CN107109012A - Curable partially fluorinated polymer composition - Google Patents

Curable partially fluorinated polymer composition Download PDF

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Publication number
CN107109012A
CN107109012A CN201580069383.0A CN201580069383A CN107109012A CN 107109012 A CN107109012 A CN 107109012A CN 201580069383 A CN201580069383 A CN 201580069383A CN 107109012 A CN107109012 A CN 107109012A
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partially fluorinated
polymer composition
curable
fluorinated polymer
amorphous fluoropolymer
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沃纳·M·A·格鲁泰尔特
米格尔·A·格拉
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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    • C08L27/00—Compositions of 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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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    • C08J2327/00—Characterised by the use of 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 a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08J2327/02—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • C08J2327/00—Characterised by the use of 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 a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract

This document describes a kind of curable partially fluorinated polymer composition and preparation method thereof.The composition is included：(i) partially fluorinated amorphous fluoropolymer, wherein described partially fluorinated amorphous fluoropolymer is comprising carbon-carbon double bond or can form carbon-carbon double bond along the partially fluorinated amorphous fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer is substantially free of bromine, iodine and nitrile；And (ii) includes the curing agent of the terminal olefin with least one olefinic hydrogen.

Description

Curable partially fluorinated polymer composition
Technical field
The invention discloses the composition comprising partially fluorinated amorphous fluoropolymer is solidified together with curing agent, The amorphous fluoropolymer of which part fluorination is substantially free of bromine, iodine and nitrile cure site, and curing agent, which is included, to be had at least The terminal olefin of one olefinic hydrogen.
The content of the invention
Expect to determine a kind of New Curing System for partially fluorinated amorphous fluoropolymer.
In one aspect, a kind of curable partially fluorinated polymer is disclosed, it is included：
(i) partially fluorinated amorphous fluoropolymer, the amorphous fluoropolymer of which part fluorination includes carbon-to-carbon Double bond can be along the partially fluorinated amorphous fluoropolymer formation carbon-to-carbon double bond, amorphous the containing of which part fluorination Fluoropolymer is substantially free of bromine, iodine and nitrile；And
(ii) curing agent of the terminal olefin with least one olefinic hydrogen is included.
On the other hand, a kind of product for including above-mentioned solidification composition filling is disclosed.
It yet still another aspect, disclosing a kind of method for preparing partially fluorinated elastomer, this method includes solidification institute above Disclosed curable partially fluorinated polymer composition.
The above content of the invention is not intended to describe each embodiment.The details of one or more embodiments of the present invention Also provide in the following description.According to present specification and claims, further feature, target and advantage will be aobvious and easy See.
Embodiment
As used herein, term
" one ", " one kind " and " described " are used interchangeably and meant one or more；And
"and/or" is used to represent that the situation illustrated by one or two may occur, for example, A and/or B includes (A and B) (A or B)；
" main chain " refers to the main continuous chain of polymer；
" crosslinking " refers to connect two preformed polymer chains using chemical bond or chemical group；
" cure site " refers to the functional group that may participate in crosslinking；And
" interpolymerized " refers to that monomer condenses together to form main polymer chain；And
" polymer " refers to be made up of a large amount of (for example, hundreds of or more) interpolymerized monomeric units and with HMW The macromolecular of (for example, more than 10,000,20,000,50,000 or even 100,000 gram/mol).
Also as described herein, the scope stated by end points includes all numerical value included in the range of this (for example, 1 to 10 Including 1.4,1.9,2.33,5.75,9.98 etc.).
Also as described herein, statement " at least one " include one and more than one it is all numeral (for example, at least 2, at least 4th, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100 etc.).
In the disclosure, it has been found that can will be partially fluorinated amorphous fluorine-containing poly- substantially free of bromine, iodine and nitrile group Compound solidifies together with the compound comprising the terminal olefin with least one olefinic hydrogen.
Fluoropolymer
The amorphous fluoropolymer of the disclosure is partially fluorinated polymer.As disclosed herein, unbodied part The polymer of fluorination is the polymer comprising at least one C-H bond and at least one carbon-fluorine bond on the main chain of polymer.One In individual embodiment, unbodied partially fluorinated polymer be it is highly fluorinated, wherein main polymer chain at least 60%, 70%th, 80% or even 90% C-F keys are included.
The amorphous fluoropolymer of the disclosure also includes carbon-carbon double bond, and/or can be double along polymer chain formation carbon carbon Key.In one embodiment, partially fluorinated amorphous fluoropolymer is along partially fluorinated amorphous fluoropolymer Main chain includes carbon-carbon double bond, or can form carbon-carbon double bond along the main chain of partially fluorinated amorphous fluoropolymer.Another In one embodiment, partially fluorinated amorphous fluoropolymer includes carbon-carbon double bond, or can be in partially fluorinated nothing Carbon-carbon double bond is formed in side base outside the main chain of amorphous fluoropolymer.
Fluoropolymer, which can form carbon-carbon double bond, means fluoropolymer comprising can form the unit of double bond.It is such Unit is included for example along main polymer chain or two adjacent carbonses of side chain, and wherein hydrogen is connected to first carbon and leaving group connects It is connected to second carbon.During elimination reaction (for example, thermal response and/or use acid or alkali), leaving group and hydrogen are left away, two Double bond is formed between individual carbon atom.Illustrative leaving groups include：Fluorine ion, alkoxide, hydroxyl, toluenesulfonic acid base, methanesulfonic acid Ester group, amine, ammonium, sulphur, sulfonium, sulfoxide, sulfone and combinations thereof.
Amorphous fluoropolymer includes these multiple groups (carbon-carbon double bond or group that can form double bond) to cause It is fully cured.Generally, it means that at least 0.1 mole %, 0.5 mole of %, 1 mole of %, 2 moles of % or even 5 moles %, most Many 7 moles of %, 10 moles of %, 15 moles of % or even 20 moles % (that is, in per moles of polymer these carbon-carbon double bonds or its before Mole of body).
In one embodiment, unbodied partially fluorinated polymer is derived from least one hydrogeneous monomer, such as Vinylidene fluoride.
In one embodiment, amorphous fluoropolymer includes vinylidene fluoride (VDF) and hexafluoropropene (HFP) Adjacent copolymerization units；VDF (or tetrafluoroethene) and the fluorinated comonomers that acid hydrogen atom can be delivered to main polymer chain (such as trifluoro-ethylene, PVF, 3,3,3- trifluoro propenes -1, pentafluoropropene are (for example, 2- hydrogen pentafluoropropene and the fluorine third of 1- hydrogen five Alkene), 2,3,3,3- tetrafluoropropenes and combinations thereof) copolymerization units.
In some embodiments, it can add a small amount of (for example, less than 10 weight %, 5 weight %, 2 weight % or even 1 Weight %) other monomer, as long as amorphous fluoropolymer can use curing agent disclosed herein to solidify.
In one embodiment, amorphous fluoropolymer is derived from hydrogeneous monomer in addition, including：Pentafluoropropene (example Such as, 2- hydrogen pentafluoropropene), propylene, ethene, isobutene and combinations thereof.
In one embodiment, amorphous fluoropolymer is derived from perfluorinated monomer in addition.Exemplary perfluorinate list Body includes：Hexafluoropropene；Tetrafluoroethene；CTFE；Perfluor (alkyl vinyl ether) such as perfluoro methyl vinyl ether, CF2=CFOCFCF2CF2OCF3、CF2=CFOCF2OCF2CF2CF3、CF2=CFOCF2OCF2CF3、CF2=CFOCF2OCF3And CF2 =CFOCF2OC3F7；Perfluor (polyoxyethylene base ether) such as perfluoro-methyl allyl ether；Perfluor (alkoxy allyl ether) is such as Perfluor -4,8- dioxa -1- nonenes (that is, CF2=CFCF2OCF2)3OCF3) and combinations thereof.
The exemplary types of polymer include those for including the interpolymerized unit derived from following item：(i) vinylidene fluoride, Tetrafluoroethene and propylene；(ii) vinylidene fluoride, tetrafluoroethene, ethene and perfluoroalkyl vinyl ether (such as perfluor (methyl second Alkene ether))；(iii) vinylidene fluoride and hexafluoropropene；(iv) hexafluoropropene, tetrafluoroethene and vinylidene fluoride；(v) hexafluoro Propylene and vinylidene fluoride；(vi) vinylidene fluoride and perfluoroalkyl vinyl ether；(vii) vinylidene fluoride, tetrafluoroethene and Perfluoroalkyl vinyl ether；(viii) vinylidene fluoride, perfluoroalkyl vinyl ether, the PVF of hydrogen five and optionally tetrafluoro second Alkene；(ix) tetrafluoroethene, propylene and 3,3,3- trifluoro propenes；(x) tetrafluoroethene and propylene；(xi) ethene, tetrafluoroethene and complete Vinyl ethers and optionally 3,3,3- trifluoro propenes；(xii) vinylidene fluoride, tetrafluoroethene and perfluoroalkyl allyl Base ether；(xiii) vinylidene fluoride and perfluoroalkyl allyl ether；(xiv) ethene, tetrafluoroethene and perfluoroalkyl vinyl ether And optionally 3,3,3- trifluoro propenes；(xv) vinylidene fluoride, tetrafluoroethene and perfluoroalkyl allyl ether；(xvi) inclined two PVF and perfluoroalkyl allyl ether；(xvii) vinylidene fluoride, tetrafluoroethene and perfluoro alkoxy allyl ether； (xviii) vinylidene fluoride and perfluoro alkoxy allyl ether；(xiv) vinylidene fluoride, tetrafluoroethene and perfluoro alkoxy alkene Propyl ether；(xv) vinylidene fluoride and perfluoro alkoxy allyl ether；And (xvi) combinations thereof.
Advantageously, by using curing agent disclosed herein, the amorphous fluoropolymer of the disclosure can not needed Along main polymer chain side base bromine, iodine or nitrile cure site in the case of solidified.Generally, among other things, it polymerize What it is into fluoropolymer and/or chain end may be expensive containing iodine and brominated cure site monomer.
The amorphous fluoropolymer of the disclosure is substantially free of iodine, bromine and nitrile group, wherein relative to total polymer, nothing Amorphous fluoropolymer includes iodine, the bromine less than 0.1 mole of %, 0.05 mole of %, 0.01 mole of % or even 0.005 mole % And nitrile group.
In one embodiment, the amorphous fluoropolymer of the disclosure is non-grafted polymers, that is to say, that it is not Containing including vinyl, pi-allyl, acrylate-based, acylamino-, sulfonate, pyridine, carboxylate, carboxylate, steric hindrance type silane (fat Race or the ether of aromatics three or three esters) including side base.In one embodiment, amorphous fluoropolymer connects not comprising monohydric phenol Branch.
Curing agent
The curing agent of the disclosure is the compound for including at least one terminal olefin with least one olefinic hydrogen.Change sentence Words say that curing agent includes end carbon-to-carbon double bond, and at least one carbon of the end carbon-to-carbon double bond includes at least one hydrogen.
In one embodiment, the curing agent of the disclosure is represented by Formulas I：
CX1X2=CX3-R (I)
Wherein X1、X2And X3Independently selected from H, Cl and F, and X1、X2And X3At least one of be H；R is univalent perssad.
R is the univalent perssad for including 1 to 20 carbon atom, can be straight chain, side chain or ring-type.R can be aromatics, aliphatic series, Or include both aromatic fractions and aliphatic part.R can for nonfluorinated (do not include fluorine atom), partially fluorinated (comprising at least One c h bond and at least one C-F key) or it is fluoridized (not including c h bond, include at least one C-F key).
In one embodiment, R includes hetero atom, such as O, S or N (for example, ehter bond) at least one chain.At one In embodiment, R includes the end group selected from following item：Alcohol (- OH), amine (- NH2,-NHR and-NRR ', wherein R and R ' be organic Group), mercaptan (- SH), carboxylic acid (- COOH), alkene.
Exemplary R group includes：- O-R '-O-CX=CX2；-CX2- O-R '-O-CX=CX2；-CX2-O-R’-O-CX2CX= CX2；-R’-OH；Wherein R ' is partially fluorinated or non fluorinated divalent group, and X is independently selected from H, Cl and F.R ' includes alkylene Base, ring alkylidene, arlydene or combinations thereof (for example, alkyl arylene), comprising at least 1,2,4 or even 6 carbon atoms, extremely Many 30,25,20 or even 15 carbon atoms.
Curing agent is non-polymeric small molecule, and molecular weight is less than 2000,1500,1000,500,250 or even 175g/ mol。
In one embodiment, curing agent is selected from least one of divinyl and diallyl compound.Change sentence Words say, the compound comprising at least two ethylene moieties or at least two allyl parts.In one embodiment, curing agent bag Containing ethylene moiety and allyl part.
In one embodiment, curing agent includes the terminal olefin group of at least one nonfluorinated.In an embodiment party In case, curing agent includes non-aromatic terminal olefin and/or non-aromatic alcohol.In one embodiment, curing agent includes at least one Individual phenolic group group.
Exemplary solidification agent includes：
And combinations thereof, wherein n independently selected from 1 to 50,1 to 20,1 to 10 or even 2 to 10 integer, and Rf be fluorine Change alkyl group.Rf can be partially fluorinated or fully fluorinated.In one embodiment, Rf can be all comprising hetero atom in chain Such as O, S or N.Rf can be straight or branched, saturation or undersaturated.In one embodiment, Rf is C1 to C12 alkyl fluorides Base group (is optionally fluoridized).
The consumption of curing agent should substantially be enough to cause amorphous fluoropolymer to solidify, such as by without rotor vulcameter As moment of torsion increase is pointed on (moving die rheometer).For example, every 100 parts of amorphous fluoropolymers are used At least 1 mM, 1.5 mMs, 2 mMs, 2.5 mMs, 3 mMs or even 4 mMs or more of curing agent.Such as Very little, then amorphous fluoropolymer will not solidify fruit curing agent used.For example, every 100 parts of amorphous fluoropolymers are used Curing agent no more than 20 mMs, 15 mMs, 10 mMs or even 8 mMs.If curing agent used is too many, nothing Amorphous fluoropolymer may become frangible.
In one embodiment, curable partially fluorinated polymer composition is substantially free of monohydric phenol, meaning Mole relative to amorphous fluoropolymer, the composition comprising amorphous fluoropolymer include be less than 0.1 mole of %, 0.01 mole of % or even 0.001 mole % monohydric phenol.
Acid acceptor
In one embodiment, acid acceptor has been used in the disclosure, such acid acceptor includes Organic acceptors, inorganic Acid acceptor or its blend.The example of inorganic acceptors includes magnesia, lead oxide, calcium oxide, calcium hydroxide, two alkali formula phosphoric acid Lead, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate, hydrotalcite etc..Organic receptor include amine, epoxides, odium stearate and Magnesium oxalate.Specially suitable acid acceptor includes calcium hydroxide, magnesia and zinc oxide.It it is also possible to use the blend of acid acceptor.Acid The amount of acceptor will generally depend upon the property of acid acceptor used.
In one embodiment, every 100 parts of amorphous fluoropolymers are using at least 0.5 part, 1 part, 2 parts, 3 parts or very To 4 parts of acid acceptors.In one embodiment, every 100 parts of amorphous fluoropolymers are used no more than 10 parts, 7 parts or even 5 Part acid acceptor.
Compound
In one embodiment, it is organicCompound is added in composition in favor of amorphous as phase transfer catalyst The crosslinking of fluoropolymer, and/or double bond is formed on fluoropolymer available for by dehydrofluorination.It is such organic Compound includes quaternary ammonium hydroxide or its salt, quaternary phosphinesHydroxide or its salt and ternary sulfonium hydroxide or its salt.
, Phosphonium in briefWith ammonium salt or the compound central atom comprising phosphorus or nitrogen respectively, by carbon-phosphorus (or carbon- Nitrogen) covalent bond mode be covalently bound to four organic moieties and with anionic ion associate.Organic moiety may be the same or different.
In brief, sulfonium compound is organic compounds containing sulfur, and wherein at least one sulphur atom passes through carbon-sulphur covalent bond Mode, which is covalently bound to three, to be had the organic moiety of 1 to 20 carbon atom and is associated with anionic ion.Organic moiety can phase It is same or different.Sulfonium compound can have the sulphur atom of more than one relative nominal price, such as [(C6H5)2S+(CH2)4S+(C6H5)2]2Cl-, and two carbon sulphur covalent bonds can be between the carbon atom of divalent organic moieties, that is to say, that and sulphur atom can be ring-type knot Hetero atom in structure.
Be adapted to use in the disclosure it is organicCompound is known and is described in the art.Referring to example Such as, United States Patent (USP) 5,262,490 (Kolb et al.) and 4,912,171 (Grootaert et al.), this two patents are by reference It is incorporated herein.
It is exemplary organicCompound includes：C3-C6Symmetrical tetraalkylammonium salt；Asymmetric tetraalkylammonium salt, wherein alkyl carbon Summation between 8 and 24；And benzyltrialkylammonium salt, wherein the summation of alkyl carbon is in (the example between 7 and 19 Such as, TBAB, tetrabutylammonium chloride, benzyl tributyl ammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate With tetrabutylammonium, phenyl trimethicone ammonium chloride, four pentyl ammonium chloride, 4-propyl bromide, four hexyl ammonium chlorides and four Heptyl ammonium bromide tetramethyl ammonium chloride)；Quaternary phosphineSalt, such as 4-butyl-phosphoniumSalt, tetraphenylphosphonium chlorideZephiran chloride triphen Ji PhosphoniumChlorination San butyl Xi Bing Ji PhosphoniumChlorination tributyl Bian Ji PhosphoniumChlorination tributyl -2- Jia epoxide Bing Ji PhosphoniumChlorine Change benzyldiphenyl (dimethylamino) PhosphoniumRing [5.4.0] the 7- chlorinations endecatylene of 8- benzyl -1,8- diazonium two, zephiran chloride Three (dimethylamino) PhosphoniumWith double (benzyldiphenyl phosphine) imines chlorine.It is other suitable organicCompound includes 1,8- phenodiazines Miscellaneous carbon -7- the alkene of two ring [5.4.0] 11 and 1,5- diazabicylos [4.3.0] nonyl- 5- alkene.Phenates is quaternary ammonium salt He PhosphoniumSalt Preferred anionic.
In one embodiment, it is organicThe consumption of compound in 1 mM of every 100 parts of amorphous fluoropolymers and Between 5 mMs (mmhr).
Peroxide
In one embodiment, curable compositions include peroxide, for triggering solidification.Such peroxide bag Include organic peroxide.It is preferred in many instances that being connected to the tert-butyl peroxide of peroxy oxygen using tertiary carbon atom.
Exemplary peroxide includes：2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane；Dicumyl peroxide；Two (2- tert-butylperoxyiso-propyls) benzene；Dialkyl；Double (dialkyl peroxides)；(the tertiary fourths of 2,5- dimethyl -2,5- two Base peroxy) 3- hexins；Dibenzoyl peroxide；2,4- dichlorobenzoperoxides；T-butyl perbenzoate；α, α '-bis- (uncles Butyl peroxy base-diisopropylbenzene (DIPB))；Tert butylperoxyisopropyl carbonic ester, t-butylperoxy 2- ethylhexyl carbonates, uncle penta Base peroxy 2- ethylhexyl carbonates, tertiary hexyl peroxy butylperoxyisopropyl carbonate, two [1,3- dimethyl -3- (tert-butyl peroxies Base) butyl] carbonic ester, carbon peroxy acid, O, O'-1, double (1, the 1- dimethyl ethyl) esters of 3- propane diyls OO, OO'- and they Combination.
The usage amount of radical source generally will be every 100 parts of amorphous fluoropolymers at least 0.1 parts by weight, 0.2 weight Part, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight or even 1.5 parts by weight；Most 2 weight Part, 2.25 parts by weight, 2.5 parts by weight, 2.75 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 weight Part or even 5.5 parts by weight.
Typical auxiliary agent is the compound for including terminal unsaturation site, and auxiliary agent is mixed in polymer with profit during curing In solidification (being usually peroxide cure).Exemplary auxiliary agent includes：Isocyanuric acid three (methyl) allyl ester (TMAIC), isocyanide Uric acid triallyl (TAIC), cyanuric acid three (methyl) allyl ester, poly- triallyl isocyanurate (poly- TAIC), cyanuric acid triolefin Propyl ester (TAC), xyxylene-bis- (diallyl isocyanurate) (XBD), N, N'- meta-phenylene bismaleimides, adjacent benzene two Formic acid diallyl, three (diallylamine)-s-triazine, triallyl phosphite, 1,2- polybutadiene, ethylene glycol diacrylate Ester, diethylene glycol diacrylate and combinations thereof.Another available auxiliary agent can be by formula CH2=CH-Rf1- CH=CH2 Represent, wherein Rf1It can be the perfluorinated alkylidene with 1 to 8 carbon atom.By using curing agent disclosed herein, the disclosure Amorphous fluoropolymer can the solidification or can be solid in the case of using these auxiliary agents in the case of without using these auxiliary agents Change, without bromine, iodine or nitrile end group.In other words, curable compositions are substantially free of (less than 1 weight %, 0.5 weight Measure % or even 0.1 weight %, or even below can detected level) typical auxiliary agent.Due to auxiliary agent cost, with fluorinated polymer not Influence (for example, being oozed out from composition, mould fouling) compatible and to technique, this can be favourable.
Curable compositions can also comprising be commonly used for preparing elastic composition (such as pigment, filler (such as carbon black), Pore creating material and known in the art those) polytype additive.
Curable amorphous fluoropolymer composition can be prepared in the following manner：In conventional rubber tooling In, mixing amorphous fluoropolymer, curing agent together with other components (for example, acid acceptor,Compound, peroxide and/or Other additive) to provide solid mixture, the i.e. solid polymer containing other composition, it is also known as in this area and " matches somebody with somebody Mixed thing ".This blending constituent " is matched somebody with somebody with preparing the technique of such solid polymerization compositions comprising other compositions and being generally called It is mixed ".This kind equipment includes rubber mill, banbury (such as Banbury mixer) and mixing extruder.During mixing, mixture Temperature will not generally rise above about 120 DEG C.During mixing, by component and additive be distributed evenly in institute it is rewarding In fluorinated polymer " blend " or polymer sheet.Then, can be by " blend " extrusion or press-in die (e.g., cavity or biography Pass mould) in, and then by curing oven.In alternative embodiment, solidification can be carried out in autoclave.
Solidification is generally realized by being heated to curable amorphous fluoropolymer composition.Effective Temperature and it is heat-treated under effective time, to produce the fluoroelastomer of solidification.Can be by checking the fluorine-containing elasticity solidified The mechanical property and physical characteristic of body tests optimum condition.Generally, at a temperature of being solidificated in more than 120 DEG C or more than 150 DEG C Carry out.Typical condition of cure is included between 160 DEG C and 210 DEG C or at a temperature of between 160 DEG C and 190 DEG C Solidification.Typical cure cycle includes 3 minutes to 90 minutes.It is preferred that being solidified under stress.For example, 10 bars can be applied extremely The pressure of 100 bars.Cost cure cycle can be applied, to ensure that solidification process is fully finished.Can be between 170 DEG C and 250 DEG C At a temperature of carry out solidify afterwards, the cycle is 1 to 24 hour.
According to ASTM D1646-06TYPE A, (the purchase of MV2000 instruments is passed through using greater trochanter (ML 1+10) at 121 DEG C From the Alpha technology companys (Alpha Technologies, Ohio, USA) of Ohio, USA) measurement, curable compositions In partially fluorinated amorphous fluoropolymer there is certain Mooney viscosity.After solidification, using disclosed herein solid Agent, amorphous fluoropolymer becomes elastomer-forming, become immobilising fluoropolymer and with infinitely great viscosity (therefore not There is measurable Mooney viscosity).
In an embodiment of the disclosure, consolidating comprising curing agent disclosed herein and amorphous fluoropolymer Change system can show the chemical-resistant of the typical Peroxide cure systems containing iodine/bromine and auxiliary agent, while it is normal to improve these The bad heat resistance (the bad heat resistance comes from it without bromine or iodine) of the fluoroelastomer containing iodine or bromine is advised, therefore causes solidification Fluoropolymer there is enough heat resistance and chemical-resistant simultaneously.
The fluoroelastomer of solidification especially can be in motor vehicle, chemical treatment, semiconductor, aviation and petroleum industry application etc. As seal, pad and moulding part.
Exemplary includes as follows：
Embodiment 1：A kind of curable partially fluorinated polymer composition, it is included：
(i) partially fluorinated amorphous fluoropolymer, the amorphous fluoropolymer of which part fluorination includes carbon-to-carbon Double bond can be along the partially fluorinated amorphous fluoropolymer formation carbon-to-carbon double bond, amorphous the containing of which part fluorination Fluoropolymer is substantially free of bromine, iodine and nitrile；And
(ii) curing agent of the terminal olefin with least one olefinic hydrogen is included.
Embodiment 2：Curable partially fluorinated polymer composition according to embodiment 1 also includes peroxide Compound.
Embodiment 3：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, wherein curing agent include phenolic group group.
Embodiment 4：Curable partially fluorinated combination of polymers according to any one of embodiment 1 and 2 Thing, wherein curing agent include non-aromatic enol.
Embodiment 5：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, wherein curing agent are selected from least one of divinyl and diallyl compound.
Embodiment 6：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, wherein curing agent are by formula CX1X2=CX3- R represents, wherein X1、X2And X3Independently selected from H, Cl and F, X1、X2And X3In extremely Few one is H；R is univalent perssad, includes the end group selected from alcohol, amine, mercaptan, carboxylic acid and alkene.
Embodiment 7：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, wherein curing agent are selected from least one of following：
And combinations thereof, wherein n is 1 to 10 integer.
Embodiment 8：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, the amorphous fluoropolymer of which part fluorination includes the carbon-to-carbon pair along the main chain of partially fluorinated amorphous polymer Key, or carbon-to-carbon double bond can be formed along the main chain of partially fluorinated amorphous fluoropolymer.
Embodiment 9：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, the amorphous fluoropolymer of which part fluorination includes (i) VDF and HFP adjacent copolymerization units；(ii) VDF and have The copolymerization units of the fluorinated comonomers of acid hydrogen atom；(iii) TFE and the fluorinated comonomers with acid hydrogen atom are total to Poly- unit；And (iv) combinations thereof.
Embodiment 10：Curable partially fluorinated polymer composition according to embodiment 8, wherein having The fluorinated comonomers of acid hydrogen atom are selected from：Trifluoro-ethylene；PVF；3,3,3- trifluoro propenes -1；Pentafluoropropene；And 2, 3,3,3- tetrafluoropropenes.
Embodiment 11：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, the amorphous fluoropolymer of which part fluorination is derived from (i) vinylidene fluoride, tetrafluoroethene and propylene；(ii) inclined two PVF, tetrafluoroethene, ethene and perfluoroalkyl vinyl ether (such as perfluor (methyl vinyl ether))；(iii) inclined difluoro second Alkene and hexafluoropropene；(iv) hexafluoropropene, tetrafluoroethene and vinylidene fluoride；(v) hexafluoropropene and vinylidene fluoride；(vi) partially Difluoroethylene and perfluoroalkyl vinyl ether；(vii) vinylidene fluoride, tetrafluoroethene and perfluoroalkyl vinyl ether；(viii) Vinylidene fluoride, perfluoroalkyl vinyl ether, the PVF of hydrogen five and optionally tetrafluoroethene；(ix) tetrafluoroethene, propylene and 3, 3,3- trifluoro propenes；(x) tetrafluoroethene and propylene；(xi) ethene, tetrafluoroethene and perfluoroalkyl vinyl ether and optionally 3,3,3- trifluoro propenes；(xii) vinylidene fluoride, tetrafluoroethene and perfluoroalkyl allyl ether；(xiii) vinylidene fluoride and Perfluoroalkyl allyl ether；(xiv) vinylidene fluoride, tetrafluoroethene and perfluoro alkoxy allyl ether；(xv) vinylidene fluoride With perfluoro alkoxy allyl ether；(xvi) vinylidene fluoride, tetrafluoroethene and perfluoro alkoxy allyl ether；(xv) inclined difluoro Ethene and perfluoro alkoxy allyl ether；And (xvi) combinations thereof.
Embodiment 12：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, wherein curable compositions are substantially free of auxiliary agent.
Embodiment 13：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, also comprising organicCompound.
Embodiment 14：Curable partially fluorinated polymer composition according to embodiment 13, wherein having MachineCompound is selected from least one of phosphorus or sulfonium.
Embodiment 15：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, also comprising acid acceptor.
Embodiment 16：Curable partially fluorinated polymer composition according to embodiment 15, wherein acid Acceptor is selected from least one of following：Magnesia, lead oxide, calcium oxide, calcium hydroxide, two alkali formula lead phosphates, zinc oxide, carbon Sour barium, strontium hydroxide, calcium carbonate and hydrotalcite.
Embodiment 17：Curable partially fluorinated polymer group according to any one of embodiment 2 to 16 Compound, wherein peroxide are selected from least one of following：2,5- dimethyl -2,5- two (tert-butyl peroxy base) hexane, peroxide Change dicumyl, two (2- tert-butylperoxyiso-propyls) benzene and combinations thereof.
Embodiment 18：Curable partially fluorinated combination of polymers according to any one of foregoing embodiments Thing, every 100 parts of partially fluorinated amorphous fluoropolymers include 1 to 10 mM of curing agent.
Embodiment 19：A kind of product of the solidification composition filling comprising according to any one of embodiment 1-18.
Embodiment 20：A kind of method for preparing partially fluorinated elastomer, including：
Curable partially fluorinated polymer composition according to any one of embodiment 1 to 18 is provided；With And
The partially fluorinated polymer composition of cure curable.
Embodiment：
Show the advantage and embodiment of the disclosure in addition by the following example, but it is cited in these embodiments Specific material and its amount and other conditions and details be not necessarily to be construed as improper restriction to the present invention.Unless referred in addition Bright, otherwise in these embodiments, all percentages, ratio and ratio are by weight.
Unless otherwise indicated or it will be apparent that otherwise all material can be for example from the west of Milwaukee, WI Ge Ma Aldrich Chemicals company (Sigma-Aldrich Chemical Company；Milwaukee, WI) it is commercially available or It is known to those skilled in the art.
These are abridged in following examples：Phr=parts/hundred parts rubber；G=grams, kg=kilograms；Min=minutes； Mol=moles；Hr=hours；DEG C=degree Celsius；ML=milliliters；L=liters；Mm=millimeters；The newton of kN=thousand；KPa=kPas this Card；GC/MS=gas chromatography-mass spectrums；Pa=Pascals；Psig=pound per square inches；The ultraviolet inspection of LC/UV=liquid chromatograies Survey；And phr=rubber (or amorphous polymers) parts per hundred parts.
Material
VDF/BTFE/MA31 preparation
Under anaerobic, 3400mL deionized waters are loaded into 4L kettles.Add 12g CF3-O-(CF2)3-O-CFH- CF2-COONH4It is used as emulsifying agent.It is heated to after 90 DEG C, adds 40g tetrafluoroethene (TFE), 77g VDF, 3g 1- bromotrifluoethylenes (BTFE) and 140g perfluor -4,8- dioxa -1- nonenes (MA31, similar to Worm et al. United States Patent (USP) 5,891,965 is added In " PMEAE " prepare) (be described as preemulsion in WO200149752).Pass through lasting feeding, addition dissolving 1.4g ammonium peroxydisulfates (APS) in 280mL deionized waters are with initiation reaction.At 10 bar pressures and 90 DEG C, at 190 minutes Feeding 200g TFE, 380gVDF, 6.2g BTFE, 560g MA31 (being used as preemulsion) in time.The latex of gained has 27% solids content, and use 12g MgCl2Cohesion.The 1.1kg polymer of gained is dried at 130 DEG C.
The composition of resulting polymers is that 13.5 moles of %MV31,69.7 moles of %VDF, 16.1 moles of %TFE and 0.7 rub You are %BTFE.Glass transition temperature (being determined by DSC) is Tg=-42 DEG C, and Mooney viscosity (1+10 ', 121 DEG C) is 51。
The diallyl ether (BF6MAE) of curing agent bisphenol AF
Add 0.3 mole of 100g's in 3 neck, 1 liter of round-bottomed flask equipped with mechanical agitator, condenser and thermocouple HO-C6H4C(CF3)2C6H40.04 mole of-OH, 0.97 mole of 117g allyl bromide, bromoallylene and 12g TBAB, wherein TBAB is dissolved in 4g deionizations (DI) water and 250g glymes.Agitating solution is simultaneously heated to 50 DEG C.30 The 0.94 mole of KOH solution for the 53g being dissolved in 34g deionized waters is added dropwise in minute, sediment, and temperature liter is obtained Up to 62 DEG C.Reaction is heated to 65 DEG C and maintained two hours, 25 DEG C are subsequently cooled to.Remove the glyme solution of top layer Phase, is put it in round-bottomed flask, and glyme is removed by air-distillation.Sticky product is dissolved in 100g methyl- tert fourths In base ether, and it is put on glass tray, evaporates solvent, then in heating under 60 DEG C/1.6kPa (12 support) in vacuum drying oven 20 hours, isolate the 124g sticky products with quantitative yield.LC/UV analyses draw following mole of %：91.6%CH2= CHCH2-OC6H4C(CF3)2C6H4O-CH2CH=CH2And 1.4%CH2=CHCH2OC6H4C(CF3)2C6H4-OH.By material as synthesized 50% solid concentration is equally diluted in methyl alcohol, to be more beneficial in incorporation polymer.
The mono allyl ether (BF6MAE) of curing agent bisphenol AF
Load in 3 neck, 2 liters of round-bottomed flasks equipped with mechanical agitator, condenser and thermocouple and be dissolved in 4g deionizations (DI) 250g (0.7mol) HO-C in water and 500g glymes6H4C(CF3)2C6H4- OH, 30g (0.3mol) pi-allyl Bromine, 5g (0.02mol) TBAB.Stir the solution and be heated to 50 DEG C.Dissolving was added dropwise in 15 minutes 16g (0.3mol) KOH solution in 18g DI water, causes precipitation and temperature rises to 62 DEG C.The reaction is heated to 65 DEG C, Kept for one hour, be subsequently cooled to 25 DEG C.Top layer glyme solution is taken out, and is placed in round-bottomed flask and 50 DEG C/2 rotary evaporations under support.Then 50 DEG C are heated to using vavuum pump under 0.13kPa (1 support), are kept for one hour, then Add 400g chloroforms and slurry be stirred for 20 hours.Slurries and rotary evaporation solution under 50 DEG C/20 supports are filtered, is isolated 50g sticky oil products.Second of chloroform extraction is carried out to solid, the additional oil products of 21g are obtained, yield is 76%.LC/ UV analyses obtain following mole of %：66.8%CH2=CHCH2-OC6H4C(CF3)2C6H4- OH, 6.6%CH2=CHCH2OC6H4C (CF3)2C6H4O-CH2CH=CH2And 23.7%HO-C6H4C(CF3)2C6H4-OH.By flash chromatography (with trade name " INTELLIFLASH 280 " is purchased from Analogix companies (the Analogix Co., Santa of Santa Clara Clara, Ca)), using silicagel column, eluted first using heptane as non-polar solution, and polarity is finally used as using ethyl acetate Solvent separates allyl ether phenyl hexafluoro fluorine isopropylidene phenol.LC/UV analyzes the CH for obtaining 99.23 moles of %2=CHCH2- OC6H4C(CF3)2C6H4-OH.The material methanol dilution so synthesized is to 50% solid concentration, to be more favorable for incorporation polymerization In thing.
Allyl ether (the OFHDAE/CH of curing agent octafluorohexane diol2=CHCH2-OCH2C4F8CH2-OH)
Load 50g (0.19mol) in the 3 neck 500mL round-bottomed flasks equipped with mechanical agitator, condenser and thermocouple HO-CH2C4F8CH2- OH (being purchased from Exfluor research companies (Exfluor Research Corporation)) and 150g methyl Tertbutyl ether.Stir the solution and add 12g (0.18mol) KOH solution being dissolved in 26g DI water, then add and be dissolved in 2g (0.01mol) TBAB in 3g DI water.Stir the solution and be heated to 50 DEG C, and in 20 minutes by It is added dropwise to 22g (0.18mol) allyl bromide, bromoallylenes and is kept for two hours at 50 DEG C, is subsequently cooled to 25 DEG C.
Upper layer methyl tertbutyl ether solution is taken out, and is placed in round-bottomed flask and in 50 DEG C/1.33kPa (10 support) Lower use Rotary Evaporators evaporate.55g hexanes are added into product mixtures and are stirred, to obtain two-phase.With other 50g oneself Alkane extracts bottom phase.With chloroform bottom mutually twice to extract desired product, and filter to remove insoluble original glycol. Chloroformic solution is removed, and is placed in round-bottomed flask, and is evaporated under 55 DEG C/10 supports using Rotary Evaporators, to isolate 19g product mixtures.GC/MS analyses obtain following mole of %：84%CH2=CHCH2-OCH2C4F8CH2- OH, 12.5%CH2= CHCH2-OCH2C4F8CH2O-CH2CH=CH2And 3.9%HO-CH2C4F8CH2-OH.The material so synthesized with methanol dilution extremely 50% solid concentration, to be more favorable in incorporation polymer.
VDF/TFE/HFP preparation
Load DI water, 50% phosphorus of 50 pounds (22.6kg) of 13,180 pounds (5978kg) in 2000 gallons of (7570L) kettles The hexamethyldisilane of the aqueous solution of potassium hydrogen phthalate, 2 pounds (0.9kg), is then heated to 160 ℉ by the solution.Stirring is set as 100rpm.Kettle is forced into 130psig with the HFP of 155 pounds (70kg), VDF and 53 pound (24kg) of 38 pounds (17kg) TFE The pressure of (896kPa).Trigger polymerization with 12 pounds of (5kg) ammonium persulfates.When the reactions start, by with 1/0.739/1.330's Ratio, which adds VDF/TFE/HFP, makes pressure be maintained at 130psig (896kPA).Holding reaction temperature is 160 ℉ (71 DEG C).When adding When entering 1726 pounds of (783kg) VDF, HFP valves are closed, and with the VDF and TFE of VDF/TFE=1.4/1 ratio addition additional amount, Until adding the VDF of 70 pounds (32kg).Latex is without coagulation and with about 28% solids content.By solidifying with magnesium chloride Knot isolates polymer, the oven drying with DI water washings and under 266 ℉ (130 DEG C), until reaching<0.5 weight % moisture Content.
VDF/TFE/P#1 preparation
Load the DI water of 12,940 pounds (5869kg) and 50% phosphoric acid of 50 pounds (23kg) in 2000 gallons of (7570L) kettles The aqueous solution of hydrogen potassium, is then heated to 160 ℉ (71 DEG C) by the solution.Stirring is set as 100rpm.With 189 pounds (86kg) Kettle is forced into 220psig (1516kPa) pressure by the TFE of VDF and 111 pound (50kg).Then with 60 pounds of (27kg) persulfuric acid Ammonium triggers polymerization.When the reactions start, it is maintained at pressure by adding VDF/TFE/ propylene with 1/1.885/0.394 ratio 220psig.Holding reaction temperature is 160 ℉ (71 DEG C).When adding the VDF of 1487 pounds (674kg), closing VDF valves, and with TFE/P=4:1 ratio adds the TFE and propylene of additional amount, until adding the TFE of 40 pounds (18kg).Latex is free of coagulation And with about 27% solids content.Polymer is isolated by being condensed with magnesium chloride, with DI water washings and in 280 ℉ (138 DEG C) under dry, until reach<0.5 weight % moisture.
Method
Hardness：
According to ASTM D-2240 (2010), Durometer A hardness (2 ") is measured in rear solidified sample, and such as table 2 and table 3 Shown in.
Tensile strength and elongation：
According to DIN 53504 (2009) (S2DIE), with 200mm/min constant cross head rate of displacement use equipped with 1KN load sensors mechanical tension verifier (Massachusetts promise Wood Instron Corporation (Instron, Norwood, MA tensile strength and elongation)) are measured in rear solidified sample, as shown in table 2 and table 3.
Solidify rheological behavior
Using the sample of uncured compounding, use with trade name Monsanto Moving Die Rheometer (MDR) the commercially available rheometer of 2000 types (purchased from St. Louis, Missouri Monsanto Company (Monsanto Company, Saint Louis, Missouri)), according to ASTM D 5289-93a, 177 DEG C, without preheating, 30 minutes elapsed times and 0.5 Spend under the conditions of radian, carry out solidification rheological behavior test.Measurement is not up to plateau or peak torque (MH) when when specified Between the minimal torque (M that obtains in sectionLBoth) and highest moment of torsion.Also measurement moment of torsion increases above MLThe time of 2 units (ts2), moment of torsion is reached equal to ML+0.5(MH-ML) value time (t ' 50) and moment of torsion reach ML+0.9(MH-ML) time (t ' 90) and measurement MLAnd MHThe tan (Δ) at place.It is (relatively low to the ratio of storage tensile modulus that Tan (Δ) is equal to stretching loss modulus Tan (Δ) mean bigger elasticity).
O-ring is moulded and compressive deformation
The O-ring (solidifying 15 minutes at 177 DEG C) of tranverse sectional thickness of the molding with 0.139 inch (3.5mm), afterwards Carry out solidify afterwards in atmosphere at 232 DEG C 16 hours.According to such as ASTM 395-89 methods B (being analyzed with triplicate) Described in similar approach make O-ring be subjected to compressive deformation test, wherein according to the variable time of table 2 and table 3 and at a temperature of With 25% initial deflection.
For each embodiment (E) and comparative example (CE), amount (wherein every 100 portions of rubbers of component used as shown in table 1 Amount in glue is listed in bracket) it is compounded in twin-roll mill.Each embodiment and comparative example are carried out using above-mentioned method of testing Solidify rheological characteristic to assess.As a result shown in table 2 and table 3.Moulded using " O-ring is moulded and compressive deformation " method as described above O-ring, makes its solidification (at 177 DEG C press curing 15 minutes, and solidify afterwards 16 hours at 232 DEG C) and is estimated.Knot Fruit is shown in Table 4.
Table 1
*=1H-NMR analyses show that VDF/TFE/P#2 (AFLAS 200P) is includedThe 1D and 2D of combination1H-NMR light The presence of the modal data component with tetrabutyl ammonium cation species a small amount of for clearly confirmation be (0.36 weight %'s (CH3CH2CH2CH2)4-N(+))。
*=also include 2phr 4- dihydroxy benaophenonels.
Table 2
E1 E2 E3 E4 E5 E6 E7 E8
ML, in-lb (N-m) 4.37 4.32 5.4 2.94 3.46 4.09 5.52 1.13
MH, in-lb (N-m) 18.9 7.85 20.1 7.44 8.48 16.0 12.1 11.8
Δ moment of torsion 14.5 3.53 14.7 4.5 5.02 11.9 6.6 10.7
ts2, min 0.69 0.65 0.4 0.48 0.49 0.43 0.51 1.49
T'50, min 1.61 0.58 1.24 0.54 0.51 0.89 0.73 3.13
T'90, min 5.54 3.25 4.98 6.86 1.97 5.74 3.33 8.05
Tan(Δ)@MH 0.046 0.118 0.047 0.152 0.168 0.048 0.104 0.100
NT=is not tested
Table 3
E9 E10 CE A E11
ML, in-lb (N-m) 1.4 1.48 1.3 1.75
MH, in-lb (N-m) 17.96 10.37 1.97 14.08
Δ moment of torsion 16.56 8.89 0.67 12.33
ts2, min 1.02 2.63 n/a 1.5
T'50, min 3.14 4.88 3.16 3.78
T'90, min 8.37 9.87 8.79 8.53
Tan(Δ)@MH 0.037 0.087 0.507 0.064
NT=is not tested
Table 4
NT=is not tested
In the case where not departing from the scope of the present invention and essence, of the invention predicts modification and change for this area Technical staff for it will be evident that.The present invention should not be so limited to embodiment party shown for example purposes in the application Case.

Claims (11)

1. a kind of curable partially fluorinated polymer composition, it is included：
(i) partially fluorinated amorphous fluoropolymer, wherein the partially fluorinated amorphous fluoropolymer includes carbon-to-carbon Double bond can be along the partially fluorinated amorphous fluoropolymer formation carbon-to-carbon double bond, wherein the partially fluorinated nothing Amorphous fluoropolymer is substantially free of bromine, iodine and nitrile；And
(ii) curing agent, the curing agent includes the terminal olefin with least one olefinic hydrogen.
2. curable partially fluorinated polymer composition according to any one of the preceding claims, wherein described solid Agent includes phenolic group group.
3. curable partially fluorinated polymer composition according to claim 1, wherein the curing agent is comprising non- Aromatics enol.
4. curable partially fluorinated polymer composition according to claim 1, wherein the curing agent is selected from two At least one of vinyl and diallyl compound.
5. curable partially fluorinated polymer composition according to claim 1, wherein the curing agent is by formula CX1X2=CX3- R represents, wherein X1、X2And X3Independently selected from H, Cl and F, and X1、X2And X3At least one of be H；R is Univalent perssad, it includes the end group selected from alcohol, amine, mercaptan, carboxylic acid and alkene.
6. curable partially fluorinated polymer composition according to claim 1, wherein the partially fluorinated nothing Amorphous fluoropolymer includes (i) VDF and HFP adjacent copolymerization units；(ii) VDF and the fluorinated copolymerizable with acid hydrogen atom The copolymerization units of monomer；(iii) copolymerization units of TFE and the fluorinated comonomers with acid hydrogen atom；And (iv) they Combination.
7. curable partially fluorinated polymer composition according to claim 1, wherein the curable compositions Substantially free of auxiliary agent.
8. curable partially fluorinated polymer composition according to claim 1, it is also comprising organicCompound.
9. curable partially fluorinated polymer composition according to claim 1, it also includes acid acceptor.
10. a kind of product, the product includes solidification composition filling according to any one of claim 1 to 9.
11. preparing the method for partially fluorinated elastomer, methods described includes：
Curable partially fluorinated polymer composition according to any one of claim 1 to 9 is provided；And
Solidify the curable partially fluorinated polymer composition.
CN201580069383.0A 2014-12-19 2015-12-16 Curable partially fluorinated polymer composition Pending CN107109012A (en)

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