CN101484476A

CN101484476A - Method for producing fluorine-containing elastomer

Info

Publication number: CN101484476A
Application number: CNA2007800249192A
Authority: CN
Inventors: 岸根充; 北市雅纪; 西村洋介; 藤泽学; 田中芳树; 尾形慎太郎; 植田豊; 守田滋
Original assignee: Daikin Industries Ltd
Current assignee: Daikin Industries Ltd
Priority date: 2006-06-30
Filing date: 2007-06-29
Publication date: 2009-07-15

Abstract

The present invention provides a method of producing a fluoroelastomer excellent in dispersion stability at low cost, at a high rate of polymerization and in high yields. The present invention is a method of producing a fluoroelastomer comprising an emulsion polymerization of a fluorinated monomer in the presence of a water-soluble radical polymerization initiator, wherein the emulsion polymerization is carried out in the presence of a compound (1) containing a functional group reactive in radical polymerization and a hydrophilic group and a fluorinated compound (2) containing a fluorocarbon group comprising 1 to 6 continuously united carbon atom with fluorine atom directly bound to each of them as well as a hydrophilic group.

Description

The manufacture method of fluoroelastomer

Technical field

The present invention relates to the manufacture method of fluoroelastomer.

Background technology

As the manufacture method of fluoropolymer, known have in the presence of fluorine-containing emulsifier carry out method of emulsion polymerization.

In this letex polymerization, fluorine-containing emulsifier mainly demonstrates following effect: (1) increases to improve polymerization velocity the growing amount of emulsified particle, and (2) make emulsified particle stable.

But it is fluoro-alkyl more than 7 that general employed fluorine-containing emulsifier has carbonatoms, therefore exists to be difficult to the problem of removing from resulting fluoropolymer.So people are studying the emulsion polymerisation process that can solve such problem always.

Instead the emulsifying agent of fluorine-containing emulsifier has document to propose to have the compound of Raolical polymerizable unsaturated link(age) and hydrophilic radical in recent years, also is so-called reactive emulsifier (for example, referring to patent documentation 1).

Polymerization as using reactive emulsifier has document to propose for example following method: contain fluoride-based emulsifying agent and chain-transfer agent in the presence of the letex polymerization (for example, referring to patent documentation 2) carried out; Contain fluoride-based emulsifying agent in the presence of use the 1st polymerization process of water-soluble radical polymerization initiator and use the method (for example, referring to patent documentation 3) of the 2nd polymerization process of oil soluble radical polymerization initiator; Contain fluoride-based emulsifying agent and have bromine atoms and/or iodine atom the saturated fatty compounds of group in the presence of the letex polymerization (for example, referring to patent documentation 4) carried out.

Reactive emulsifier utilizes the effect of Raolical polymerizable unsaturated link(age) to carry out copolymerization, even therefore a small amount of use also can access a large amount of emulsified particles, has " not remaining with the form of emulsifying agent " such advantage.But, reactive emulsifier is aggregated reaction and consumes, be directed in the fluoropolymer, if thereby add separately the reactive emulsifier of necessary amount that is enough to keep the dispersion stabilization of resulting dispersion liquid with it, then might damage the characteristic of fluoropolymer.

In addition, there is document also to propose not use fluorine-containing emulsifier and the emulsion polymerisation process (for example, referring to patent documentation 5) that in the presence of the hydro carbons emulsifying agent, carries out.This hydro carbons emulsifying agent can increase the emulsified particle number, but the stabilization of emulsion is insufficient sometimes.

Patent documentation 1: Japanese kokai publication hei 8-67795 communique

Patent documentation 2: the international brochure that discloses No. 05/097835

Patent documentation 3: the international brochure that discloses No. 05/097836

Patent documentation 4: the international brochure that discloses No. 05/097846

Patent documentation 5: the international brochure that discloses No. 05/063827

Summary of the invention

In view of above-mentioned problem, the invention provides a kind of manufacture method of fluoroelastomer, this method can not produce the problems referred to above, and cost is low, polymerization velocity is fast and yield is high, and can produce the fluoroelastomer of dispersion stabilization excellence.

The present invention relates to a kind of manufacture method of fluoroelastomer, it is to add water-soluble radical polymerization initiator to carry out the letex polymerization of fluorochemical monomer to make the method for fluoroelastomer, this manufacture method is characterised in that, described letex polymerization is to carry out in the presence of compound (1) and fluorochemicals (2), the functional group that described compound (1) has hydrophilic radical and can react in the radical polymerization mode, described fluorochemicals (2) has fluorocarbon radicals and hydrophilic radical, and described fluorocarbon radicals is the group that 1～6 Direct Bonding has the continuous bonding of carbon atom of fluorine atom.

Describe the present invention below in detail.

In the manufacture method of fluoroelastomer of the present invention, letex polymerization is to carry out in the presence of compound (1) and fluorochemicals (2), the functional group that described compound (1) has hydrophilic radical and can react in the radical polymerization mode, fluorochemicals (2) has fluorocarbon radicals and hydrophilic radical, and described fluorocarbon radicals is the group that 1～6 Direct Bonding has the continuous bonding of carbon atom of fluorine atom.

Above-claimed cpd (1) has emulsifying effect, even therefore under the condition that does not have the fluorochemical surfactant that used, also can carry out letex polymerization in the past always, and, therefore polymerization velocity and polymer yield are improved because this compound (1) has the functional group that can react in the radical polymerization mode.But, above-claimed cpd (1) when letex polymerization easily with the fluorochemical monomer copolymerization, therefore when using it for letex polymerization, its content in resulting emulsion is lower than polymerization begin before, thereby have the tendency of dispersion stabilization reduction.If address this problem and at above-claimed cpd (1) thus a large amount of down carrying out letex polymerization keeps dispersion stabilization, the copolymerization units amount that then is derived from compound (1) increases, and exists generation to vulcanize the problem of the relatively poor fluoroelastomer of rerum natura such as property.

On the other hand, the emulsified particle formation effect of above-mentioned fluorochemicals (2) in letex polymerization is not high, but it demonstrates the effect of keeping dispersion stabilization, in addition owing to its solubleness height in water, thereby is easy to clean.

In the manufacture method of fluoroelastomer of the present invention, by share compound (1) that can improve polymerization velocity and polymer yield and the fluorochemicals (2) that is used to keep dispersion stabilization, can carry out letex polymerization and keep dispersion stabilization with good polymerization velocity and polymer yield need not to use in a large number under the condition of above-claimed cpd (1), and can access the fluoroelastomer of physical properties excellent such as impurity is few, sulfuration property.

The functional group that above-claimed cpd (1) has hydrophilic radical and can react in the radical polymerization mode.

As the hydrophilic radical in the above-claimed cpd (1), for example can enumerate-NH ₂,-PO ₃M ,-OPO ₃M ,-SO ₃M ,-OSO ₃M ,-(in various, M represents H, NH to COOM ₄Or basic metal).As above-mentioned hydrophilic radical, especially preferably-SO ₃M and-COOM.

As " functional group that can react in the radical polymerization mode " in the above-claimed cpd (1), can enumerate the group that for example vinyl, allyl group etc. have unsaturated link(age), the group that demonstrates chain transfer.

As the above-mentioned group that demonstrates chain transfer, preference is as with-R ^a-CHY-R ^b-(in the formula, R ^aAnd R ^bExpression has or does not have substituent alkyl, and Y represents hydrophilic radical) group that on the carbon of the α position of hydrophilic radical, has methyne hydrogen of expression.

Above-claimed cpd (1) is owing to have the functional group that can react in the radical polymerization mode, when therefore using it for the above-mentioned emulsion polymerization, can react with fluorochemical monomer at the polyreaction initial stage, have hydrophilic radical and the reactive higher particle that is derived from compound (1) thereby form.Therefore, if carry out letex polymerization in the presence of above-claimed cpd (1), then the emulsified particle number increases.

In the above-mentioned emulsion polymerization, can have a kind of above-claimed cpd (1), also can have two or more above-claimed cpd (1).

In the above-mentioned emulsion polymerization,, can use the compound with unsaturated link(age), compound etc. with chain transfer as above-claimed cpd (1).

Among above-claimed cpd (1),, can enumerate the compound of representing with any same form in the following formula (1a)～(1e) as compound with unsaturated link(age).

Perfluorovinyl sulfide alkylate with following formula (1a) expression:

CF ₂＝CF—(CF ₂) _n1-Y ¹ (1a)

(in the formula (1a), n ₁The integer of expression 1～10, Y ¹Expression-SO ₃M ¹Or-COOM ¹, M ¹Expression H, NH ₄Or basic metal).

In following formula (1a), said n ₁Be preferably the integer below 5, more preferably the integer below 2.From obtaining the water-soluble and surface-active aspect of appropriateness, above-mentioned Y ¹Be preferably-COOM ¹, from being difficult for the aspect that thermotolerance residual as impurity, resulting formed body is improved, M ¹Be preferably H or NH ₄

Perfluorovinyl sulfide alkylate with following formula (1b) expression:

CF ₂＝CF—(CF ₂C(CF ₃)F) _n2-Y ¹ (1b)

(in the formula (1b), n ₂The integer of expression 1～5, Y ¹Identical with above-mentioned definition).

In following formula (1b), consider n from the aspect of emulsifying capacity ₂Be preferably the integer below 3, from obtaining the water-soluble and surface-active aspect of appropriateness, Y ¹Be preferably-COOM ¹, from being difficult for the aspect that thermotolerance residual as impurity, resulting formed body is improved, M ¹Be preferably H or NH ₄

Perfluorovinyl sulfide ether compound with following formula (1c) expression:

CF ₂＝CF—O—(CFX ¹) _n3Y ¹ (1c)

(in the formula (1c), X ¹Expression F or CF ₃, n ₃The integer of expression 1～10, Y ¹Identical with above-mentioned definition).

In following formula (1c), consider said n from water miscible aspect ₃Be preferably the integer below 5, from obtaining the water-soluble and surface-active aspect of appropriateness, above-mentioned Y ¹Be preferably-COOM ¹, from improving the aspect of dispersion stabilization, above-mentioned M ¹Be preferably H or NH ₄

Perfluorovinyl sulfide ether compound with following formula (1d) expression:

CF ₂＝CF—O—(CF ₂CFX ¹O) _n4CF ₂CF ₂Y ¹ (1d)

(in the formula (1d), n ₄The integer of expression 1～10, Y ¹And X ¹Identical with above-mentioned definition).

In following formula (1d), consider above-mentioned X from the aspect of surfactivity energy ¹Be preferably-CF ₃, consider said n from water miscible aspect ₄Be preferably the integer below 5, from obtaining the water-soluble and surface-active aspect of appropriateness, above-mentioned Y ¹Be preferably-COOM ¹, above-mentioned M ¹Be preferably H or NH ₄

Perfluor allyl ether compound with following formula (1e) expression:

CX ² ₂＝CFCF ₂—O—(CF(CF ₃)CF ₂O) _n5-CF(CF ₃)—Y ¹ (1e)

(in the formula (1e), each X ²Identical, expression F or H.n ₅The integer of expression 0 or 1～10, Y ¹Identical with above-mentioned definition).

In following formula (1e), consider said n from the aspect of emulsifying capacity ₅Be preferably 0 or 1～5 integer, 0～2 integer more preferably, more preferably 0 or 1.From obtaining the water-soluble and surface-active aspect of appropriateness, above-mentioned Y ¹Be preferably-COOM ¹, from being difficult for the aspect that thermotolerance residual as impurity, resulting formed body is improved, above-mentioned M ¹Be preferably H or NH ₄

Among above-claimed cpd (1),, can enumerate compound with following formula (1f) expression as compound with chain transfer.

Compound with formula (1f) expression:

R ¹—CR ²Y ²—R ³ (1f)

(in the formula, R ¹And R ³Identical or different, the carbonatoms that expression has straight or branched and contains or do not contain 1 ester bond is 1～14 alkyl.Wherein, under the situation that does not contain ester bond, R ¹Carbonatoms and R ³Carbonatoms add up to 13～16, containing under the situation of ester bond R ¹And R ³All has ester bond.R ²For H or-CH ₃Y ²The expression hydrophilic radical).

In following formula (1f), R ¹Be preferably carbonatoms and be 1～13 alkyl, R ²Be preferably H, R ³Be preferably carbonatoms and be 1～13 alkyl.Above-mentioned Y ²Be preferably-SO ₃M ²With-COOM ², M ²Be preferably H or-NH ₄

Above-claimed cpd (1) is preferably with the compound of following formula (1g) expression or the compound of representing with following formula (1h).

Formula (1g):

R ⁴—CHY ³—R ⁵ (1g)

(in the formula (1g), R ⁴And R ⁵It for carbonatoms 1～14 alkyl with straight or branched.Wherein, R ⁴Carbonatoms and R ⁵Carbonatoms add up to 13～16.Y ³The expression hydrophilic radical).

Formula (1h):

R ⁶—COO—CHY ⁴—CH ₂-COO—R ⁷ (1h)

(in the formula (1h), R ⁶And R ⁷It for carbonatoms 5～10 alkyl with straight or branched.Y ⁴The expression hydrophilic radical).

In following formula (1g), R ⁴And R ⁵Preferably be respectively carbonatoms and be 1～13 alkyl.

As compound, can enumerate for example HostapurSAS93 (Clariant Japan society makes, secondary paraffin sulfonate) with following formula (1g) expression.

As above-mentioned sulfo-dialkyl succinate salt, can enumerate sulfo-dioctyl succinate salt, wherein preferred sulfo-dioctyl succinate sodium salt.

In following formula (1h), R ⁶And R ⁷Preferably be respectively carbonatoms and be 6～8 alkyl, be more preferably the 2-ethylhexyl.

In the above-mentioned emulsion polymerization, the amount of above-claimed cpd (1) preferably is equivalent to 1～200ppm of aqueous medium.

When above-claimed cpd (1) for less than the amount of the 1ppm level that is equivalent to aqueous medium the time, resulting fluoroelastomer increases at the adhesion amount of reactive tank inside, be in the tendency that productivity reduces, when above-claimed cpd (1) for greater than the amount of the 200ppm level that is equivalent to aqueous medium the time, the sulfuration of resulting fluoroelastomer, intensity etc. may reduce.

The preferred lower limit of the amount of above-claimed cpd (1) is equivalent to the 10ppm of aqueous medium, and further preferred lower limit is equivalent to the 50ppm of aqueous medium; The preferred upper limit is equivalent to the 150ppm of aqueous medium, and the further preferred upper limit is equivalent to the 100ppm of aqueous medium.

Letex polymerization among the present invention be above-claimed cpd (1) and have hydrophilic radical and the fluorochemicals of fluorocarbon radicals (2) in the presence of carry out, described fluorocarbon radicals is the group that 1～6 Direct Bonding has the continuous bonding of carbon atom of fluorine atom.

Hydrophilic radical in the above-mentioned fluorochemicals (2) is identical with the hydrophilic radical of explanation in above-claimed cpd (1).

In the present invention, " 1～6 continuous bonding of carbon atom that Direct Bonding has fluorine atom " represents following implication.

Above-mentioned " Direct Bonding has the carbon atom of fluorine atom " is meant-CF ₃Carbon ,-CF ₂-carbon ,-CFH-carbon ,-CFR-carbon bondings such as (R represent alkyl) has the carbon atom of fluorine atom.Above-mentioned " 1～6 (Direct Bonding has the carbon atom of fluorine atom) continuously bonding " be meant, is present in this carbon atom in the molecule with 1～6 continuous bondings, and do not comprise more than 7 continuously the unit that bonding forms.That is, above-mentioned in view of comprising " Direct Bonding has the carbon atom of fluorine atom " is with the solvability reduction of the unitary compound of bonding in water continuously more than 7, thereby selection the fluorochemicals of such problem can not take place as fluorochemicals (2) among the present invention.

The structure of above-mentioned " 1～6 continuous bonding of carbon atom that Direct Bonding has fluorine atom " can have more than 2 in 1 molecule.In above-mentioned fluorochemicals (2), the structure (hereinafter being referred to as " current structure " in this section) of " 1～6 continuous bonding of carbon atom that Direct Bonding has fluorine atom " can be with such as-Rf ^Aa-O-Rf ^As-,-Rf ^As-Rh-Rf ^Bb-,-Rf ^Aa-COO-Rf ^Bb-(in various, Rf ^Aa, Rf ^AsAnd Rf ^BbRepresent current structure arbitrarily respectively, Rh represents alkenyl arbitrarily) etc. the structural unit of form beyond the current structure have more than 2.

In the above-mentioned emulsion polymerization, can there be a kind of above-mentioned fluorochemicals (2), also can there be two or more above-mentioned fluorochemicalss (2).

As above-mentioned fluorochemicals (2), for example can enumerate:

With Z ¹-(CF ₂) _AaIn-COOH[the formula, Z ¹Expression F, Cl or H, aa represents 1～6 integer] carboxylic acid fluoride and an alkali metal salt, ammonium salt, amine salt and the quaternary ammonium salt of expression;

With Z ²-(CH ₂CF ₂) _BbIn-COOH[the formula, Z ²Expression H, F or Cl, bb represents 1～2 integer] carboxylic acid fluoride and an alkali metal salt, ammonium salt, amine salt and the quaternary ammonium salt of expression;

With RfO-(CF (CF ₃) CF ₂O) _Cc-CF (CF ₃)-Z ³[in the formula, Rf represents that carbonatoms is 1～6 perfluoroalkyl, and cc represents 1～10 integer, Z ³Expression-COOM or-SO ₃M, M represent H, NH ₄Or basic metal] acidic cpd etc. of expression.

The fluorine-containing alkylate that above-mentioned fluorochemicals (2) is preferably represented with following formula (2a):

CF ₃—(CF ₂) _n7-(CH ₂) _n8-Y ⁵ (2a)

(in the formula (2a), n ₇The integer of expression 1～5, Y ⁵Expression-SO ₃M ³Or-COOM ³, n ₈The integer of expression 0～4, M ³Expression H, NH ₄Or basic metal).

In following formula (2a), n ₇Be preferably 4 or 5, n ₈Be preferably 0～2, Y ³Be preferably-COOM ³, M ³Be preferably H or NH ₄

As above-mentioned fluorine-containing alkylate, can enumerate for example F (CF ₂) ₆CH ₂CH ₂SO ₃NH ₄

As above-mentioned fluorochemicals (2a), especially preferably with the all-fluoroalkyl compound of formula (2b) expression:

CF ₃—(CF ₂) _n7Y ⁵ (2b)

(in the formula (2b), n ₇The integer of expression 1～5, Y ⁵Expression-SO ₃M ³Or-COOM ³, M ³Expression H, NH ₄Or basic metal).

In the above-mentioned emulsion polymerization, can be according to above-mentioned fluorochemicalss of suitable setting (2) such as the composition of the fluoroelastomer of manufacturing and productive rates, consider that from the aspect of dispersion stabilization, cleaning the amount of above-mentioned fluorochemicals (2) preferably is equivalent to 200～5000ppm of aqueous medium.

The preferred lower limit of amount of above-mentioned fluorochemicals (2) is equivalent to the 400ppm of aqueous medium, and further preferred lower limit is equivalent to the 800ppm of aqueous medium; The preferred upper limit is equivalent to the 4000ppm of aqueous medium, and the further preferred upper limit is equivalent to the 2000ppm of aqueous medium.

Letex polymerization among the present invention preferably use respectively with the perfluor allyl ether compound of following formula (1e) expression and with the all-fluoroalkyl compound of following formula (2b) as above-mentioned compound (1) and compound (2), more preferably use CH ₂=CFCF ₂OCF (CF ₃) CF ₂OCF (CF ₃) COONH ₄And F (CF ₂) ₅COONH ₄

Letex polymerization among the present invention is as long as carries out in the presence of above-claimed cpd (1) and above-mentioned fluorochemicals (2), then also can add additive such as chain-transfer agent and carry out.

For example, if in the presence of chain-transfer agent, carry out the above-mentioned emulsion polymerization, then can adjust the molecular weight and the molecular weight distribution of resulting fluoroelastomer.

As above-mentioned chain-transfer agent, be not particularly limited, only otherwise having above-mentioned hydrophilic radical gets final product, can enumerate carbonatoms and be 1～6 stable hydrocarbon, carbonatoms be 3～5 ketone, carbonatoms be 10～12 mercaptan, such as malonic esters such as diethyl malonates etc.

As above-mentioned chain-transfer agent, preferred carbonatoms is 1～6 stable hydrocarbon, wherein more preferably has the chain-transfer agent of iodine substituting group and fluoro substituents.

The manufacture method of fluoroelastomer of the present invention comprises that adding water-soluble radical polymerization initiator carries out the letex polymerization of fluorochemical monomer.

Above-mentioned fluoroelastomer is so long as have the amorphous fluoropolymer of caoutchouc elasticity and get final product.

Above-mentioned fluoropolymer is that fluorine atom is at least that 58 quality % are above, to be preferably 64 quality % above and be the following polymkeric substance of 74 quality %, and it can be partially fluorinated polymkeric substance, also can be (per) fluoropolymer.

The second-order transition temperature of above-mentioned fluoroelastomer (Tg) is preferably below the room temperature (25 ℃).Above-mentioned second-order transition temperature is more preferably below 5 ℃.

In this manual, second-order transition temperature (Tg) is to use DSC (the SEIKO electronic industry is made: RDC220) mean value calculation of low temperature side by the caloric receptivity flex point and high temperature side determines.

Above-mentioned fluoroelastomer has the 1st monomeric copolymerization units of 30～80 quality % usually.

In this manual, above-mentioned " the 1st monomer " be meant, in the molecular structure of fluoroelastomer, is formed in the monomer that accounts for the copolymerization units of maximum quality among all copolymerization units.As the 1st monomer, can enumerate for example vinylidene fluoride [VDF], tetrafluoroethylene [TFE], perfluor (alkyl vinyl ether) [PAVE], R 1216 [HFP] etc.

In this manual, above-mentioned copolymerization units is meant the pairing monomeric part that is derived from the molecular structure of fluoroelastomer.For example, the VDF unit is the part that is derived from VDF on the molecular structure of VDF based copolymer, with-(CH ₂-CF ₂) expression.Above-mentioned " all copolymerization units " is that all are derived from monomeric part on the molecular structure of fluoroelastomer.

The content of above-mentioned copolymerization units is by measuring F ¹⁹-NMR obtains.

In above-mentioned fluoroelastomer, be derived from monomeric copolymerization units except that above-mentioned the 1st monomer and can be only be derived from can with any one the monomeric unit in the monomer of above-mentioned the 1st monomer copolymerization, also can be derived from can with the two or more monomeric unit in the monomer of the 1st monomer copolymerization.

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 (hydrocarbon olefin).

As above-mentioned Fluorine containing olefine, have no particular limits, can enumerate for example R 1216 [HFP], 1,2,3,3,3-five fluorine propylene [1-HPFP], trifluorochloroethylene [CTFE], vinyl fluoride [VF] etc.

The above-mentioned fluorovinyl ether that contains is preferably perfluor (vinyl ether).

As above-mentioned perfluor (vinyl ether), can enumerate for example with 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 of each other, Rf ^cBe that carbonatoms is 1～6 perfluoroalkyl] expression compound, with formula CF 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] compound etc. of expression.

As above-mentioned perfluor (vinyl ether), preferably with formula (i) CF ₂=CFO[(CF ₂CF (CF ₃) O) _m(CF ₂CF ₂CF ₂O) _n(CF ₂) _y] C _zF _2z+1The compound of [in the formula, m and n are 0～10 integer independently of each other, and y is 0～3 integer, and z (carbonatoms) is 1～5 integer] expression, with (ii) CF of formula ₂=CFOCF ₂CF (CF ₃) O (CF ₃O) _wC _xF _2x+1The compound of [in the formula, w is 1～5 integer, and x is 1～3 integer] expression, with (iii) CF of formula 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 ¹Be-F or-CF ₃] expression compound.In following formula (i), preferred m and n are 0 or 1 integer independently of each other, and z is integer 1 preferably.

Following formula (ii) in, x is preferably integer 1.

Following formula (iii) in, above-mentioned Rf ^eBe preferably C ₃F ₇, and above-mentioned u is preferably integer 0, and above-mentioned v is preferably integer 1.

Above-mentioned perfluor (vinyl ether) is perfluor (alkyl vinyl ether) [PAVE] more preferably.As described PAVE, can enumerate for example perfluor (methylvinylether) [PMVE], perfluor (ethyl vinyl ether) [PEVE], perfluor (propyl vinyl ether) [PPVE].

When above-mentioned fluoroelastomer had perfluor (vinyl ether) unit, preferred perfluor (vinyl ether) unit was 20～70 quality %.

When above-mentioned fluoroelastomer had the PMVE unit, preferred PMVE unit was 30～55 quality %.

As above-mentioned hydrocarbon olefin, have no particular limits, can enumerate for example ethene, propylene etc., preferred propylene.

When above-mentioned fluoroelastomer had the hydrocarbon olefin unit, preferred hydro carbons olefin unit was 4～20 quality %.

As above-mentioned fluoroelastomer, can enumerate for example TFE/ perfluor (alkyl vinyl ether) based copolymer, TFE/ perfluor (alkoxy vinyl ethers) based copolymer, TFE/ propylene series copolymer, TFE/ propylene/TFE based copolymers such as VDF based copolymer; VDF/HFP multipolymer, VDF/CTFE based copolymer, VDF/CTFE/TFE based copolymer, VDF/HFP/TFE multipolymer, VDF/HFP/TFE/4-bromo-3,3,4,4-tetrafluoro-butene-1 copolymer, VDF/HFP/TFE/4-iodo-3,3,4,4-tetrafluoro-butene-1 copolymer, VDF/PMVE/TFE/4-bromo-3,3,4,4-tetrafluoro-butene-1 copolymer, VDF/PMVE/TFE/4-iodo-3,3,4,4-tetrafluoro-butene-1 copolymer, VDF/PMVE/TFE/1,1,3,3, VDF based copolymers such as 3-five fluorine propylene copolymers; Ethene/fluorinated copolymers such as HFP based copolymer.

As above-mentioned TFE/ propylene series copolymer, can enumerate TFE/ propylene copolymer etc.

As above-mentioned TFE/ perfluor (vinyl ether) based copolymer, can enumerate TFE/PAVE multipolymers such as TFE/PMVE multipolymer, TFE/PEVE multipolymer, TFE/PPVE multipolymer; TFE/[CF ₂=CF-O-(CF ₂CFCF ₃O) ₂-(CF ₂) ₂-CF ₃] multipolymer, TFE/PMVE/ ethylene copolymer, TFE/PMVE/ ethene/4-bromo-3,3,4,4-tetrafluoro-butene-1 copolymer, TFE/PMVE/ ethene/4-iodo-3,3,4,4-tetrafluoro-butene-1 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-butene-1 copolymer, TFE/PMVE/ perfluor (2-benzene oxygen propyl ethylene base) ether copolymer etc.

When above-mentioned fluoroelastomer was the TFE/PAVE multipolymer, the content of preferred PAVE was 40～75 quality %.

When above-mentioned fluoroelastomer was Perfluoroelastomer, can comprise the following perfluoroalkyl vinyl ether to contain iodine or cyano group etc. of 10 moles of % was the what is called sulfuration point monomer (cure sitemonomer) of representative.

As the fluorochemical monomer among the present invention, can enumerate as the 1st above-mentioned monomer and Fluorine containing olefine that can example goes out with the monomer of above-mentioned the 1st monomer copolymerization, contain fluorovinyl ether, hydrocarbon olefin.

As the water-soluble radical polymerization initiator among the present invention, commonly used is the superoxide of water-soluble inorganic compound or water-soluble organic compounds, for example persulphate such as ammonium persulphate and Potassium Persulphate, peroxidation disuccinic acid (bissuccinoyl peroxide), peroxidation two pentanedioic acids (bisglutaroyl peroxide), these superoxide can use or make up two or more the use separately.For the polymerization of low-temperature region, preferably use the initiator of reducto oxydative system.And, in the scope of the stability of not damaging emulsion, can use water-insoluble organo-peroxide and/or azo-compound separately, perhaps also water-insoluble organo-peroxide and/or the azo-compound superoxide with water-soluble inorganic compound or water-soluble organic compounds can be used.

The addition of above-mentioned water-soluble radical polymerization initiator can suit to set according to the composition of resulting fluoroelastomer and the consumption of productive rate, above-mentioned fluorochemical monomer etc.

With respect to the resulting fluoroelastomer of 100 mass parts, above-mentioned water-soluble radical polymerization initiator preferably adds with the amount of 0.01～0.4 mass parts, more preferably adds with the amount of 0.05～0.3 mass parts.

In the present invention, letex polymerization can be carried out with any operating method in batchwise operation, semi-batch operation and the operate continuously, preferably carries out in the mode of semi-batch operation.

In the above-mentioned emulsion polymerization, above-mentioned fluorochemical monomer, water-soluble radical polymerization initiator, above-claimed cpd (1) and above-mentioned fluorochemicals (2) can suitably append by composition and the productive rate according to desired fluoroelastomer during polyreaction.

And then the above-mentioned emulsion polymerization can utilize the international multistage polymerization operation of putting down in writing in No. 00/001741 brochure that disclose to carry out, thereby makes resulting fluoroelastomer have desired copolymerization composition.

The above-mentioned emulsion polymerization generally maintains the temperature of 10～120 ℃ scope and carries out.When said temperature is lower than 10 ℃, on technical scale, can not reach the speed of response of effective size; When being higher than 120 ℃, keeping the required reaction pressure of polyreaction and raise, reaction can't be kept.

The pressure that the above-mentioned emulsion polymerization generally maintains the scope of 0.5～10MPa carries out.Above-mentioned pressure preferably is limited to 1.0MPa down, is limited to 6.2MPa on preferred.

When above-mentioned pressure during less than 0.5MPa, the monomer concentration in polymerization reaction system falls lowly excessively, thereby may not reach gratifying speed of response, and the molecular weight of resulting fluoroelastomer molecule may not can reach enough big degree.When above-mentioned pressure during greater than 10MPa, the device of keeping pressure is expensive.

When the above-mentioned emulsion polymerization was carried out with semi-batch operation, the amount of the monomer gas when supplying with by the adjustment initial stage can reach desired polymerization pressure at the polymerization initial stage, after the reaction beginning, adjusted pressure by the additional services amount of adjusting monomer gas.

When above-mentioned polymerization was carried out in the operate continuously mode, the back pressure of the outlet pipe by adjusting resulting fluoroelastomer aqueous liquid dispersion was adjusted polymerization pressure.

Above-mentioned polymerization was generally carried out 0.5～100 hour.

Obtain with the amount that equals addition substantially by carrying out the fluoroelastomer that the above-mentioned emulsion polymerization obtains (the so-called fluoroelastomer of finishing after the polymerization), generally obtain with 10～30 quality % of resulting aqueous liquid dispersion, the amount that is preferably 20～25 quality %.

The above-mentioned fluoroelastomer particulate median size of finishing after the polymerization is generally 10～500nm, the dispersion stabilization excellence.

The above-mentioned fluoroelastomer particle of finishing after the polymerization is 1 * 10 in every 1g water usually ¹³Individual (1 * 10 ¹³Individual/1g water) more than.

When above-mentioned fluoroelastomer after finishing polymerization being carried out condensation prepare fluoroelastomer,, then can improve condensation if after the above-mentioned emulsion polymerization, further add fluorochemicals (2).

The fluoroelastomer that obtained by the manufacture method of fluoroelastomer of the present invention is so long as obtained by above-mentioned polymerization, just can be in arbitrary form, can use with the form of finishing the aqueous liquid dispersion after the polymerization, the sizing material (gum) that can also obtain to utilize existing known method that the above-mentioned fluoroelastomer aqueous liquid dispersion of finishing after the polymerization is carried out condensation, drying etc. or the form of fragment (crumb) are used.

Above-mentioned sizing material (gum) is meant the granulous fritter that is made of fluoroelastomer, and above-mentioned fragment (crumb) is meant that fluoroelastomer can not keep as the little granulous form of sizing material in room temperature and fuses formed unbodied block-shape morphology mutually.

Above-mentioned fluoroelastomer can be processed into fluoroelastomer composition by adding 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.

Therefore above-mentioned fluoroelastomer composition is formed by above-mentioned fluoroelastomer, does not contain existing fluorine-containing emulsifier in fact, is easy to crosslinkedly when forming process, puts from this, and above-mentioned fluoroelastomer composition is excellent.

By using above-mentioned fluoroelastomer to carry out forming process, can obtain the fluoroelastomer formed body.Method as carrying out above-mentioned forming process is not particularly limited, and can enumerate and use above-mentioned solidifying agent to carry out the known method of forming process.

Above-mentioned fluoroelastomer formed body is owing to formed by above-mentioned fluoroelastomer, therefore permanent compression set is low, physical strength is excellent, be suitable as sealing member, electric wire coatings, pipe, laminate etc., be specially adapted to use in semiconductor manufacturing apparatus parts, trolley part etc.

Therefore the manufacture method of fluoroelastomer of the present invention can go out the fluoroelastomer of dispersion stabilization excellence with low cost, high polymerization velocity and high produced in yields owing to have above-mentioned formation.

Embodiment

Below provide embodiment, the present invention is specifically described, but the present invention is not limited to these embodiment.

When special declaration not, the amount of the composition in each embodiment and the comparative example is a quality criteria.

In addition, the measuring method and the evaluation method of the characteristic of using in this manual are as follows.

(1) copolymerization is formed

Carrying out NMR under the following conditions measures.

Determinator: BRUKER society makes

¹H-NMR condition determination: 300MHz (tetramethylsilane=0ppm)

¹⁹F-NMR condition determination: 282MHz (trichlorofluoromethane=0ppm)

(2) median size of fluoroelastomer (fluorinated copolymer)

With 8ml pure water dilution 0.05ml emulsion to be determined, make sample, use MicrotracUPA (manufacturing of HONEYWELL society), measure in room temperature (dynamic light scattering method).Form with median size writes down resulting data.

(3) solid component concentration

In 120 ℃ resulting dispersion is carried out 2 hours dryings, the quality in the time of thus reduces obtains solid component concentration.

(4) iodine atom content

By flask combustion method the 10mg sample is incinerated, be dissolved in the 20cc pure water, utilize liquid phase chromatography (L-4000 that the Hitachi makes, post: the iodine atom content in the resulting solution of mensuration DIONEX IonPac AS4A-SC).

(5) granule number

The ratio of fluorinated copolymer is reset to 1.9, calculates granule number based on the median size of the fluorinated copolymer in resulting elastomeric fluorinated copolymer and the dispersion.

(6) mooney viscosity

Use the viscometer of machine MOONEY MV2000 (manufacturing of Alpha Technologies society) by name, measure mooney viscosity according to JIS K 6300-1.

(7) sulfuration rerum natura

Use JSR CURASTOMETER V-type to measure the sulfuration rerum natura.

(8) normality rerum natura

Tensile strength, elongation, tensile stress are measured according to JIS K 6251.For permanent compression set,, measure the value of using circular rings (P-24) to obtain based on JIS K 6262.Shore hardness is measured according to JIS K 6253.

Embodiment 1

In the stainless steel autoclave of 3L, drop into the CH of 0.99L pure water, 0.2g ₂=CFCF ₂CF (CF ₃) OCF ₂CF ₂COONH ₄F (the CF of (emulsifying agent A) 50% aqueous solution, 1.54g ₂) ₅COONH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer (initial stage monomer) vinylidene fluoride [VDF]/tetrafluoroethylene [TFE]/R 1216 [HFP] (=19/11/70 mole of %) then and in system, press to 1.52MPa with 600rpm.

Then, [APS] is dissolved in the 5ml pure water with the 23.6mg ammonium persulphate, obtains polymerization starter solution, is pressed into this polymerization starter solution with nitrogen, begins reaction.

Along with polymeric carries out, in the low moment of internal drop, be pressed into the mix monomer (monomer continuously) of VDF/TFE/HFP (=51/20/29 mole of %) to 1.42MPa, be 1.52MPa up to interior pressure.Be pressed into 1.531g diiodo-compound I (CF this moment ₂) ₄I.Boosting repeatedly, in the step-down, being pressed into above-mentioned APS (23.6mg/5ml pure water) aqueous solution with nitrogen in per 3 hours, polyreaction is proceeded.In the moment of having appended the 333g mix monomer, emit unreacted monomer, the cooling autoclave obtains the dispersion that solid component concentration is 22.6 quality %.Fluorinated copolymer particulate median size is 100nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=52/22/26 (mole %) as a result, the granule number in the dispersion is 3.4 * 10 ¹⁴(individual/1g water).And though want and will reclaim attached to the fluorinated copolymer on the polymerization tank, adhesion amount is not able to the degree that reclaims.Yield attached to the fluorinated copolymer on the polymerization tank is the index of the dispersion stabilization of dispersion, and its yield is few more, and dispersion stabilization is excellent more.

In above-mentioned dispersion, add 4 quality % aluminum sulfate aqueous solutions, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.The iodine that is contained in the above-mentioned elastomeric fluorinated copolymer is 0.22 quality %, and mooney viscosity is ML ₁₊₁₀(100 ℃)=53.

With respect to the above-mentioned elastomeric fluorinated copolymer of 100phr, carry out mixingly with the ratio of 20phr N990,4phr TAIC, 1.5phr PERHEXA 25B with mixing roll, obtain sulfuration and use composition.Rerum natura after resulting sulfuration is vulcanized with the vulcanization characteristics of composition, first press vulcanization reheat is as shown in table 3, demonstrates good characteristic.

Embodiment 2

In the stainless steel autoclave of 3L, drop into 0.99L pure water, the emulsifying agent A50% aqueous solution of 0.2g, the F (CF of 1.072g ₂) ₃COONH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/HFP (=19/11/70 mole of %) then and in system, press to 1.52MPa with 600rpm.Then, 23.6mg APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution, begin reaction with nitrogen.

Along with polymeric carries out, in the low moment of internal drop, be pressed into the mix monomer of VDF/TFE/HFP=51/20/29 mole % to 1.42MPa, be 1.52MPa up to interior pressure.Be pressed into 1.531g diiodo-compound I (CF this moment ₂) ₄I.Boosting repeatedly, in the step-down, being pressed into APS (23.6mg/5ml pure water) aqueous solution with nitrogen in per 3 hours, polyreaction is proceeded.In the moment of having appended the 333g mix monomer, emit unreacted monomer, with the autoclave cooling, obtain the dispersion that solid component concentration is 23.4 quality %.Fluorinated copolymer particulate median size is 129nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=52/22/26 (mole %) as a result, the granule number in the dispersion is 1.7 * 10 ¹⁴(individual/1g water).

And, will reclaim attached to the fluorinated copolymer on the polymerization tank, carry out 120 ℃ * 8 hours dryings, it is 2.4g that the result reclaims the fluoropolymer that obtains.

In above-mentioned dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.And the iodine that is contained in the described elastomeric fluorinated copolymer is 0.20 quality %, and mooney viscosity is ML ₁₊₁₀(100 ℃)=64.

Embodiment 3

In the stainless steel autoclave of 3L, drop into 0.99L pure water, emulsifying agent (A) 50% aqueous solution of 0.2g, the F (CF of 2.06g ₂) ₆CH ₂CH ₂SO ₃NH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/HFP (=19/11/70 mole of %) then and in system, press to 1.52MPa with 600rpm.Then, 23.6mg APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution, begin reaction with nitrogen.

Along with polymeric carries out, in the low moment of internal drop, be pressed into the mix monomer of VDF/TFE/HFP=51/20/29 mole % to 1.42MPa, be 1.52MPa up to interior pressure.Be pressed into 1.531g diiodo-compound I (CF this moment ₂) ₄I.Boosting repeatedly, in the step-down, being pressed into APS (23.6mg/5ml pure water) aqueous solution with nitrogen in per 3 hours, polyreaction is proceeded.In the moment of having appended the 333g mix monomer, emit unreacted monomer, the cooling autoclave, thus obtain the dispersion that solid component concentration is 22.2 quality %.Fluorinated copolymer particulate median size is 117nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=53/23/24 (mole %) as a result, the granule number in the described dispersion is 2.3 * 10 ¹⁴(individual/1g water).And though want and will reclaim attached to the fluorinated copolymer on the polymerization tank, adhesion amount is not able to the degree that reclaims.

In above-mentioned dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.And the iodine that is contained in the described elastomeric fluorinated copolymer is 0.26 quality %, and mooney viscosity is ML ₁₊₁₀(100 ℃)=50.

Embodiment 4

In the stainless steel autoclave of 3.14L, drop into 1.716L pure water, the emulsifying agent A50% aqueous solution of 0.0343g, the F (CF of 1.386g ₂) ₅COONH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/HFP (=42/58 mole of %) then and in system, press to 6MPa with 560rpm.

Then, 0.257g APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution and 9.95g diethyl malonate, begin reaction with nitrogen.

Along with polymeric carries out, in the interior moment that presses off the beginning reduction, be pressed into the mix monomer of VDF/HFP (=78/22 mole of %), be 6MPa up to interior pressure.In the moment of having appended the 470g mix monomer, emit unreacted monomer, with the autoclave cooling, obtain the dispersion that solid component concentration is 27.1 quality %.Fluorinated copolymer particulate median size is 192nm.

Utilize the copolymerization of NMR analysis and investigation to form, VDF/HFP=78/22 (mole %) as a result, the granule number in the described dispersion is 5.6 * 10 ¹³(individual/1g water).And, will reclaim attached to the fluorinated copolymer on the polymerization tank, and carry out 120 ℃ * 8 hours dryings, it is 3.6g that the result reclaims the fluoropolymer that obtains.

In above-mentioned dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.Mooney viscosity is ML ₁₊₁₀(100 ℃)=49.

With respect to the above-mentioned elastomeric fluorinated copolymer of 100phr, carry out mixingly with mixing roll with the ratio of 20phr N990,2.17phr bisphenol AF, 0.43phr Bian base triphenyl phosphonium chloride (BTPPC), 3phr magnesium oxide (MA-150), 6phr calcium hydroxide (caldic2000), obtain the sulfuration composition.Rerum natura after resulting sulfuration is vulcanized with the vulcanization characteristics of composition, first press vulcanization reheat demonstrates characteristic as shown in table 3.

Embodiment 5

In the stainless steel autoclave of 3.14L, drop into the CH of 1.716L pure water, 0.0343g ₃(CH ₂) _mCH (SO ₃Na) (CH ₂) _nCH ₃F (the CF of (m+n=10～14) 50% aqueous solution, 1.386g ₂) ₅COONH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/HFP (=42/58 mole of %) then and in system, press to 6MPa with 560rpm.Then, 0.257g APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution and 9.95g diethyl malonate, begin reaction with nitrogen.

Along with polymeric carries out, in the interior moment that presses off the beginning reduction, be pressed into the mix monomer of VDF/HFP (=78/22 mole of %), be 6MPa up to interior pressure.In the moment of having appended the 470g mix monomer, emit unreacted monomer, with the autoclave cooling, obtain the dispersion that solid component concentration is 26.1 quality %.Fluorinated copolymer particulate median size is 334nm.

Utilize the copolymerization of NMR analysis and investigation to form, VDF/HFP=78/22 (mole %) as a result, the granule number in the described dispersion is 1.0 * 10 ¹³(individual/1g water).And, will reclaim attached to the fluorinated copolymer on the polymerization tank, and carry out 120 ℃ * 8 hours dryings, it is 3.7g that the result reclaims the fluorinated copolymer that obtains.

In above-mentioned dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.Mooney viscosity is ML ₁₊₁₀(100 ℃)=51.

Embodiment 6

In the stainless steel autoclave of 3L, drop into 1.48L pure water, emulsifying agent (A) 50% aqueous solution of 0.15g, the F (CF of 6.0g ₂) ₅COONH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/ perfluoro methyl vinyl ether [PMVE] (=64/8/28 mole of %) then and in system, press to 1.52MPa with 560rpm.Then, 22.5mgAPS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution, begin reaction with nitrogen.

Along with polymeric carries out, in the low moment of internal drop, be pressed into the mix monomer of VDF/TFE/PMVE (=69/11/20 mole of %) to 1.42MPa, be 1.52MPa up to interior pressure.Be pressed into 1.616g diiodo-compound I (CF this moment ₂) ₄I.Next, be pressed into 3.312g and contain iodine fluorinated vinyl ether CF ₂=CFOCF ₂CF ₂CH ₂I.Boosting repeatedly, in the step-down, being pressed into APS (11.0mg/5ml pure water) aqueous solution with nitrogen in per 3 hours, polyreaction is proceeded.In the moment of having appended the 540g mix monomer, emit unreacted monomer, with the autoclave cooling, obtain the dispersion that solid component concentration is 26.2 quality %.Fluorinated copolymer particulate median size is 160nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/PMVE=67/14/19 (mole %) as a result, the granule number in the described dispersion is 9.2 * 10 ¹³(individual/1g water).

And though want and will reclaim attached to the fluorinated copolymer on the polymerization tank, adhesion amount is not able to the degree that reclaims.In above-mentioned dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.And the iodine that is contained in the described elastomeric fluorinated copolymer is 0.33 quality %, and mooney viscosity is ML ₁₊₁₀(100 ℃)=59.

With respect to the above-mentioned elastomeric fluorinated copolymer of 100phr, carry out mixingly with the ratio of 20phr N990,3phr TAIC, 1.5phr PERHEXA 25B with mixing roll, obtain sulfuration and use composition.Rerum natura after resulting sulfuration is vulcanized with the vulcanization characteristics of composition, first press vulcanization reheat is as shown in table 3, demonstrates good characteristic.

Embodiment 7

In the SUS of internal volume 3L system polymerization tank, add the 1530ml pure water, and add the CH of 0.153g ₂=CFCF ₂OCF (CF ₃) CF ₂OCF (CF ₃) COONH ₄The 50 quality % aqueous solution and 3.06gC ₅F ₁₁COONH ₄, carry out vacuum nitrogen displacement after, in 80 ℃ of mixed gass that inject VDF/HFP (=65/35 mole of %), being pressed into this mixed gas is 1.52MPa up to interior pressure.Under stirring, add and the 0.04g ammonium persulphate is dissolved in the solution that obtains in the 4ml pure water, the beginning polymerization with stirring velocity 600r.p.m..

When pressure is reduced to 1.422MPa in the polymerization, be pressed into the mixed gas of VDF/HFP (=78/22 mole of %), boost to 1.52MPa.After carrying out three these operations repeatedly, temperature is reduced to 60 ℃, is pressed into the mixed gas of VDF/HFP (=78/22 mole of %) once more, boost to 1.47MPa.At this moment, again with nitrogen be pressed into 6.81g pass through make di-isopropyl peroxydicarbonate be dissolved in HCF with 40 quality % ₂CF ₂CH ₂OH and the solution that obtains carries out polymerization.When pressure is reduced to 1.422MPa, be pressed into the mixed gas of VDF/HFP (=78/22 mole of %), boost to 1.52MPa, carry out this operation repeatedly, when the monomeric total mass that drops into reaches 555g, stop monomeric supply, blow away the gaseous monomer in the polymerization tank, cool off, take out content.The dispersion that is reclaimed is 2048.5g, for white translucent.

The solid component content of resulting dispersion is 26.41 quality %, and fluorinated copolymer particulate median size is 150nm.Utilize the copolymerization of the above-mentioned fluorinated copolymer of NMR analysis and investigation to form, as a result VDF/HFP=78/22 (mole %).Attached to the polymkeric substance on stirring rake etc. is 2.25g (moisture state).With above-mentioned dispersion condensation, and make its drying with 4 quality % alum liquors, obtain elastomeric fluorinated copolymer.This elastomeric fluorinated copolymer is ML at 100 ℃ mooney viscosity ₁₊₁₀(100 ℃)=57.3.

Embodiment 8

In 3000ml horizontal high-pressure still, drop into the CH of 1000ml pure water, 0.1089g ₂=CFCF ₂OCF (CF ₃) CF ₂OCF (CF ₃) COONH ₄The C of the 50 quality % aqueous solution and 4.0032g ₅F ₁₁COONH ₄The 50 quality % aqueous solution until 3.2MPa, are confirmed not gas leakage with nitrogen pressure, make it to form vacuum, replace with nitrogen then, and confirming oxygen concn is below the 1ppm.

Making this container is vacuum state, forms little pressurized state with propylene gas, is warmed up to 60 ℃ under stirring with 400r.p.m., further is pressed into propylene gas, and making pressure is 0.511MPa.In described container, be pressed into TFE gas with compressor, boost to 2.70MPa simultaneously.The 1.6291g ammonium persulphate is dissolved in the pure water as polymerization starter, obtains the polymerization starter solution of 11.7392g, 0.605g NaOH is dissolved in the pure water, obtain 5.2051g NaOH solution, two kinds of solution are pressed in the described container simultaneously with nitrogen.Basically the pressure of not finding polymerization tank reduces.

Add polymerization starter after 20 minutes, when temperature was risen to 65 ℃, pressure rose to the maximum value of 2.77MPa, but pressure begins to reduce immediately.Pressure underspeeds and accelerates gradually, and behind the adding polymerization starter, pressure reduces and sharply becomes big after 344 minutes, so in 2.2MPa stopped reaction (blow away gas, cool off), has reclaimed the dispersion of 1035.4g.The solid component content of resulting dispersion is 8.42 quality %.Fluorinated copolymer particulate median size is about 110nm.Granule number in the above-mentioned dispersion is about 7.6 * 10 ¹³Individual/ml.Use 4 quality % aluminum sulfate aqueous solutions with above-mentioned dispersion condensation,, in 120 ℃ of dryings 12 hours, obtain elastomeric fluffy drying solid thereafter in 80 ℃ of dryings 8 hours.With ultimate analysis as can be known, above-mentioned fluorinated copolymer comprises 65 moles of %TFE.Measure above-mentioned fluorinated copolymer with DSC, its second-order transition temperature [Tg] is 2.6 ℃ as a result.

Embodiment 9

In the stainless steel autoclave of 3.14L, drop into the CH of 1.716L pure water, 0.341g ₂=CFCF ₂OCF (CF ₃) CF ₂OCF (CF ₃) COONH ₄The C of the 50 quality % aqueous solution and 1.363g ₅F ₁₁COONH ₄The 50 quality % aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/HFP (=7/5/88 mole of %) then and in system, press to 3.5MPa with 560rpm.

Then, 204mg APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution, begin reaction with nitrogen.

Along with polymeric carries out, in the interior moment that presses off the beginning reduction, be pressed into the mix monomer of VDF/TFE/HFP (=67/25/8 mole of %), reach 3.5MPa up to interior pressure.Be pressed into 2.06g diiodo-compound I (CF this moment ₂) ₄I.Then, in the moment of having appended the 190g mix monomer, be pressed into 2.59g and contain iodine fluorinated vinyl ether CF ₂=CFOCF ₂CF ₂CH ₂I.In the moment of having appended the 383g mix monomer, emit unreacted monomer, with the autoclave cooling, obtain the dispersion that solid component concentration is 27.7 quality %.Fluorinated copolymer particulate median size is 132nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=49/21/30 (mole %) as a result, the granule number in the described dispersion is 1.7 * 10 ¹⁴(individual/1g water).And though want and will reclaim attached to the fluorinated copolymer on the polymerization tank, adhesion amount is not able to the degree that reclaims.

Embodiment 10

In the stainless steel autoclave of 3.14L, drop into the CH of 1.716L pure water, 0.341g ₂=CFCF ₂OCF (CF ₃) CF ₂OCF (CF ₃) COONH ₄The C of the 50 quality % aqueous solution and 1.363g ₅F ₁₁COONH ₄The 50 quality % aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/HFP (=32/5/63 mole of %) then and in system, press to 4.2MPa with 560rpm.

Then, 255mg APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution and 10.7g diethyl malonate, begin reaction with nitrogen.

Along with polymeric carries out, in the interior moment that presses off the beginning reduction, be pressed into the mix monomer of VDF/TFE/HFP (=68/23/9 mole of %), be 4.2MPa up to interior pressure.In the moment of having appended the 280g mix monomer, emit unreacted monomer, with the autoclave cooling, obtain the dispersion that solid component concentration is 25.9 quality %.Fluorinated copolymer particulate median size is 119nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=61/21/18 (mole %) as a result, the granule number in the described dispersion is 2.2 * 10 ¹⁴(individual/1g water).And though want and will reclaim attached to the fluorinated copolymer on the polymerization tank, adhesion amount is not able to the degree that reclaims.

In above-mentioned dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.Mooney viscosity is ML ₁₊₁₀(100 ℃)=56.

Comparative example 1

In the stainless steel autoclave of 3L, drop into the CH of 0.99L pure water, 0.2g ₂=CFCF ₂CF (CF ₃) OCF ₂CF ₂COONH ₄(emulsifying agent A) 50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/HFP=19/11/70 mole % then and in system, press to 1.52MPa with 600rpm.Then, 23.6mgAPS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution, begin reaction with nitrogen.

Along with polymeric carries out, in the low moment of internal drop, be pressed into the mix monomer of VDF/TFE/HFP=51/20/29 mole % to 1.42MPa, be 1.52MPa up to interior pressure.Be pressed into 1.531g diiodo-compound I (CF this moment ₂) ₄I.Boosting repeatedly, in the step-down, being pressed into APS (23.6mg/5ml pure water) aqueous solution with nitrogen in per 3 hours, polyreaction is proceeded.In the moment of having appended the 333g mix monomer, emit unreacted monomer, the cooling autoclave, thus obtain the dispersion that solid component concentration is 22.0 quality %.Polymerization time adds up to 13.3 hours.Fluorinated copolymer particulate median size is 101nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=53/23/24 (mole %) as a result, the granule number in the described dispersion is 3.4 * 10 ¹⁴(individual/1g water).

And, will reclaim attached to the fluorinated copolymer on the polymerization tank, and carry out 120 ℃ * 8 hours dryings, it is 33.6g that the result reclaims the fluoropolymer that obtains.

In this dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.And the iodine that is contained in the described elastomeric fluorinated copolymer is 0.21 quality %, and mooney viscosity is ML ₁₊₁₀(100 ℃)=51.

With respect to the above-mentioned elastomeric fluorinated copolymer of 100phr, carry out mixingly with the ratio of 20phr N990,4phr TAIC, 1.5phr PERHEXA 25B with mixing roller, obtain sulfuration and use composition.Rerum natura after the vulcanization characteristics of the molten composition of resulting sulfuration, the sulfuration of first press vulcanization reheat demonstrates characteristic as shown in table 3.

Comparative example 2

In the stainless steel autoclave of 3L, drop into the F (CF of 0.99L pure water, 1.54g ₂) ₅COONH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/HFP (=19/11/70 mole of %) then and in system, press to 1.52MPa with 600rpm.Then, 23.6mg APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution, begin reaction with nitrogen.

Along with polymeric carries out, in the low moment of internal drop, be pressed into the mix monomer of VDF/TFE/HFP (=51/20/29 mole of %) to 1.42MPa, be 1.52MPa up to interior pressure.Be pressed into 1.531g diiodo-compound I (CF this moment ₂) ₄I.Boosting repeatedly, in the step-down, being pressed into APS (23.6mg/5ml pure water) aqueous solution with nitrogen in per 3 hours, polyreaction is proceeded.In the moment of having appended the 333g mix monomer, emit unreacted monomer, the cooling autoclave obtains the dispersion that solid component concentration is 22.8 quality %.Fluorinated copolymer particulate median size is 381nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=52/22/26 (mole %) as a result, the granule number in the described dispersion is 5.4 * 10 ¹²(individual/1g water).And, will reclaim attached to the fluorinated copolymer on the polymerization tank, carry out 120 ℃ * 8 hours dryings, it is 2.3g that the result reclaims the fluoropolymer that obtains.

In above-mentioned dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.The iodine that is contained in the above-mentioned elastomeric fluorinated copolymer is 0.22 quality %, and mooney viscosity is ML ₁₊₁₀(100 ℃)=53.

Comparative example 3

In the stainless steel autoclave of 3.14L, drop into the emulsifying agent A50% aqueous solution of 1.716L pure water, 0.0343g, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/HFP (=42/58 mole of %) then and in system, press to 6MPa with 560rpm.Then, 0.257g APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution and 9.95g diethyl malonate, begin reaction with nitrogen.

Along with polymeric carries out, in the interior moment that presses off the beginning reduction, be pressed into the mix monomer of VDF/HFP (=78/22 mole of %), be 6MPa up to interior pressure.In the moment of having appended the 470g mix monomer, emit unreacted monomer, with the autoclave cooling, obtain the dispersion that solid component concentration is 25.0 quality %.Fluorinated copolymer particulate median size is 220nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/HFP=77/23 (mole %) as a result, the granule number in the described dispersion is 4.8 * 10 ¹³(individual/1g water).And, will reclaim attached to the fluorinated copolymer on the polymerization tank, carry out 120 ℃ * 8 hours dryings, it is 20.0g that the result reclaims the fluoropolymer that obtains.

In this dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain rubbery polymer.Mooney viscosity is ML ₁₊₁₀(100 ℃)=43.

Comparative example 4

In the stainless steel autoclave of 3L, drop into the F (CF of 0.99L pure water, 2.0g ₂) ₇COONH ₄50% aqueous solution, with nitrogen to fully replacing in the system.Under stirring, be warmed up to 80 ℃, be pressed into monomer VDF/TFE/HFP (=19/11/70 mole of %) then and in system, press to 1.52MPa with 600rpm.Then, 23.6mg APS is dissolved in the 5ml pure water, obtains polymerization starter solution, be pressed into this polymerization starter solution, begin reaction with nitrogen.

Along with polymeric carries out, in the low moment of internal drop, be pressed into the mix monomer of VDF/TFE/HFP (=51/20/29 mole of %) to 1.42MPa, be 1.52MPa up to interior pressure.Be pressed into 1.531g diiodo-compound I (CF this moment ₂) ₄I.Boosting repeatedly, in the step-down, being pressed into APS (23.6mg/5ml pure water) aqueous solution with nitrogen in per 3 hours, polyreaction is proceeded.In the moment of having appended the 333g mix monomer, emit unreacted monomer, the cooling autoclave obtains the dispersion that solid component concentration is 23.8 quality %.About polymerization time, fluorinated copolymer particulate median size is 142nm.Utilize the copolymerization of NMR analysis and investigation to form, VDF/TFE/HFP=52/22/26 (mole %) as a result, the granule number in the described dispersion is 1.1 * 10 ¹⁴(individual/1g water).

And though want and will reclaim attached to the fluorinated copolymer on the polymerization tank, adhesion amount is not able to the degree that reclaims.

In this dispersion, add the aluminum sulfate aqueous solution of 4 quality %, carry out condensation.To resulting condensate wash, drying, obtain elastomeric fluorinated copolymer.And the iodine that is contained in the described elastomeric fluorinated copolymer is 0.24 quality %, and mooney viscosity is ML ₁₊₁₀(100 ℃)=60.

With respect to the above-mentioned elastomeric fluorinated copolymer of 100phr, carry out mixingly with the ratio of 20phr N990,4phr TAIC, 1.5phr PERHEXA 25B with mixing roll, obtain sulfuration and use composition.Rerum natura after the vulcanization characteristics of the molten composition of resulting sulfuration, the sulfuration of first press vulcanization reheat demonstrates characteristic as shown in table 3.

Comparative example 5

Remove and do not use CH fully ₂=CFCF ₂OCF (CF ₃) CF ₂OCF (CF ₃) COONH ₄In addition, carry out polymerization similarly to Example 7, but to be that the moment stirring rake of 525g occurs unusual appending monomer, therefore ends polymerization, is recovered to the milky dispersion of 1883.8g.The solid component content of above-mentioned dispersion only is 23.11 quality %.The median size of resulting fluorinated copolymer is 460nm.And, in polymerization tank, there is huge polymer blocks, total mass reaches 123.1g (moisture state).Utilize the copolymerization of the above-mentioned fluorinated copolymer of NMR analysis and investigation to form, as a result VDF/HFP=78/22 (mole %).With 4 quality % alum liquors above-mentioned dispersion is carried out condensation and dry, obtain elastomeric fluorinated copolymer.And the mooney viscosity of above-mentioned elastomeric fluorinated copolymer is ML ₁₊₁₀(100 ℃)=65.3.

Table 2

By above result as can be known, less attached to the fluorinated copolymer amount on the polymerization tank in each embodiment, the polymer beads number of resulting fluoroelastomer aqueous liquid dispersion is at least 1.0 * 10 ¹³Individual/more than the 1g water, with respect to this, in the comparative example 1 that only uses emulsifying agent A as emulsifying agent, the polymer beads number of the diffusing liquid of resulting fluoroelastomer water-based is 3.4 * 10 ¹⁴Individual/1g water, but more attached to the fluorinated copolymer amount on the polymerization tank.And, only using F (CF ₂) ₅COONH ₄In the comparative example 2 as emulsifying agent, polymerization time adds up to 13 hours, for more than 2 times of total polymerization time of embodiment 1, is 2.3g attached to the fluorinated copolymer amount on the polymerization tank, but the polymer beads number of resulting fluoroelastomer aqueous liquid dispersion is less, is 5.4 * 10 ¹²Individual/1g water.And, in embodiment 1, only use 0.1g emulsifying agent A, just demonstrate excellent productivity, with respect to this, in comparative example 4, need 1.0gF (CF ₂) ₇COONH ₄In addition as can be known, the sulfuration that is obtained by each embodiment similarly demonstrates excellent vulcanization characteristics with composition and each comparative example.

Industrial applicibility

The manufacture method of fluoroelastomer of the present invention therefore can be with low owing to having above-mentioned formation Cost, high polymerization speed and high produced in yields go out the fluoroelastomer of dispersion stabilization excellence. By upper The permanent compression set of stating the resulting fluoroelastomer formed body of fluoroelastomer is low, mechanical strength Excellence is suitable as seal, electric wire coatings, pipe, laminate, is specially adapted to semiconductor system Manufacturing apparatus parts, automobile component etc.

Claims

1. the manufacture method of a fluoroelastomer, it is to add water-soluble radical polymerization initiator to carry out the letex polymerization of fluorochemical monomer to make the method for fluoroelastomer, this manufacture method is characterised in that, described letex polymerization is to carry out in the presence of compound (1) and fluorochemicals (2), the functional group that described compound (1) has hydrophilic radical and can react in the radical polymerization mode, described fluorochemicals (2) has fluorocarbon radicals and hydrophilic radical, and described fluorocarbon radicals is the group that 1～6 Direct Bonding has the continuous bonding of carbon atom of fluorine atom.

2. the manufacture method of fluoroelastomer as claimed in claim 1, wherein, described compound (1) is for having the compound of unsaturated link(age) or having the compound of chain transfer.

3. the manufacture method of fluoroelastomer as claimed in claim 1 or 2, wherein, described compound (1) be with following formula (1a) expression the perfluorovinyl sulfide alkylate, with the perfluorovinyl sulfide alkylate of following formula (1b) expression, with the perfluorovinyl sulfide ether compound of following formula (1c) expression, with the perfluorovinyl sulfide ether compound of following formula (1d) expression, with the perfluor allyl ether compound of following formula (1e) expression or with the compound of following formula (1f) expression

Formula (1a):

CF＝CF ₂—(CF ₂) _n1—Y ¹ (1a)

In the formula, n ₁The integer of expression 1～10, Y ¹Expression-SO ₃M ¹Or-COOM ¹, M ¹Expression H, NH ₄Or basic metal;

Formula (1b):

CF ₂＝CF—(CF ₂C(CF ₃)F) _n2—Y ¹ (1b)

In the formula, n ₂The integer of expression 1～5, Y ¹Identical with above-mentioned definition;

Formula (1c):

CF ₂＝CF—O—(CFX ¹) _n3—Y ¹ (1c)

In the formula, X ¹Expression F or CF ₃, n ₃The integer of expression 1～10, Y ¹Identical with above-mentioned definition;

Formula (1d):

CF ₂＝CF—O—(CF ₂CFX ¹O) _n4—CF ₂CF ₂—Y ¹ (1d)

In the formula, n ₄The integer of expression 1～10, Y ¹And X ¹Identical with above-mentioned definition;

Formula (1e):

CX ² ₂＝CFCF ₂—O—(CF(CF ₃)CF ₂O) _n5—CF(CF ₃)—Y ¹ (1e)

In the formula, each X ²Identical and expression F or H, n ₅The integer of expression 0 or 1～10, Y ¹Identical with above-mentioned definition;

Formula (1f):

R ¹—CR ²Y ²—R ³ (1f)

In the formula, R ¹And R ³Identical or different, the carbonatoms that expression has straight or branched and contains or do not contain 1 ester bond is 1～14 alkyl, wherein, under the situation that does not contain ester bond, R ¹Carbonatoms and R ³Carbonatoms add up to 13～16, containing under the situation of ester bond R ¹And R ³All has ester bond, R ²For H or-CH ₃, Y ²The expression hydrophilic radical.

4. as the manufacture method of claim 1,2 or 3 described fluoroelastomers, wherein, described compound (1) is the compound with following formula (1g) expression,

R ⁴—CHY ³—R ⁵ (1g)

In the formula, R ⁴And R ⁵For the carbonatoms with straight or branched is 1～14 alkyl, wherein, R ⁴Carbonatoms and R ⁵Carbonatoms add up to 13～16, Y ³The expression hydrophilic radical.

5. as the manufacture method of claim 1,2 or 3 described fluoroelastomers, wherein, described compound (1) is the compound with following formula (1h) expression,

R ⁶—COO—CHY ⁴—CH ₂—COO—R ⁷ (1h)

In the formula, R ⁶And R ⁷For the carbonatoms with straight or branched is 5～10 alkyl, Y ⁴The expression hydrophilic radical.

6. as the manufacture method of claim 1,2,3,4 or 5 described fluoroelastomers, wherein, described fluorochemicals (2) is the fluorine-containing alkylate with following formula (2a) expression,

CF ₃—(CF ₂) _n7—(CH ₂) _n8—Y ⁵ (2a)

In the formula, n ₇The integer of expression 1～5, Y ⁵Expression-SO ₃M ³Or-COOM ³, n8 represents 0～4 integer, M ³Expression H, NH ₄Or basic metal.

7. as the manufacture method of claim 1,2,3,4,5 or 6 described fluoroelastomers, wherein, the amount of described compound (1) is equivalent to the 10ppm～200ppm of aqueous medium.

8. as the manufacture method of claim 1,2,3,4,5,6 or 7 described fluoroelastomers, wherein, the amount of described fluorochemicals (2) is equivalent to the 200ppm～5000ppm of aqueous medium.