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WO2012074051A1 - Polymère hyper-ramifié fluoré et son procédé de fabrication - Google Patents

Polymère hyper-ramifié fluoré et son procédé de fabrication Download PDF

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Publication number
WO2012074051A1
WO2012074051A1 PCT/JP2011/077797 JP2011077797W WO2012074051A1 WO 2012074051 A1 WO2012074051 A1 WO 2012074051A1 JP 2011077797 W JP2011077797 W JP 2011077797W WO 2012074051 A1 WO2012074051 A1 WO 2012074051A1
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group
carbon atoms
formula
hyperbranched polymer
fluorine
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Japanese (ja)
Inventor
永島　英夫
和宣 井川
孝司 西形
小島　圭介
章博 田中
理 上杉
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Kyushu University NUC
Nissan Chemical Corp
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Kyushu University NUC
Nissan Chemical Corp
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Priority to JP2012546933A priority Critical patent/JP5872484B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/002—Dendritic macromolecules
    • C08G83/005—Hyperbranched macromolecules
    • C08G83/006—After treatment of hyperbranched macromolecules

Definitions

  • the present invention relates to a fluorine-containing hyperbranched polymer, and more specifically, a hyperbranched polymer having a fluorinated alkyl group that can be used as a surface modifier for a resin, a resin composition containing the same, and a method for producing the hyperbranched polymer About.
  • Polymer (polymer) materials are increasingly used in many fields in recent years. Along with this, the characteristics of the surface and interface of the polymer as a matrix, as well as the properties of the polymer, have become important for each field. For example, by using a fluorine compound with a low surface energy as a surface modifier, water and oil repellency, antifouling properties, non-adhesiveness, peelability, release properties, slipperiness, wear resistance, antireflection properties, Various improvements relating to interface control such as chemical resistance are expected and various proposals have been made.
  • thermoplastic resin using a fluorine-based polymer includes, for example, poly (4-methyl-1-pentene having improved releasability by blending a tetrafluoroethylene-ethylene copolymer (ETFE). ) (PMP) resin film (Patent Document 1) and fluorine-containing polyolefin (Patent Document 2) excellent in water and oil repellency have been proposed.
  • Patent Document 3 a surface treatment agent for a thermosetting epoxy resin using a fluoropolymer having fluoropolyether
  • Patent Document 4 a photocurable acrylic resin containing a fluorine-containing surfactant and / or a fluorine-based polymer having a cyclic structure is excellent in releasability and has been surface-modified
  • fluorine compound having a multi-branched structure an ether and / or ester derivative of a polyalcohol in which a specific fluorine-containing group is arranged in a multi-branched manner via an ether or ester bond on a polyalcohol skeleton is disclosed.
  • the fluorine compound having the multi-branched structure is, for example, an ester derivative formed from glycerin 10-mer and hexafluoropropylene oxide trimer, which is a low-molecular weight compound, and a highly branched polymer.
  • a method for modifying the surface of the used light and thermosetting transparent resin has not been proposed.
  • linear fluoropolymers can give a certain surface modification effect to some thermoplastic resins, they are generally poorly mixed and dispersible with the resin, and particularly represented by polymethyl methacrylate (PMMA).
  • PMMA polymethyl methacrylate
  • phase separation may occur and the transparency of the transparent resin may be impaired.
  • these fluorine-based polymers have low solubility in organic solvents, and even if surface modification of light and thermosetting resins is performed using these polymers, the process for film formation using organic solvents is not possible. Application was difficult.
  • the fluorine compound having the above-mentioned multi-branched structure has been confirmed to have a solubility in water or propylene glycol monomethylol of only 1% by mass, and this is also applied to a process for forming a film using an organic solvent. It was difficult. That is, a new compound that has sufficient transparency, has high solubility in an organic solvent, and also has a surface modification effect has been demanded.
  • the present inventors have introduced a fluoroalkyl group into a hyperbranched polymer that has not been studied in the past, and the resulting fluorine-containing hyperbranched polymer is modified with a resin surface.
  • a fluoroalkyl group By adopting it as an agent, it not only has excellent solubility in organic solvents, but also has excellent mixing and dispersibility in the matrix resin, does not cause aggregation in the matrix resin, and has excellent surface modification and high transparency.
  • a molded object was obtained and completed this invention.
  • this invention relates to the fluorine-containing hyperbranched polymer represented by Formula [1] whose weight average molecular weight Mw measured by polystyrene conversion by gel permeation chromatography is 1,000 to 500,000 as a 1st viewpoint.
  • R 1 represents a hydrogen atom or a methyl group
  • a 1 represents a structure represented by the formula [2] or [3]
  • L represents —SC ( ⁇ O) — or —O—.
  • Rf represents a fluoroalkyl group having 2 to 12 carbon atoms which may be the same or different, and n represents the number of repeating unit structures and represents an integer of 2 to 3,000.
  • a 2 is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond.
  • the present invention relates to the fluorine-containing hyperbranched polymer according to the first aspect, wherein Rf represents a C2-C12 fluoroalkyl group in which a hydrogen atom and a fluorine atom are bonded to a main chain or a terminal carbon atom. .
  • the present invention relates to the fluorine-containing hyperbranched polymer according to the second aspect, in which the fluoroalkyl group is a fluoroalkyl group having a difluoromethyl structure at its terminal.
  • the present invention relates to the fluorine-containing hyperbranched polymer according to the first aspect, in which Rf represents a fluoroalkyl group having 2 to 12 carbon atoms represented by the formula [4].
  • X represents a hydrogen atom or a fluorine atom
  • k represents 1 or 2
  • m represents an integer of 0 to 5).
  • the present invention relates to the fluorine-containing hyperbranched polymer according to the fourth aspect, in which X represents a hydrogen atom.
  • the present invention relates to a varnish containing the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect.
  • the present invention relates to a thin film comprising the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect.
  • the present invention relates to a resin composition containing (a) the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect, and (b) a thermoplastic resin or a curable resin.
  • a 9th viewpoint it is related with the resin molded product produced from the resin composition as described in an 8th viewpoint.
  • a polymerizable composition comprising (a) the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect, (c) a polymerizable compound, and (d) a polymerization initiator.
  • a polymerizable composition comprising (a) the fluorine-containing hyperbranched polymer according to any one of the first aspect to the fifth aspect, (c) a polymerizable compound, and (d) a polymerization initiator.
  • an 11th viewpoint it is related with the resin molded product produced by polymerizing the polymeric composition as described in a 10th viewpoint.
  • the present invention relates to a method for producing a polymer.
  • R 1 represents a hydrogen atom or a methyl group
  • a 1 represents a structure represented by the formula [2] or [3]
  • Hal represents a halogen atom
  • Rf may be the same.
  • a 2 is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond.
  • the present invention relates to a method for producing a hyperbranched polymer.
  • R 1 , A 1 and n are as defined in the formula [5], and R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms, the number of carbon atoms. It represents a 1 to 5 hydroxyalkyl group or an arylalkyl group having 7 to 12 carbon atoms, or R 2 and R 3 may form a ring together with the nitrogen atom bonded thereto.
  • (C) a step of converting the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the formula [7] into a thiol anion (—S ⁇ ) by treating with a base
  • (D) The present invention relates to a method for producing a fluorine-containing hyperbranched polymer represented by the formula [9], comprising a step of reacting the thiol anion with a carboxylic acid derivative represented by the formula [8].
  • R 1 represents a hydrogen atom or a methyl group
  • a 1 represents a structure represented by Formula [2] or Formula [3]
  • R 2 and R 3 each independently represents 1 carbon atom.
  • a ring may be formed, and n is the number of repeating unit structures and represents an integer of 2 to 3,000, and Rf may be the same or different and has 2 to 12 carbon atoms.
  • Z represents a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
  • a 2 is a linear alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, or a C 3 to 30 carbon atom which may contain an ether bond or an ester bond.
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently a hydrogen atom.
  • the fluorine-containing hyperbranched polymer of the present invention can form a thin-film structure as it is by a simple coating / drying operation by taking advantage of the characteristics of a polymer compound.
  • the fluorine-containing hyperbranched polymer of the present invention is soluble not only in N, N-dimethylformamide (DMF) and tetrahydrofuran (THF), but also in N-methyl-2-pyrrolidone (NMP), cyclohexanone, acetone, and the like. Since it exists, it can be set as the form of a varnish, without limiting a solvent, and a thin film can be formed. Further, since the fluorine-containing hyperbranched polymer can be dissolved in such a solvent at a high concentration, it can be used as a coating material.
  • the fluorine-containing hyperbranched polymer of the present invention has a molecular structure compared to the linear polymer because the conventional linear polymer generally has a string-like shape, but actively introduces a branched structure. There is little entanglement between them and it shows a fine particle behavior. That is, movement in the resin as a matrix is facilitated. Therefore, when the fluorine-containing hyperbranched polymer of the present invention is blended with a polymerizable composition or a resin composition containing a thermoplastic resin or a thermosetting resin to form a resin molded product, it is easy at the interface (molded product surface). This can contribute to interface control and improve the surface modification of the resin. Moreover, the fluorine-containing hyperbranched polymer of the present invention has a high mixing / dispersibility with the matrix resin, and can be mixed / dispersed without causing aggregation in the resin. Can be manufactured.
  • the resin molded product of the present invention is not only a molded product having excellent transparency as described above, but can also be a surface-modified resin molded product. It is possible to obtain a molded product having excellent mold releasability or releasability from other resin molded products such as a film, water / oil repellency, and antifouling properties.
  • FIG. 1 is a diagram showing 1 H NMR spectra of hyperbranched polymers: HPS-SC3F-1 to HPS-SC3F-4 produced in Examples 1 to 4.
  • FIG. 2 shows the 1 H NMR spectrum of the hyperbranched polymer: HPS-OC1F produced in Example 9.
  • FIG. 3 is a diagram showing the 1 H NMR spectrum of the hyperbranched polymer: HPS-OC4H produced in Example 10.
  • FIG. 4 shows the 1 H NMR spectrum of the hyperbranched polymer: HPS-OC6F produced in Example 11.
  • FIG. 5 shows the 1 H NMR spectrum of the hyperbranched polymer: HPS-OC6H produced in Example 12.
  • 6 is a diagram showing a 1 H NMR spectrum of hyperbranched polymer: HPS-OC7F produced in Example 13.
  • the fluorine-containing hyperbranched polymer of the present invention has a structure represented by the following formula [1].
  • R 1 represents a hydrogen atom or a methyl group.
  • a 1 represents a structure represented by the following formula [2] or formula [3].
  • L represents —SC ( ⁇ O) — or —O—.
  • Rf represents a fluoroalkyl group having 2 to 12 carbon atoms, which may be the same or different.
  • N is the number of repeating unit structures and represents an integer of 2 to 3,000.
  • Rf preferably represents a fluoroalkyl group having 2 to 12 carbon atoms in which a hydrogen atom and a fluorine atom are bonded to a main chain or a terminal carbon atom, and in particular, the fluoroalkyl group is A fluoroalkyl group having a difluoromethyl structure at the terminal is preferable.
  • Rf represents a fluoroalkyl group having 2 to 12 carbon atoms represented by the following formula [4].
  • X represents a hydrogen atom or a fluorine atom
  • k represents 1 or 2
  • m represents an integer of 0 to 5.
  • X preferably represents a hydrogen atom.
  • Rf examples include —CH 2 CF 3 group, —CH 2 CF 2 CF 3 group, —CH 2 (CF 2 ) 2 CF 3 group, —CH 2 (CF 2 ) 3 CF 3 group, —CH 2 (CF 2 ) 4 CF 3 group, —CH 2 (CF 2 ) 5 CF 3 group, —CH 2 (CF 2 ) 6 CF 3 group, —CH 2 CF 2 CHF 2 group, —CH 2 (CF 2 ) 3 CHF 2 groups, —CH 2 (CF 2 ) 5 CHF 2 groups, —CH 2 (CF 2 ) 7 CHF 2 groups, —CH (CF 3 ) CF 3 groups, —CH 2 CF 2 CHFCF 3 groups, —CH 2 CF (CF 3 ) CHF 2 group, —CH 2 CF 2 CClF 2 group, — (CH 2 ) 2 (CF 2 ) 3 CF 3 group, — (CH 2 ) 5 CF 3 group, ——CH 2 CF 2
  • a 2 may contain an ether bond or an ester bond and may contain a C 1-30 linear alkylene group, an ether bond or an ester bond.
  • a branched alkylene group having 3 to 30 carbon atoms or a cyclic alkylene group having 3 to 20 carbon atoms which may contain an ether bond or an ester bond is represented.
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, Represents a carboxyl group or a cyano group
  • linear alkylene group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group.
  • branched alkylene group examples include isopropylene group, isobutylene group and 2-methylpropylene group.
  • the cyclic alkylene group examples include alicyclic aliphatic groups having a cyclic structure of 3 to 30 carbon atoms, such as monocyclic, polycyclic and bridged cyclic structures. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms.
  • the structural examples (a) to (s) of the alicyclic moiety in the alicyclic aliphatic group are shown below.
  • Examples of the alkyl group having 1 to 20 carbon atoms in Y 1 , Y 2 , Y 3 and Y 4 include a methyl group, an ethyl group, an isopropyl group, an n-pentyl group and a cyclohexyl group.
  • Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, n-pentyloxy group and cyclohexyloxy group.
  • Y 1 , Y 2 , Y 3 and Y 4 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of the fluorine-containing hyperbranched polymer of the present invention is 1,000 to 500,000, preferably 2,000 to 500,000, most preferably. 3,000 to 200,000.
  • the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, or 1.1 to 6.0, or 1.2 to 5.0. is there.
  • R 1 , A 1 , Rf and n represent the same as defined in formula [1], and Hal represents a halogen atom.
  • the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
  • (A) Process Reaction process of the hyperbranched polymer represented by Formula [5] and a fluoroalkoxide [fluoroalkoxide]
  • an alkali metal fluoroalkoxide is used as the fluoroalkoxide having 2 to 12 carbon atoms used in this step.
  • the alkali metal include lithium, sodium, potassium, and the like. Among them, those using sodium as the alkali metal are preferable.
  • an alkali metal fluoroalkoxide represented by NaO—Rf Rf is the same as defined in the formula [1]
  • the fluoroalkoxide can be produced from the corresponding fluoroalkyl alcohol Rf—OH (Rf is the same as defined in the formula [1]) by a known method.
  • solvent This step is usually performed in a solvent.
  • the solvent used in this step is not particularly limited, and among various solvents used for general organic synthesis, those that do not affect the above step can be appropriately selected and used.
  • Specific examples include amide compounds such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc); nitrile compounds such as acetonitrile, propionitrile and butyronitrile; methyl acetate, ethyl acetate, butyl acetate, Ester compounds such as methyl propionate; ketone compounds such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone; aliphatic hydrocarbon compounds such as pentane, hexane, cyclohexane, octane, decane, decalin, petroleum ether; benzene, Aromatic hydrocarbon compounds
  • solvents may be used alone or in combination of two or more.
  • THF aprotic polar organic solvent
  • DMSO aprotic polar organic solvent
  • the mixing ratio of DMSO when THF is set to 1 is preferably 0.5 or less.
  • This step can be carried out at any temperature below the boiling point of the solvent, and is preferably carried out at 30 to 150 ° C., more preferably 40 to 120 ° C. from the viewpoint of obtaining the desired product in a high yield in a short time. Is done.
  • reaction time The reaction time of the hyperbranched polymer having a halogen atom at the molecular terminal and the fluoroalkoxide varies depending on the type of the hyperbranched polymer, the type of the fluoroalkoxide, the type of base, the solvent used, the reaction temperature to be applied, etc. However, it is usually about 1 to 24 hours.
  • this step can be performed under air, it is preferable to perform under a nitrogen atmosphere. Moreover, since it is not desirable to mix water into the reaction system, the use of a dehydrated solvent is preferred.
  • the crude product can be separated by a known method such as evaporation of the solvent, filtration, reprecipitation, etc., and the crude product is distilled, silica gel column chromatography, recrystallization, etc. And can be purified.
  • the hyperbranched polymer having a halogen atom at the molecular end represented by the above formula [5] is a halogenating agent for (B) the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the following formula [7]. Substituting with a halogen atom at Is manufactured.
  • R 1 , A 1 and n represent the same as defined in the formula [5].
  • R 2 and R 3 each independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms, or R 2 and R 3 may form a ring together with the nitrogen atom bonded thereto.
  • Examples of the alkyl group having 1 to 5 carbon atoms in R 2 and R 3 include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-pentyl group, and a cyclopentyl group.
  • Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
  • Examples of the arylalkyl group having 7 to 12 carbon atoms include a benzyl group and a phenethyl group.
  • Examples of the ring formed by R 2 and R 3 together with the nitrogen atom bonded to them include 4- to 8-membered rings.
  • the ring examples include a ring containing 4 to 6 methylene groups. Moreover, the ring containing an oxygen atom or a sulfur atom and 4 to 6 methylene groups as a ring is also mentioned. Specific examples of the ring formed by R 2 and R 3 together with the nitrogen atom bonded thereto include a piperidine ring, a pyrrolidine ring, a morpholine ring, a thiomorpholine ring, and a homopiperidine ring.
  • the hyperbranched polymer having a dithiocarbamate group at the molecular end represented by the formula [7] has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 500 to 5,000,000, preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000, and most preferably 3,000 to 200,000.
  • the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, or 1.1 to 6.0, or 1.2 to 5.0. is there.
  • Hyperbranched polymers having a dithiocarbamate group at the molecular end represented by the above formula [7] are, for example, Koji Ishizu, Akihide Mori, Polymer International 50, 906-910 (2001), Koji Ishizu, TakeshiPhiMiyaPhiMhiPhiMhiPhiMakiPhi International 51, 424-428 (2002), Koji Ishizu, Yoshihiro Ohta, Journal of Materials Science Letters, 22 (9), 647-650 (2003).
  • the method for halogenating the dithiocarbamate group at the molecular end of the hyperbranched polymer represented by the following formula [7] is not particularly limited as long as it can convert the dithiocarbamate group to a halogen atom.
  • halogenating agent examples include chlorine, N-chlorosuccinimide, chlorinated isocyanuric acid, sulfuryl chloride, tert-butyl hypochloride, phosphorus trichloride, phosphorus pentachloride, triphenylphosphine dichloride, and secondary chloride.
  • Chlorinating agents such as copper and antimony pentachloride, bromine, N-bromosuccinimide, N-bromoglutarimide, N, N ′, N ′′ -tribromoisocyanuric acid, sodium N, N′-dibromoisocyanurate, N, N'-bromoisocyanuric acid potassium, N, N'-dibromoisocyanuric acid, sodium N-bromoisocyanurate, N, N'-dibromohydantoin, N-bromohydantoin potassium, N, N'-bromohydantoin sodium, N-bromo -N'-methylhydantoin, 1,3-dibromo-5,5'-dimethylhy Tontoin, 3-bromo-5,5'-dimethylhydantoin, 1-bromo-5,5'-dimethylhydantoin sodium, 1-bromo-5,5'-dimethylhydantoin potassium,
  • the amount of the halogenating agent used may be 1 to 20 times molar equivalent, preferably 1.5 to 15 times molar equivalent, more preferably 2 to 10 times molar equivalent to the number of dithiocarbamate groups in the hyperbranched polymer. That's fine.
  • the reaction for substituting the dithiocarbamate group at the molecular end with a halogen atom is preferably carried out in water or an organic solvent.
  • the solvent used is preferably a solvent capable of dissolving the hyperbranched polymer having a dithiocarbamate group and the halogenating agent.
  • the solvent is the same as the solvent used when producing the hyperbranched polymer having a dithiocarbamate group because the reaction operation is simplified.
  • the halogenation method is preferably a reaction carried out by heating and refluxing using a halogenating agent such as bromine in an organic solvent solution.
  • a halogenating agent such as bromine in an organic solvent solution.
  • Any organic solvent may be used as long as it does not significantly inhibit the progress of this reaction, such as an organic acid compound such as acetic acid, an aromatic hydrocarbon compound such as benzene, toluene, xylene, ethylbenzene, 1,2-dichlorobenzene, tetrahydrofuran, Used ether compounds such as diethyl ether, ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic hydrocarbon compounds such as chloroform, dichloromethane, 1,2-dichloroethane, n-heptane, n-hexane, cyclohexane, etc.
  • the mass of the hyperbranched polymer having a dithiocarbamate group at the molecular end is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably 10 to It is preferable to use 50 times mass organic solvent.
  • the reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C.
  • the reaction time is preferably 0.1 to 10 hours and the reaction temperature is 20 to 150 ° C.
  • an aqueous solution of a reducing agent such as sodium thiosulfate and sodium sulfite, or sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.
  • a reducing agent such as sodium thiosulfate and sodium sulfite
  • sodium hydroxide potassium hydroxide
  • calcium hydroxide etc.
  • An alkaline aqueous solution can be used.
  • the amount used may be 0.1 to 50 equivalents, preferably 0.5 to 10 equivalents, more preferably 1 to 3 equivalents, relative to the halogenating agent used.
  • the hyperbranched polymer having a halogen atom at the molecular end of the present invention obtained by the reaction as described above can be separated from the solvent from the reaction solution by solvent distillation or solid-liquid separation. Moreover, the hyperbranched polymer which has a halogen atom in the molecular terminal of this invention can be precipitated by adding a reaction solution in a poor solvent, and it can also collect
  • a part of the molecular end may remain as a dithiocarbamate group, but preferably most of them are substituted with halogen atoms. preferable.
  • Rf represents the same as defined in the formula [1].
  • Z represents a hydroxy group, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom.
  • the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and n-pentoxy group. , Isopentoxy group, neopentoxy group, tert-pentoxy group and the like.
  • the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
  • the base used for conversion of the dithiocarbamate group to a thiol anion includes alkali metal inorganic acid salt, alkali metal hydroxide, alkali metal hydride, alkali metal alkoxide, aliphatic amine, alicyclic An amine, an aromatic amine, etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
  • alkali metal inorganic acid salt examples include sodium carbonate, potassium carbonate, cesium carbonate, sodium phosphate, and potassium phosphate.
  • alkali metal hydroxide examples include sodium hydroxide and potassium hydroxide.
  • alkali metal hydride examples include lithium hydride, sodium hydride, potassium hydride and the like.
  • Alkali metal alkoxides include lithium methoxide, lithium ethoxide, lithium butoxide, lithium tert-butoxide, sodium methoxide, sodium ethoxide, sodium butoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium butoxide, potassium Examples thereof include tert-butoxide.
  • aliphatic amine examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, triisopropylamine, triisobutylamine and the like.
  • alicyclic amine examples include 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5-diazabicyclo [4.3.0] nonene.
  • Aromatic amines include pyridine, 5-ethyl-2-methylpyridine, 2-phenylpyridine and the like.
  • alkali metal inorganic acid salts alkali metal hydroxides or alkali metal alkoxides are preferable from the viewpoint of high conversion ratio of dithiocarbamate groups to thiol anions, and it is particularly preferable that the base is selected from alkali metal alkoxides.
  • the alkali metal alkoxides those using potassium as the alkali metal, particularly potassium methoxide, potassium ethoxide, and potassium tert-butoxide are more preferable.
  • the amount of the base used is not particularly limited, but it is usually 1 to 10 molar equivalents, preferably 1 to 5 molar equivalents, most preferably 1 to 3 molar equivalents relative to the dithiocarbamate group.
  • a part of the dithiocarbamate group-containing compound is converted to thiol, and in particular, when the dithiocarbamate-containing compound is a polymer compound, a plurality or many dithiocarbamate groups are present in the molecule. Will be partly converted.
  • step (D) When used in an amount larger than the above numerical range, the conversion of the dithiocarbamate group into thiol itself is not affected, but the carboxylic acid derivative (required) that the unreacted base is introduced in the subsequent step (step (D)).
  • the economy becomes worse, for example, it reacts with the electronic agent).
  • solvent Both the conversion step of a dithiocarbamate group into a thiol and the reaction step with a carboxylic acid derivative described later are performed in a solvent.
  • the solvent used in this step is not particularly limited, and among various solvents used for general organic synthesis, those that do not affect the above step can be appropriately selected and used.
  • amide compounds such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMAc); nitrile compounds such as acetonitrile, propionitrile and butyronitrile; methyl acetate, ethyl acetate, butyl acetate, Ester compounds such as methyl propionate; ketone compounds such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone; aliphatic hydrocarbon compounds such as pentane, hexane, cyclohexane, octane, decane, decalin, petroleum ether; benzene, Aromatic hydrocarbon compounds such as toluene and xylene; diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran (THF), 1,
  • the above solvents it is most preferable to use at least one solvent selected from a nitrile compound or an ether compound, particularly THF, dioxane, acetonitrile, particularly THF, from the viewpoint of high solubility of the dithiocarbamate group-containing compound.
  • a mixed solvent of THF and acetonitrile the mixing ratio of acetonitrile when THF is 1 is preferably 0.5 or less.
  • This step can be carried out at any temperature below the boiling point of the solvent, and is preferably carried out at 40 to 70 ° C., more preferably 50 to 60 ° C. from the viewpoint of obtaining the desired product in a high yield in a short time. Is done. Even if it exceeds the said temperature range, if it is the temperature below a boiling point, it can implement, but since the reaction process with the below-mentioned electrophile becomes disadvantageous at high temperature and cooling operation is needed, it is not economical.
  • reaction time The reaction time of the dithiocarbamate group-containing compound and the base varies depending on the type of dithiocarbamate group-containing compound, the type of base, the type of solvent used, the reaction temperature to be applied, etc., but is usually about 1 to 24 hours. .
  • step (D) it is necessary to sufficiently remove oxygen in the reaction system before the start of the reaction, and the system may be replaced with an inert gas such as nitrogen or argon.
  • the solvent can be separated and collected in the form of a thiol salt by a known method such as distillation, filtration, reprecipitation, etc., but the obtained reaction solution can be used as it is in step (D). it can.
  • solvent used in this step the same solvent as used in the above-mentioned step (C) can be used. This step is preferably carried out at a reaction temperature of room temperature (approximately 25 ° C.) to 60 ° C. Accordingly, when the steps (C) and (D) are continuously performed, it is preferable to perform the steps at a temperature of 50 to 60 ° C.
  • reaction time of the thiol anion (containing compound) and the carboxylic acid derivative varies depending on the type of thiol anion (containing compound), the type of electrophile, the type of solvent used, the reaction temperature to be applied, etc. Usually about 1 to 24 hours.
  • the crude product can be separated by a known method such as evaporation of the solvent, filtration, reprecipitation, etc., and the crude product is distilled, silica gel column chromatography, recrystallization, etc. And can be purified.
  • a fluorine-containing hyperbranched polymer is dissolved or dispersed in a solvent to form a varnish (film forming material). It is applied on the material by cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, ink jet method, printing method (letter plate, intaglio plate, planographic plate, screen printing, etc.) Thereafter, the film is dried by a hot plate or an oven to form a film.
  • the spin coating method is preferable. In the case of using the spin coating method, since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.
  • the solvent used in the form of the varnish may be any solvent that dissolves the fluorine-containing hyperbranched polymer, such as benzene, toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether.
  • PGME propylene glycol monomethyl ether
  • PMEA diisopropyl ether
  • IPE diisopropyl ether
  • cPME cyclopentyl methyl ether
  • THF tetrahydrofuran
  • MEK ethyl methyl ketone
  • MIBK isobutyl methyl ketone
  • CHN cyclohexanone
  • Ethyl acetate dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), chloroform, 1,2-dichloroethane (EDC), o Todichlorobenzene (ODB), N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), trichloromethane, propylene glycol monoethyl ether, ethyl lactate, diethylene glycol monoethyl ether, butyl cellosolve, ⁇ -butyrolactone, etc.
  • DMSO dimethyl sul
  • the concentration in which the solvent is dissolved or dispersed is arbitrary, but the concentration of the fluorine-containing hyperbranched polymer is 0.001 to 90% by mass with respect to the total mass (total mass) of the fluorine-containing hyperbranched polymer and the solvent.
  • the content is preferably 0.002 to 80% by mass, more preferably 0.005 to 70% by mass.
  • the thickness of the thin film formed of the fluorine-containing hyperbranched polymer is not particularly limited, but is usually 0.01 ⁇ m to 50 ⁇ m, preferably 0.05 ⁇ m to 20 ⁇ m.
  • the present invention also relates to a resin composition containing (a) the fluorine-containing hyperbranched polymer, (b) a thermoplastic resin or a thermosetting resin.
  • the thermoplastic resin is not particularly limited.
  • a polyolefin resin such as PE (polyethylene), PP (polypropylene), EVA (ethylene-vinyl acetate copolymer), EEA (ethylene-ethyl acrylate copolymer);
  • Polystyrene resins such as PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile-styrene copolymer), ABS (acrylonitrile-butadiene-styrene copolymer), MS (methyl methacrylate-styrene copolymer)
  • Polycarbonate resin polyamide resin; polyimide resin; (meth) acrylic resin such as PMMA (polymethyl methacrylate); PET (polyethylene terephthalate), polybutylene terephthalate, polyethylene naphthalate Polybutylene naphthalate, PLA (polylactic acid), poly-3-hydroxybutyric acid, polycaprolactone
  • polymethyl methacrylate resin or polylactic acid resin is preferable.
  • thermosetting resin For example, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin etc. are mentioned.
  • the blending amount of (a) the fluorine-containing hyperbranched polymer with respect to (b) the thermoplastic resin or the thermosetting resin is preferably 0.01% by mass to 20% by mass, and particularly 0.1% by mass. % To 20% by mass is preferable.
  • additives generally added together with a thermoplastic resin or a thermosetting resin, for example, an antistatic agent, a lubricant, a heat stabilizer, an antioxidant, a light stabilizer, a fluorescent agent, a processing aid, You may use together a crosslinking agent, a dispersing agent, a foaming agent, a flame retardant, an antifoamer, a reinforcing agent, a pigment, etc.
  • the resin composition of the present invention can obtain a resin molded product such as a film, a sheet, or a molded product by any molding method such as injection molding, extrusion molding, press molding, blow molding and the like.
  • the present invention also relates to a polymerizable composition containing (a) the fluorine-containing hyperbranched polymer, (c) a polymerizable compound, and (d) a polymerization initiator.
  • the polymerizable compound (c) is not particularly limited as long as it is a compound having one or more, preferably one to six, polymerizable sites that are polymerized by the action of a polymerization initiator.
  • the meaning of the polymerizable compound in the present invention is a compound that is not a so-called polymer substance, and not only a monomer compound (monomer) in a narrow sense but also a dimer, trimer, oligomer, and reactive polymer. Is also included.
  • examples of the polymerizable moiety include an ethylenically unsaturated bond that is a radical polymerizable moiety, or a vinyl ether structure, a vinyl thioether structure that is a cationic polymerizable moiety, and a cyclic ether structure such as an epoxy ring or an oxetane ring.
  • examples of the polymerizable compound include a compound having an ethylenically unsaturated bond which is a radically polymerizable site, or a compound having a vinyl ether structure, an epoxy ring or an oxetane ring which is a cationically polymerizable site.
  • a polyfunctional (meth) acrylate compound having two or more (meth) acrylic groups having an ethylenically unsaturated bond site is preferable.
  • examples of such polymerizable compounds include the following (meth) acrylic acid esters and vinyl compounds having a polyalkylene glycol chain.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (meth) acrylic acid refers to acrylic acid and methacrylic acid.
  • -Vinyl compounds having a polyalkylene glycol chain Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, and the like.
  • tricyclo [5.2.1.0 2,6 ] decanedimethanol di (meth) acrylate ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dioxane glycol di (meth) acrylate, 9,9-bis [4- (2- (Meth) acryloyloxyethoxy) phenyl] fluorene, ethoxylated bisphenol A (meth) acrylate, and the like are preferable, and tricyclo [5.2.1.0 2,6 ] decanedimethanol di (meth) acrylate is particularly preferable.
  • polymerization initiator known ones can be used.
  • benzoins for example, benzophenones; benzyl ketals; ⁇ -hydroxy ketones; ⁇ -amino ketones; acyl phosphine oxides; Class; iodonium salt; or sulfonium salt.
  • Such a polymerization initiator can also be used in combination of multiple types.
  • the blending amounts of (a) a fluorine-containing hyperbranched polymer, (c) a polymerizable compound, and (d) a polymerization initiator are as follows. That is, (a) the fluorine-containing hyperbranched polymer is preferably 0.01% by mass to 20% by mass, and particularly preferably 0.1% by mass to 20% by mass with respect to (c) the polymerizable compound. . Further, (d) the polymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to (c) the polymerizable compound. Within the above range, the polymerizable compound (c) can be polymerized without lowering the transmittance.
  • Additives generally added as necessary to the polymerizable composition for example, sensitizers, polymerization inhibitors, polymerization initiators, leveling agents, surfactants, as long as the effects of the present invention are not impaired.
  • Adhesion imparting agents, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, dyes and the like may be appropriately blended.
  • the polymerizable composition of the present invention can form a molded product such as a cured film or a laminate by being coated on a substrate and polymerized (cured).
  • the substrate include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate, and the like.
  • the shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
  • various coating methods described above in ⁇ Method for producing varnish and thin film> can be used.
  • the polymerizable composition is filtered in advance using a filter having a pore diameter of about 0.2 ⁇ m in advance and then used for coating. After coating, it is preferably followed by preliminary drying with a hot plate or oven, followed by photocuring by irradiating with actinic rays such as ultraviolet rays.
  • actinic rays include ultraviolet rays, electron beams, and X-rays.
  • a light source used for ultraviolet irradiation sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like can be used.
  • the thickness of the film formed by coating is usually 0.01 ⁇ m to 50 ⁇ m, preferably 0.05 ⁇ m to 20 ⁇ m after drying and curing.
  • HPS Hyperbranched polystyrene [Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd.]
  • THF Tetrahydrofuran IPA: Isopropanol NMP: N-methyl-2-pyrrolidone
  • DMSO Dimethyl sulfoxide
  • PGME Propylene glycol monomethyl ether
  • PGMEA Propylene glycol monomethyl ether acetate
  • IPE Diisopropyl ether cPME: Cyclopentyl methyl ether
  • CHN Cyclohexanone
  • DMAc N, N- Dimethylacetamide
  • DMF N, N-dimethylformamide
  • EDC 1,2-dichloroethane
  • perfluorobutyryl chloride manufactured by Tokyo Chemical Industry Co., Ltd. 0.35 g (1.5 mmol, 30 mol% with respect to HPS) was added to 15 mL of a THF / acetonitrile (volume ratio 4: 1) mixed solution. The dissolved solution was dropped with a syringe and further stirred at 60 ° C. for 6 hours. Next, this reaction solution was added to 300 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered under reduced pressure and dried under reduced pressure to obtain 1.3 g of the desired product (HPS-SC3F-1) as a white solid (yield 92%).
  • a 1 H NMR spectrum of the obtained target product is shown in FIG.
  • the introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 8%.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 35,000, and dispersion degree: Mw (weight average molecular weight) / Mn (number average molecular weight) was 4.2.
  • Example 2 Synthesis of HPS-SC3F-2 Except that the amount of potassium methoxide used was changed to 0.15 g (2 mmol) and the amount of perfluorobutyryl chloride was changed to 0.70 g (3 mmol), respectively. The same operation as in Example 1 was performed to obtain 1.3 g of the target product (HPS-SC3F-2) as a white solid (yield 90%).
  • the 1 H NMR spectrum of the obtained target product is also shown in FIG.
  • the introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 28%.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 46,000, and dispersion degree: Mw / Mn was 5.2.
  • Example 3 Synthesis of HPS-SC3F-3 Except that the amount of potassium methoxide used was changed to 0.22 g (3 mmol) and the amount of perfluorobutyryl chloride was changed to 1.1 g (4.5 mmol). In the same manner as in Example 1, 1.4 g of the white solid target product (HPS-SC3F-3) was obtained (yield: 90%). The 1 H NMR spectrum of the obtained target product is also shown in FIG. The introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 41%. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of the target object was 63,000, and dispersion degree: Mw / Mn was 5.5.
  • Example 4 Synthesis of HPS-SC3F-4 Except that the amount of potassium methoxide used was changed to 0.29 g (4 mmol) and the amount of perfluorobutyryl chloride was changed to 1.4 g (6 mmol), respectively. The same operation as in Example 1 was carried out to obtain 1.3 g of the desired product (HPS-SC3F-4) as a white solid (yield 85%).
  • the 1 H NMR spectrum of the obtained target product is also shown in FIG.
  • the introduction rate of the fluoroalkyl group calculated from the NMR spectrum was 50%.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of a target object was 74,000, and dispersion degree: Mw / Mn was 5.3.
  • Example 5 to 8 Preparation and evaluation of HPS-SC3F thin films 0.1 g of each hyperbranched polymer obtained in Examples 1 to 4 was dissolved in 10 g of NMP to prepare varnishes. The obtained varnishes were each spin-coated (1,000 rpm ⁇ 30 seconds) on a glass substrate and dried by heating on a 130 ° C. hot plate for 30 minutes to form a film. About each obtained thin film, the HAZE value, the refractive index in wavelength 633nm, and the film thickness were measured. The results are also shown in Table 2.
  • Example 9 Synthesis of HPS-OC1F
  • 0.43 g (10.8 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] was charged, and the atmosphere in the flask was replaced with nitrogen. Hexane was added thereto, and the mixture was stirred and allowed to stand, and the sodium hydride was washed by removing the supernatant by decantation.
  • this reaction solution was added to 60 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer.
  • the precipitated polymer was filtered through a membrane filter and dried under reduced pressure to obtain 1.1 g of the desired product (HPS-OC1F) (yield 71%).
  • the 1 H NMR spectrum of the obtained target product is shown in FIG.
  • the target product had a Tg (glass transition temperature) of 91.0 ° C. and a Td 5% (5% weight loss temperature) of 194.0 ° C.
  • the solubility to the GPC solvent of the obtained target object was low, and the molecular weight measurement by GPC was not able to be performed.
  • the obtained solid was dried under reduced pressure to obtain 1.9 g of the desired product (HPS-OC4H) (yield: 55%).
  • the 1 H NMR spectrum of the obtained target product is shown in FIG.
  • the obtained target product had a Tg of 92.0 ° C., a Td 5% of 279.5 ° C., a weight average molecular weight Mw measured in terms of polystyrene by GPC of 29,000, and a degree of dispersion: Mw / Mn of 2. It was 5.
  • Example 11 Synthesis of HPS-OC6F To a 300 mL two-necked reaction flask, 0.30 g (7.5 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] was charged, and the atmosphere in the flask was replaced with nitrogen. Hexane was added thereto, and the mixture was stirred and allowed to stand, and the sodium hydride was washed by removing the supernatant by decantation.
  • 60% sodium hydride manufactured by Kanto Chemical Co., Ltd.
  • Example 12 Synthesis of HPS-OC6H To a 300 mL two-necked reaction flask, 0.30 g (7.5 mmol) of 60% sodium hydride [manufactured by Kanto Chemical Co., Ltd.] was charged, and the atmosphere in the flask was replaced with nitrogen. Hexane was added thereto, and the mixture was stirred and allowed to stand, and the sodium hydride was washed by removing the supernatant by decantation.
  • 60% sodium hydride manufactured by Kanto Chemical Co., Ltd.
  • the reaction solution was stirred at room temperature (approximately 25 ° C.) for 30 minutes, and further stirred at 50 ° C. for 15 hours. Next, this reaction solution was added to 60 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered through a membrane filter and dried under reduced pressure to obtain 1.2 g of the desired product (HPS-OC6F) (yield 85%).
  • the 1 H NMR spectrum of the obtained target product is shown in FIG.
  • the target product had a Tg of 96.7 ° C. and a Td 5% of 257.8 ° C.
  • the solubility to the GPC solvent of the obtained target object was low, and the molecular weight measurement by GPC was not able to be performed.
  • the reaction solution was stirred at room temperature (approximately 25 ° C.) for 30 minutes, and further stirred at 50 ° C. for 4 hours. Next, this reaction solution was added to 60 mL of IPA / water (volume ratio 4: 1) to precipitate the polymer. The precipitated polymer was filtered through a membrane filter and dried under reduced pressure to obtain 1.8 g of the desired product (HPS-OC7F) (yield: 66%).
  • the 1 H NMR spectrum of the obtained target product is shown in FIG.
  • the target product had a Tg of 97.0 ° C. and a Td 5% of 258.0 ° C.
  • the solubility to the GPC solvent of the obtained target object was low, and the molecular weight measurement by GPC was not able to be performed.
  • Examples 14 to 18 Production and Evaluation of Hyperbranched Polymer Thin Films
  • Each hyperbranched polymer obtained in Examples 9 to 13 was dissolved in perfluorobenzene [manufactured by Tokyo Chemical Industry Co., Ltd.].
  • a 10% by weight varnish was prepared.
  • the obtained varnishes were each spin-coated (500 rpm ⁇ 20 seconds) on a glass substrate and dried by heating on a hot plate at 100 ° C. for 30 minutes to form a film.
  • the refractive index in wavelength 589nm, a film thickness, and the contact angle of water and diiodomethane were measured.
  • the surface free energy of each thin film was computed from the contact angle of the obtained water and diiodomethane.
  • Table 5 the contact angle measured the contact angle 10 seconds after dripping a measuring liquid on each thin film surface.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention a pour but de proposer un nouveau composé qui peut garder une transparence satisfaisante, qui a une solubilité élevée dans les solvants organiques et d'excellentes propriétés de mélange/dispersion dans des résines de matrice, qui ne forme pas d'agrégats dans des résines de matrice et qui permet la fabrication d'un film mince ou d'un article moulé ayant d'excellentes propriétés de modification de surface et une transparence élevée. À cet effet, l'invention propose un polymère hyper-ramifié fluoré spécifique ayant une masse moléculaire moyenne en poids de 1000 à 500000 en termes de teneur en polystyrène telle que mesurée par chromatographie par perméation de gel ; et un film mince comprenant un polymère hyper-ramifié fluoré. (Dans la formule [1], R1 représente un atome d'hydrogène ou un groupe méthyle ; A1 représente une structure représentée par la formule [2] ou la formule [3] ; L représente -SC(=O)- ou -O- ; les Rf peuvent être identiques ou différents les uns des autres et représentent indépendamment un groupe fluoroalkyle ayant de 2 à 12 atomes de carbone ; et n est le nombre de structures de motifs répétitifs et représente un entier de 2 à 3000) (Dans les formules [2] et [3], A2 représente un groupe alkylène linéaire, ramifié ou cyclique, qui peut contenir une liaison éther ou une liaison ester ; et Y1-Y4 représentent indépendamment un atome d'hydrogène, un groupe alkyle, un groupe alcoxy, un groupe nitro, un groupe hydroxy, un groupe amino, un groupe carboxyle ou un groupe cyano).
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CN112608419A (zh) * 2020-12-16 2021-04-06 济南大学 一种超支化型含氟脱模剂及其应用
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CN112608419B (zh) * 2020-12-16 2022-12-06 济南大学 一种超支化型含氟脱模剂及其应用
CN118684840A (zh) * 2024-08-22 2024-09-24 余姚市远东化工有限公司 一种易分离橡胶脱模剂及其制备方法

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