CN107318265A - Curable partially fluorinated polymer composition - Google Patents

Curable partially fluorinated polymer composition Download PDF

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Publication number
CN107318265A
CN107318265A CN201580069377.5A CN201580069377A CN107318265A CN 107318265 A CN107318265 A CN 107318265A CN 201580069377 A CN201580069377 A CN 201580069377A CN 107318265 A CN107318265 A CN 107318265A
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partially fluorinated
vinylidene fluoride
polymer composition
tetrafluoroethene
curable
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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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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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    • C08F214/28—Hexyfluoropropene
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    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
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    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
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    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
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    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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 the partially fluorinated amorphous fluoropolymer is comprising carbon-carbon double bond or can form carbon-carbon double bond along the partially fluorinated amorphous fluoropolymer chain；(ii) curing agent of every 100 parts 1 part to 10 parts partially fluorinated of the amorphous fluoropolymers, wherein the curing agent is formula CX1X2=CX3L M curing agent, wherein X1、X2And X3Independently selected from H, Cl and F, and X1、X2And X3At least one of be H；L is key or linking group；And M is nucleophilic group；(iii) acid acceptor；And (iv) is organic

Description

Curable partially fluorinated polymer composition
Technical field
The invention discloses the composition that partially fluorinated amorphous fluoropolymer is included with curing agent solidification, the solidification Agent includes terminal olefin and nucleophilic group with least 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, the polymer is included：
(i) partially fluorinated amorphous fluoropolymer, the amorphous fluoropolymer of which part fluorination includes carbon-to-carbon Double bond can be along partially fluorinated amorphous fluoropolymer chain formation carbon-to-carbon double bond；
(ii) curing agent of every 100 parts 1 mM to 10 mMs partially fluorinated of amorphous fluoropolymers, wherein should Curing agent is formula CX1X2=CX3- L-M curing agent, wherein X1、X2And X3Independently selected from H, Cl and F, and X1、X2And X3In At least one be H；L is key or linking group；And M is nucleophilic group；
(iii) acid acceptor；And
(iv) it is organicCompound.
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 evident.
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.
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 was found that partially fluorinated amorphous fluoropolymer (such as disclosed herein those) can Using curing agent together with acid acceptor andCompound solidifies, and the curing agent includes 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-to-carbon double bond, and/or can be along polymer chain formation carbon-to-carbon Double bond.In one embodiment, partially fluorinated amorphous fluoropolymer is along partially fluorinated amorphous fluoropolymer Main chain include carbon-to-carbon double bond, or can along partially fluorinated amorphous fluoropolymer main chain formation carbon-to-carbon double bond. In another embodiment, partially fluorinated amorphous fluoropolymer includes carbon-to-carbon double bond, or can be partially fluorinated Amorphous fluoropolymer main chain outside side base in form carbon-to-carbon double bond.
Fluoropolymer, which can form carbon-to-carbon double bond, means fluoropolymer comprising can form the unit of double bond.This Class 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 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, Double bond is formed between two carbon atoms.Illustrative leaving groups include：Halogen ion, alkoxide, hydroxyl, toluenesulfonic acid base, first sulphur Perester radical, amine, ammonium, sulphur, sulfonium, sulfoxide, sulfone and combinations thereof.Fluoropolymer will also be contemplated, the fluoropolymer includes adjacent carbons, Two carbon atoms of the adjacent carbons are respectively connected with bromine atoms or are respectively connected with iodine atom, cause Br2Or I2Leave away.
Amorphous fluoropolymer includes these multiple groups (carbon-to-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-to-carbon double bonds or its Mole of precursor).
In one embodiment, unbodied partially fluorinated polymer comes from least one hydrogeneous monomer, for example partially Difluoroethylene.
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 further from hydrogeneous monomer, including：Pentafluoropropene (for example, 2- hydrogen pentafluoropropene), propylene, ethene, isobutene and combinations thereof.
In one embodiment, amorphous fluoropolymer is further from perfluorinated monomer.Exemplary perfluorinated monomer Including：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 for example complete Fluoro- 4,8- dioxas -1- nonenes (that is, CF2=CFCF2OCF2)3OCF3) and combinations thereof.
The exemplary types of polymer include those for including the interpolymerized unit from following item：(i) vinylidene fluoride, four PVF 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 curable disclosure, without Side base bromine or iodine cure site.Generally, among other things, aggregate into fluoropolymer and/or chain end containing iodine and contain Bromine cure site monomer may be expensive.But, in one embodiment, partially fluorinated amorphous polymer includes iodine And/or bromine cure site, solidification of these cure sites available for such as enhancing fluoropolymer.
In one embodiment, partially fluorinated amorphous polymer is also from that peroxide cure reaction can be participated in Brominated and/or cure site monomer containing iodine.
Such brominated and/or cure site monomer containing iodine includes：
(a) there is bromo (complete) fluoroalkyl-(complete) fluorovinyl ether or iodo (complete) fluoroalkyl-(complete) PVF of following formula Base ether：
Z-Rf- O-CX=CX2
Wherein each X can be with identical or different, and represents that H or F, Z are Br or I, RfFor (complete) fluorine C1-C12Alkylidene, Optionally include chlorine and/or ether oxygen atom；For example：BrCF2- O-CF=CF2、BrCF2CF2- O-CF=CF2、BrCF2CF2CF2-O- CF=CF2、CF3CFBrCF2- O-CF=CF2、ICF2CF2CH=CH2、ICF2CF2CF2- O-CF=CF2Deng；
(b) bromo perfluoroolefine or iodo perfluoro alkene, such as with those of the formula：
Z’-(Rf’)r- CX=CX2；
Wherein each X independently represents H or F, Z ' it is Br or I, R'fFor perfluor C1-C12Alkylidene, it is optionally former comprising chlorine Sub and r is 0 or 1；For example：Bromo trifluoro-ethylene, the bromo- perfluorobuttenes -1 of 4- etc.；Or bromine fluoroolefins, bromo- 2, the 2- bis- of such as 1- PVF and the bromo- 3,3,4,4- tetrafluoros butene-1s of 4-；
(c) the bromo- 1- butylene of nonfluorinated bromo alkene, such as bromine ethene and 4-.
In one embodiment, amorphous fluoropolymer in brominated and/or chain-transferring agent containing iodine (such as with formula RfPxThose, wherein P be Br or I, it is therefore preferable to I, RfFor the x valency alkyl diradicals with 1 to 12 carbon atom, its is optional Ground can also include chlorine atom) in the presence of polymerize, as known in the art.Generally, x is 1 or 2.Available chain-transferring agent bag Monoiodide containing perfluorinated alkyl, perfluorinated alkyl diiodide, perfluorinated alkyl monobromide, perfluorinated alkyl dibrominated Thing and combinations thereof.Specific example includes CF2Br2、Br(CF2)2Br、Br(CF2)4Br、CF2ClBr、CF3CFBrCF2Br、 I(CF2)n(wherein n is 3 to 10 integer (e.g., I (CF to I2)4)), and combinations thereof I.
In one embodiment, amorphous fluoropolymer is substantially free of I or Br, wherein relative to total polymer, Amorphous fluoropolymer includes the I or Br less than 0.1 mole of %, 0.05 mole of %, 0.01 mole of % or even 0.005 mole %.
In one embodiment, the amorphous fluoropolymer of the disclosure is non-grafted, it means that it is free of side Base group, these groups include vinyl, pi-allyl, acrylate-based, acylamino-, sulfonate, pyridine, carboxylate, carboxylate, Steric hindrance type silane (for aliphatic series or the ether of aromatics three or three esters).In one embodiment, amorphous fluoropolymer does not include one First phenol grafting.
Curing agent
The curing agent of the disclosure is the compound for including at least one terminal olefin with least one olefinic hydrogen.One In individual embodiment, the curing agent of the disclosure is represented by Formulas I：
CX1X2=CX3-L-M (I)
Wherein X1、X2And X3Independently selected from H, Cl and F, and X1、X2And X3At least one of be H；L is key or linker Group；And M is nucleophilic group.
L represents singly-bound or linking group.Linking group can be O, S or N atom (for example, ehter bond) or divalent organic base in chain Group's (optionally comprising hetero atom in chain (for example, O, S or N) and/or being optionally substituted).Divalent organic group can for straight chain, Side chain or ring-type.Divalent organic group can be aromatics or aliphatic series.Divalent organic group can be (the not fluorine-containing original of nonfluorinated Son), partially fluorinated (including at least one c h bond and at least one C-F key) or fluoridized (be free of c h bond, and containing extremely A few C-F key).
In one embodiment, divalent organic group is-(CH2)n(O)m-P-(Rf)p-(P)q-, wherein n is 1 to 10 Integer；M is 0 or 1；P is selected from least one of following：Aromatics, the aromatics and (CH of substitution2)n, wherein n is 1 to 10 integer； Rf is selected from least one of following：(CF2)n(wherein n is 1 to 10 integer) and C (CF3)2, wherein Rf can for ring-type or Aliphatic series and/or include hetero atom such as O, S and N at least one chain；P is 0 or 1；And q is 0 or 1.Exemplary divalent has Machine group includes：-CH2-C6H4(OCH3)-、-CH2-O-CH2(CF2)4-CH2- and-CH2-O-C6H4-C(CF3)2-C6H4- and-CH2- O-C6H4-C(CF3)2-C6H4-O-CH2-。
M is nucleophilic group, it is meant that it includes not shared electronics pair.Exemplary nucleophilic group includes：Alcohol (- OH), amine (-NH2,-NHR and-NRR ', wherein R and R ' be organic group), mercaptan (- SH) and carboxylic acid (- COOH).
In one embodiment, curing agent includes at least one nonfluorinated terminal olefin group, and in other words, alkene is not Include any fluorine atom.In one embodiment, curing agent includes non-aromatic terminal olefin and/or non-aromatic alcohol.
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 include hetero atom example 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 PhosphoniumChlorination 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- diazas Carbon -7- the alkene of two rings [5.4.0] 11 and 1,5- diazabicylos [4.3.0] nonyl- 5- alkene.Phenates is quaternary ammonium salt He PhosphoniumSalt it is excellent Select anion.
In one embodiment, it is organicThe consumption of compound in 1 mM of every 100 parts of amorphous fluoropolymers and Between 5 mMs (mmhr).
Radical source
In one embodiment, curable compositions include the radical source for being used for triggering solidification.Such radical source Including peroxide, such as organic peroxide.In many cases it is preferred to use former with the tertiary carbon for being connected to peroxy oxygen The tert-butyl peroxide of son.
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.In one embodiment, curable compositions are substantially free of radical source, in other words, often 100 parts of amorphous fluoropolymers are less than 0.05 parts by weight or even 0.01 parts by weight radical source.
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.It is curable by using curing agent disclosed herein The amorphous fluoropolymer of the disclosure, without using these auxiliary agents.In other words, curable compositions are substantially free of (every 100 parts of amorphous fluoropolymers are less than 1 part, 0.5 part or even 0.1 part, or even can't detect) typical auxiliary agent.Due to helping Agent is spent, influence (for example, being oozed out from composition, mould fouling) incompatible with fluorinated polymer and to technique, and this can To 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 and curing agent together with other components (for example, acid acceptor,Compound, radical source and/ Or other additive) to provide solid mixture, the i.e. solid polymer containing other composition, it is also known as in this area " blend ".This blending constituent is generally called with the technique for preparing such solid polymerization compositions comprising other compositions " compounding ".This kind equipment includes rubber mill, banbury (such as Banbury mixer) and mixing extruder.During mixing, mix The temperature of compound will not generally rise above about 120 DEG C.During mixing, component and additive are distributed evenly in all institutes In the fluorinated polymer " blend " or polymer sheet that obtain.Then, can be by " blend " extrusion or press-in die (e.g., cavity Or transmission 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 D1646-06 TYPE A, MV2000 instruments are passed through using greater trochanter (ML 1+10) at 121 DEG C (the Alpha technology companys (Alpha Technologies, Ohio, USA) for being purchased from Ohio, USA) measurement, curable composition Partially fluorinated amorphous fluoropolymer has certain Mooney viscosity in thing.After solidification, using disclosed herein Curing agent, amorphous fluoropolymer becomes elastomer-forming, becomes immobilising fluoropolymer and has infinitely great viscosity (therefore In the absence of 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.
The exemplary of the disclosure includes：
Embodiment 1：A kind of curable partially fluorinated polymer composition, the polymer composition 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 chain formation carbon-to-carbon double bond；
(ii) curing agent of every 100 parts 1 mM to 10 mMs partially fluorinated of amorphous fluoropolymers, wherein should Curing agent is formula CX1X2=CX3- L-M curing agent, wherein X1、X2And X3Independently selected from H, Cl and F, and X1、X2And X3In At least one be H；L is key or linking group；And M is nucleophilic group；
(iii) acid acceptor；And
(iv) it is organicCompound.
Embodiment 2：Curable partially fluorinated polymer composition according to embodiment 1, which part The amorphous fluoropolymer of fluorination includes (i) VDF and HFP adjacent copolymerization units；(ii) VDF and with acid hydrogen atom The copolymerization units of fluorinated comonomers；(iii) copolymerization units of TFE and the fluorinated comonomers with acid hydrogen atom；And (iv) combinations thereof.
Embodiment 3：Curable partially fluorinated polymer composition according to embodiment 2, 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 4：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, the amorphous fluoropolymer of which part fluorination comes 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 5：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, main chain of the amorphous fluoropolymer which part is fluorinated along the partially fluorinated amorphous fluoropolymer is included Carbon-to-carbon double bond, or carbon-to-carbon double bond can be formed along the main chain of the partially fluorinated amorphous fluoropolymer.
Embodiment 6：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, wherein nucleophilic group are selected from alcohol, amine and mercaptan.
Embodiment 7：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, wherein curing agent include nonfluorinated terminal olefin group.
Embodiment 8：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, wherein curing agent include non-aromatic alcohol.
Embodiment 9：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, wherein curable partially fluorinated polymer composition is substantially free of monohydric phenol.
Embodiment 10：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, wherein curing agent are selected from least one of following：
And combinations thereof, wherein n is 1 to 10 integer.
Embodiment 11：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, wherein organicCompound Xuan Zi PhosphoniumAt least one of or sulfonium.
Embodiment 12：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, the amorphous fluoropolymer of which part fluorination is also from including at least one of I and Br cure site monomer.
Embodiment 13：Curable partially fluorinated polymer according to any one of embodiment 1 to 11 Composition, wherein fluoropolymer is substantially free of I, Br and Cl.
Embodiment 14：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, wherein acid acceptor are selected from least one of following：Magnesia, lead oxide, calcium oxide, calcium hydroxide, two alkali formula phosphoric acid Lead, zinc oxide, barium carbonate, strontium hydroxide, calcium carbonate and hydrotalcite.
Embodiment 15：Curable partially fluorinated polymer group according to any one of foregoing embodiments Compound, it also includes radical source.
Embodiment 16：Curable partially fluorinated polymer composition according to embodiment 15, wherein certainly At least one of peroxide is selected from by Ji Yuan.
Embodiment 17：Curable partially fluorinated polymer composition according to embodiment 16, wherein group Compound is substantially free of assistant agent.
Embodiment 18：A kind of product, the product is comprising solidification according to any one of embodiment 1 to 17 Composition.
Embodiment 19：A kind of method for preparing partially fluorinated elastomer, this method includes：
Curable partially fluorinated polymer composition according to any one of embodiment 1 to 17 is provided； 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, 380g VDF, 6.2g BTFE, 560g MA31 (being used as preemulsion) in time.The latex tool of gained There is 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 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 (is purchased from Exfluor research companies (the Exfluor Research of the bright moral Roc in Texas Corporation, Round Rock, TX)) and 150g methyl tertiary butyl ether(MTBE)s.Stir the solution and add and be dissolved in 26g DI water In 12g (0.18mol) KOH solution, then add and be dissolved in 2g (0.01mol) TBAB in 3g DI water.Stirring The solution is simultaneously heated to 50 DEG C, and 22g (0.18mol) allyl bromide, bromoallylenes were added dropwise in 20 minutes and are kept at 50 DEG C Two hours, it 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-2240-05 (2010), Durometer A hardness (2 ") is measured in rear solidified sample, and such as the He of table 2 Shown in table 3.
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 in such as ASTM395-89 methods B (being analyzed with triplicate) Described similar approach makes O-ring be subjected to compressive deformation test, wherein having according to the variable time of table 2 and table 3 with a temperature of There is 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(+))。
Table 2
E1 E2 E3 E5 E6 E7 E8
ML, in-lb (N-m) 4.37 4.32 5.4 3.46 4.09 5.52 1.13
MH, in-lb (N-m) 18.9 7.85 20.1 8.48 16.0 12.1 11.8
Δ moment of torsion 14.5 3.53 14.7 5.02 11.9 6.6 10.7
ts2, min 0.69 0.65 0.4 0.49 0.43 0.51 1.49
T ' 50, min 1.61 0.58 1.24 0.51 0.89 0.73 3.13
T ' 90, min 5.54 3.25 4.98 1.97 5.74 3.33 8.05
Tan(Δ)@MH 0.046 0.118 0.047 0.168 0.048 0.104 0.100
NT=is not tested
Table 3
E9 E10 CEA 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 (10)

1. a kind of curable partially fluorinated polymer composition, the polymer composition 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 chain formation carbon-to-carbon double bond；
(ii) curing agent of every 100 parts 1 mM to 10 mMs partially fluorinated of the amorphous fluoropolymers, wherein institute It is formula CX to state curing agent1X2=CX3- L-M curing agent, wherein X1、X2And X3Independently selected from H, Cl and F, and X1、X2And X3 At least one of be H；L is key or linking group；And M is nucleophilic group；
(iii) acid acceptor；And
(iv) it is organicCompound.
2. 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.
3. curable partially fluorinated polymer composition according to claim 1, wherein the partially fluorinated nothing Amorphous fluoropolymer comes from (i) vinylidene fluoride, tetrafluoroethene and propylene；(ii) vinylidene fluoride, tetrafluoroethene, ethene, And perfluoroalkyl vinyl ether, such as perfluor (methyl vinyl ether)；(iii) vinylidene fluoride and hexafluoropropene；(iv) hexafluoro Propylene, tetrafluoroethene and vinylidene fluoride；(v) hexafluoropropene and vinylidene fluoride；(vi) vinylidene fluoride and perfluoroalkyl second Alkene ether；(vii) vinylidene fluoride, tetrafluoroethene and perfluoroalkyl vinyl ether；(viii) vinylidene fluoride, perfluoroalkyl second Alkene ether, the PVF of hydrogen five and optionally tetrafluoroethene；(ix) tetrafluoroethene, propylene and 3,3,3- trifluoro propenes；(x) tetrafluoro second Alkene and propylene；(xi) ethene, tetrafluoroethene and perfluoroalkyl vinyl ether and optionally 3,3,3- trifluoro propenes；(xii) partially Difluoroethylene, tetrafluoroethene and perfluoroalkyl allyl ether；(xiii) vinylidene fluoride and perfluoroalkyl allyl ether；(xiv) Vinylidene fluoride, tetrafluoroethene and perfluoro alkoxy allyl ether；(xv) vinylidene fluoride and perfluoro alkoxy allyl ether； (xvi) vinylidene fluoride, tetrafluoroethene and perfluoro alkoxy allyl ether；(xv) vinylidene fluoride and perfluoro alkoxy pi-allyl Ether；And (xvi) combinations thereof.
4. curable partially fluorinated polymer composition according to claim 1, wherein the partially fluorinated nothing Main chain of the amorphous fluoropolymer along the partially fluorinated amorphous fluoropolymer includes carbon-to-carbon double bond, or being capable of edge The main chain formation carbon-to-carbon double bond of the partially fluorinated amorphous fluoropolymer.
5. curable partially fluorinated polymer composition according to claim 1, wherein the nucleophilic group is selected from Alcohol, amine and mercaptan.
6. curable partially fluorinated polymer composition according to claim 1, wherein the curing agent is comprising non- Aromatic alcohol.
7. curable partially fluorinated polymer composition according to claim 1, wherein the curable part The polymer composition of fluorination is substantially free of monohydric phenol.
8. the curable partially fluorinated polymer composition according to claim 1,1, wherein the fluoropolymer Substantially free of I, Br and Cl.
9. a kind of product, the product includes the composition according to any one of claim 1 to 8 of solidification.
10. a kind of method for preparing partially fluorinated elastomer, methods described includes：
Curable partially fluorinated polymer composition according to any one of claim 1 to 8 is provided；And
Solidify the curable partially fluorinated polymer composition.
CN201580069377.5A 2014-12-19 2015-12-16 Curable partially fluorinated polymer composition Pending CN107318265A (en)

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