Z2 and Z3 are independently selected from the group consisting of Ci-10-alkylene, C5-8- cycloalkylene, C6-14- arylene and 5 to 14 membered heteroarylene,
wherein
Ci-10-alkylene, Cs-s-cycloalkylene, C6-14 membered arylene and 5 to 14 membered het- eroarylene can be substituted with one to five Ci-10-alkyl or phenyl.
Examples of 5 to 14 membered heteroarylene are
Figure imgf000064_0002
Examples of linking groups Lx are 64
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000066_0002
Figure imgf000066_0003
Figure imgf000066_0004
More preferably, the composition essentially contains
(i) 10 to 500 mg of a polymer of the present invention per 1 mL of the solvent,
(ii) solvent, and
(iii) 0.1 to 20% by weight of a crosslinker based on the weight of the polymer. Most preferably, the composition essentially contains
(i) 30 to 200 mg of a polymer of the present invention per 1 ml. of the solvent,
(ii) solvent, and
(iii) 1 to 10% by weight of a crosslinker based on the weight of the polymer.
Also part of the present invention is a process for preparing an electronic device which comprises a layer formed from the composition of the present invention, which process comprises the step of applying the composition of the present invention on a pre-cursor of the electronic device in order to form the layer.
Also part of the present invention is an electronic device comprising the polymers of the present invention or a layer formed from the composition of the present invention.
The composition of the present invention can be applied by techniques known in the art. Preferably, the composition is applied by liquid processing techniques such as spin coating, blading, slot-die coating, drop-casting, spray-coating, ink-jetting or soaking of the precursor of the electronic device in the composition. Preferably, the composition is applied by spin-coating.
If the composition comprises a crosslinker of formula (C1 ), the composition is preferably treated with light of a suitable wavelength, for example 365 nm, after being applied on the precursor of the electronic device. Alternatively, the composition can be heated, for example at temperatures of 1 10 to 160 °C.
The electronic device can be a field-effect transistor, a capacitor, a light emitting diode, a photovoltaic device, a sensing device or a radio-frequency identification (RFID) tag.
Preferably, the electronic device is a field-effect transistor, more preferably an organic field ef- feet transistor. An organic field effect transistor is a field effect transistor, where the semiconducting layer comprises an organic semiconducting material.
The layer formed from the composition of the present invention can be a dielectric layer, a resist layer, an insulating layer, a passivation layer, a planarization layer, an encapsulation layer or a coating layer. Preferably, the layer formed from the composition of the present invention is a dielectric layer.
Preferably, the electronic device is an organic field-effect transistor, and the layer formed from the composition of the present invention is the dielectric layer.
Usually, an organic field effect transistor comprises a dielectric layer, a semiconducting layer, a substrate, a gate electrode and source/drain electrodes. The dielectric layer can have a thickness of 10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800 nm. If the dielectric layer is formed from the composition of the present invention, the dielectric layer usually has a thickness of 100 to 1000 nm, preferably from 200 to 600 nm, more preferably from 300 to 500 nm.
The semiconducting layer comprises an organic semiconducting material. Examples of organic semiconducting materials are polythiophenes such as poly(3-hexylthiophene) (P3HT), polyfluo- renes, polydiacetylene, poly(2,5-thienylene vinylene), poly(p-phenylene vinylene) (PPV) and polymers comprising repeating units having a diketopyrrolopyrrole group (DPP polymers).
Examples of DPP polymers and their synthesis are, for example, described in EP1078970, WO 2005/049695, WO 2008/000664, WO 2010/049321 , WO 2010/049323, WO 2010/108873, WO 2010/1 15767, WO 2010/136353 and WO 2010/136352. Preferably the semiconducting material is a polymer comprising units having a diketopyrrolopyrrole group (DPP polymer).
Preferably, the semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.
The source/drain electrodes can be made from any suitable organic or inorganic source/drain material. Examples of inorganic source/drain materials are gold (Au), silver (Ag), chromium (Cr) or copper (Cu), as well as alloys comprising at least one of these metals. The source/drain electrodes can have a thickness of 1 to 100 nm, preferably from 20 to 70 nm.
The gate electrode can be made from any suitable gate material such as highly doped silicon, aluminium (Al), tungsten (W), indium tin oxide or gold (Au), or alloys comprising at least one of these metals. The gate electrode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm.
The substrate can be any suitable substrate such as glass, or a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Depending on the design of the organic field effect transistor, the gate electrode, for example highly doped silicon can also function as substrate.
The channel width (W) of the organic field effect transistor is typically in the range of 10 to 2000 μΠΊ and the channel length (L) of the organic field effect transistor is typically in the range of 5 to 100 μΓΠ. The precursor of the electronic device can be any suitable precursor. If the electronic device is an organic field effect transistor, the precursor can be the substrate with the gate, or the substrate with the source/drain electrodes and the semiconducting layer. If the electronic device is an organic field-effect transistor, and the layer formed from the composition of the present invention is the dielectric layer, the organic field effect transistor can be, for example, prepared as follows:
The source and drain electrodes can be formed by lithographically patterning a suitable source/drain material, for example gold, on a suitable substrate, for example PET. The source/drain electrodes can then be covered with a semiconducting layer by spin-coating a so- lution of a semiconducting material, for example a DPP polymer, in a suitable solvent, for example toluene, on the substrate. The wet semiconducting layer can be heated. The semiconducting layer can then be covered with a dielectric layer by spin-coating the composition of the present invention on the semiconducting layer. The wet dielectric layer can be heated to 80 to 100 °C, and then, if the composition of the present invention comprises a crosslinker of formula (12), cured by light treatment. The gate electrode can then be deposited on the dielectric layer for example by vapour deposition of a suitable source/drain material, for example gold.
Also part of the present invention is the use of the polymers of the present invention or of the composition of the present invention for forming a dielectric layer, a resist layer, an insulating layer, a passivation layer, a planarization layer, an encapsulation layer or a coating layer, preferably a dielectric layer.
A passivation layer is an electrically insulating layer on top of the semiconducting layer, which protects the semiconducting layer from damages caused by further processing steps, for exam- pie solvents or plasma used in the deposition of further layers.
An encapsulation layer is an electrically insulating layer that is deposited in order to protect the device from damages caused by the environment such as ambient gases, light and mechanical forces.
A planarization layer is an electrically insulating layer, which smooth the surface on which the next layer is to be applied, and optionally improves the wetting and adhesion of the subsequently deposited layers.
The polymers of the present invention are advantageous as they have a high glass temperature T(g) in the range of 120 to 180 °C, and when used in fabrication of a field effect transistor allow fabrication steps, which require higher temperatures such as applying the source/drain electrodes or the gate electrode on top of the dielectric layer by annealing, without resulting in an electrode misplacement or interface defects between the dielectric layer and the semiconducting layer. In addition, the polymers of the present invention are soluble in organic solvents and can be applied by liquid processing techniques such as spin coating, which allow the production of low cost field effect transistors. In addition, the polymers of the present invention show good film forming properties, and the films formed from the organic polymers are elastic and allow the production of flexible displays. Figure 1 shows the drain current Ids in relation to the gate voltage Vgs (transfer curve) for the top- gate, bottom-contact (TGBC) field effect transistor comprising polymer Pd at a source voltage Vds of -5V (triangle), respectively, -30V (square).
Examples Example 1
Preparation of the star-shaped polymer Pa from the monomers 1 ,1-diphenylethylene and sty- rene, and using p-divinylbenzene to form the n-valent unit X
First Step: Preparation of a multifunctional initiator oligomer
In a 500 mL three-necked flask equipped with a stainless steel stirrer, 100 g (560 mmol) 1 ,1-di- phenylethylene (DPE) was heated to 60 °C and titrated with s-BuLi (1.6 M in cyclohexane) until a stable orange-red color remained. Then 0.71 mL (1.0 mmol) of s-BuLi (1.6 M in cyclohexane) was added to the reaction mixture. The solution turned black-red. After 10 min 0.12 mL (0.76 mmol) p-divinylbenzene (80%) was added to the reaction mixture and the reaction mixture was stirred for 10 min. Then, 1.15 ml (10 mmol) styrene was added and the reaction mixture was stirred for further 10 min.
Second Step: Preparation of a star-shaped polymer from the multifunctional initiator oligomer Styrene (47.9 g, 460.6 mmol) in 135 g cyclohexane was added dropwise within 60 min to the reaction mixture of the first step, the temperature was kept at 60 °C for further 15 min. Then, 0.6 mL (3.75 mmol) p-divinylbenzene (80%) was added and the reaction mixture was stirred for 10 min and then quenched by addition of 1 mL isopropanol and 4 drops of acetic acid. The polymer was precipitated by drop-wise addition of the quenched reaction mixture into ethanol. The polymer was isolated and re-dissolved in 250 ml toluene and again precipitated into isopropa- nol. The solid polymer was filtered and dried under vacuum affording 95 g of polymer Pa as a white powder. Mn = 61000 g/mol. Mw = 1 12000 g/mol. PDI 1 .84. Tg = 168°C.
Example 2
Preparation of the star-shaped polymer Pb from the monomers 1 ,1-diphenylethylene and styrene, and using p-divinylbenzene to form the n-valent unit X First Step: Preparation of a multifunctional initiator oligomer
In a 500 mL three-necked flask equipped with a stainless steel stirrer, 170 g (944 mmol) 1 ,2-diphenylethylene (DPE) was heated to 60 °C and titrated with s-BuLi (1 .6 M in cyclohexane) until a stable orange-red color remained. Then 0.71 mL (1 .0 mmol) of s-BuLi (1 .6 M in cyclo- hexane) was added to the reaction mixture. The solution turned black-red. After 10 min 0.12 mL (0.76 mmol) p-divinylbenzene (80%) was added to the reaction mixture and the reaction mixture was stirred for 10 min. Then, 1.15 ml (10 mmol) styrene was added and the reaction mixture was stirred for further 10 min. Second Step: Preparation of a star-shaped polymer from the multifunctional initiator oligomer Styrene (47.9 g, 460.6 mmol) in 135 g cyclohexane was added drop-wise within 60 min to the reaction mixture of the first step, the temperature was kept at 60 °C for further 15 min. Then, the reaction mixture was stirred for 10 min and quenched by addition of 1 mL isopropanol and diluted with 400 mL toluene. The polymer was precipitated by drop-wise addition of the quenched and diluted reaction mixture into isopropanol. The polymer was re-dissolved in 400 mL toluene and again precipitated into isopropanol. The solid polymer was filtered and dried under vacuum affording 130 g of polymer Pb as a white powder. Mn = 98000 g/mol. Mw = 257000 g/mol. PDI 2.62. Tg = 167°C. Example 3
Preparation of the star-shaped polymer Pc from the monomers 1 ,1-diphenylethylene and styrene, and using p-divinylbenzene to form the n-valent unit X
First Step: Preparation of a multifunctional initiator oligomer
In a 10 L stainless steel reactor equipped with a cross-bar stirrer, 962 mL cyclohexane and
389.7 g (2165 mmol) 1 ,1-diphenylethylene (DPE) were heated to 60 °C and titrated with s-BuLi (1.4 M in cyclohexane) until a stable orange-red color remained. Then, 13.4 mL s-BuLi (1.4 M in cyclohexane) was added to the reaction mixture and the reaction mixture was stirred for 30 min. Then, 2.94 mL (18.62 mmol) divinylbenzene (80%) was added to the reaction mixture and the reaction mixture was stirred for 10 min. Then 10 mL (87 mmol) styrene was added and the reaction mixture was stirred for further 10 min.
Second Step: Preparation of a star-shaped polymer from the multifunctional initiator oligomer The reaction mixture of the first step was diluted with 962 mL cyclohexane and 261.1 g (251 1 mmol) styrene was added and the reaction mixture was stirred for 30 min. Then, further 321 mL cyclohexane and 90.1 g (866 mmol) styrene were added and the reaction mixture was stirred for further 30 min. The reaction mixture was decolorized by addition of 1.5 mL isopropanol and acidified with 1.5 mL acetic acid. To the colorless reaction mixture 1500 mL toluene was added and then cyclohexane was removed at the rotavap. The remaining reaction mixture was de- canted from some gel particles, filtered over a G4 fritte and then precipitated into isopropanol while stirring with a Ultraturrax. The white precipitate was filtered off and washed 10 times with 300 mL isopropanol each. The polymer was then re-dissolved in 500 mL dry toluene and filtered over a 29 mm column filled with a layer of 15 cm dried silicagel and 5 cm kieselgur, followed by washing of the column with toluene until the wash-solution was polymer-free. The combined solutions were concentrated at the rotavap to 600 mL and precipitated into 6000 mL isopropanol while stirring with an Ultraturrax, the white precipitate was filtrated and washed 10 times with 300 mL isopropanol each and finally dried at 90°C under vacuum. A white powder was obtained with the following characteristics. Mn = 52000 g/mol. Mw = 88000 g/mol. PDI 1.7. Tg = 148 °C.
Example 4
Preparation of the star-shaped polymer Pd from the monomers 1 ,1-diphenylethylene, styrene and butadiene, and using p-divinylbenzene to form the n-valent unit X
First Step: Preparation of a multifunctional initiator oligomer
In a 10 L stainless steel reactor equipped with a cross-bar stirrer, 2244 ml cyclohexane and 223.1 g (1239 mmol) 1 ,1-diphenylethylene (DPE) were heated to 60 °C and titrated with s-BuLi (1.4 M in cyclohexane) until a stable orange-red color remained. Then, 13.4 mL (18.76 mmol) s- BuLi (1 .4 M in cyclohexane) was added to the reaction mixture and the reaction mixture was stirred for 30 min. Then, 2.94 mL (18.62 mmol) divinylbenzene (80%, Aldrich technical grade) was added to the reaction mixture and the reaction mixture was stirred for 10 min. Then, 10 mL (87 mmol) styrene was added and the reaction mixture was stirred for further 10 min.
Second Step: Preparation of a star-shaped polymer from the multifunctional initiator oligomer 310.8 g (2988 mmol) styrene was added to the reaction mixture of the first step and the reaction mixture was stirred for 30 min. Then, 103.6 g (996 mmol) styrene were added and the reaction mixture was stirred for further 30 min. 172 mL (1 12.5 g, 2009 mmol) butadiene was added to the reaction mixture and the reaction mixture was stirred at 70 °C for 30 min. The reaction mixture was quenched with 1.5 mL isopropanol and acidified with 1 .5 mL acetic acid. The polymer Pd was isolated from the reaction mixture in analogy to the polymer Pc in example 3. The polymer Pd was obtained as white powder. Mn = 76000 g/mol. Mw = 152000 g/mol. PDI 2.0. Tg = - 102 and 125°C.
Example 5
Preparation of the star-shaped polymer Pe from the monomers 1 ,1-diphenylethylene and sty- rene, and using epoxidized soybean oil to form the n-valent unit X
In a 500 mL three-necked flask equipped with a stainless steel stirrer, 164 mL cyclohexane and 15 g (83 mmol) 1 ,2-diphenylethylene (DPE) were heated to 60 °C and titrated with s-BuLi (1 .6 M in cyclohexane) until a stable orange-red color remained. Then 0.2 mL (0.28 mmol) of s-BuLi (1.6 M in cyclohexane) was added to the reaction mixture. Then, 21 .74 g (209 mmol) styrene was added resulting in an increase of temperature up to 70 °C. Then 5 g (48 mmol) styrene was added drop-wise during 45 minutes. Finally, 1 g (9.6 mmol) styrene was added. Then, 0.45 mL of epoxidized soybean oil (Edenol D82) (20% in toluene) was added to the reaction mixture and the reaction mixture was stirred for additional 30 min. The reaction mixture turned yellowish. The reaction mixture was finally quenched by addition of 1 ml. isopropanol and acidified with C02/water (1 .0/0.5g). The polymer Pe was then precipitated by drop-wise addition of the reac- tion mixture into ethanol affording 38 g of polymer Pe as a white powder. Mn = 84000 g/mol. Mw = 143000 g/mol. PDI 1 .70. Tg = 132°C.
Example 6
Preparation of the star-shaped polymer Pf from the monomers 1 ,1 -diphenylethylene and styrene, and using epoxidized soybean oil to form the n-valent unit X
In a 2000 ml. three-necked flask equipped with a stainless steel stirrer, 1279 ml. cyclohexane and 85.5 g (475 mmol) 1 ,2-diphenylethylene (DPE) were heated to 60 °C and titrated with s- BuLi (1 .6 M in cyclohexane) until a stable orange-red color remained. Then 0.9 ml. (1 .25 mmol) of s-BuLi (1 .6 M in cyclohexane) and 60.9 g (586 mmol) styrene were added, resulting in an increase of temperature up to 65 °C. After 30 min the temperature dropped again to 63 °C and further 60.9 g (586 mmol) styrene was added. After 40 min further 40.6 g (390 mmol) styrene was added. After 25 min further 1 g (9.6 mmol) styrene was added and the reaction mixture was stirred for further 10 min. Then 1 .95 ml. of epoxidized soybean oil (Edenol D82) (20% in toluene) was added to the reaction mixture and the reaction mixture was stirred for additional 30 min. The solution turned yellowish. The reaction mixture was finally quenched by addition of 5 ml. isopropanol and acidified with C02/water (2,5g/1.25g). The polymer Pf was precipitated by dropwise addition of the reaction mixture into ethanol affording 245 g of polymer Pf as a white powder. Mn = 142000 g/mol. Mw = 257000 g/mol. PDI 1 .81. Tg = 145°C.
Example 7
Preparation of a top-gate, bottom-contact field effect transistor comprising polymer Pd of exam- pie 4 as dielectric material
Gold was sputtered onto PET substrate to form approximately 40 nm thick gold source/drain electrodes. A 0.75 % (weight/weight) solution of the diketopyrrolopyrrole semiconducting polymer of example 1 of WO 2013/083506 in toluene was filtered through a 0.45 micrometer polytet- rafluoroethylene (PTFE) filter and then applied by spin coating (1 ,000 rpm, 30 seconds). The wet organic semiconducting layer was dried at 90 °C on a hot plate for 60 seconds. A solution of 80 mg/mL of polymer Pd, prepared as described in example 4, in mixture of propylene glycol monomethyl ether acetate (PGMEA) and cyclopentanone (CP) (70/30), containing 4% by weight of 2,7-bis[2-(4-azido-2,3,5,6-tetrafluoro-phenyl)ethynyl]-9,9-dihexyl-fluorene as crosslinker based on the weight of polymer Pd, was filtered through a 1 micrometer filter. The solution was spin-coated (1800 rpm, 30 seconds) on the semiconducting layer. The wet dielectric layer was pre-baked at 90 °C for 2 minutes and subsequently UV-cured by irradiating at 365 nm with a dosage of ~100mJ/cm2 under ambient conditions. Afterwards, the device was wetted with a solution of PGMEA/CP (70/30) for 1 minute to develop the dielectric and spin-coated dry at (2000 rpm, 1 min) followed by a post-bake of 15 minutes at 90°C on a hot plate. Gate electrodes of gold (thickness approximately 80 nm) were evaporated through a shadow mask on the dielectric layer.
The top gate, bottom contact (TGBC) field effect transistor was measured by using a Keithley 4200-SCS semiconductor characterization system. The drain current lds in relation to the gate voltage Vgs (transfer curve) for the top-gate, bottom- contact (TGBC) field effect transistor at a source voltage VdS of -5V (triangle), respectively, -30V (square) is shown in Figure 1.
The charge-carrier mobility was extracted in the saturation regime from the slope of the square root drain current Ids1'2 versus gate-source voltage Vgs. The threshold voltage Von was obtained using the following equation: μ = 2 Ids / {(W/L)Ci (Vgs-V0n)2}, wherein Ci is the capacitance per unit of the dielectric layer. The thickness of the dielectric has been measured by a profilometer to 466nm. The average values of the charge carrier mobility μ, the lon/loff ratio and the onset voltage Von for the organic field effect transistor are given in table 1 .
Figure imgf000074_0001
Table 1. Example 8
Preparation of a capacitor comprising polymer Pd as dielectric material
A solution of 80mg/ml_ of polymer Pd prepared as described in example 4 in PGMEA/CP (70/30) containing 4% by weight of 2,7-bis[2-(4-azido-2,3,5,6-tetrafluoro-phenyl)ethynyl]-9,9- dihexyl-fluorene as crosslinker based on the weight of polymer was filtered through a
1 micrometer filter and applied on a clean glass substrate pre-coated with indium tin oxide (ITO) electrodes by spin coating (1500 rpm, 30 seconds). The wet dielectric layer was dried at 90 °C for 2 minutes on a hot plate and subsequently UV-cured by irradiating at 365 nm with a dosage of ~100mJ/cm2 under ambient conditions to obtain a ~ 560 nm thick layer. Gold electrodes (area = 3.0 mm2) were then vacuum-deposited through a shadow mask on the dielectric layer at < 1 x10"5 mbar The capacitor obtained was characterized in the following way: The relative permittivity was deduced from the capacitance measured with Agilent E4980A Precision LCR Meter (signal amplitude 1 V). The results are depicted in table 2.
Figure imgf000075_0001
Table 2.
Example 9
Evaluation of the effect of the radiation dosage on the retention of the photo-cross-linked polymer layer A solution of 80mg/ml_ of polymer Pd prepared as described in example 4 in PGMEA/CP
(70/30) containing 4% by weight of 2,7-bis[2-(4-azido-2,3,5,6-tetrafluoro-phenyl)ethynyl]-9,9- dihexyl-fluorene as crosslinker based on the weight of polymer was filtered through a
1 micrometer filter and applied on a silicon dioxide substrate by spin coating (1800 rpm, 30 seconds). The wet dielectric layer was pre-baked at 90 °C for 2 minutes on a hot plate to obtain a 400 nm thick layer. The polymer dielectric layer was UV-cured using 365 nm (dose of 100 mJ/cm2) under ambient conditions.
Development of the dielectric layer was done by immersing the dielectric layer into a mixture of PGEMA and CP for 1 minute followed by heating at 90 °C for 5 minutes. The thickness of the dielectric layer was measured after curing before development (d1 ) and after development (d2) using Veeco Dektak 150 to obtain the film retention ratio (d2/d1 ). The film retention ratio (d2/d1 ) was 80%.

Claims

Claims
1. Star-shaped polymers comprising units of formulae
Figure imgf000076_0001
(1 ) (2) wherein
a wavy line represents a valency,
Ar1, Ar2 and Ar3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and
R1 is H or Ci-4-alkyl, and at least one n-valent unit X,
wherein n is an integer from 3 to 10.
2. The polymers of claim 1 , wherein Ar1 , Ar2 and Ar3 are independently from each other Ce-ιο- aryl, which can be substituted with 1 to 7 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-30-alkyl, O-Ci-30-alkyl, C6-io-aryl and 0-C6-io-aryl.
3. The polymers of claim 1 , wherein Ar1 , Ar2 and Ar3 are all phenyl.
4. The polymers of any of claims 1 to 3, wherein R1 is H.
5. The polymers of claims 1 to 4, wherein the n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
Figure imgf000076_0002
(X1 ) (X2) 76
Figure imgf000077_0001
Figure imgf000077_0002
Figure imgf000077_0003
Figure imgf000077_0004
Figure imgf000078_0001
(V12) (V13)
Figure imgf000078_0002
(V14) (V15) (V16)
Figure imgf000078_0003
(V17) (V18) (V19)
Figure imgf000078_0004
(V22) (V23) (V24) wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, Cs-i cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group V to another valency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000079_0001
(YD (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
6. The polymers of any of claims 1 to 4, wherein the n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 10, and which n-valent unit X is
Figure imgf000080_0001
(X2) or comprises
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000080_0002
Figure imgf000080_0003
Figure imgf000081_0001
(V9)
Figure imgf000081_0002
(V14) (V15) (V16)
Figure imgf000081_0003
(V17)
(V18)
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
R5 and R6 are independently from each other and at each occurrence Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5 cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group V to another valency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000082_0001
(YD (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
7. The polymers of any of claims 1 to 4, wherein the n-valent unit X is an n-valent unit X, wherein n is an integer from 3 to 8, and which n-valent unit X comprises
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000083_0001
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb, wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group V to another valency group V or to a linking group Y, and b) at least one linking group Y each independently selected from the group consisting of
Figure imgf000084_0001
(Y1 ) (Y2) (Y3) wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L2 is trivalent Ci-30-alkylene, trivalent Cs-s-cycloalkylene, trivalent C6-i4-arylene, trivalent C1-20- alkylene-C6-io-arylene, trivalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8-cycloalkylene, trivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, trivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or trivalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
L3 is tetravalent Ci-30-alkylene, tetravalent Cs-s-cycloalkylene, tetravalent C6-i4-arylene, tetra- valent Ci-2o-alkylene-C6-io-arylene, tetravalent Cs-8-cycloalkylene-Ci-3o-alkylene-Cs-8- cycloalkylene, tetravalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, tetravalent C6-io-arylene- Ci-2o-alkylene-C6-io-arylene or tetravalent C6-io-arylene-C6-io-arylene-C6-io-arylene,
wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
8. The polymers of any of claims 1 to 4, wherein the n-valent unit X is an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000085_0001
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H, Ci-30-alkyl, C5-8- cycloalkyl or C6-i4-aryl, which C6-i4-aryl can be substituted with 1 to 9 substituents Rb,
wherein Rb is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the valency group V to another valency group V or to a linking group Y, and b) at least one linking group Y each independently
Figure imgf000086_0001
wherein
L1 is bivalent Ci-30-alkylene, bivalent Cs-s-cycloalkylene, bivalent C6-i4-arylene, bivalent C1-20- alkylene-C6-io-arylene, bivalent Cs-s-cycloalkylene-Ci-so-alkylene-Cs-s-cycloalkylene, bivalent Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, bivalent C6-io-arylene-Ci-2o-alkylene-C6-io-arylene or bivalent C6-io-arylene-C6-io-arylene-C6-io-arylene, wherein Ci-30-alkylene, Cs-s-cycloalkylene, C6-i4-arylene, Ci-2o-alkylene-C6-io-arylene, C5-8- cycloalkylene-Ci-3o-alkylene-C5-8-cycloalkylene, Ci-2o-alkylene-C6-io-arylene-Ci-2o-alkylene, C6-io-arylene-Ci-2o-alkylene-C6-io-arylene and C6-io-arylene-C6-io-arylene-C6-io-arylene can be substituted with 1 to 9 substituents Rc,
wherein Rc is at each occurrence selected from the group consisting of Ci-10-alkyl, C5-6- cycloalkyl, O-Ci-10-alkyl, C6-io-aryl and 0-C6-io-aryl, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
9. The polymer of any of claims 1 to 4, wherein the n-valent unit X is an n-valent unit X, wherein n is an integer from 4 to 6, and which n-valent unit X essentially consists of
a) at least one valency-group V each independently selected from the group consisting of
Figure imgf000087_0001
wherein
a wavy line represents one valency of the n-valent unit X,
R2, R3 and R4 are independently from each other at each occurrence H or Ci-30-alkyl, and a line marked with a star represents the connecting side of the valency group V to another valency group V or to a linking group Y, and least one linking group Y each independently
Figure imgf000088_0001
wherein
L1 is bivalent Ci-30-alkylene or bivalent C6-i4-arylene, and a line marked with a star represents the connecting side of the linking group Y to another linking group Y or to a valency group V, and a connecting side of a linking group Y together with a connecting side of another linking group Y forms the connecting bond between the linking group Y and the other linking group Y, and the connecting side of a linking group Y together with a connecting side of a valency group V forms the connecting bond between the linking group Y and the valency group V.
10. Polymers of any of claims 1 to 9, wherein the sum of the units of formulae (1 ) and (2) is at least 70% by weight based on the weight of the polymer.
1 1 . Polymers of any of claims 1 to 10, which further comprise units S comprising one C-C- double bond.
12. Polymers of claim 1 1 , wherein the unit S is selected from the group consisting of
Figure imgf000088_0002
Figure imgf000089_0001
(SIV) wherein
a wavy line represents a valency, and
R10, R11, R12 and R13 are independently of each other H or Ci-20-alkyl, and s is an integer from 1 to 4.
13. The polymers of claims 1 1 or 12, wherein the units of formula S are present as blocks at the terminal ends of the arms of the star-shaped polymer.
14. A process for the preparation of the polymers of claim 1 , which process comprises the steps of polymerizing a monomer of formula
Figure imgf000089_0002
(M1 ) with a monomer of formula
Figure imgf000089_0003
(M2)
wherein Ar1, Ar2 and Ar3 are independently from each other C6-i4-aryl, which can be substituted with 1 to 9 substituents Ra, wherein Ra is at each occurrence selected from the group consisting of Ci-3o-alkyl, O-Ci-30-alkyl, C6-i4-aryl and 0-C6-i4-aryl, and R1 is H or Ci-4-alkyl, in the presence of an anion and a precursor PX of the n-valent unit X.
15. The process of claim 14, which comprises a second step of polymerizing monomers MS comprising two C-C-double bonds with the polymer intermediate of the first step.
16. The process of claim 15, wherein the monomer MS is selected from the group consisting of
Figure imgf000090_0001
(MS 1-1 ) (MS 11-1 ) wherein
R10, R11, R12 and R13 are independently of each other H or Ci-20-alkyl, and s is an integer from 1 to 4.
17. A composition comprising a polymer of any of claims 1 to 13 and an organic solvent.
18. The compositions of claim 17, wherein the composition also comprises a crosslinker.
19. An electronic device comprising the polymers of any of claims 1 to 13 or a layer formed from the composition of any of claims 17 or 18.
20. The electronic device of claim 19, which electronic device is a field effect transistor.
21. Use of the polymers of any of claims 1 to 13 or of the composition of any of claims 17 or 18 for forming a dielectric layer, a resist layer, an insulating layer, a passivation layer, a planar- ization layer, an encapsulation layer or a coating layer.
PCT/EP2017/073688 2016-09-27 2017-09-20 Star-shaped styrene polymers with enhanced glass transition temperature Ceased WO2018060015A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16190845 2016-09-27
EP16190845.4 2016-09-27

Publications (1)

Publication Number Publication Date
WO2018060015A1 true WO2018060015A1 (en) 2018-04-05

Family

ID=57042664

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2017/073688 Ceased WO2018060015A1 (en) 2016-09-27 2017-09-20 Star-shaped styrene polymers with enhanced glass transition temperature

Country Status (1)

Country Link
WO (1) WO2018060015A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110105498A (en) * 2019-05-15 2019-08-09 大连理工大学 One kind is suitable for single silicon hydrogen functionalization star polymer and preparation method thereof of Si―H addition reaction chemical reaction
US11248080B2 (en) 2017-05-17 2022-02-15 Basf Se Brominated flame retardant
US11434587B2 (en) 2016-12-13 2022-09-06 Basf Se Filaments for use as a support material in fused deposition modeling

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5984910A (en) 1982-11-02 1984-05-16 Koichi Hatada Novel copolymer and production thereof
US5854353A (en) 1994-06-16 1998-12-29 Basf Aktiengesellschaft Thermoplastic molding compound
WO1999001487A1 (en) 1997-06-30 1999-01-14 Basf Aktiengesellschaft 1,1-diphenyl ethylene-based thermoplastic elastomers
EP1078970A1 (en) 1999-08-26 2001-02-28 Ciba SC Holding AG DPP-containing conjugated polymers and electroluminescent devices
WO2005049695A1 (en) 2003-10-28 2005-06-02 Ciba Specialty Chemicals Holding Inc. Novel diketopyrrolopyrrole polymers
WO2008000664A1 (en) 2006-06-30 2008-01-03 Ciba Holding Inc. Diketopyrrolopyrrole polymers as organic semiconductors
US20100010147A1 (en) 2008-07-08 2010-01-14 Kraton Polymer U.S. Llc Adhesives prepared from diphenylethylene containing block copolymers
WO2010049321A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic field effect transistors
WO2010049323A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010108873A1 (en) 2009-03-23 2010-09-30 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010115767A1 (en) 2009-04-08 2010-10-14 Basf Se Pyrrolopyrrole derivatives, their manufacture and use as semiconductors
WO2010136353A1 (en) 2009-05-27 2010-12-02 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010136352A1 (en) 2009-05-27 2010-12-02 Basf Se A process for polymerising (hetero)aromatic compounds
WO2011001007A1 (en) 2009-07-03 2011-01-06 Upm Raflatac Oy Manufacturing of electronic components
US20120141757A1 (en) 2010-12-01 2012-06-07 Xerox Corporation Dielectric composition
WO2013083506A1 (en) 2011-12-07 2013-06-13 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
CN105845553A (en) * 2016-04-01 2016-08-10 江苏大学 Graphene FET array manufacturing method based on silicon carbide substrate

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5984910A (en) 1982-11-02 1984-05-16 Koichi Hatada Novel copolymer and production thereof
US5854353A (en) 1994-06-16 1998-12-29 Basf Aktiengesellschaft Thermoplastic molding compound
WO1999001487A1 (en) 1997-06-30 1999-01-14 Basf Aktiengesellschaft 1,1-diphenyl ethylene-based thermoplastic elastomers
EP1078970A1 (en) 1999-08-26 2001-02-28 Ciba SC Holding AG DPP-containing conjugated polymers and electroluminescent devices
WO2005049695A1 (en) 2003-10-28 2005-06-02 Ciba Specialty Chemicals Holding Inc. Novel diketopyrrolopyrrole polymers
WO2008000664A1 (en) 2006-06-30 2008-01-03 Ciba Holding Inc. Diketopyrrolopyrrole polymers as organic semiconductors
US20100010147A1 (en) 2008-07-08 2010-01-14 Kraton Polymer U.S. Llc Adhesives prepared from diphenylethylene containing block copolymers
WO2010049321A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic field effect transistors
WO2010049323A1 (en) 2008-10-31 2010-05-06 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010108873A1 (en) 2009-03-23 2010-09-30 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010115767A1 (en) 2009-04-08 2010-10-14 Basf Se Pyrrolopyrrole derivatives, their manufacture and use as semiconductors
WO2010136353A1 (en) 2009-05-27 2010-12-02 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
WO2010136352A1 (en) 2009-05-27 2010-12-02 Basf Se A process for polymerising (hetero)aromatic compounds
WO2011001007A1 (en) 2009-07-03 2011-01-06 Upm Raflatac Oy Manufacturing of electronic components
US20120141757A1 (en) 2010-12-01 2012-06-07 Xerox Corporation Dielectric composition
WO2013083506A1 (en) 2011-12-07 2013-06-13 Basf Se Diketopyrrolopyrrole polymers for use in organic semiconductor devices
CN105845553A (en) * 2016-04-01 2016-08-10 江苏大学 Graphene FET array manufacturing method based on silicon carbide substrate

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GAUSEPOHL H ET AL: "SUPER-POLYSTYRENE: A NEW CLASS OF ENGINEERING PLASTICS WITH VERSATILE PROPERTIES", DESIGNED MONOMERS AND POLYMERS, VSP, UTRECHT, NL, vol. 3, no. 3, 1 January 2000 (2000-01-01), pages 299 - 315, XP001015286, ISSN: 1385-772X, DOI: 10.1163/156855500300160258 *
H. GAUSEPOHL; S. OEPEN; K. KNOLL; M. SCHNEIDER; G. MCKEE; W. LOTH: "Super-Polystyrene", DESIGNED MONOMERS AND POLYMERS, vol. 3, no. 3, 2000, pages 299 - 315, XP001015286, DOI: doi:10.1163/156855500300160258
HADJICHRISTIDIS N ET AL: "LINKING CHEMISTRY AND ANIONIC POLYMERIZATION", CURRENT ORGANIC CHEMISTRY,, vol. 6, no. 2, 1 January 2002 (2002-01-01), pages 155 - 176, XP008075632, ISSN: 1385-2728, DOI: 10.2174/1385272023374463 *
N. HADJICHRISTIDIS; S.PISPAS; H. LATROU; M. PITSIKALIS: "Linking Chemistry and anionic polymerization", CURRENT ORGANIC CHEMISTRY, vol. 6, 2002, pages 155 - 176, XP008075632, DOI: doi:10.2174/1385272023374463

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11434587B2 (en) 2016-12-13 2022-09-06 Basf Se Filaments for use as a support material in fused deposition modeling
US11248080B2 (en) 2017-05-17 2022-02-15 Basf Se Brominated flame retardant
CN110105498A (en) * 2019-05-15 2019-08-09 大连理工大学 One kind is suitable for single silicon hydrogen functionalization star polymer and preparation method thereof of Si―H addition reaction chemical reaction
CN110105498B (en) * 2019-05-15 2021-07-30 大连理工大学 A class of monosilylation functionalized star polymers suitable for hydrosilylation chemical reaction and preparation method thereof

Similar Documents

Publication Publication Date Title
JP6214768B2 (en) Azide crosslinking agent
Yang et al. Patternable conjugated polymers with latent hydrogen-bonding on the main chain
TWI678378B (en) Organic electronic compositions and device thereof
Won et al. Photo-patternable polyimide gate insulator with fluorine groups for improving performance of 2, 7-didecyl [1] benzothieno [3, 2-b][1] benzothiopene (C10-BTBT) thin-film transistors
WO2018060015A1 (en) Star-shaped styrene polymers with enhanced glass transition temperature
WO2008016110A1 (en) Insulating layer, electronic device, field effect transistor, and polyvinylthiophenol
US20180175300A1 (en) Organic thin film transistor, method of manufacturing organic thin film transistor, organic semiconductor composition, organic semiconductor film, and method of manufacturing organic semiconductor film
CN104221177B (en) Photocurable polymeric material and related electronic device
EP3198614B1 (en) Ether-based polymers as photo-crosslinkable dielectrics
KR101888326B1 (en) A photo-patterned gate dielectric for OFET
US12291587B2 (en) Photocrosslinkable polymer, insulating film, planarization film, lyophilic/liquid repellent patterned film, and organic field effect transistor device comprising same
Yang et al. Organic Field-Effect Transistors with Bottlebrush Polymer Gate Dielectrics Thermally Cross-Linked in Less Than 1 min
WO2018104367A2 (en) Thieno-indeno-monomers and polymers
Wu et al. Biaxially extended thiophene–isoindigo donor–acceptor conjugated polymers for high-performance flexible field-effect transistors
KR102546718B1 (en) Star and triblock polymers with improved crosslinkability
JP7046395B2 (en) Patterning method for manufacturing top gate / bottom contact organic field effect transistors
Matsukawa et al. Polysilsesquioxanes for Gate‐Insulating Materials of Organic Thin‐Film Transistors
Ding Large area vacuum fabrication of organic thin-film transistors

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17768147

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17768147

Country of ref document: EP

Kind code of ref document: A1