CN1942491A - Fluorine-containing elastomer polymer and method for producing same - Google Patents

Fluorine-containing elastomer polymer and method for producing same Download PDF

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CN1942491A
CN1942491A CN 200580010876 CN200580010876A CN1942491A CN 1942491 A CN1942491 A CN 1942491A CN 200580010876 CN200580010876 CN 200580010876 CN 200580010876 A CN200580010876 A CN 200580010876A CN 1942491 A CN1942491 A CN 1942491A
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fluorine
containing elastomer
elastomer polymer
general formula
integer
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CN100475865C (en
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津田畅彦
田中芳树
守田滋
泽田又彦
清水哲男
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Daikin Industries Ltd
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Abstract

Disclosed is a fluorine-containing elastomer polymer which is excellent in productivity and crosslinkability. Also disclosed is a method for producing such a fluorine-containing elastomer polymer. A fluorine-containing elastomer polymer having a unit (A) derived from an emulsifying agent containing a fluorine-containing vinyl group, and a unit (B) derived from a cure site monomer (b1) and/or a saturated aliphatic compound (b2) having a bromine atom and/or an iodine atom is characterized in that the emulsifying agent containing a fluorine-containing vinyl group is composed of a compound having a radically polymerizable unsaturated bond and a hydrophilic group in a molecule.

Description

Fluorine-containing elastomer polymer and manufacture method thereof
Technical field
The present invention relates to fluorine-containing elastomer polymer and manufacture method thereof.
Background technology
When in aqueous medium, carrying out polymerization in order to obtain fluoroelastomer, in the past often with fluorochemical surfactant as emulsifying agent, but remaining usually in the fluoroelastomer that is obtained by this polymerization have a fluorochemical surfactant.Because remaining in the fluoroelastomer have fluorochemical surfactant, thereby there is the problem that the vulcanization process as a process of moulding is had obstruction.
As the method for making fluoroelastomer, known at CF 2=CFO-(CF 2) sUnder the existence of-COOT (in the formula, s is 1～7 integer, and T is a basic metal etc.), in being 5～10 aqueous medium, pH make fluorochemical monomer carry out polymeric method (for example, with reference to patent documentation 1).But the method for patent documentation 1 exists must be adjusted to the pH of aqueous medium the problem that narrow scope is carried out.Not on the books in the patent documentation 1 for the manufacturing of fluoroelastomer useful in peroxide cure with iodine end or bromine end.
As the method for making fluoroelastomer, known have a following method: at CF 2=CF-(CF 2) tUnder the existence of-Y (in the formula, t is 1～10 integer, and Y is a carboxyl), obtain the aqueous liquid dispersion (for example, with reference to patent documentation 2) of vinylidene [VDF] analog copolymer.But in the patent documentation 2, not on the books for elastomerics with iodine and/or bromine, even also do not have hint in addition in the presence of chain-transfer agent, also can stably carry out polymerization.Further, make non-fluorochemical monomer carry out the record of seeding polymerization, do not have to make fluorochemical monomer carry out the record of seeding polymerization though have in the presence of the aqueous liquid dispersion of this VDF analog copolymer.
As the method for making fluoroelastomer, known have a following method: in aqueous medium, under the state that has more than or equal to 0.5 weight % emulsifying agent of aqueous medium, carry out the polymerization of fs, after the resulting emulsion dilution that contains seed particles, add monomer and carry out multistage polymerization (for example, with reference to patent documentation 3).According to this method, enhance productivity simultaneously with the amount that reduces employed emulsifying agent by carrying out multistage polymerization, but remaining have a certain amount of emulsifying agent.Further, patent documentation 3 do not have yet the hint contain fluoride-based emulsifying agent in the presence of carry out this multistage polymerization.
Patent documentation 1: Japanese Patent Publication 61-33848 communique
Patent documentation 2: Japanese kokai publication hei 8-67795 communique
Patent documentation 3: Japan internationality discloses brochure No. 00/001741
Summary of the invention
The present invention has proposed the fluorine-containing elastomer polymer and the manufacture method thereof of productivity and bridging property excellence in view of the above problems.
Fluorine-containing elastomer polymer of the present invention has unit (A) and unit (B), described unit (A) derives from and contains fluoride-based emulsifying agent, described unit (B) derives from sulfuration point monomer (b1) and/or saturated fatty compounds of group (b2), described saturated fatty compounds of group (b2) has bromine atoms and/or iodine atom, this fluorine-containing elastomer polymer is characterised in that, describedly contains fluoride-based emulsifying agent and contains the compound that has free-radical polymerised unsaturated link(age) and hydrophilic radical in molecule.
Fluorine-containing elastomer polymer of the present invention has unit (A) and unit (B), described unit (A) derives from and contains fluoride-based emulsifying agent, (B) derives from the monomer that contains cross-linking part in described unit, this fluorine-containing elastomer polymer is characterised in that, describedly contains fluoride-based emulsifying agent and contains and contain fluoride-based compound (I) shown in the following general formula (I), contain fluoride-based compound (II) shown in the following general formula (II), contain fluoride-based compound (III) shown in the following general formula (III), contain fluoride-based compound (IV) shown in the following general formula (IV), contain fluoride-based compound (V) shown in the following logical formula V, contain fluoride-based compound (VI) shown in the following general formula (VI), contain fluoride-based compound (VII) shown in the following general formula (VII), and/or contain fluoride-based compound (VIII) shown in the following general formula (VIII);
CF 2＝CF-(CF 2) a-Y (I)
In the general formula (I), a represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF-(CF 2C(CF 3)F) b-Y (II)
In the general formula (II), b represents 1～5 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CFO-(CF 2) c-Y (III)
In the general formula (III), c represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF(CF 2) d-O-(CF 2CFXO) e-(CF 2) f-Y(IV)
In the general formula (IV), X represent F or-CF 3, d represents 0～2 integer, and e represents 1～10 integer, and f represents 1～3 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CH 2＝CFCF 2O(CF(CF 3)CF 2O) gCF(CF 3)Y (V)
In the logical formula V, g represents 0～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF(CF 2) hO-(CF(CF 3)CF 2O) i-CF(CF 3)-Y (VI)
In the general formula (VI), h represents 1～6 integer, and i represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CH 2＝CH(CF 2) p1-Y (VII)
In the general formula (VII), p1 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CFO-(CH 2) q-(CF 2) p2-Y (VIII)
In the general formula (VIII), q represents 1～4 integer, and p2 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
The manufacture method of fluorine-containing elastomer polymer of the present invention be contain fluoride-based emulsifying agent in the presence of and sulfuration point monomer (b1) and/or have bromine atoms and/or the saturated fatty compounds of group of iodine atom (b2) in the presence of, in aqueous medium, make fluorochemical monomer carry out polymerization and generate the manufacture method of fluorine-containing elastomer polymer, the method is characterized in that, describedly contain fluoride-based emulsifying agent and contain the compound that in molecule, has free-radical polymerised unsaturated link(age) and hydrophilic radical.
The manufacture method of fluorine-containing elastomer polymer of the present invention is to contain fluoride-based emulsifying agent and containing in the presence of cross-linking part monomeric, in aqueous medium, make fluorochemical monomer carry out polymerization and generate the manufacture method of fluorine-containing elastomer polymer, this manufacture method is characterised in that, describedly contains fluoride-based emulsifying agent and contains following substances: the above-mentioned fluoride-based compound (I) that contains, the above-mentioned fluoride-based compound (II) that contains, the above-mentioned fluoride-based compound (III) that contains, the above-mentioned fluoride-based compound (IV) that contains, the above-mentioned fluoride-based compound (V) that contains, the above-mentioned fluoride-based compound (VI) that contains, the above-mentioned fluoride-based compound (VII) that contains, and/or the above-mentioned fluoride-based compound (VIII) that contains.
Fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention is that the particle that contains fluorine-containing elastomer polymer is dispersed in the fluorine-containing elastomer polymer aqueous liquid dispersion in the aqueous medium, it is characterized in that, described fluorine-containing elastomer polymer is above-mentioned fluorine-containing elastomer polymer or the fluorine-containing elastomer polymer of making by the manufacture method of above-mentioned fluorine-containing elastomer polymer, described fluorine-containing elastomer polymer aqueous liquid dispersion contains or does not contain fluoride-based emulsifying agent, the described 1000ppm that contains fluoride-based emulsifying agent less than described fluorine-containing elastomer polymer aqueous liquid dispersion.
Fluorine-containing elastomer polymer composition of the present invention is characterised in that it contains above-mentioned fluorine-containing elastomer polymer.
Fluorine-containing elastomer polymer formed body of the present invention is characterised in that it carries out above-mentioned fluorine-containing elastomer polymer crosslinked and obtains.
Embodiment
Hereinafter the present invention will be described in detail.
Fluorine-containing elastomer polymer of the present invention is the amorphous fluoropolymer with caoutchouc elasticity.Above-mentioned fluoropolymer is the polymkeric substance with fluorine atom of at least 58 quality %, preferred 64 quality %, can be partially fluorinated polymkeric substance or (per) fluoropolymer.
Fluorine-containing elastomer polymer of the present invention has the 1st monomeric copolymerization units of 30 quality %～80 quality %.
In this specification sheets, above-mentioned " the 1st monomer " refers to, and in the molecular structure of fluorine-containing elastomer polymer, is formed in the vinylidene [VDF] or the tetrafluoroethylene [TFE] that account for the copolymerization units of maximum quality in whole copolymerization units.For fluorine-containing elastomer polymer of the present invention, hereinafter the multipolymer that is VDF with above-mentioned the 1st monomer is called " VDF analog copolymer ", and the polymkeric substance that is TFE with above-mentioned the 1st monomer is called " TFE analog copolymer ".
In this specification sheets, above-mentioned copolymerization units is the part on the molecular structure of fluorine-containing elastomer polymer, refers to and derives from corresponding monomeric part.For example, the VDF unit is the part on the molecular structure of VDF analog copolymer, is the part that derives from VDF, with-(CH 2-CF 2)-expression.Above-mentioned " all copolymerization units " refers on the molecular structure of fluorine-containing elastomer polymer, derives from the whole of monomeric part.
The content of above-mentioned copolymerization units passes through with F 19-NMR measures and obtains.
In the fluorine-containing elastomer polymer of the present invention, derive from monomeric copolymerization units outside above-mentioned the 1st monomer and can be only derive from can with the monomer of above-mentioned the 1st monomer copolymerization in any a kind, also can be derive from can with the monomer of the 1st monomer copolymerization at least 2 kinds.
As can with the monomer of above-mentioned the 1st monomer copolymerization, for example can enumerate, Fluorine containing olefine, contain fluorovinyl ether and hydrocarbon olefin.
As above-mentioned Fluorine containing olefine, do not limit especially, for example can enumerate R 1216 [HFP], tetrafluoroethylene [TFE], 1,2,3,3,3-five fluorine propylene [1-HPFP], chlorotrifluoroethylene [CTFE], fluorinated ethylene [VF] etc.
As the above-mentioned fluorovinyl ether that contains, do not limit especially, can enumerate perfluor (alkyl vinyl ether).
As above-mentioned perfluor (alkyl vinyl ether) [PAVE], be preferably formula CF 2=CFO (Rf aO) n(Rf bO) mRf c[in the formula, Rf aAnd Rf bDifference, the carbonatoms that is straight or branched are 2～6 perfluorinated alkylidene, and m and n are 0～10 integer independently, Rf cBe that carbonatoms is 1～6 perfluoroalkyl] shown in compound.
Above-mentioned PAVE is formula CF more preferably 2=CFO (CF 2CFXO) rRf d[X is-F or-CF 3, r is 0～5 integer, Rf dBe that carbonatoms is 1～6 perfluoroalkyl] shown in compound.
Above-mentioned PAVE is preferably perfluor (methylvinylether) [PMVE], perfluor (ethyl vinyl ether) [PEVE], perfluor (propyl vinyl ether) [PPVE].
Above-mentioned PAVE is preferably formula CF 2=CFO[(CF 2) uCF 2CFZ 1O] vRf e[in the formula, Rf eBe that carbonatoms is 1～6 perfluoroalkyl, u is 0 or 1 integer, and v is 0～5 integer, Z 1For-F or-CF 3] shown in compound.
Above-mentioned Rf eBe preferably-C 3F 7, preferred above-mentioned u is that integer 0 and above-mentioned v are integer 1.
Above-mentioned PAVE is preferably formula CF 2=CFO[(CF 2CF (CF 3) O) m(CF 2CF 2CF 2O) n(CF 2) y] C zF 2z+1Compound shown in [in the formula, m and n are 0～10 integer independently, and y is 0～3 integer, and z is the integer of carbonatoms 1～5].
Above-mentioned m and n are integer 0 or 1 independently preferably, and z is preferably integer 1.
Above-mentioned PAVE is preferably formula CF 2=CFOCF 2CF (CF 3) O (CF 3O) wC xF 2x+1Compound shown in [in the formula, w is 1～5 integer, and x is 1～3 integer].
Above-mentioned x is preferably integer 1.
When fluorine-containing elastomer polymer of the present invention had the PAVE unit, preferred PAVE unit was 20 quality %～70 quality %.
When fluorine-containing elastomer polymer of the present invention had the PMVE unit, preferred PMVE unit was 30 quality %～55 quality %.
As above-mentioned hydrocarbon olefin, do not limit especially, can enumerate ethene, propylene etc., be preferably propylene.
When fluorine-containing elastomer polymer of the present invention had the hydrocarbon olefin unit, preferred hydro carbons olefin unit was 4 quality %～20 quality %.
As fluorine-containing elastomer polymer of the present invention, so long as have the fluorine-containing elastomer polymer of the fluorine atom of at least 58 quality %, then do not limit especially, for example can enumerate TFE/ perfluor (vinyl ether) analog copolymer, VdF/HFP analog copolymer, VdF/CTFE analog copolymer, VdF/HFP/TFE analog copolymer, VdF/CTFE/TFE analog copolymer, TFE/ propylene copolymers, TFE/ propylene/VdF analog copolymer, ethene/fluorinated copolymers such as HFP analog copolymer etc.; The fluoropolymer that can make by letex polymerization etc.
As fluorine-containing elastomer polymer of the present invention, be preferably VDF analog copolymer or TFE analog copolymer.As above-mentioned TFE analog copolymer, be preferably TFE/ propylene copolymers or TFE/ perfluoroalkyl vinyl ether analog copolymer.
As above-mentioned VDF analog copolymer, for example can enumerate VDF/HFP multipolymer, VDF/HFP/TFE multipolymer, VDF/HFP/TFE/4-bromo-3,3,4,4-tetrafluoro 1-Butylene copolymer, VDF/HFP/TFE/4-iodo-3,3,4,4-tetrafluoro 1-Butylene copolymer, VDF/PMVE/TFE/4-bromo-3,3,4,4-tetrafluoro 1-Butylene copolymer, VDF/PMVE/TFE/4-iodo-3,3,4,4-tetrafluoro 1-Butylene copolymer, VDF/PMVE/TFE/1,1,3,3,3-five fluorine propylene copolymers etc.
As above-mentioned TFE/ propylene copolymers, can enumerate TFE/ propylene copolymer etc.
As above-mentioned TFE/ perfluor (vinyl ether) analog copolymer, can enumerate TFE/PMVE/ ethylene copolymer, TFE/PMVE/ ethene/4-bromo-3,3,4,4-tetrafluoro 1-Butylene copolymer, TFE/PMVE/ ethene/4-iodo-3,3,4,4-tetrafluoro 1-Butylene copolymer, TFE/PMVE multipolymer, TFE/PMVE/ perfluor (8-cyano group-5-methyl-3,6-two oxa-s-1-octene) multipolymer, TFE/PMVE/4-iodo-3,3,4,4-tetrafluoro 1-Butylene copolymer, TFE/PMVE/ perfluor (2-phenoxy propyl vinyl) ether copolymer etc.
Fluorine-containing elastomer polymer of the present invention has unit (A) and unit (B), described unit (A) derives from and contains fluoride-based emulsifying agent, described unit (B) derives from sulfuration point monomer (b1) and/or saturated fatty compounds of group (b2), and described saturated fatty compounds of group (b2) has bromine atoms and/or iodine atom.
Above-mentionedly contain fluoride-based emulsifying agent and contain the compound that in molecule, has free-radical polymerised unsaturated link(age) and hydrophilic radical.
Above-mentioned " compound that has free-radical polymerised unsaturated link(age) and hydrophilic radical in molecule " is preferably and contains fluoride-based compound (1) shown in the following general formula (1);
CR 1R 2＝CR 3(CR 4R 5) j-(O) k-R-Y (1)
In the general formula (1), R 1, R 2, R 3, R 4And R 5Identical or different, perfluoroalkyl, H, F, Cl, Br or I that expression is replaced by H or do not replaced by H, R is illustrated in the fluoro alkylidene group that has or do not have the straight or branched that Sauerstoffatom [O-] and all or part of H replaced by F on the main chain, j represents 0～6 integer, k represents 0 or 1 integer, and Y represents hydrophilic radical.
In the above-mentioned general formula (1), as above-mentioned R 1, R 2, R 3, R 4And R 5, identical or inequality, be preferably H or F.
In the above-mentioned general formula (1), as above-mentioned R, the backbone c atoms number that is preferably the straight or branched that has or do not have Sauerstoffatom [O-] on main chain is 1～23 perfluorinated alkylidene, when having Sauerstoffatom [O-] on the main chain,, be preferably the Sauerstoffatom that constitutes polyoxyalkylene as this Sauerstoffatom, this polyoxyalkylene is to be made of 1～10 alkylidene oxide unit (preferred carbonatoms is 2～3 oxidation alkylene unit), when R has side chain, as side chain, be preferably-CF 3
In the above-mentioned general formula (1),, be preferably 0～2 integer as above-mentioned j.
In the above-mentioned general formula (1), the hydrophilic radical as shown in the above-mentioned Y is preferably-SO 3M or-(M represents H, NH to COOM 4Or basic metal).
Above-mentionedly contain fluoride-based emulsifying agent and preferably contain following substances: contain fluoride-based compound (I), contain fluoride-based compound (II), contain fluoride-based compound (III), contain fluoride-based compound (IV), contain fluoride-based compound (V), contain fluoride-based compound (VI), contain fluoride-based compound (VII) and/or contain and contain fluoride-based compound (VIII).
Above-mentioned containing in the fluoride-based emulsifying agent, can there be a kind or have different mutually at least 2 kinds respectively in the above-mentioned fluoride-based compound (I)～(VIII) that contains.
The above-mentioned fluoride-based compound (I)～(VIII) that contains is as described later an ethene compound, is present in when above-mentioned polymerization and carries out addition in the reaction system, thereby constitute the part of the polymer chain of above-mentioned fluorine-containing elastomer polymer.
In this specification sheets,, hereinafter will derive from the part that contains fluoride-based emulsifying agent sometimes and be called " emulsifying agent unit " for the part on the molecular structure of fluorine-containing elastomer polymer.
The above-mentioned fluoride-based compound (I) that contains is shown in following general formula (I);
CF 2＝CF-(CF 2) a-Y (I)
In the general formula (I), a represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (I), above-mentioned a is preferably the integer smaller or equal to 5, more preferably smaller or equal to 2 integer.Consider that from obtaining suitable water-soluble and surfactivity aspect above-mentioned Y is preferably-COOM, thermotolerance aspect residual as impurity from being difficult for, that improve resulting formed body considers that M is preferably H or NH 4
As the above-mentioned fluorine-containing vinyl compound (I) that contains, can enumerate for example following substances:
CF 2＝CF-CF 2-COOH、
CF 2＝CF-CF 2-COONH 4、
CF 2＝CF-CF 2CF 2-COOH、
CF 2＝CF-CF 2-COONH 4、
CF 2＝CF-CF 2-SO 3H、
CF 2＝CF-CF 2-SO 3Na、
CF 2＝CF-CF 2CF 2-SO 3H、
CF 2＝CF-CF 2CF 2-SO 3Na
Wherein consider to be preferably CF from the better aspect of dispersion stabilization 2=CFCF 2-COONH 4
The above-mentioned fluoride-based compound (II) that contains is shown in following general formula (II):
CF 2＝CF-(CF 2C(CF 3)F) b-Y (II)
In the general formula (II), b represents 1～5 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (II), consider that from the aspect of emulsifying capacity b is preferably the integer smaller or equal to 3, consider from obtaining suitable water-soluble and surfactivity, Y is preferably-COOM, and thermotolerance aspect residual as impurity from being difficult for, that improve resulting formed body considers that M is preferably H or NH 4
As the above-mentioned fluoride-based compound (II) that contains, can enumerate for example following substances:
[changing 1]
Wherein consider to be preferably following substances from the better aspect of dispersion stabilization:
[changing 2]
Figure A20058001087600162
The above-mentioned fluoride-based compound (III) that contains is shown in following general formula (III):
CF 2＝CFO-(CF 2) c-Y (III)
In the general formula (III), c represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (III), consider that from water miscible aspect above-mentioned c is preferably the integer smaller or equal to 5, consider from obtaining suitable water-soluble and surfactivity aspect, above-mentioned Y is preferably-COOM, considers that from the better aspect of dispersion stabilization above-mentioned M is preferably H or NH 4
As the above-mentioned fluoride-based compound (III) that contains, can enumerate for example following substances:
CF 2＝CF-OCF 2-COOH
CF 2＝CF-OCF 2-COONH 4
CF 2＝CF-OCF 2CF 2-COOH、
CF 2＝CF-OCF 2CF 2-COONH 4、
CF 2＝CF-OCF 2CF 2CF 2-COOH、
CF 2＝CF-OCF 2CF 2CF 2-COONH 4
Wherein consider, be preferably CF from the better aspect of dispersion stabilization 2=CF-OCF 2CF 2CF 2-COONH 4
The above-mentioned fluoride-based compound (IV) that contains is shown in following general formula (IV):
CF 2＝CF(CF 2) d-O-(CF 2CFXO) e-(CF 2) f-Y (IV)
In the general formula (IV), X represents-F or-CF 3, d represents 0～2 integer, and e represents 1～10 integer, and f represents 1～3 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (IV), consider that from surfactivity ability aspect above-mentioned X is preferably-CF 3, consider that from the copolymerization aspect above-mentioned d is preferably integer 0, consider that from water-soluble aspect above-mentioned e is preferably the integer smaller or equal to 5, consider from obtaining suitable water-soluble and surfactivity aspect, above-mentioned Y is preferably-COOM, and above-mentioned f is preferably smaller or equal to 2, and above-mentioned M is preferably H or NH 4
As the above-mentioned fluoride-based compound (IV) that contains, can enumerate for example following substances:
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2-COOH、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2-COONH 4、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2SO 3H、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2SO 3Na、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2-COOH、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2-COONH 4、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2SO 3H、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2SO 3Na、
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-COOH、
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-COONH 4、
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2SO 3H、
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2SO 3Na、
CF 2＝CF-CF 2-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-COOH、
CF 2＝CF-CF 2-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-COONH 4、
CF 2＝CF-CF 2-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2SO 3H、
CF 2＝CF-CF 2-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2SO 3Na
Wherein consider to be preferably following substances from the better aspect of dispersion stabilization:
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2-COOH、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2-COONH 4、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2SO 3H、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2SO 3Na、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2-COOH、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2-COONH 4、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2SO 3H、
CF 2＝CF-O-CF 2CF(CF 3)-OCF 2CF 2SO 3Na、
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-COOH、
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-COONH 4
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-SO 3H、
CF 2＝CF-CF 2-O-CF 2CF(CF 3)-OCF 2CF 2-SO 3Na。
The above-mentioned fluoride-based compound (V) that contains is shown in following general formula (V):
CH 2＝CFCF 2O(CF(CF 3)CF 2O) gCF(CF 3)Y (V)
In the logical formula V, g represents 0 or 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned logical formula V, consider from the emulsifying capacity aspect, above-mentioned g is preferably 0 or 1～5 integer, 0～2 integer more preferably, more preferably 0 or 1, consider that from obtaining suitable water-soluble and surface-active aspect above-mentioned Y is preferably-COOM, thermotolerance aspect residual as impurity from being difficult for, that improve resulting formed body considers that above-mentioned M is preferably H or NH 4
As the above-mentioned fluoride-based compound (V) that contains, can enumerate for example following substances:
[changing 5]
Figure A20058001087600201
Stable on heating aspect wherein residual as impurity from being difficult for, that improve resulting formed body is considered, is preferably following substances:
CH 2＝CFCF 2OCF(CF 3)-COOH、
CH 2＝CFCF 2OCF(CF 3)-COONH 4、
CH 2=CFCF 2OCF (CF 3)-CF 2OCF (CF 3)-COOH or
CH 2＝CFCF 2OCF(CF 3)-CF 2OCF(CF 3)-COONH 4。
The above-mentioned fluoride-based compound (VI) that contains is shown in following general formula (VI);
CF 2＝CF(CF 2) hO-(CF(CF 3)CF 2O) i-CF(CF 3)-Y (VI)
In the general formula (VI), h represents 1～6 integer, and i represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (VI), consider from the copolymerization aspect, h is preferably the integer smaller or equal to 2, more preferably, consider that from the emulsifying capacity aspect above-mentioned i is preferably the integer smaller or equal to 3 smaller or equal to 1 integer, consider from obtaining suitable water-soluble and surface-active aspect, above-mentioned Y is preferably-COOM, and stable on heating aspect residual as impurity from being difficult for, that improve resulting formed body considers that above-mentioned M is preferably H or NH 4
As the above-mentioned fluoride-based compound (VI) that contains, can enumerate for example following substances:
[changing 6]
Figure A20058001087600211
Stable on heating aspect wherein residual as impurity from being difficult for, that improve resulting formed body is considered, is preferably following substances:
[changing 7]
Figure A20058001087600212
The above-mentioned fluoride-based compound (VII) that contains is shown in following general formula (VII);
CH 2＝CH(CF 2) p1-Y (VII)
In the general formula (VII), p1 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (VII), consider that from the emulsifying capacity aspect above-mentioned p1 is preferably the integer smaller or equal to 5, more preferably smaller or equal to 2 integer.Consider that from obtaining suitable water-soluble and surface-active aspect above-mentioned Y is preferably-COOM, stable on heating aspect residual as impurity from being difficult for, that improve resulting formed body considers that above-mentioned M is preferably H or NH 4
As the above-mentioned fluoride-based compound (VII) that contains, can enumerate for example following substances:
CH 2＝CH-CF 2CF 2-COOH、
CH 2＝CH-CF 2CF 2-COONH 4、
CH 2＝CH-CF 2CF 2-SO 3H、
CH 2＝CH-CF 2CF 2-SO 3Na、
CH 2＝CH-CF 2CF 2CF 2-COOH、
CH 2＝CH-CF 2CF 2CF 2-COONH 4、
CH 2＝CH-CF 2CF 2CF 2-SO 3H、
CH 2＝CH-CF 2CF 2CF 2-SO 3Na
Wherein consider to be preferably CH from the better aspect of dispersion stabilization 2=CH-CF 2CF 2-COONH 4
The above-mentioned fluoride-based compound (VIII) that contains is shown in following general formula (VIII):
CF 2＝CFO-(CH 2) q-(CF 2) p2-Y (VIII)
In the general formula (VIII), q represents 1～4 integer, and p2 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (VIII), above-mentioned q is preferably the integer smaller or equal to 2, and more preferably 1.Consider that from the emulsifying capacity aspect above-mentioned p2 is preferably the integer smaller or equal to 5, more preferably smaller or equal to 2 integer.Consider that from obtaining suitable water-soluble and surfactivity aspect above-mentioned Y is preferably-COOM, stable on heating aspect residual as impurity from being difficult for, that improve resulting formed body considers that above-mentioned M is preferably H or NH 4
As the above-mentioned fluoride-based compound (VIII) that contains, can enumerate for example following substances:
CF 2＝CFO-CH 2CF 2CF 2-COOH、
CF 2＝CFO-CH 2CF 2CF 2-COONH 4、
CF 2＝CFO-CH 2CF 2CF 2-SO 3H、
CF 2＝CFO-CH 2CF 2CF 2-SO 3Na
Wherein consider to be preferably CF from the better aspect of dispersion stabilization 2=CFO-CH 2CF 2CF 2-COONH 4
Contain fluoride-based emulsifying agent as above-mentioned, consider from the better aspect of copolymerization, preferably contain following substances: above-mentionedly contain fluoride-based compound (I), above-mentionedly contain fluoride-based compound (III), above-mentionedly contain fluoride-based compound (IV), above-mentionedly contain fluoride-based compound (V), above-mentionedly contain fluoride-based compound (VI), above-mentionedly contain fluoride-based compound (VII) and/or above-mentioned containing contains fluoride-based compound (VIII); More preferably contain above-mentioned fluoride-based compound (V) and/or the above-mentioned fluoride-based compound (VI) that contains of containing, further preferably contain the above-mentioned fluoride-based compound (V) that contains.
Contain fluoride-based emulsifying agent as above-mentioned, consider, especially preferably contain and contain fluoride-based compound (i) shown in the following general formula (i) from the better aspect of dispersion stabilization;
CH 2＝CFCF 2O-(CF(CF 3)CF 2O) k-CF(CF 3)-Y (i)
In the general formula (i), k represents 0～3 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
In the above-mentioned general formula (i), k is preferably 0～2 integer, integer 0 or 1 more preferably, Y be preferably-COOH or-COONH 4
The mixture of the above-mentioned various fluoride-based emulsifying agent that contains can be an above-mentioned general formula (I)～(VIII) compound different with the adduct number of alkylidene oxide in (i).
Above-mentionedly contain fluoride-based emulsifying agent, constitute above-mentioned contain fluoride-based emulsifying agent above-mentioned and contain fluoride-based compound (I)～(VIII), above-mentionedly contain fluoride-based compound (i), contain fluoride-based compound " compounds that has free-radical polymerised unsaturated link(age) and hydrophilic radical in the molecule " such as (1), can use known method to modulate.
In the fluorine-containing elastomer polymer of the present invention, the emulsifying agent unit is preferably the 10ppm～10 quality % of fluorine-containing elastomer polymer.If less than 10ppm, then do not using under the situation of non-copolymerization emulsifying agent in the past, the dispersion stabilization possible deviation in the aqueous medium, if surpass 10 quality %, then rerum natura such as thermotolerance might variation.
The unitary preferred 25ppm that is limited to down fluorine-containing elastomer polymer of mentioned emulsifier is limited to 50ppm under further preferred.Mentioned emulsifier is unitary to be limited to 5 quality % on preferred, is limited to 2.5 quality % on further preferred.
The unitary content of mentioned emulsifier is by carrying out F 19-NMR measures the value that obtains.
Fluorine-containing elastomer polymer of the present invention derives from the above-mentioned unit that contains fluoride-based emulsifying agent owing to having, even thereby use in the past non-copolymerization emulsifying agent, also have dispersion stabilization preferably in aqueous medium, rate of crosslinking has the trend of rising.
Fluorine-containing elastomer polymer of the present invention not only has the mentioned emulsifier unit, promptly derives from the unit (A) that contains fluoride-based emulsifying agent, also has to derive from sulfuration point monomer (b1) and/or have bromine atoms and/or the unit of the saturated fatty compounds of group of iodine atom (b2) (B).
Above-mentioned sulfuration point monomer (b1) be selected from by the alkene that contains bromine, contain iodine alkene, contain bromine vinyl ether, contain iodine vinyl ether, have itrile group Fluorine containing olefine, have an itrile group contain fluorovinyl ether, 1,1,3,3, at least a kind compound in the group that 3-five fluorine propylene [2-HPFP], perfluor (2-phenoxy propyl vinyl) ether and non-conjugated diene are formed.
As the above-mentioned alkene that contains bromine, the above-mentioned alkene that contains iodine, the above-mentioned vinyl ether that contains bromine, the above-mentioned vinyl ether that contains iodine, above-mentioned Fluorine containing olefine with itrile group, above-mentioned have an itrile group contain fluorovinyl ether and above-mentioned non-conjugated diene, for example can enumerate, compound described in No. 2002/0040119 specification sheets of U.S. Patent Application Publication, as belonging to the above-mentioned compound that contains all cpds groups such as alkene of bromine, can use a kind or at least 2 kinds respectively, preferably use following substances:
CH 2=CH-Rf-CH 2CH 2I (Rf is a perfluorinated alkylidene),
CH 2＝CHCF 2CF 2I、
CF 2＝CFOCF 2CF 2CH 2I。
As above-mentioned " saturated fatty compounds of group (b2) " with bromine atoms and/or iodine atom, be preferably perfluoro-carbon that 1～2 fluorine atoms are replaced by bromine atoms and/or iodine atom etc., can enumerate for example following substances: 1-bromo-2-iodine R 116,1-bromo-3-iodine perfluoropropane, 1-iodo-2-bromo-1, the compound described in No. 5151492 specification sheetss of United States Patent (USP) such as 1-C2H4F2 C2H4F2; The methylene radical iodide; 1,4-diiodo perfluo normal butane; 1,6-two iodo-3,3,4,4-tetrafluoro hexane; 1,3-diiodo perfluo propane; 1,6-diiodo perfluo hexane; 1,3-two iodo-2-chlorine perfluoropropane; 1,2-two (iodine difluoromethyl)-perfluorocyclobutane; One iodine R 116; One iodine perfluoropropane; One iodine perfluorinated butane; 2-iodo-1-hydrogen R 116; European patent application disclose No. 0868447 specification sheets described have cyano group contain iodine alkane etc., be preferably diiodo-compound.
In this specification sheets, sometimes above-mentioned " sulfuration point monomer (b1) " and above-mentioned " the saturated fatty compounds of group (b2) with iodine atom and/or bromine atoms " are collectively referred to as " monomer that contains cross-linking part ".That is, fluorine-containing elastomer polymer of the present invention has and derives from the monomeric unit (B) that contains cross-linking part.
In this specification sheets, " deriving from the monomeric unit (B) that contains cross-linking part " is the part on the molecular structure of fluorine-containing elastomer polymer, refers to and derives from the monomeric part that contains cross-linking part described later.
The above-mentioned monomeric unit (B) that contains cross-linking part that derives from is preferably the 0.01 quality %～10 quality % of fluorine-containing elastomer polymer, is limited to 0.05 quality % under preferred, is limited to 5 quality % on preferred, is limited to 3 quality % on further preferred.
Can only there be a kind of above-mentioned monomeric unit (B) or existence at least 2 kinds of these unit (B) that contain cross-linking part that derive from the fluorine-containing elastomer polymer of the present invention.
In this specification sheets, the above-mentioned amount that derives from the monomeric unit (B) that contains cross-linking part is by with F 19-NMR measures and the value that obtains.
As the above-mentioned monomer that contains cross-linking part, consider from the molecular weight and the molecular weight distribution aspect of the resulting fluorine-containing elastomer polymer of easy adjustment, be preferably above-mentioned saturated fatty compounds of group (b2) with bromine atoms and/or iodine atom, the saturated fatty compounds of group that more preferably has the iodine atom, further preferred saturated fatty compounds of group as diiodo-compound.As the above-mentioned monomer that contains cross-linking part, more preferably 1,4-diiodo perfluo butane.
As fluorine-containing elastomer polymer of the present invention, wherein, consider from the aspect of bridging property excellence, more preferably have the unitary fluorine-containing elastomer polymer that derives from saturated fatty compounds of group (b2) of 0.01 quality %～10 quality %, described saturated fatty compounds of group (b2) has bromine atoms and/or iodine atom.
For fluorine-containing elastomer polymer of the present invention, the mooney viscosity in the time of 100 ℃ is generally 10～100.As above-mentioned mooney viscosity, consider that from physical strength, chemical strength aspect it preferably is limited to 30 down, from the consideration of forming process aspect, it is limited to 80 on preferably.In this specification sheets, above-mentioned mooney viscosity [ML (1+10)] is to measure the value that obtains according to ASTM D-1646.
Fluorine-containing elastomer polymer of the present invention for example can be made by the manufacture method of fluorine-containing elastomer polymer of the present invention described later.Fluorine-containing elastomer polymer of the present invention can be a mode arbitrarily such as the decorating film of water-based emulsion, colloid (gum), granule (crumb) etc.
Above-mentioned colloid (gum) is the granulous fritter that contains fluorine-containing elastomer polymer, above-mentioned granule (crumb) refers to that fluorine-containing elastomer polymer at room temperature can not keep as the little granulous shape of gelationus and the result who merges mutually forms atypic blocky form.Fluorine-containing elastomer polymer of the present invention owing to have derives from and above-mentionedly contains the unit (A) of fluoride-based emulsifying agent and derive from the above-mentioned monomeric unit (B) that contains cross-linking part, thereby shorten the set time in when sulfuration, be easy to forming process, when carrying out the polyvalent alcohol sulfuration, excellence aspect the permanent compression set that reduces resulting formed body.
Fluorine-containing elastomer polymer of the present invention contains the iodine atomic time of 0.01 quality %～10 quality %, and is excellent especially aspect the bridging property when forming process, thereby preferred.
The preferred of above-mentioned iodine nucleidic mass is limited to 0.1 quality % down, is limited to 5 quality % on preferably.
The manufacture method of fluorine-containing elastomer polymer of the present invention be contain fluoride-based emulsifying agent, sulfuration point monomer (b1) and/or have bromine atoms and/or the saturated fatty compounds of group of iodine atom (b2) in the presence of, the manufacture method of the fluorine-containing elastomer polymer of polymerization fluorochemical monomer in aqueous medium.
Above-mentioned fluoride-based emulsifying agent and the preferred thing thereof of containing is identical with the material that describes in the fluorine-containing elastomer polymer of the invention described above.
In the manufacture method of fluorine-containing elastomer polymer of the present invention, above-mentionedly contain fluoride-based emulsifying agent and preferably add with the amount of the 1ppm～5 quality % of aqueous medium.
The above-mentioned addition that contains fluoride-based emulsifying agent is during less than the 1ppm of aqueous medium, and the amount that resulting fluorine-containing elastomer polymer is attached to retort inside increases, and productivity has the trend of reduction; When surpassing 5 quality % of aqueous medium, the thermostability of resulting fluorine-containing elastomer polymer might reduce.
For the above-mentioned addition that contains fluoride-based emulsifying agent, the preferred 10ppm that is limited to aqueous medium down, the further preferred 50ppm that is limited to aqueous medium down is limited to 2 quality % of aqueous medium on preferred, is limited to 1 quality % of aqueous medium on further preferred.
In the manufacture method of fluorine-containing elastomer polymer of the present invention, contain fluoride-based emulsifying agent in the presence of fluorochemical monomer is carried out polymerization, thereby resulting fluorine-containing elastomer polymer excellence aspect dispersion stabilization, rate of crosslinking is big.
In the manufacture method of fluorine-containing elastomer polymer of the present invention, not only above-mentioned contain fluoride-based emulsifying agent in the presence of, also sulfuration point monomer (b1) and/or have bromine atoms and/or the saturated fatty compounds of group of iodine atom (b2) in the presence of, the polymerization fluorochemical monomer.
Above-mentioned sulfuration point monomer (b1) and/or have bromine atoms and/or saturated fatty compounds of group of iodine atom (b2) and their preferred thing, identical with the material that in the fluorine-containing elastomer polymer of the invention described above, describes, hereinafter, similarly be sometimes referred to as " monomer that contains cross-linking part ".
In the manufacture method of fluorine-containing elastomer polymer of the present invention, the above-mentioned monomer that contains cross-linking part preferably adds with the amount of the 0.01 quality %～10 quality % of the monomer total amount supplied with.More than the 0.05 quality % of the monomer total amount that the above-mentioned monomer that contains cross-linking part that is added is more preferably supplied with, in addition, below the 5 quality % of the monomer total amount of more preferably being supplied with, more preferably below the 3 quality %.
In the manufacture method of fluorine-containing elastomer polymer of the present invention, in aqueous medium, make the fluorochemical monomer polymerization.
In the manufacture method of fluorine-containing elastomer polymer of the present invention, the copolymerization compound that has 1 fluorine atom at least that above-mentioned fluorochemical monomer refers to above-mentioned the 1st monomer and added according to expectation.
In the manufacture method of fluorine-containing elastomer polymer of the present invention,, can also add non-fluorochemical monomer according to expectation and carry out polymerization except above-mentioned fluorochemical monomer.
As above-mentioned fluorochemical monomer and above-mentioned non-fluorochemical monomer, can enumerate for example identical with non-fluorochemical monomer fluorochemical monomer and non-fluorochemical monomer with the fluorochemical monomer that in fluorine-containing elastomer polymer of the present invention, describes.
Total feed rate for above-mentioned fluorochemical monomer and non-fluorochemical monomer, consider from the dispersion stabilization aspect of resulting fluorine-containing elastomer polymer, preferred its lower limit is 10 mass parts with respect to the above-mentioned aqueous medium of 100 mass parts, this lower limit is 20 mass parts more preferably, consider from the yield aspect of fluoroelastomer, preferred its upper limit is 100 mass parts with respect to the above-mentioned aqueous medium of 100 mass parts, and this upper limit is 80 mass parts more preferably.
The total amount of initial stage addition when the total feed rate of above-mentioned fluorochemical monomer and non-fluorochemical monomer is the polyreaction initiation and the continuous addition that in polyreaction, is added.
Wherein, the feed rate of above-mentioned non-fluorochemical monomer can suitably be set according to the composition of desired fluorine-containing elastomer polymer.
In the above-mentioned polymerization,, can also add radical polymerization initiator in the aqueous medium according to being desirably in except above-mentioned fluoride-based emulsifying agent, the above-mentioned non-fluorochemical monomer that contains the monomer of cross-linking part, above-mentioned fluorochemical monomer and added of containing according to expectation.
As above-mentioned radical polymerization initiator, be generally the superoxide such as water-soluble inorganic compounds such as persulphates such as ammonium persulphate, Potassium Persulphate or peroxidation disuccinic acid, peroxidation two pentanedioic acids or water-soluble organic compounds, these radical polymerization initiators can use separately or make up at least 2 kinds and use.For the polymerization of low-temperature region, preferably use redox class initiator.Further, in the scope of not damaging oxidation-reduction stability, can be separately or use any one or both in water-insoluble organo-peroxide or the azo-compound to use with the superoxide of water-soluble inorganic compound or water-soluble organic compounds.
The addition of above-mentioned radical polymerization initiator can suitably be set according to the composition of the fluorine-containing elastomer polymer of manufacturing and the usage quantity of yield and the above-mentioned monomer that contains cross-linking part etc.For above-mentioned radical polymerization initiator, preferably it adds with the amount of 0.01 mass parts～0.4 mass parts with respect to the resulting fluorine-containing elastomer polymer of 100 weight parts, more preferably adds with the amount of 0.05 mass parts～0.3 mass parts.
In the above-mentioned polymerization, can add further except the above-mentioned additives such as fluorochemical surfactant the fluoride-based emulsifying agent, chain-transfer agent, free radical scavenger etc. that contain.
As above-mentioned fluorochemical surfactant, for example can enumerate, contain the fluorochemical surfactant of following substances: with Z 2-(CF 2) AaIn-COOH[the formula, Z 2Expression F or H, aa represents 3～20 integer] shown in fluorocarboxylic acid and an alkali metal salt, ammonium salt, amine salt and quaternary ammonium salt; With Z 3-(CH 2CF 2) BbIn-COOH[the formula, Z 3Expression F or Cl, bb represents 3～13 integer] shown in fluorocarboxylic acid and an alkali metal salt, ammonium salt, amine salt and quaternary ammonium salt; With RfO-(CF (CF 3) CF 2O) Cc-CF (CF 3)-Z 4[in the formula, Rf represents that carbonatoms is 1～7 perfluoroalkyl, and cc represents 0～10 integer, Z 4Expression-COOM or-SO 3M, M represent H, NH 4Or basic metal] shown in acidic cpd etc.
When above-mentioned polymerization, above-mentioned fluorochemical surfactant can add a kind or at least 2 kinds.
The addition of above-mentioned fluorochemical surfactant can suitably be set according to the composition of the fluorine-containing elastomer polymer of manufacturing and the usage quantity of yield and the above-mentioned monomer that contains cross-linking part etc.But the aspect that can be processed as excellent formed body such as physical strength, chemical strength from resulting fluorine-containing elastomer polymer considers that above-mentioned polymerization is preferably carried out under the state that does not have fluorochemical surfactant.
In this specification sheets, above-mentioned fluorochemical surfactant does not comprise the above-mentioned fluoride-based emulsifying agent that contains.
As above-mentioned chain-transfer agent, so long as be used for the chain-transfer agent of the manufacturing of fluoroelastomer, then do not limit especially, for example can enumerate, carbonatoms is that 1～12 alkanol, carbonatoms are that 1～12 ester, carbonatoms are that 1～12 alkane, carbonatoms are that 1～12 ketone or carbonatoms are mercaptan of 1～12 etc.Above-mentioned all cpds can partly be replaced by fluorine and/or chlorine.
In this specification sheets, above-mentioned chain-transfer agent does not comprise that 1～2 fluorine atoms are replaced by bromine atoms and/or iodine atom and the perfluoro-carbon that obtains etc. have the saturated fatty compounds of group of bromine atoms and/or iodine atom.
As above-mentioned carbonatoms is 1～12 alkanol, for example can enumerate methyl alcohol, ethanol, propyl alcohol, butanols etc.
As above-mentioned carbonatoms is 1～12 ester, for example can enumerate methyl acetate, ethyl acetate, butylacetate, ethyl propionate, dimethyl malonate, diethyl malonate, Succinic acid dimethylester, ethyl succinate etc.
As above-mentioned carbonatoms is 1～12 alkane, for example can enumerate methane, ethane, propane, butane, pentane, hexane etc.
As above-mentioned carbonatoms is 1～12 ketone, for example can enumerate acetone, methyl ethyl diketone, methyl ethyl ketone, pimelinketone etc.
As above-mentioned carbonatoms is 1～12 mercaptan, for example can enumerate lauryl mercaptan etc.
As the above-mentioned compound that is partly replaced, for example can enumerate chlorination carbon, chloroform, tetracol phenixin etc. by halogen.
It is that 1～6 stable hydrocarbon, carbonatoms are that 1～4 alkanol, carbonatoms are that 4～8 carbonate, carbonatoms are that to replace hydrocarbon, carbonatoms be that 3～5 ketone and/or carbonatoms are 10～12 mercaptan for 1～2 chlorine that above-mentioned chain-transfer agent is preferably carbonatoms.In the above-mentioned chain-transfer agent, aspect the dispersiveness polymerisation medium, chain transfer, removing property from the purpose goods, consider, more preferably iso-pentane, Virahol, diethyl malonate, tetracol phenixin, acetone, ethyl acetate and/or lauryl mercaptan, consider from the few aspect of the performance of chain transfer reduction suitable, polymerization velocity, more preferably iso-pentane, diethyl malonate, ethyl acetate etc.
In the manufacture method of fluorine-containing elastomer polymer of the present invention, the above-mentioned chain-transfer agent that is added is 0.0001 mass parts～5 mass parts with respect to the 1st monomer of 100 mass parts and the monomeric total addition except the 1st monomer preferably.Consider from the molecular weight of adjusting fluorine-containing elastomer polymer and the aspect of molecular weight distribution, the above-mentioned chain-transfer agent that is added with respect to the above-mentioned total addition of 100 mass parts more preferably more than or equal to 0.0005 mass parts, further be preferably greater than and equal 0.001 mass parts, the above-mentioned chain-transfer agent that is added in addition with respect to the above-mentioned total addition of 100 mass parts more preferably smaller or equal to 1 quality %, more preferably smaller or equal to 0.1 quality %.
Above-mentioned polymerization can be operated with any one of batchwise operation, semi-batch operation and operate continuously and carry out, and preferably carries out with semi-batch operation.
In above-mentioned polymerization, above-mentioned fluorochemical monomer, above-mentioned non-fluorochemical monomer, the monomer that contains cross-linking part, polymerization starter, the above-mentioned additives such as fluoride-based emulsifying agent, above-mentioned fluorochemical surfactant, above-mentioned chain-transfer agent and/or free radical scavenger that contain can suitably append by composition or the yield according to desired fluorine-containing elastomer polymer in polyreaction.Above-mentioned polymerization is further carried out according to disclose No. 00/001741 described multistage polymerization operation of brochure with the world, can modulate to have the fluorine-containing elastomer polymer that desired monomer is formed.
Above-mentioned polymerization maintains the temperature of 10 ℃～120 ℃ of scopes usually and carries out.When said temperature is lower than 10 ℃, can not obtain effective bigger speed of response on industrial level, when surpassing 120 ℃, keep the required reaction pressure of polyreaction and increase, it is bigger to be used to keep the cost that spends on the device of reaction.
The pressure that above-mentioned polymerization maintains 0.5MPa～10MPa scope usually carries out.The preferred of above-mentioned scope is limited to 1.0MPa down, above-mentioned scope preferably on be limited to 6.2MPa.
When above-mentioned polymerization was carried out with semi-batch operation, the amount of the monomer gas when desired polymerization pressure can be supplied with by the adjustment initial stage was reached at the polymerization initial stage, after the initiation reaction, adjusted pressure by the additional services amount of adjusting monomer gas.
When above-mentioned polymerization was carried out with operate continuously, for desired polymerization pressure, the back-pressure of the outlet pipe by adjusting resulting fluorine-containing elastomer polymer dispersion liquid was adjusted pressure.
When above-mentioned pressure was lower than 0.5MPa, the monomer concentration in the polymerization reaction system was low excessively, can not obtain satisfied speed of response, and the molecular weight of resulting fluorine-containing elastomer polymer molecule might be fully big inadequately.When above-mentioned pressure surpassed 10MPa, the cost that spends on the device of pressure was bigger keeping.
Above-mentioned polymerization was carried out 0.5 hour～100 hours usually.
Obtain the amount that equates substantially with the additional services amount by carrying out fluorine-containing elastomer polymer that above-mentioned polymerization obtains,, obtain 10 mass parts～30 mass parts with respect to 100 mass parts aqueous mediums.With respect to 100 mass parts aqueous mediums, above-mentioned fluorine-containing elastomer polymer is preferably more than and equals 20 mass parts, is preferably smaller or equal to 25 mass parts.The amount of above-mentioned fluorine-containing elastomer polymer is during less than 10 mass parts, and productivity is lower and not preferred, and when surpassing 30 mass parts, above-mentioned fluorine-containing elastomer polymer might be difficult to disperse.
When above-mentioned polymerization is above-mentioned multistage polymerization operation, the amount of above-mentioned fluorine-containing elastomer polymer is through the value after all stages of polymerization process, with respect to 100 mass parts aqueous mediums, the amount of the fluorine-containing elastomer polymer that is obtained by the 1st polymerization process is sometimes less than 10 mass parts.Be generally 10nm～500nm, excellent dispersion by carrying out the median size of finishing polymeric fluorine-containing elastomer polymer particle that above-mentioned polymerization obtains.
The fluorine-containing elastomer polymer (hereinafter being sometimes referred to as fluorine-containing elastomer polymer (P)) that obtains by the manufacture method of fluorine-containing elastomer polymer of the present invention, so long as obtain by above-mentioned polymerization, it then can be mode arbitrarily, can constitute the water-based emulsion of finishing polymkeric substance, can constitute fluorine-containing elastomer polymer aqueous liquid dispersion described later, also can constitute by above-mentioned water-based emulsion is carried out condensation, drying wait the colloid that obtains or granule.
The manufacture method of fluorine-containing elastomer polymer of the present invention is owing to be to contain fluoride-based emulsifying agent and above-mentioned containing in the presence of cross-linking part monomeric carries out above-mentioned, thereby can suitably adjust the molecular weight and the molecular weight distribution of resulting fluorine-containing elastomer polymer, obtain being directed into fluorine-containing elastomer polymer in the polymkeric substance with deriving from the above-mentioned monomeric unit that contains cross-linking part.When utilizing the manufacture method of fluorine-containing elastomer polymer in the past, there is following problems: when (1) uses halide-containing to carry out polyreaction as chain-transfer agent, the dispersion stabilization reduction of resulting fluorine-containing elastomer polymer, the addition of (2) fluorochemical surfactant are more after a little while, resulting fluorine-containing elastomer polymer is attached to retort inside, thereby yield reduces.Yet, when utilizing the manufacture method of fluorine-containing elastomer polymer of the present invention, even use halide-containing as the above-mentioned monomer that contains cross-linking part, carry out polyreaction having under a spot of condition that contains fluoride-based emulsifying agent, yield is also better, further, can obtain having in the polymkeric substance and derive from the monomeric unit that contains cross-linking part and dispersion stabilization fluorine-containing elastomer polymer preferably.
The fluorine-containing elastomer polymer aqueous liquid dispersion also is one of the present invention, it is that the particle that will contain fluorine-containing elastomer polymer is dispersed in the fluorine-containing elastomer polymer aqueous liquid dispersion in the aqueous medium, and described fluorine-containing elastomer polymer is the fluorine-containing elastomer polymer or the above-mentioned fluorine-containing elastomer polymer (P) of the invention described above.
Fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention contains or does not contain fluoride-based emulsifying agent.
In the fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention,, thereby in aqueous medium, can not contain fluoride-based emulsifying agent because fluorine-containing elastomer polymer has the mentioned emulsifier unit.
In the fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention, for example, above-mentioned contain fluoride-based emulsifying agent can be less than 1000ppm.
In the fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention, the better aspect of the bridging property during from forming process considers, preferred above-mentionedly contains fluoride-based emulsifying agent less than 100ppm, is more preferably less than 10ppm.
For fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention, can to make fluorine-containing elastomer polymer of the present invention be 10 mass parts～70 mass parts with respect to 100 mass parts aqueous mediums by operation such as concentrating.
Fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention can be as modulated: that will carry out obtaining after the polyreaction of fluorine-containing elastomer polymer of the invention described above finishes the polymeric water-based emulsion, with the known method cohesion, modulate by making with extra care then.
As above-mentioned purified method, do not limit especially, for example can enumerate methods such as extraction, ion exchange resin treatment, ultrafiltration membrane treatment.
Fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention is because the concentration that contains fluoride-based emulsifying agent in above-mentioned scope, thereby can be processed as the aggregate that do not contain fluoride-based emulsifying agent in fact, composition, formed body etc.
Contain the fluorine-containing elastomer polymer of the invention described above and/or the fluorine-containing elastomer polymer colloid or the granule of above-mentioned fluorine-containing elastomer polymer (P) and can not contain fluorochemical surfactant in fact.
Above-mentioned fluorine-containing elastomer polymer colloid or granule can be by obtaining fluorine-containing elastomer polymer aqueous liquid dispersion of the present invention condensation, drying.
As the condensation agent that can use when the above-mentioned condensation, can enumerate aluminium salt such as Tai-Ace S 150, potassium aluminium sulfate; Calcium salts such as calcium sulfate; Magnesium salts such as sal epsom; Flocculant aids such as monovalent cation such as sodium-chlor or Repone K salt.
Containing the fluorine-containing elastomer polymer of the invention described above and/or the fluorine-containing elastomer polymer composition of above-mentioned fluorine-containing elastomer polymer (P) also is one of the present invention.Fluorine-containing elastomer polymer composition of the present invention not only contains the fluorine-containing elastomer polymer and/or the above-mentioned fluorine-containing elastomer polymer (P) of the invention described above, can also contain solidifying agent, weighting agent etc.
As above-mentioned solidifying agent, can enumerate polyvalent alcohol, polyamine, organo-peroxide, organotin, two (amino-phenol) tetramine or two (sulfo-amino phenol) etc.
Fluorine-containing elastomer polymer composition of the present invention is owing to contain fluorine-containing elastomer polymer of the present invention and/or above-mentioned fluorine-containing elastomer polymer (P), thereby do not contain fluoride-based emulsifying agent in fact, when forming process easy crosslinked aspect excellence.
For fluorine-containing elastomer polymer composition of the present invention, for example when carrying out the polyvalent alcohol sulfuration, show the sulfuration more excellent than the composition that contains fluorine-containing elastomer polymer in the past.
Fluorine-containing elastomer polymer formed body of the present invention carries out crosslinked obtaining with fluorine-containing elastomer polymer of the present invention or above-mentioned fluorine-containing elastomer polymer (P).Above-mentionedly crosslinkedly for example can use above-mentioned solidifying agent to carry out.
For fluorine-containing elastomer polymer formed body of the present invention, for example carrying out polyvalent alcohol when sulfuration, its compression set is lower than the formed body that is obtained by in the past fluorine-containing elastomer polymer.
Fluorine-containing elastomer polymer formed body of the present invention is owing to contain above-mentioned fluorine-containing elastomer polymer, thereby compression set is lower, physical strength is excellent, as sealing material, wire covering materials, pipe (tube), flexible pipe (hose), film, laminate etc. is suitable, is particularly suitable for use in semiconductor manufacturing apparatus parts, vehicle part etc.
Fluorine-containing elastomer polymer of the present invention is owing to contain said structure, and when carrying out forming process, vulcanization rate is very fast, and cross-linking density is higher in addition, and further, resulting formed body shows the less excellent specific property of compression set.
The manufacture method of fluorine-containing elastomer polymer of the present invention is owing to contain above-mentioned formation, can make operation easy, polymerization rate increases, further, for resulting fluorine-containing elastomer polymer, when carrying out forming process, vulcanization rate is fast, cross-linking density is higher in addition, and further, the compression set of resulting formed body is less.
The present invention will be described in more detail below by embodiment, but the present invention is not limited to these embodiment.
The mensuration of carrying out in each embodiment, comparative example is undertaken by following method.
(1) solid component concentration: 150 ℃ of dryings 1 hour, the quality by this moment reduces tried to achieve with resulting aqueous liquid dispersion.
(2) mooney viscosity [ML (1+10)]: measure according to ASTM D-1646.
(3) composition of fluorine-containing elastomer polymer: by passing through F 19-NMR measures the value that obtains and calculates.
(4) contain fluoride-based emulsifier concentration in the fluorine-containing elastomer polymer emulsion: after adding methyl alcohol with water-based emulsion equivalent and carrying out Soxhlet (Soxhlet) extraction, carry out HPLC and measure, try to achieve thus.
(5) median size: measure by the dynamic light scattering method.
(6) iodine atom content: measure by carrying out ultimate analysis.
Embodiment 1
At the internal volume with agitator is in the stainless steel pressure vessel of 3L, the deionized water that adds 1000ml, conduct contains the perfluor (9 of fluoride-based emulsifying agent with 1g, 9-dihydro-2,5-two (trifluoromethyl)-3,6-two oxa-s)-ammonium salt [RS-1] of 8-nonenoic acid, repeat nitrogen pressure, after the decompression degassing, under the decompression of-700mHg, the mixture of the fluorochemical monomer of importing VDF/HFP=65 mole %/35 moles of % (hereinafter, the mixture of fluorochemical monomer is called " mix monomer "), boost to 1.5MPa at 80 ℃, be pressed into the 0.5 quality % ammonium persulfate aqueous solution of 10g, initiated polymerization can be seen pressure and reduce this moment, thereby when pressure is reduced to 1.4MPa, append the I (CF of 2.98g 2CF 2) 2The mix monomer of I and VDF/HFP=78 mole %/22 moles of % makes pressure be back to 1.5MPa.
Then, in polyreaction, repeat following operation: when the jar internal pressure is reduced to 1.4MPa, append the mix monomer of VDF/HFP=78 mole %/22 moles of %, make a jar internal pressure be back to 1.5MPa.In polyreaction, appended the 0.5 quality % ammonium persulfate aqueous solution of 10g in per 3 hours, make reaction continue 8.1 hours, obtain the 1325g water-based emulsion.In the resulting water-based emulsion, solid component concentration is 23 quality %, and the concentration of unreacted RS-1 is 42ppm, and median size is 198nm.
In resulting water-based emulsion, add hydrochloric acid, carry out condensation, washing,, reclaim fluorine-containing elastomer polymer 120 ℃ of dryings 12 hours.
Resulting fluorine-containing elastomer polymer consist of VDF/HFP/RS-1=77.95 mole %/22.00 moles of %/0.05 mole % (69.2 quality %/30.5 quality %/0.3 quality %), the mooney viscosity in the time of 100 ℃ is 46.
Embodiment 2～5
Change the polymerizing condition except as shown in table 1, operation obtains fluorine-containing elastomer polymer similarly to Example 1.
The result of embodiment 1～5 is as shown in table 2.
[table 1]
Deionized water (g) APS(ppm) RS-1(g) I(CF 2CF 2) 2I(g) Pressure (MPa) Polymerization time (hour)
Embodiment 1 1000 150 1 2.98 1.5 8.1
Embodiment 2 1000 50 0.1 2.98 1.5 1.3
Embodiment 3 1000 200 10 2.98 1.5 10.3
Embodiment 4 1000 50 1 0.3 1.5 2.8
Embodiment 5 1000 300 1 12 1.5 17.2
In the table 1, APS represents with the concentration with respect to deionized water.
[table 2]
PC (quality %) Output (g) Form Form Mooney viscosity (100 ℃ time value)
VDF (mole %) HFP (mole %) RS-1 (mole %) VDF (quality %) HFP (quality %) RS-1 (quality %) I content (quality %)
Embodiment 1 23 1325 77.95 22.00 0.05 69.2 30.5 0.3 0.29 46
Embodiment 2 3 1031 77.95 22.00 0.05 69.2 30.5 0.3 3.02 34
Embodiment 3 27 1411 77.70 21.93 0.38 67.7 29.9 2.4 0.25 43
Embodiment 4 10 1111 77.88 21.98 0.14 68.8 30.3 0.9 0.11 65
Embodiment 5 13 1207 77.93 21.99 0.07 69.1 30.5 0.5 1.54 11
In the table 2, PC represents the concentration of solids component, and output is represented the quality of the water-based emulsion after the polyreaction, and I content is represented the iodine atom content of fluorine-containing elastomer polymer.
Embodiment 6
At the internal volume with agitator is in the stainless steel pressure vessel of 3L, adding 1000g deionized water, conduct contain the RS-1 (1g) of fluoride-based emulsifying agent and 0.09g adjusts agent as pH Sodium phosphate dibasic 12 water salt, after repeating nitrogen pressure, the decompression degassing, under the decompression of-700mHg, import the mix monomer of TFE/Pr=85 mole %/15 moles of %, boost to 2.5MPa at 70 ℃.Then be pressed into the 0.5 quality % ammonium persulfate aqueous solution of 10g, initiated polymerization can be seen pressure and reduce, thereby when pressure is reduced to 2.4MPa, append the I (CF of 2.98g this moment 2CF 2) 2The mix monomer of I and TFE/Pr=55 mole %/45 moles of % makes pressure be back to 2.5MPa.
Then, in polyreaction, repeat following operation: when the jar internal pressure is reduced to 2.4MPa, append the mix monomer of TFE/Pr=55 mole %/45 moles of %, make a jar internal pressure be back to 2.5MPa.In polyreaction, appended the 0.5 quality % ammonium persulfate aqueous solution of 10g in per 3 hours, make reaction continue 13 hours, obtain the 1248g water-based emulsion.
In the resulting water-based emulsion, solid component concentration is 20 quality %, and the concentration of unreacted RS-1 is 127ppm, and median size is 156nm.
In resulting water-based emulsion, add hydrochloric acid, carry out condensation, washing,, reclaim fluoroelastomer copolymer 120 ℃ of dryings 12 hours.
Resulting fluorine-containing elastomer polymer consist of TFE/Pr/RS-1=54.94 mole %/45.01 moles of %/0.05 mole % (74.16 quality %/25.52 quality %/0.32 quality %), the mooney viscosity in the time of 100 ℃ is 43.
Embodiment 7
At the internal volume with agitator is in the stainless steel pressure vessel of 3L, add 1000g deionized water, 5g and contain fluoride-based emulsifying agent [RS-1] and 0.09g adjust agent as pH Sodium phosphate dibasic 12 water salt, after repeating nitrogen pressure, the decompression degassing, under the decompression of-700mHg, import the mix monomer of TFE/PMVE=25 mole %/75 moles of %, boost to 0.78MPa at 53 ℃.Then be pressed into 264mg/ml ammonium persulphate [APS] aqueous solution of 20ml, initiated polymerization with nitrogen pressure.When since polyreaction make internal drop to 0.69MPa the time, be pressed into the CF of 1.8g with nitrogen pressure 2=CFOCF 2CF (CF 3) OCF 2CF 2CN[CNVE].Then respectively with the PMVE of the TFE that is pressed into 4.7g certainly and 5.3g so that pressure is 0.78Mpa.Then, be accompanied by the carrying out of polyreaction, similarly be pressed into TFE, PMVE, between 0.69MPa～0.78MPa, repeat to boost, step-down, when the total addition of TFE and PMVE is 70g, be pressed into the CNVE of 1.8g with nitrogen pressure simultaneously.
Polyreaction caused after 7 hours, when the total addition of TFE and PMVE is 130g, with the autoclave cooling, discharged unreacted monomer, and obtaining solid component concentration is the aqueous dispersion 1100g of 11.2 quality %.
1000g in this aqueous dispersion with the dilution of 3000g water, is stirred, simultaneously it is made an addition to lentamente in the 3.5 quality % aqueous hydrochloric acids of 2800g.Add the back and stirred 5 minutes, filter condensate then, resulting polymkeric substance is further poured among the HCFC-141b of 2kg, stirred 5 minutes, filter once more.Then, further repeat 4 washings, filterable operation, follow 60 ℃ of vacuum-dryings 72 hours, obtain the fluorine-containing elastomer polymer (elastomerics that contains itrile group) of 110g based on this HCFC-141b.
Resulting fluorine-containing elastomer polymer consist of TFE/PMVE/CNVE/RS-1=59.6 mole %/39.7 moles of %/0.6 mole %/0.1 mole of %, the mooney viscosity in the time of 100 ℃ is 65.
Embodiment 8
At the internal volume with agitator is in the stainless steel pressure vessel of 3L, add the 1480ml deionized water, and 0.1g is as the perfluor (6 that contains fluoride-based emulsifying agent, 6-dihydro-2-trifluoromethyl-3-oxa-)-ammonium salt [RS-2] of 5-hexenoic acid, repeat nitrogen pressure, after the decompression degassing, under the decompression of-700mHg, the mixture of the fluorochemical monomer of importing VDF/HFP=55 mole %/45 moles of % (hereinafter, the mixture of fluorochemical monomer is called " mix monomer "), boost to 1.5MPa at 80 ℃, be pressed into the 0.5 quality % ammonium persulfate aqueous solution of 14g, initiated polymerization, can see pressure this moment reduces, thereby when pressure is reduced to 1.4MPa, append the I (CF of 2.59g 2CF 2) 2The mix monomer of I and VDF/HPF=78 mole %/22 moles of % makes pressure be back to 1.5MPa.
Then, in polyreaction, repeat following operation: when the jar internal pressure is reduced to 1.4MPa, append the mix monomer of VDF/HFP=78 mole %/22 moles of %, make a jar internal pressure be back to 1.5MPa.In polyreaction, appended the 0.5 quality % ammonium persulfate aqueous solution of 6g in per 3 hours, make reaction continue 10 hours, obtain the 2228g water-based emulsion.In the resulting water-based emulsion, solid component concentration is 24.7 quality %, and median size is 118nm.
In resulting water-based emulsion, add hydrochloric acid, carry out condensation, washing,, reclaim fluorine-containing elastomer polymer 120 ℃ of dryings 12 hours.
Resulting fluorine-containing elastomer polymer (dry thing is washed in the condensation of water-based emulsion) consist of VDF/HFP=77.7 mole %/22.3 moles of % (59.8 quality %/40.2 quality %), by ultimate analysis as can be known iodine content be 0.2 quality %, the mooney viscosity in the time of 100 ℃ is 49.
Dry thing is washed in the condensation of the above-mentioned water-based emulsion of 1g to be dissolved in the 10g acetone, this polymers soln is scattered in the 30g ion exchanged water, utilize liquid chromatography/cascade connection type mass analysis (LC-MS/MS) that the unreacted RS-2 that removes in the aqueous acetone solution behind the solids component is carried out quantitatively, it (detects and is limited to 1ppb) below detection limit as can be known.Carry out quantitatively with LC-MS/MS for the condensation water vent, it is also below detection limit as can be known.
And, among the above-mentioned LC/MS/MS, measure the RS-2 that is contained in the aqueous acetone solution remove behind the solids component under the following conditions, obtain the weight ratio that washs dry thing with respect to condensation.In the said determination, use Waters 2695 Separation module, Micromass Quattro micro TMAPI, Waters 2996 Photodiode Array detector (all being the Waters corporate system).Utilize above-mentioned liquid chromatography, by Waters atlantis dC-18 (30mm * 2.1mm i.d.) chromatographic column, 0.01M ammonium acetate: acetonitrile (55: 45 v: v), carry out wash-out with 0.15ml/ minute flow velocity.In the above-mentioned cascade connection type mass analysis, carry out negatron spraying (negative electro spray) type (ESP -) ionization.
Embodiment 9
Except ammonium salt [RS-3] conduct of using 0.15g perfluor (5-trifluoromethyl-4,7-two oxa-s)-8-nonenoic acid contains outside the fluoride-based emulsifying agent, operation similarly to Example 8, sustained reaction 15 hours obtains the 2173g water-based emulsion.The solid component concentration of resulting water-based emulsion is 22.9 quality %, and median size is 134nm.
In resulting water-based emulsion, add hydrochloric acid, carry out condensation, washing,, reclaim fluorine-containing elastomer polymer 120 ℃ of dryings 12 hours.
Resulting fluorine-containing elastomer polymer (dry thing is washed in the condensation of water-based emulsion) consist of VDF/HFP=77.6 mole %/22.4 moles of % (59.6 quality %/40.4 quality %), by ultimate analysis as can be known iodine content be 0.2 quality %, the mooney viscosity in the time of 100 ℃ is 44.In addition, wash dry thing for the condensation of above-mentioned water-based emulsion, after measuring with LC/MS/MS similarly to Example 8, unreacted as can be known RS-3 carries out same mensuration for the condensation draining below detection limit, and it is also below detection limit as can be known.
Embodiment 10
At the internal volume with agitator is in the stainless steel pressure vessel of 3L, add the 1650ml deionized water, and 0.1g is as the perfluor (6 that contains fluoride-based emulsifying agent, 6-dihydro-2-trifluoromethyl-3-oxa-)-ammonium salt [RS-2] of 5-hexenoic acid, repeat nitrogen pressure, after the decompression degassing, under the decompression of-700mHg, after importing the 0.07ml iso-pentane, the mixture of the fluorochemical monomer of importing VDF/TFE/HFP=45 mole %/15 moles of %/40 mole % (hereinafter, the mixture of fluorochemical monomer is called " mix monomer "), boost to 1.5MPa at 80 ℃, be pressed into the 5 quality % ammonium persulfate aqueous solutions of 5.2g, initiated polymerization, can see pressure this moment reduces, thereby when pressure is reduced to 1.4MPa, append the mix monomer of VDF/TFE/HFP=60 mole %/20 moles of %/20 mole %, make pressure be back to 1.5MPa.
Then, in polyreaction, repeat following operation: when the jar internal pressure is reduced to 1.4MPa, append the mix monomer of VDF/TFE/HFP=60 mole %/20 moles of %/20 mole %, make a jar internal pressure be back to 1.5MPa.When having appended the 285g mix monomer, append 6.7g one iodine perfluoropropane, the additional quantity of further proceeding to react until mix monomer is 265g, obtains the 2227g water-based emulsion after 7.5 hours.The solid component concentration of resulting water-based emulsion is 25.7 quality %, and median size is 99nm.
In resulting water-based emulsion, add hydrochloric acid, carry out condensation, washing,, reclaim fluorine-containing elastomer polymer 120 ℃ of dryings 12 hours.
Resulting fluorine-containing elastomer polymer (dry thing is washed in the condensation of water-based emulsion) consist of VDF/TFE/HFP=61.6 mole %/17.2 moles of %/21.2 mole % (44.6 quality %/19.5 quality %/36.0 quality %), by ultimate analysis as can be known iodine content be 0.1 quality %, the mooney viscosity in the time of 100 ℃ is 43.In addition, wash dry thing for the condensation of above-mentioned water-based emulsion, measure with LC/MS/MS similarly to Example 8, unreacted as can be known RS-2 carries out after the same mensuration as can be known for the condensation draining below detection limit, and it is also below detection limit.
Comparative example 1
In embodiment 1, use the ammonium salt [APFO] of 2g Perfluorocaprylic Acid to substitute RS-1,12 hours reaction is carried out in operation similarly to Example 1 in addition, obtains the 1370g water-based emulsion.
In the resulting water-based emulsion, solid component concentration is 27.3 quality %, and median size is 266nm.
Then to adopting the composition in the fluorinated copolymer that condensation, washing, the drying process identical with embodiment 1 obtain to measure back discovery, VDF/HFP=77.9 mole %/22.1 moles of %.Mooney viscosity 100 ℃ the time is 45 in addition.
Test example 1
In fluoroelastomer copolymer that obtains by embodiment 1 and the fluorinated copolymer that obtains by comparative example 1, mix composition as shown in table 3, method by defined is carried out uniform mixing with rubber rollers, and the modulation vulcanising composition comes sulfuration property is estimated with vulkameter.In addition, under condition as shown in table 3, composition is vulcanized, measure the rerum natura of formed body.
In test conditions, tensile strength, extensibility, tensile stress, compression set are based on JIS K 6301, and Shore hardness is based on ASTM D-2240.For sulfuration property, use vulkameter (JSRII) to come sulfuration property to be measured at 170 ℃.
The result is as shown in table 3.
[table 3]
Embodiment 1 Comparative example 1
Multipolymer (mass parts) bisphenol AF (mass parts) BTPPC (mass parts) carbon black (mass parts) magnesium oxide (mass parts) calcium hydroxide (mass parts) 100 2 0.6 20 3 6 100 2 0.6 20 3 6
The press vulcanization baking 170 ℃ * 15 minutes 230 ℃ * 24 hours 170 ℃ * 15 minutes 230 ℃ * 24 hours
Tensile strength [MPa] extensibility [%] tensile stress M 100[MPa] compression set [%] Shore hardness 14 245 4.2 10 76 13 240 4.5 15 77
Sulfuration property T 10 T 90 μ 4.0 5.0 3.15 6.1 8.2 2.56
In the table 3, T 10The expression induction time, T 90The expression sulfurizing time, μ represents sulphidity.
The fluoroelastomer copolymer that is obtained by embodiment 1 is than the vulcanization rate (T of the fluorinated copolymer that is obtained by comparative example 1 10, T 90) fast, further, resulting sulfidization molding body surface reveals the excellent specific property of less compression set.
Utilizability on the industry
Fluorine-containing elastomer polymer of the present invention is owing to contain said structure, and when carrying out processing and forming, curingprocess rate is very fast, and crosslink density is higher in addition, and further, resulting formed body shows the less excellent specific property of compression set.
The manufacture method of fluorine-containing elastomer polymer of the present invention is owing to contain above-mentioned formation, can make operation easy, polymerization rate increases, further, for resulting fluorine-containing elastomer polymer, when carrying out processing and forming, curingprocess rate is fast, crosslink density is higher in addition, and the compression set of resulting formed body is less.

Claims (21)

1. fluorine-containing elastomer polymer, this fluorine-containing elastomer polymer has unit (A) and unit (B), described unit (A) derives from and contains fluoride-based emulsifying agent, described unit (B) derives from sulfuration point monomer (b1) and/or saturated fatty compounds of group (b2), described saturated fatty compounds of group (b2) has bromine atoms and/or iodine atom, this fluorine-containing elastomer polymer is characterised in that, describedly contains fluoride-based emulsifying agent and contains the compound that has free-radical polymerised unsaturated link(age) and hydrophilic radical in molecule.
2. fluorine-containing elastomer polymer as claimed in claim 1, wherein, the described compound that has free-radical polymerised unsaturated link(age) and hydrophilic radical in molecule is to contain fluoride-based compound (1) shown in the following general formula (1);
CR 1R 2＝CR 3(CR 4R 5) j-(O) k-R-Y (1)
In the general formula (1), R 1, R 2, R 3, R 4And R 5Identical or different, perfluoroalkyl, H, F, Cl, Br or I that expression is replaced by H or do not replaced by H, R is illustrated in the fluoro alkylidene group that has or do not have the straight or branched that Sauerstoffatom and all or part of H replaced by F on the main chain, j represents 0～6 integer, k represents 0 or 1 integer, and Y represents hydrophilic radical.
3. fluorine-containing elastomer polymer, this fluorine-containing elastomer polymer has unit (A) and unit (B), described unit (A) derives from and contains fluoride-based emulsifying agent, (B) derives from the monomer that contains cross-linking part in described unit, this fluorine-containing elastomer polymer is characterised in that, describedly contains fluoride-based emulsifying agent and contains and contain fluoride-based compound (I) shown in the following general formula (I), contain fluoride-based compound (II) shown in the following general formula (II), contain fluoride-based compound (III) shown in the following general formula (III), contain fluoride-based compound (IV) shown in the following general formula (IV), contain fluoride-based compound (V) shown in the following logical formula V, contain fluoride-based compound (VI) shown in the following general formula (VI), contain fluoride-based compound (VII) shown in the following general formula (VII), and/or contain fluoride-based compound (VIII) shown in the following general formula (VIII);
CF 2＝CF-(CF 2) a-Y (I)
In the general formula (I), a represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF-(CF 2C(CF 3)F) b-Y (II)
In the general formula (II), b represents 1～5 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CFO-(CF 2) c-Y (III)
In the general formula (III), c represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF(CF 2) d-O-(CF 2CFXO) e-(CF 2) f-Y (IV)
In the general formula (IV), X represent F or-CF 3, d represents 0～2 integer, and e represents 1～10 integer, and f represents 1～3 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CH 2＝CFCF 2O(CF(CF 3)CF 2O) gCF(CF 3)Y (V)
In the logical formula V, g represents 0～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF(CF 2) hO-(CF(CF 3)CF 2O) i-CF(CF 3)-Y (VI)
In the general formula (VI), h represents 1～6 integer, and i represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CH 2＝CH(CF 2) p1-Y (VII)
In the general formula (VII), p1 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CFO-(CH 2) q-(CF 2) p2-Y (VIII)
In the general formula (VIII), q represents 1～4 integer, and p2 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
4. as claim 1,2 or 3 described fluorine-containing elastomer polymer, wherein, described fluorine-containing elastomer polymer is the vinylidene analog copolymer.
5. as claim 1,2 or 3 described fluorine-containing elastomer polymer, wherein, described fluorine-containing elastomer polymer is tetrafluoroethylene/propylene copolymers.
6. as claim 1,2 or 3 described fluorine-containing elastomer polymer, wherein, described fluorine-containing elastomer polymer is a tetrafluoroethylene/perfluoro vinyl ether analog copolymer.
7. as claim 3,4,5 or 6 described fluorine-containing elastomer polymer, wherein, describedly contain fluoride-based emulsifying agent and contain following compound: contain fluoride-based compound (I), contain fluoride-based compound (III), contain fluoride-based compound (IV), contain fluoride-based compound (V), contain fluoride-based compound (VI), contain fluoride-based compound (VII) and/or have and contain fluoride-based compound (VIII).
8. fluorine-containing elastomer polymer as claimed in claim 7 wherein, describedly contains fluoride-based emulsifying agent and contains and contain fluoride-based compound (i) shown in the following general formula (i);
CH 2＝CFCF 2O-(CF(CF 3)CF 2O) k-CF(CF 3)-Y (i)
In the general formula (i), k represents 0～3 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
9. as claim 1,2,3,4,5,6,7 or 8 described fluorine-containing elastomer polymer, wherein, the described 10ppm that the unit (A) that contains fluoride-based emulsifying agent the is a fluorine-containing elastomer polymer～10 quality % that derive from.
10. as claim 1,2,3,4,5,6,7,8 or 9 described fluorine-containing elastomer polymer, wherein, described unit (B) is the 0.01 quality %～10 quality % of fluorine-containing elastomer polymer.
11. the manufacture method of a fluorine-containing elastomer polymer, this manufacture method be contain fluoride-based emulsifying agent in the presence of and sulfuration point monomer (b1) and/or have bromine atoms and/or the saturated fatty compounds of group of iodine atom (b2) in the presence of, in aqueous medium, make fluorochemical monomer carry out polymerization and generate the manufacture method of fluorine-containing elastomer polymer, the method is characterized in that, describedly contain fluoride-based emulsifying agent and contain the compound that in molecule, has free-radical polymerised unsaturated link(age) and hydrophilic radical.
12. the manufacture method of fluorine-containing elastomer polymer as claimed in claim 11, wherein, the described compound that has free-radical polymerised unsaturated link(age) and hydrophilic radical in molecule is to contain fluoride-based compound (1) shown in the following general formula (1);
CR 1R 2＝CR 3(CR 4R 5) j-(O) k-R-Y (1)
In the general formula (1), R 1, R 2, R 3, R 4And R 5Identical or different, perfluoroalkyl, H, F, Cl, Br or I that expression is replaced by H or do not replaced by H, R is illustrated in the fluoro alkylidene group that has or do not have the straight or branched that Sauerstoffatom and all or part of H replaced by F on the main chain, j represents 0～6 integer, k represents 0 or 1 integer, and Y represents hydrophilic radical.
13. the manufacture method of a fluorine-containing elastomer polymer, this manufacture method is to contain fluoride-based emulsifying agent and containing in the presence of cross-linking part monomeric, in aqueous medium, make fluorochemical monomer carry out polymerization and generate the manufacture method of fluorine-containing elastomer polymer, this manufacture method is characterised in that, describedly contains fluoride-based emulsifying agent and contains and contain fluoride-based compound (I) shown in the following general formula (I), contain fluoride-based compound (II) shown in the following general formula (II), contain fluoride-based compound (III) shown in the following general formula (III), contain fluoride-based compound (IV) shown in the following general formula (IV), contain fluoride-based compound (V) shown in the following logical formula V, contain fluoride-based compound (VI) shown in the following general formula (VI), contain fluoride-based compound (VII) shown in the following general formula (VII), and/or contain fluoride-based compound (VIII) shown in the following general formula (VIII);
CF 2＝CF-(CF 2) a-Y (I)
In the general formula (I), a represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF-(CF 2C(CF 3)F) b-Y (II)
In the general formula (II), b represents 1～5 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CFO-(CF 2) c-Y (III)
In the general formula (III), c represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF(CF 2) d-O-(CF 2CFXO) e-(CF 2) f-Y (IV)
In the general formula (IV), X represent F or-CF 3, d represents 0～2 integer, and e represents 1～10 integer, and f represents 1～3 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CH 2＝CFCF 2O(CF(CF 3)CF 2O) gCF(CF 3)Y (V)
In the logical formula V, g represents 0～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CF(CF 2) hO-(CF(CF 3)CF 2O) i-CF(CF 3)-Y (VI)
In the general formula (VI), h represents 1～6 integer, and i represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CH 2＝CH(CF 2) p1-Y (VII)
In the general formula (VII), p1 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal;
CF 2＝CFO-(CH 2) q-(CF 2) p2-Y (VIII)
In the general formula (VIII), q represents 1～4 integer, and p2 represents 1～10 integer, and Y represents-SO 3M or-COOM, M represents H, NH 4Or basic metal.
14. the manufacture method of fluorine-containing elastomer polymer as claimed in claim 13, wherein, the described monomer that contains cross-linking part is the saturated fatty compounds of group (b2) with bromine atoms and/or iodine atom.
15. as the manufacture method of claim 11,12,13 or 14 described fluorine-containing elastomer polymer, wherein, described fluorine-containing elastomer polymer is the vinylidene analog copolymer.
16. as the manufacture method of claim 11,12,13 or 14 described fluorine-containing elastomer polymer, wherein, described fluorine-containing elastomer polymer is tetrafluoroethylene/propylene copolymers.
17. as the manufacture method of claim 11,12,13 or 14 described fluorine-containing elastomer polymer, wherein, described fluorine-containing elastomer polymer is a tetrafluoroethylene/perfluoro vinyl ether analog copolymer.
18. as the manufacture method of claim 11,12,13,14,15,16 or 17 described fluorine-containing elastomer polymer, wherein, being aggregated under the condition that does not have fluorochemical surfactant of described fluorochemical monomer carried out.
Be dispersed in fluorine-containing elastomer polymer aqueous liquid dispersion in the aqueous medium 19. a fluorine-containing elastomer polymer aqueous liquid dispersion, this fluorine-containing elastomer polymer aqueous liquid dispersion are the particles that contain fluorine-containing elastomer polymer, it is characterized in that,
Described fluorine-containing elastomer polymer is claim 1,2,3,4,5,6,7,8,9 or 10 described fluorine-containing elastomer polymer, or the fluorine-containing elastomer polymer of making by the manufacture method of claim 11,12,13,14,15,16,17 or 18 described fluorine-containing elastomer polymer
Described fluorine-containing elastomer polymer aqueous liquid dispersion contains or does not contain fluoride-based emulsifying agent,
The described 1000ppm that contains fluoride-based emulsifying agent less than described fluorine-containing elastomer polymer aqueous liquid dispersion.
20. fluorine-containing elastomer polymer composition, this fluorine-containing elastomer polymer composition is characterised in that, it contains claim 1,2,3,4,5,6,7,8,9 or 10 described fluorine-containing elastomer polymer, or contains the fluorine-containing elastomer polymer of making by the manufacture method of claim 11,12,13,14,15,16,17 or 18 described fluorine-containing elastomer polymer.
21. fluorine-containing elastomer polymer formed body, this fluorine-containing elastomer polymer formed body is characterised in that, it carries out following fluorine-containing elastomer polymer crosslinked and obtains, described fluorine-containing elastomer polymer is claim 1,2,3,4,5,6,7,8,9 or 10 described fluorine-containing elastomer polymer, or the fluorine-containing elastomer polymer for making by the manufacture method of claim 11,12,13,14,15,16,17 or 18 described fluorine-containing elastomer polymer.
CNB2005800108763A 2004-04-07 2005-04-05 Fluorine-containing elastomer polymer and method for producing same Expired - Fee Related CN100475865C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104813232A (en) * 2012-09-28 2015-07-29 纳幕尔杜邦公司 Imageable article comprising substrate having imageable crosslinkable fluoropolymer film disposed thereupon, and imaged article prepared therefrom
CN113748135A (en) * 2019-04-26 2021-12-03 大金工业株式会社 Method for producing composition and composition
CN114096573A (en) * 2019-07-16 2022-02-25 大金工业株式会社 Process for producing fluoroelastomer and composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104813232A (en) * 2012-09-28 2015-07-29 纳幕尔杜邦公司 Imageable article comprising substrate having imageable crosslinkable fluoropolymer film disposed thereupon, and imaged article prepared therefrom
CN113748135A (en) * 2019-04-26 2021-12-03 大金工业株式会社 Method for producing composition and composition
CN114096573A (en) * 2019-07-16 2022-02-25 大金工业株式会社 Process for producing fluoroelastomer and composition

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