CN1823094A - Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent - Google Patents

Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent Download PDF

Info

Publication number
CN1823094A
CN1823094A CN 200480020478 CN200480020478A CN1823094A CN 1823094 A CN1823094 A CN 1823094A CN 200480020478 CN200480020478 CN 200480020478 CN 200480020478 A CN200480020478 A CN 200480020478A CN 1823094 A CN1823094 A CN 1823094A
Authority
CN
China
Prior art keywords
carboxylic acid
mentioned
fluoropolymer
acid derivative
integer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 200480020478
Other languages
Chinese (zh)
Inventor
津田畅彦
山本祯洋
难波义典
泽田又彦
清水哲男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of CN1823094A publication Critical patent/CN1823094A/en
Pending legal-status Critical Current

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a method of producing a fluoropolymer, wherein polymerization using a carboxylate ester bond-containing carboxylic acid derivative as a surfactant in an aqueous medium to give the fluoropolymer is conducted, the above carboxylate ester bond-containing carboxylic acid derivative has a carboxylate ester bond and -COOM (M representing H, NH 4 , Li, Na or K), the above carboxylate ester bond may optionally be substituted by fluorine atom.

Description

The preparation method of fluoropolymer, fluoropolymer aqueous liquid dispersion, 2-acyloxycarboxylic acid derivative and tensio-active agent
Technical field
The present invention relates to preparation method, fluoropolymer aqueous liquid dispersion, 2-acyloxycarboxylic acid derivative and the tensio-active agent of fluoropolymer.
Background technology
The preparation method of the fluoropolymer of most of document records, be by in aqueous medium, the carbonatoms that employing contains straight chain or part side chain is that 7～10 fluorocarboxylic acid is as tensio-active agent, Paratetrafluoroethylene (TFE) carries out polymerization (for example, refer to Patent Document 1, patent documentation 2 and patent documentation 3).
Also disclose the preparation method of following fluoropolymer, in the method, used and contain the carboxylic acid of fluoro polyoxy alkylidene as tensio-active agent (for example, referring to Patent Document 4).
These tensio-active agents have very strong thermostability and chemical stability, can suppress side reactions such as chain transfer during polymerization, this is very favorable, but these tensio-active agents have following problems: in order to remove these tensio-active agents the resin that obtains from polymerization, clean, the condition of heating etc. is limited in the extremely narrow scope.
Among the preparation method of disclosed fluoropolymer, the method (for example, refer to Patent Document 5) of sulfosuccinic ester as tensio-active agent of using arranged.But, be difficult to wait sulfosuccinic ester is removed from resin by heating, if it remains in the resin, after processing treatment such as heating, can produce problems such as painted.
As the ester of fluoridizing the 2-hydroxycarboxylic acid, known have seven fluorine iso-butylene alkyl oxide [(CF 3) 2C=CFOR, R represents alkyl] with KMnO 4The hydroxycarboxylic acid esters [(CF that oxidation obtains 3) 2C (OH) COOR] (for example) with reference to non-patent literature 1, wherein, the by product octafluoroisobutene of described seven fluorine iso-butylene alkyl oxides when making R 1216 obtains as starting raw material.But by KMnO 4The by product MnO that produces 2Intractable.
The known H that adopts in addition 2O 2Replace KMnO 4Oxidation (CF 3) 2The H of C=CFOR 2O 2Method (for example, referring to Patent Document 6).But, H 2O 2There are problems such as yield is low in method.
As the ester of fluoro 2-hydroxycarboxylic acid, known [CF in addition 3(CF 2) K1] [CF 3(CF 2) K2] C (OH) COOR, it is by will be with [CF 3(CF 2) K1] [CF 3(CF 2) K2] (in the formula, R is an alkyl to C=CF (OR); K1, k2 represent 0～10) compound of expression carries out oxidation and obtains (for example, referring to Patent Document 7) in the presence of ruthenium compound or osmium compound.
Knownly can obtain fluoro 2-hydroxycarboxylic acid (for example, referring to Patent Document 7) from this fluoro 2-hydroxycarboxylic acid esters.
Yet, on the OH base of this fluoro 2-hydroxycarboxylic acid, introduce acyl group and the ester compound that forms is still unknown by the people.
Patent documentation 1: the spy opens clear 61-207413 communique
Patent documentation 2: the spy opens clear 61-228008 communique
Patent documentation 3: the spy opens flat 10-212261 communique
Patent documentation 4: No. 6429258 specification sheetss of United States Patent (USP)
Patent documentation 5: the spy opens the 2003-119204 communique
Patent documentation 6: the spy opens clear 61-286348 communique (claim 1)
Patent documentation 7: the spy opens clear 2002-234860 communique (claim 1)
Non-patent literature: Utebaev U.et al.; Izv.Akad.Nauk SSSR Ser.Khim., 2 (1974) 387)
Summary of the invention
In view of above-mentioned present situation, the object of the present invention is to provide the manufacture method and the fluoropolymer aqueous liquid dispersion of fluoropolymer, the manufacture method of described fluoropolymer utilizes tensio-active agent to make fluoropolymer in aqueous medium, stability when this tensio-active agent does not damage polymerization, and the remaining quantity of this tensio-active agent in fluoropolymer particles is few after processing treatment such as aggegation; Described fluoropolymer aqueous liquid dispersion contains tensio-active agent, the dispersion stabilization excellence of fluoropolymer in this fluoropolymer aqueous liquid dispersion, and the remaining quantity of this tensio-active agent in fluoropolymer particles is few after processing treatment such as aggegation.
The present invention also aims to the tensio-active agent that the 2-acyloxycarboxylic acid derivative is provided and contains above-mentioned 2-acyloxycarboxylic acid derivative.
Among the preparation method of fluoropolymer of the present invention, in aqueous medium, use and have the carboxylic acid derivative of carboxylic acid ester bond as tensio-active agent polymerization fluoropolymer, it is characterized in that, described carboxylic acid derivative with carboxylic acid ester bond have the carboxylic acid ester bond that replaced by fluorine atom or do not replaced by fluorine atom and-COOM, wherein M represents H, NH 4, Li, Na or K.
Fluoropolymer aqueous liquid dispersion of the present invention contains the particle that is made of fluoropolymer, the carboxylic acid derivative with carboxylic acid ester bond and aqueous medium, it is characterized in that, described carboxylic acid derivative with carboxylic acid ester bond have the carboxylic acid ester bond that replaced by fluorine atom or do not replaced by fluorine atom and-COOM, wherein M represents H, NH 4, Li, Na or K.
2-acyloxycarboxylic acid derivative of the present invention is characterised in that it is represented with following general formula (1):
[changing 1]
Figure A20048002047800071
In the above-mentioned general formula (1), Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; Rf represents that carbonatoms is that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; M represents H, NH 4, Li, Na or K; A and b represent 0～2 integer; D represents 1～3 integer; A, b and d satisfy a+b+d=3; Rf 1, Rf 2Identical with Rf or inequality.
Tensio-active agent of the present invention is characterised in that it contains above-mentioned 2-acyloxycarboxylic acid derivative.
Among the preparation method of 2-acyloxycarboxylic acid derivative of the present invention, the 2-alpha-hydroxy carboxylic acid derivatives by making following general formula (5) expression and the alkanol compounds of following general formula (6) expression are carried out esterification and are prepared above-mentioned 2-acyloxycarboxylic acid derivative:
[changing 2]
Figure A20048002047800081
In the described general formula (5), Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen, and M represents H, NH 4, Li, Na or K, a and b represent 0～2 integer, d represents 1～3 integer, a, b and d satisfy a+b+d=3;
RfCOZ (6)
In the described general formula (6), Rf represents that carbonatoms is that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen, and Z represents-OM 1Perhaps Y, M 1Expression H, NH 4, Li, Na or K, Y represents F or Cl.
Embodiment
Below the present invention is described in detail.
In the manufacture method of fluoropolymer, in aqueous medium, use carboxylic acid derivative among the present invention, constitute the manufacture method of fluoropolymer thus as tensio-active agent polymerization fluoropolymer with carboxylic acid ester bond.
Above-mentioned " fluoropolymer " is the polymkeric substance that has with carbon atom bonded fluorine atom.Among the present invention, described fluoropolymer obtains by a kind of polymerization or 2 kinds of fluorochemical monomers at least, also can by with not fluorine-containing non-fluorine be that monomer copolymerization obtains.Described fluorochemical monomer will contain 1 and carbon atom bonded fluorine atom at least.About above-mentioned fluoropolymer, be described afterwards.
Described carboxylic acid derivative with carboxylic acid ester bond is the carboxylic acid derivative that contains carboxylic acid ester bond and-COOM (M is identical with above-mentioned definition).
" carboxylic acid ester bond " in this specification sheets is meant the structure that is formed by following (1) and (2) bonding, wherein (1) be-COO-or-OCO-, (2) be alkyl, can have 1 or at least 2 hydrogen atoms to be replaced in this alkyl, and can have ether oxygen in the main chain by substituted radicals such as fluorine atoms.As above-mentioned carboxylic acid ester bond, for example can enumerate with the represented structure of R-COO-, with the represented structure of R-OCO-(R represents to replace or unsubstituted alkyl, and perhaps expression has or do not have the above-mentioned substituent fluoro-alkyl that contains ether oxygen).
Described carboxylic acid derivative with carboxylic acid ester bond by the aftertreatments of being carried out after the above-mentioned polymerization such as condensation, is easy to produce the ester hydrolysis, and the hydrolysate of generation has volatility usually, can be by adding heat abstraction.
Described carboxylic acid ester bond is preferably acyloxy of representing with RfCOO-or the carbalkoxy of representing with RfOCO-, and wherein Rf represents that carbonatoms is that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen.
" fluoro-alkyl " in this specification sheets is meant the alkyl that has at least 1 H atom to be replaced by the F atom.
" fluoro-alkyl that contains ether oxygen " in this specification sheets is meant that containing with carbonatoms in the main chain is the alkyl of 1～3 alkylene oxide group as repeating unit, and described alkyl has at least 1 H atom to be replaced by the F atom.
As the described fluoro-alkyl that contains ether oxygen, enumerated-(CF 2O) k-,-(CH 2CF 2O) k-,-(CF 2CF 2O) k-,-(CF (CF 3) CF 2O) k-and the combination of above-mentioned group, for example-(CF 2CF 2O) k-(CF (CF 3) CF 2O) K-etc., wherein K is identical or different, and each carbonatoms that contains the fluoro-alkyl of ether oxygen is 1～20 integer.
As mentioned above, in this manual, described " fluoro-alkyl that contains ether oxygen " contains ether oxygen base, and they are different with above-mentioned " fluoro-alkyl " in this.
Described Rf is under the situation of above-mentioned fluoro-alkyl, and carbonatoms preferably is limited to 2 down, is limited to 3 under preferred; The preferred upper limit is 9, and the preferred upper limit is 4.
When above-mentioned Rf was the above-mentioned fluoro-alkyl that contains ether oxygen, carbonatoms preferably was limited to 2 down, was limited to 8 on preferred, was limited to 4 on preferred.
As the described M in the above-mentioned carboxylic acid derivative with carboxylic acid ester bond, from being easy to from the fluoropolymer that is generated, to consider that by adding this carboxylic acid derivative angle of heat extraction preferred M is NH 4, consider that from the angle of emulsifying power and dispersion force preferred M is Li, Na and K.
Among the preparation method of fluoropolymer of the present invention,, be preferably with the 2-acyloxycarboxylic acid derivative of following general formula (1) expression and the dicarboxylic acid half ester of representing with following general formula (2) as carboxylic acid derivative with carboxylic acid ester bond:
Figure A20048002047800101
In the above-mentioned general formula (1), Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; A and b represent 0～2 integer; D represents 1～3 integer; A, b and d satisfy a+b+d=3; Rf and M are with described identical; Rf 1, Rf 2Identical with Rf or inequality;
RfOCO-Rf 3-COOM (2)
In the above-mentioned general formula (2), Rf 3Expression backbone c atoms number is 1～8 alkylidene group, and can contain 1 substituent R f 4And/or 1 two key, Rf 4Expression F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro alkylidene group that contains ether oxygen.Rf and M are identical with above-mentioned definition.
Below the carboxylic acid derivative with carboxylic acid ester bond in above-mentioned general formula (1) and the general formula (2) is elaborated.
The 2-acyloxycarboxylic acid derivative
In the above-mentioned general formula (1), for Rf 1, Rf 2And Rf, only need to determine that carbonatoms, d value make the 2-acyloxycarboxylic acid derivative can bring into play some surface active property and get final product; From emulsifying agent aspect used the polymerization of 2-acyloxycarboxylic acid derivative as the preparation method of fluoropolymer of the present invention is considered, the character of preferably considering chain transfer reaction is determined the number of c h bond; From not residual above-mentioned 2-acyloxycarboxylic acid derivative behind the above-mentioned some surface active property of performance, particularly, never damage volatile aspect of said hydrolyzed product and consider that importantly the carbonatoms of each group can not be too many.
In the above-mentioned general formula (1), a and b represent 0～2 integer, and d represents 1～3 integer.But a, b and d will satisfy a+b+d=3.Consider that from the viewpoint of easy preparation above-mentioned d is preferably 1～2 integer, more preferably 1.
In the above-mentioned general formula (1), Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are 1～20 the fluoro-alkyl or the fluoro-alkyl that contains ether oxygen of carbonatoms 1～20.
At above-mentioned Rf 1And Rf 2In, the preferred upper limit of the carbonatoms of above-mentioned fluoro-alkyl is 9, and the preferred upper limit is 5, and the further preferred upper limit is 3, and the particularly preferred upper limit is 2.
At above-mentioned Rf 1And Rf 2In, the above-mentioned preferred upper limit of carbonatoms that contains the fluoro-alkyl of ether oxygen is 8, and the preferred upper limit is 5, and the further preferred upper limit is 2.
Above-mentioned Rf 1And Rf 2Identical or different, be preferably following general formula:
A(CF 2) j(CH 2) p-
Wherein, A represents H or F, and j represents 1～6 integer, and p represents 0～3 integer.
Above-mentioned A is preferably F.
The preferred upper limit of above-mentioned j is 4, and the preferred upper limit is 3, and the further preferred upper limit is 2.
The preferred upper limit of above-mentioned p is 1, and more preferably above-mentioned p is 0.
Above-mentioned Rf 1Perhaps Rf 2Identical or different, preferred respectively expression CF 3-, CF 3CF 2-, Cf 3CF 2CF 2-or CF 3CF 2CF 2CF 2-.
In the above-mentioned general formula (1), Rf is identical with aforementioned definitions.
In this specification sheets, " acyl group " in described " 2-acyloxycarboxylic acid derivative " is-CORf shown in above-mentioned general formula (1), as the definition of above-mentioned Rf, also comprise the fluoro-alkyl with ether oxygen as mentioned above.
Among the above-mentioned Rf, the preferred lower limit of the carbonatoms of described fluoro-alkyl is 2, and preferred lower limit is 3, and the preferred upper limit is 9, and the preferred upper limit is 4.
Among the above-mentioned Rf, the described preferred lower limit of carbonatoms that contains the fluoro-alkyl of ether oxygen is 2, and the preferred upper limit is 8, and the preferred upper limit is 4.
Above-mentioned Rf is preferably A (CF 2) n(CH 2) m-(wherein, A is identical with above-mentioned definition, and n represents 1～4 integer, and m represents 0～3 integer) perhaps is preferably
A(CF 2) q-O-[CFX-CF 2(CH 2) rO] tCFX-
(wherein, X represents F or CF 3, q represents 0～3 integer, and r represents 0～2 integer, and t represents 0～3 integer.A is identical with above-mentioned definition).
The upper limit of said n is preferably 3, and the upper limit of above-mentioned q is preferably 2.
Above-mentioned m, r and t are preferably 0 respectively.
Above-mentioned Rf is preferably CF 3-, CF 3CF 2-, CF 3CF 2CF 2-, CF 3CF 2CF 2CF 2-, HCF 2-, HCF 2CF 2-, HCF 2CF 2CF 2-or HCF 2CF 2CF 2CF 2-.
In the above-mentioned general formula (1), Rf 1, Rf 2And Rf can be the same or different.
In above-mentioned general formula (1), when described d represented 2～3 integer, d Rf can be the same or different; A is 2 o'clock, a Rf 1Can be the same or different; B is 2 o'clock, b Rf 2Can be identical also can be different.
In the above-mentioned general formula (1), Rf 1And Rf 2Identical or different, be preferably A (CF 2) u-, in this formula, A is identical with above-mentioned definition, and u represents 1～3 integer; And Rf is preferably A (CF 2) w(CH 2) v-, in this formula, A is same as described above, and w represents 2～4 integer, and y represents 0～1 integer.
In the above-mentioned general formula (1), M is identical with above-mentioned definition.The viewpoint that is easy to remove by heat treated after the material of general formula (1) is used as tensio-active agent considers that above-mentioned M is preferably NH 4
Consider that from the volatile viewpoint of above-mentioned some surface active property and hydrolysate above-mentioned general formula (1) is preferably with the material of following chemical formulation:
(CF 3) 2C(OCOCF 2CF 2CF 2CF 3)COOM、
(CF 3)(CF 3CF 2)C(OCOCF 2CF 2CF 2CF 3)COOM
(CF 3CF 2) 2C(OCOCF 2CF 2CF 2CF 3)COOM、
(CF 3)C(OCOCF 2CF 2CF 2CF 3) 2COOM、
(CF 3CF 2)C(OCOCF 2CF 2CF 2CF 3)2COOM
(CF 3)C(OCOCF 2CF 2CF 3) 2COOM、
(CF 3CF 2)C(OCOCF 2CF 2CF 3) 2COOM
(CF 3)C(OCOCF 2CF 3) 2COOM、
(CF 3CF 2)C(OCOCF 2CF 3) 2COOM
(CF 3)C(OCOCF 2CF 3)(OCOCF 2CF 2CF 3)COOM、
(CF 3)C(OCOCF 2CF 3)(OCOCF 2CF 2CF 2CF 3)COOM、
(CF 3)C(OCOCF 2CF 2CF 3)(OCOCF 2CF 2CF 2CF 3)COOM、
(CF 3CF 2)C(OCOCF 2CF 3)(OCOCF 2CF 2CF 3)COOM、
(CF 3CF 2)C(OCOCF 2CF 3)(OCOCF 2CF 2CF 2CF 3)COOM、
(CF 3CF 2)C(OCOCF 2CF 2CF 3)(OCOCF 2CF 2CF 2CF 3)COOM
Wherein, M and above-mentioned definition is identical.
Preparation method about above-mentioned 2-acyloxycarboxylic acid derivative narrates in the back.
The dicarboxylic acid half ester
In the above-mentioned general formula (2), described Rf 3Be preferably-C fH 2f-, C gH 2g-2-or-(CH 2) h-T-(CH 2) i-, wherein, f represents 1～6 integer, and g represents 2～6 integer, and h is identical with i or different, the integer of expression 0～3, T represents-CRf 4=CH-,-CH=CRf 4-or-CHRf 4-.Rf 4Same as described above.
The dicarboxylic acid half ester of above-mentioned general formula (2) expression can be the dicarboxylic acid half ester (A) of following general formula (3) expression, also can be the dicarboxylic acid half ester (B) of following general formula (4) expression:
RfOCORf 5COOM (3)
Rf in the general formula (3) and M are identical with above-mentioned definition, RF 5Be with-C fH 2f-or-C gH2 G-2The carbonatoms of-expression is the alkylidene group of 1～6 unsubstituted, and f and g are identical with above-mentioned definition;
RfOCO(CH 2) h-T-(CH 2) iCOOM (4)
T in the general formula (4) represents-CRf 4=CH-,-CH=CRf 4-or-CHRf 4-.Rf, M, h, i and Rf 4Identical with above-mentioned definition.
Shown in above-mentioned general formula (3) and above-mentioned general formula (4), described dicarboxylic acid half ester (A) is Rf in the above-mentioned general formula (2) 3The alkylidene group that does not have substituent nothing to replace; Described dicarboxylic acid half ester (B) is above-mentioned Rf 3Has 1 substituent R f 4(Rf 4Identical with above-mentioned definition) the alkylidene group that replacement is arranged or the inferior alkylene of replacement is arranged.
In the above-mentioned general formula (3), described f and g distinguish preferably smaller or equal to 5, are more preferably less than to equal 2.Above-mentioned f and g can be identical also can be different.
In the above-mentioned general formula (3), above-mentioned Rf 5If number of hydrogen atoms increase, just be easy to generate polymerization velocity and reduce, can not obtain problem such as high molecular, above-mentioned f and g are preferably in above-mentioned scope.
Above-mentioned Rf 5Be preferably-CH 2-,-CH 2CH 2-,-CH 2CH 2CH 2CH 2-,-CH=CH-,-CH 2-CH=CH-CH 2-, more preferably-CH 2-,-CH 2CH 2-,-CH=CH-,-CH 2-CH=CH-CH 2-.
Above-mentioned dicarboxylic acid half ester (A) can pass through for example following method manufacturing, that is, utilize known method etc. with RfOM 2(Rf is identical with above-mentioned definition, M 2Expression H, NH 4, Li, Na or K) and HOOCRf 5COOM (Rf 5Identical with M and above-mentioned definition) or its acid anhydrides carry out esterification, prepare above-mentioned dicarboxylic acid half ester (A) with this.
In the above-mentioned general formula (4), described Rf 4Be preferably F, carbonatoms smaller or equal to 8 fluoro-alkyl and carbonatoms smaller or equal to 8 the fluoro alkylidene group that contains ether oxygen, more preferably F, carbonatoms smaller or equal to 4 fluoro-alkyl and carbonatoms smaller or equal to 4 the fluoro alkylidene group that contains ether oxygen.
In the above-mentioned general formula (4), described h and i are preferably 0 or 1, and more preferably 0.
Above-mentioned dicarboxylic acid half ester (B) is represented by following general formula:
[changing 4]
Wherein, Rf, Rf 4And M and above-mentioned definition is identical, and h and i are identical or different, the integer of expression 0～3.
Above-mentioned dicarboxylic acid half ester (B) for example can promptly, adopt known method by following method manufacturing, makes RfOH (Rf is identical with above-mentioned definition) act on M 3OOC (CH 2) h-T-(CH 2) iCOOM (M 3Expression H, NH 4, Li, Na or K, T, M, h and i are identical with above-mentioned definition) or its acid anhydrides, carry out half esterization, prepare above-mentioned dicarboxylic acid half ester (B) thus.
Among the preparation method of fluoropolymer in the present invention, for above-mentioned carboxylic acid derivative with carboxylic acid ester bond, if it is 30～70Nm/m 25 ℃ of surface tension of measuring down that the 0.1 quality % aqueous solution adopts the Wilhelmy method, consider from the some surface active property aspect that then this carboxylic acid derivative is preferred.The preferred lower limit of above-mentioned surface tension is 40Nm/m, and the preferred upper limit is 60Nm/m.
For above-mentioned carboxylic acid derivative with carboxylic acid ester bond, the fluoropolymer that obtains by polymerization among the preparation method of part or all of its usage quantity and fluoropolymer of the present invention remains in the aqueous liquid dispersion jointly, if and do not change in the envrionment conditions that substantive hydrolysis does not take place, then also can be mixed in the above-mentioned aqueous liquid dispersion of condensation as required and in the moistening powder that obtains.
Above-mentioned carboxylic acid derivative with carboxylic acid ester bond after for example using as tensio-active agent, can reclaim, and uses repeatedly.
Above-mentioned carboxylic acid derivative with carboxylic acid ester bond generally generates hydrolysate because of hydrolysis.Described hydrolysis mainly can be carried out under the following conditions: among the fluoropolymer preparation method of the present invention, after polymerization, in aftertreatments such as aggegation, can under the condition that acid or alkali exist, carry out described hydrolysis, can be as required 10 ℃～250 ℃, preferably under 100 ℃～200 ℃ temperature, carry out described hydrolysis.Among the present invention, described hydrolysate is meant by what hydrolysis produced and is no less than 2 molecule, that is, have-COOM the compound of (M is identical with above-mentioned definition) and RfCOOH (Rf and above-mentioned definition identical) or its esters or have-COOM compound and RfOH (Rf is same as described above) or its pure salt of (M and above-mentioned definition identical).The salt of above-mentioned RfCOOH is RfCOOM (Rf and M are identical with above-mentioned definition) etc. for example, and above-mentioned pure salt is RfOM (Rf and M are identical with above-mentioned definition) etc. for example.
For the above-mentioned carboxylic acid derivative with carboxylic acid ester bond, preferably its described hydrolysate has volatility.If described hydrolysate has volatility, then can remove by heating at an easy rate.
Described heating is meant the heating in for example following step, and described step for example is applied to above-mentioned coating composition by fluoropolymer aqueous liquid dispersion preparation the moistening powder that carries out drying behind the base material or fire, the above-mentioned fluoropolymer aqueous liquid dispersion of condensation is obtained and carries out drying or pelletization or utilize the dried powder that obtains or spherolite carries out moulding and adds fourth etc.
After the aftertreatment of having carried out routines such as condensation, heating, the above-mentioned concentration with carboxylic acid derivative of carboxylic acid ester bond in the above-mentioned fluoropolymer aqueous liquid dispersion can be reduced to smaller or equal to 10ppm, preferably is reduced to smaller or equal to 1ppm.In addition, when carrying out aftertreatment such as condensation, the fluidity by making above-mentioned fluoropolymer aqueous liquid dispersion is cleaned by improving temperature for acid or alkaline, can improve cleaning efficiency.
Thus, the above-mentioned emulsifying agent of carboxylic acid derivative as the fluoropolymer polymerization time with carboxylic acid ester bond brought into play in the some surface active property, can easily remove by hydrolysis in aftertreatment.Therefore, among the preparation method of fluoropolymer of the present invention, described residual quantity with carboxylic acid derivative of carboxylic acid ester bond with the fluoropolymer coexistence that obtains can be controlled to seldom, and the powder, spherolite, the formed body that form by fluoropolymer in processing, when filming etc., can suppress to foam, improve rerum natura, prevent painted etc.
Among the preparation method of the fluoropolymer among the present invention, be easy to by adding heat extraction for making the said hydrolyzed product, preferably with fluorine atom bonded carbonatoms smaller or equal to 6.
From the angle consideration that is easy to remove, above-mentioned being preferably greater than with fluorine atom bonded carbonatoms equals 2, is more preferably less than to equal 4, further preferably smaller or equal to 3.
Among the preparation method of the fluoropolymer among the present invention,, just can prepare fluoropolymer efficiently if at least a kind of carboxylic acid derivative with carboxylic acid ester bond can be used as tensio-active agent.In addition, among the preparation method of fluoropolymer of the present invention, at least 2 kinds of carboxylic acid derivative with carboxylic acid ester bond can be used simultaneously as tensio-active agent, except above-mentioned carboxylic acid derivative with carboxylic acid ester bond, also can use other compound simultaneously, as long as this compound has volatility or can remain in the formed body that is made by fluoropolymer with some surface active property.
Above-mentioned other compounds with some surface active property have no particular limits, and for example, can be a kind of of cationic, anionic species, nonionic class or betaines tensio-active agent, and these tensio-active agents also can be hydro carbons.
Among the preparation method of fluoropolymer of the present invention, except described other compounds that have the carboxylic acid derivative of carboxylic acid ester bond and use as required, can also add the additive that is used to stablize each compound with some surface active property.Above-mentioned additive has no particular limits, and for example, can be the stablizer that often uses in general tensio-active agent etc.
Among the preparation method of the fluoropolymer among the present invention, polymerization is carried out as follows: aqueous solvent, above-mentioned carboxylic acid derivative, monomer and other necessary additive with carboxylic acid ester bond are added in the polymerization reactor, content in the stirred reactor, make and keep required polymerization temperature in the reactor, add a certain amount of polymerization starter then, initiated polymerization.After polyreaction begins, can append monomer, polymerization starter, chain-transfer agent and above-mentioned carboxylic acid derivative according to different purposes with carboxylic acid ester bond.
In the above-mentioned polymerization, polymerization temperature is 5 ℃～120 ℃ usually, and polymerization pressure is 0.05～10MpaG.Molecular weight, speed of response according to employed monomeric species, purpose polymers are suitably determined polymerization temperature, polymerization pressure.
In total addition level, the above-mentioned carboxylic acid derivative of the amount of the 0.0001 quality %～15 quality % of preferred interpolation aqueous medium with carboxylic acid ester bond, be limited to 0.001 quality % under preferred, be limited to 10 quality % on preferred, be limited to 1 quality % on further preferred.If less than 0.0001 quality %, dispersion force is insufficient easily; If surpass 15 quality %, not only can not get the effect of institute's dosage, polymerization velocity is descended or make to react to stop.The addition of above-mentioned carboxylic acid derivative with carboxylic acid ester bond should carry out suitable determining according to the molecular weight of employed monomeric kind, purpose polymers etc.
As polymerization starter, get final product so long as in above-mentioned polymerization temperature scope, can produce the material of free radical, be not particularly limited, can use known oil soluble and/or water miscible polymerization starter.Further, can with combination such as reductive agent with redox form initiated polymerization.The concentration of above-mentioned polymerization starter is according to the molecular weight and suitable the determining of speed of response of monomeric kind, purpose polymers.
Above-mentioned " aqueous medium " is to carry out the polymeric reaction medium, is meant the liquid that contains water.Above-mentioned aqueous medium so long as moisture getting final product be not particularly limited, this liquid can contain water and contain not fluorine-containing organic solvent such as for example alcohol, ether, ketone etc. and/or boiling point smaller or equal to 40 ℃ fluorine-containing organic solvent.For example, when hanging turbid polymerization, can use fluorine-containing organic solvents such as C318.
In the above-mentioned polymerization, further can add known chain-transfer agent, radical scavenger as required, to adjust polymerization velocity and molecular weight.
Above-mentioned fluoropolymer obtains by the polymerization fluorochemical monomer, also can be as required carries out copolymerization with not fluorine-containing monomer.
As above-mentioned fluorochemical monomer, for example can enumerate: fluoroolefins is preferably the fluoroolefins with 2～10 carbon atoms; The ring-type fluoromonomers; With general formula CY 2 2=CY 2OR 4Perhaps CY 2 2=CYOR 5OR 6Represented fluoro-alkyl vinyl ether etc. are at above-mentioned general formula CY 2 2=CY 2OR 4Perhaps CY 2 2=CYOR 5OR 6In, Y 2Be H or F, R 4And R 6The carbonatoms that is replaced by fluorine atom for part or all of hydrogen atom is 1～8 alkyl, R 5The carbonatoms that is replaced by fluorine atom for part or all of hydrogen atom is 1～8 alkylidene group.
Above-mentioned fluoroolefins preferably has 2～6 carbon atoms.As above-mentioned fluoroolefins, for example can enumerate: tetrafluoroethylene (TFE), R 1216 (HFP), chlorotrifluoroethylene (CTFE), vinyl fluoride, vinylidene (VDF), trifluoro-ethylene, hexafluoro-isobutene and perfluorobutyl ethylene etc. with 2～6 carbon atoms.As above-mentioned ring-type fluoromonomers, for example can be preferably perfluor-2,2-dimethyl-1,3-diox alcohol [PDD], perfluor-2-methylene radical-4-methyl isophthalic acid, 3-diox [PMD] etc.
In the above-mentioned fluoro-alkyl vinyl ether, described R 4And R 6Preferably have 1～4 carbon atom, more preferably all hydrogen atom is replaced by fluorine atom; Described R 5Preferably have 2～4 carbon atoms, more preferably all hydrogen atom is replaced by fluorine atom.
As above-mentioned not fluorine-containing monomer, for example can enumerate and have reactive hydro carbons monomer with above-mentioned fluorochemical monomer.As above-mentioned hydro carbons monomer, for example can enumerate: the olefines of ethene, propylene, butylene, iso-butylene etc.; Alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, IVE, cyclohexyl vinyl ether; Vinyl acetate between to for plastic base ester, vinyl propionate base ester, the butanic acid vinyl ester, the isopropylformic acid vinyl ester, the valeric acid vinyl ester, the trimethylacetic acid vinyl ester, the caproic acid vinyl ester, sad vinyl ester, the capric acid vinyl ester, tertiary monocarboxylic acid (versatic) vinyl ester, the lauric acid vinyl ester, the tetradecanoic acid vinyl ester, the palmitinic acid vinyl ester, vinyl stearate base ester, the phenylformic acid vinyl ester, the p-tert-butyl benzoic acid vinyl ester, the hexahydrobenzoic acid vinyl ester, the monochloro vinyl-acetic ester, hexanedioic acid vinyl base ester, the vinylformic acid vinyl ester, the methacrylic acid vinyl ester, the Ba Dousuan vinyl ester, the Sorbic Acid vinyl ester, the styracin vinyl ester, the undecylenic acid vinyl ester, the oxyacetic acid vinyl ester, the hydroxy-propionic acid vinyl ester, the hydroxybutyric acid vinyl ester, the hydroxypentanoic acid vinyl ester, the hydroxy-iso-butyric acid vinyl ester, vinyl esters such as hydroxyl hexahydrobenzoic acid vinyl ester; Alkyl allyl ether series such as ethyl allyl ether, propyl group allyl ethers, butyl allyl ethers, isobutyl-allyl ethers, cyclohexyl allyl ethers; Alkyl allyl ester classes such as allyl ethyl ester, propyl group allyl ester, butyl allyl ester, isobutyl-allyl ester, cyclohexyl allyl ester etc.
As above-mentioned not fluorochemical monomer, also can be the hydro carbons monomer that contains functional group.As the above-mentioned hydro carbons monomer that contains functional group, for example can enumerate: hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxy butyl vinyl ether, hydroxyl IVE, hydroxyl cyclohexyl vinyl ether; Methylene-succinic acid, succsinic acid, succinyl oxide, fumaric acid, fumaric acid anhydride, Ba Dousuan, toxilic acid, maleic anhydride, perfluorobuttene acid etc. contain the not fluorine-containing monomer of carboxyl; Glycidyl vinyl ether, glycidyl allyl ethers etc. contain the not fluorine-containing monomer of glycidyl; Aminoalkyl group vinyl ether, aminoalkyl group allyl ethers etc. contain amino not fluorine-containing monomer; Methacrylamide, n-methylolacrylamide etc. contain amino not fluorine-containing monomer.
As fluoropolymer, for example can enumerate: the VDF polymkeric substance that the monomer that monomeric molar ratio is maximum in the polymkeric substance (hereinafter to be referred as " monomer at most ") is VDF for the TFE polymkeric substance of TFE, maximum monomer, the CTFE polymkeric substance that maximum monomer is CTFE etc. by the suitable preparation of fluoropolymer preparation method of the present invention.
As the TFE polymkeric substance, the TFE homopolymer that can be best suited for, also can be to contain following monomeric multipolymer: (1) TFE, (2) 1 or at least 2 TFE fluorochemical monomer that contains 2～8 carbon atoms, particularly HFP or CTFE and (3) other monomer in addition.As other monomers in above-mentioned (3), for example can enumerate: comprise have 1～5, the fluoro of the alkyl of 1～3 carbon atom (alkyl vinyl ether) particularly; Fluoro diox alcohol; The perfluoroalkyl vinyl acetate; ω-hydroxyl perfluoro alkene etc.
As the TFE polymkeric substance, can also be TFE and 1 or at least 2 not fluorine-containing monomeric multipolymers.As above-mentioned not fluorine-containing monomer, for example can enumerate: olefines such as ethene, propylene; Vinyl ester; Vinyl ethers etc.As the TFE polymkeric substance, can also be that TFE and 1 or at least 2 are contained the not multipolymer of fluorochemical monomer of the fluorochemical monomer of 2～8 carbon atoms and 1 or at least 2.
As the VDF polymkeric substance, the VDF homopolymer [PVDF] that can be best suited for, also can be to contain following monomeric multipolymer: the fluoroolefins that contains 2～8 carbon atoms, particularly TFE, HFP or the CTFE beyond (1) VDF, (2) 1 or at least 2 VDF and (3) have and contain 1～5, the perfluor of the alkyl of 1～3 carbon atom (alkyl vinyl ether) particularly.
As the CTFE polymkeric substance, the CTFE homopolymer that can be best suited for, also can be to contain following monomeric multipolymer: fluoroolefins that contains 2～8 carbon atoms, particularly TFE beyond (1) CTFE, (2) 1 or at least 2 CTFE or HFP and (3) contain 1～5, the perfluor of the alkyl of 1～3 carbon atom (alkyl vinyl ether) particularly by having.
As the CTFE polymkeric substance, can also be the not multipolymer of fluorochemical monomer of CTFE and 1 or at least 2.As above-mentioned not fluorine-containing monomer, for example can enumerate: olefines such as ethene, propylene; Vinyl ester; Vinyl ethers etc.
Can be glassy, plasticity-or elastomerics by the prepared fluoropolymer of the preparation method of fluoropolymer among the present invention.These materials can be amorphism or are partially crystalline, can be used for compression and fire processing, melt-processed or non-molten-mix processing.
The preparation method of fluoropolymer of the present invention can be suitable for preparation example such as following material: (I) as the polytetrafluoroethylene polymer [PTFE polymkeric substance] of non-molten-mix processibility resin; (II) as the ethene/TFE multipolymer [ETFE], TFE/HFP multipolymer [FEP] and TFE/ perfluor (alkyl vinyl ether) multipolymer [PFA, MFA etc.] that dissolve the processibility resin; (III) multipolymer that forms as the TFE/ propylene copolymer of elastomerics multipolymer, TFE/ propylene copolymer/the 3rd monomer copolymer (above-mentioned the 3rd monomer is meant VDF, HFP, CTFE, perfluor (alkyl vinyl ether) class etc.), TFE and perfluor (alkyl vinyl ether) class; HFP/ ethylene copolymer, HFP/ ethene/TFE multipolymer; PVDF; Thermoplastic elastomers such as VDF/HFP multipolymer, HFP/ ethylene copolymer, VDF/TFE/HFP multipolymer; And the fluorine-containing groups polymkeric substance of putting down in writing in the special public clear 61-49327 communique etc.
Above-mentioned perfluor (alkyl vinyl ether) is expressed from the next:
Rf 6(OCFQ 5CF 2) k3(OCR 7Q 6CF 2CF 2) k4(OCF 2) k5OCF＝CF 2
Wherein, Rf 6The expression carbonatoms is 1～6 perfluoroalkyl; K3, K4 and K5 can be identical also can be different, the integer of expression 0～5; Q 5, Q 6And R 7Identical or different, expression F or CF 3
The preparation method of the fluoropolymer among the present invention is the method for preparing fluoropolymer.The 10 quality %～50 quality % of the aqueous liquid dispersion that the concentration of above-mentioned fluoropolymer is normally obtained by above-mentioned polyreaction.In above-mentioned aqueous liquid dispersion, the preferred of fluoropolymer substrate concentration is limited to 10 quality % down, preferredly is limited to 15 quality % down, is limited to 40 quality % on preferred, is limited to 35 quality % on preferred, further is limited to 30 quality % on preferably.
Aqueous liquid dispersion by above-mentioned polymerization obtains can become suspension (ヂ イ ス パ one ジ ョ Application) after concentrated or decentralized stabilization are handled; Also condensation or aggegation be can carry out, dry resulting powder or other solid substances reclaimed.The preparation method of the fluoropolymer among the present invention is the method for preparing fluoropolymer, resulting fluoropolymer can be the fluoropolymer that is dispersed in the above-mentioned aqueous liquid dispersion, also can be the fluoropolymer that is dispersed in the above-mentioned suspension, can also be the fluoropolymer of other solid substance forms such as powder.
Be fit to above-mentioned (I) non-molten-mix processibility resin, (II) that the preparation method by fluoropolymer of the present invention prepares dissolve the processibility resin and (III) the elastomerics polymkeric substance preferably be prepared in the following manner.
(I) non-molten-mix processibility resin
Among the preparation method of fluoropolymer of the present invention, the polymerization of PTFE polymkeric substance is that 10 ℃～100 ℃, polymerization pressure are to carry out under 0.05MpaG～5MpaG at polymerization temperature usually.
Above-mentioned polyreaction is following carrying out: add pure water and above-mentioned carboxylic acid derivative with carboxylic acid ester bond in having the pressure-resistant reaction vessel of stirrer, after the deoxidation, add TFE, under specific temperature, add the polymerization starter initiation reaction.Along with the pressure that carries out of reaction is understood step-down, for keeping initial pressure, the continuous or step TFE that appends.TFE be supplied to a certain amount of after, stop to supply with, the TFE in the cleaning reaction container makes temperature return to room temperature, finishes reaction.
When preparing above-mentioned PTFE polymkeric substance, can share known various modified monomer.In this specification sheets, described polytetrafluoroethylene polymer (PTFE polymkeric substance) not only comprises the TFE homopolymer, also comprises the TFE of non-molten-mix processibility and the multipolymer of modified monomer (hereinafter to be referred as " modified ptfe ").
Above-mentioned modified monomer can be perfluoroolefine such as HFP, a CTFE class for example; Have and contain 1～5, particularly contain the fluoro (alkyl vinyl ether) of the alkyl of 1～3 carbon atom; Ring-type fluoromonomers such as fluoro diox alcohol; Whole haloalkyl ethene; ω-hydroxyl perhalogeno olefines etc.Can be according to the supply of purpose or TFE, at the disposable interpolation modified monomer of beginning, perhaps continuous or intermittent type ground separately adds modified monomer.
The content of the modified monomer in the modified ptfe is 0.001 mole of %～2 mole % scope normally.
In the preparation of above-mentioned PTFE polymkeric substance, above-mentioned carboxylic acid derivative with carboxylic acid ester bond can use in the use range among the preparation method of the invention described above fluoropolymer, and usually, addition is the 0.0001 quality %～5 quality % of aqueous medium.Above-mentioned concentration with carboxylic acid derivative of carboxylic acid ester bond needs only in above-mentioned scope, is not particularly limited, and usually, adds with the concentration below the critical micelle concentration (CMC) (CMC) when polymerization begins.If addition is too much, will generate the bigger acicular particles of long-width ratio, aqueous dispersion will become glue, destroys stability.
In the preparation of above-mentioned PTFE polymkeric substance, as polymerization starter, can be separately or use following substances: persulphate (for example, ammonium persulphate), and organo-peroxides such as peroxidation disuccinic acid, peroxidation two pentanedioic acids with form of mixtures.In addition, polymerization starter also can be shared with reductive agent such as S-WAT, adopts redox system.Further, in polymerization, also can add free radical scavengers such as Resorcinol, pyrocatechol, or add the decomposition agent of superoxide such as ammonium sulphite, thus the number of free radical in the adjustment system.
In the preparation of above-mentioned PTFE polymkeric substance,, can use known material as chain-transfer agent, for example, saturated hydrocarbons such as methane, ethane, propane, butane, halogenated hydrocarbons such as monochloro methane, methylene dichloride, C2H4F2 C2H4F2, alcohols such as methyl alcohol, ethanol, and hydrogen etc.The preferred material that uses at normal temperatures and pressures to gaseous phase.
The usage quantity of above-mentioned chain-transfer agent is the 1ppm～1000ppm of the TFE total amount supplied with, is preferably 1ppm～500ppm.
In the preparation of above-mentioned PTFE polymkeric substance, dispersion stabilizer as reaction system can also use following saturated hydrocarbons, its reactionless in fact activity, under above-mentioned reaction conditions, be liquid state, carbonatoms is more than or equal to 12, with respect to the aqueous medium of 100 mass parts, the usage quantity of above-mentioned dispersion stabilizer is 2 mass parts～10 mass parts.In addition, as the buffer reagent that is used for adjusting reaction pH, can also add volatile salt, ammonium phosphate etc.
When above-mentioned PTFE polymer polymerizing finishes, can obtain following aqueous liquid dispersion, the solid formation branch concentration of described aqueous liquid dispersion is 10 quality %～50 quality %, has following particle by the PTFE polymer formation, this average particle size is 0.05 μ m～5000 μ m, and particularly owing to using the carboxylic acid derivative contain the carboxylic acid ester bond to have nominal particle size particle smaller or equal to 0.3 μ m.The number-average molecular weight of the PTFE polymkeric substance when above-mentioned polymerization finishes is 1000～10000000.
The aqueous liquid dispersion of above-mentioned PTFE polymkeric substance can be used for various uses through condensation and the dry fine powder that obtains.
When the aqueous liquid dispersion of above-mentioned PTFE polymkeric substance is carried out condensation, usually, it is 10 quality %～20 quality % that the aqueous liquid dispersion that polymer emulsion (polymer latex) etc. is obtained by letex polymerization is diluted with water to polymer concentration, as required pH is adjusted to neutrality or alkalescence, then in having the container of whipping appts by carrying out condensation than stirring more violent stirring in the reaction.Above-mentioned condensation also can be stirred under the situation of adding the condensation agent, mineral acids such as inorganic salt such as described condensation agent such as water-soluble organic compounds such as methyl alcohol, acetone, saltpetre, volatile salt or hydrochloric acid, sulfuric acid, nitric acid.Above-mentioned condensation can use internal stirrers etc. to carry out continuously.
Before the above-mentioned condensation or condensation carry out in the process, if add the various weighting agents that are used for painted pigment or are used for improved mechanical properties, then can obtain the fine powder of the PTFE polymkeric substance that has pigment or weighting agent that pigment or additive mix.
The drying of the moistening powder that the aqueous liquid dispersion of the above-mentioned PTFE polymkeric substance of condensation is obtained is carried out usually under the following conditions: make this moistening powder keep not too the mobile state, preferably it be remained static, adopt modes such as vacuum, high frequency, hot blast to carry out drying.Between the powder, particularly at high temperature friction generally can produce bad influence to the PTFE polymkeric substance of fine powder type.Here it is because had under very little shearing force by the particle of such PTFE polymer formation and just easily the fibrillation effect to take place, and loses the character of original stable particle structure state.
Above-mentioned drying 10 ℃～250 ℃, preferably under 100 ℃～200 ℃ drying temperature, carry out.
In the aftertreatment of being carried out after the above-mentioned polymerization, usually above-mentioned carboxylic acid derivative with carboxylic acid ester bond is hydrolyzed, to generate hydrolysate.
The fine powder of the PTFE polymkeric substance that obtains is preferred for moulding, and suitable purposes for example can be used as the oil hydraulic system of aircraft and automobile, the pipeline of fuel system etc., also can be used for soup, steam etc. flexible hose, cover in the purposes such as electric wire.
The aqueous liquid dispersion of the PTFE polymkeric substance that obtains for above-mentioned polymerization, also can make it stable by adding nonionic surfactant, further concentrate then,, also can add organic or inorganic filler and be used for various uses with the form of composition according to different purposes.Above-mentioned composition can cover on the base material that is formed by metal or pottery etc. to form film coated surface, this film coated surface has non-adhesive, frictional coefficient is low, and glossiness, smoothness, wear resistance, weathering resistance and excellent heat resistance are applicable to the coating of cylinder or cooking appliance etc., the dipping processing of woven fiber glass etc.
(II) dissolve the processibility resin
(1) among the preparation method of fluoropolymer of the present invention, the polymerization of FEP is that 60 ℃～100 ℃, polymerization pressure are to carry out under 0.7MpaG～4.5MpaG at polymerization temperature preferably usually.
It is TFE: HFP=(60～95) that the preferred monomer of FEP is formed (quality %): (5～40), more preferably (85～90): (10～15).As above-mentioned FEP, can also use perfluor (alkyl vinyl ether) class as the 3rd kind of composition, in the scope of whole monomeric 0.5 quality %～2 quality %, carry out modification.
In the polymerization of above-mentioned FEP, above-mentioned carboxylic acid derivative with carboxylic acid ester bond can use in the preparation method's of described fluoropolymer of the present invention use range, and its addition is generally the 0.0001 quality %～5 quality % of aqueous medium.
In the polymerization of above-mentioned FEP,, preferably use hexanaphthene, methyl alcohol, ethanol, tetracol phenixin, chloroform, methylene dichloride, methyl chloride etc. as chain-transfer agent; As the pH buffer reagent, can use volatile salt, Sodium phosphate dibasic etc.
(2) among the preparation method of fluoropolymer of the present invention, the polymerization of TFE/ perfluor (alkyl vinyl ether) multipolymers such as PFA, MFA is that 60 ℃～100 ℃, polymerization pressure are to carry out under 0.7MpaG～2.5MpaG at polymerization temperature preferably usually.
It is TFE that the preferred monomer of TFE/ perfluor (alkyl vinyl ether) multipolymer is formed (mole %): perfluor (alkyl vinyl ether)=(95～99.7): (0.3～5), more preferably (98～99.5): (0.5～2).As above-mentioned perfluor (alkyl vinyl ether), preferably use by general formula CF 2The material of=CFORf (wherein, Rf represents that carbonatoms is 1～6 perfluoroalkyl) expression.
In the polymerization of above-mentioned TFE/ perfluor (alkyl vinyl ether) multipolymer, above-mentioned carboxylic acid derivative with carboxylic acid ester bond can use in the preparation method's of described fluoropolymer of the present invention use range, usually, its addition is the 0.0001 quality %～2 quality % of aqueous medium.
In the polymerization of above-mentioned TFE/ perfluor (alkyl vinyl ether) multipolymer,, preferably use hexanaphthene, methyl alcohol, ethanol, tetracol phenixin, chloroform, methylene dichloride, methyl chloride, methane, ethane etc. as chain-transfer agent; As the pH buffer reagent, preferably use volatile salt, Sodium phosphate dibasic etc.
(3) among the preparation method of fluoropolymer of the present invention, the polymerization of ETFE is that 20 ℃～100 ℃, polymerization pressure are to carry out under 0.5MpaG～0.8MpaG at polymerization temperature preferably usually.
The preferred monomeric composition of ETFE (mole %) is TFE: ethene=(50～99): (50～1).As above-mentioned ETFE, can also further use the 3rd monomer, the material in whole monomeric 0 quality %～20 quality % scopes after the modification.Preferred TFE: ethene: the 3rd monomer=(70～98): (30～2): (4～10).As above-mentioned the 3rd monomer, preferably use perfluorobutyl ethylene, perfluorobutyl ethylene, 2,3,3,4,4,5,5-seven fluoro-1-amylene (CH 2=CFCF 2CF 2CF 2H), 2-trifluoromethyl-3,3,3-trifluoro propene ((CF 3) 2C=CH 2).
In the polymerization of above-mentioned ETFE, above-mentioned carboxylic acid derivative with carboxylic acid ester bond can use in the preparation method's of described fluoropolymer of the present invention use range, and its addition is 0.0001 quality % of aqueous medium～2 quality % normally.
In the polymerization of above-mentioned ETFE,, can use hexanaphthene, methyl alcohol, ethanol, tetracol phenixin, chloroform, methylene dichloride, methyl chloride etc. as chain-transfer agent.
(III) elastomerics polymkeric substance
Among the preparation method of fluoropolymer of the present invention, the polymerization of elastomerics polymkeric substance is following carrying out: add pure water and above-mentioned carboxylic acid derivative with carboxylic acid ester bond in having the pressure vessel of whipping appts, after the deoxidation, add monomer, at a certain temperature, add polymerization starter, initiation reaction.Reaction carries out that pressure can reduce in the process, for keeping original pressure, be continuously or intermittent type append the supply monomer.After supplying a certain amount of monomer, stop supplies, the monomer in the cleaning reaction container makes temperature turn back to room temperature, finishes reaction.During letex polymerization, preferably polymer emulsion is taken out in reaction vessel continuously.
Particularly, when the preparation thermoplastic elastomer, disclosed in the WO00/01741 brochure, behind synthetic fluoropolymer particulate under the dense condition of carboxylic acid derivative with carboxylic acid ester bond, can carry out further polymerization by dilution, this situation and common polymerization comparison can reach final polymerization velocity rapidly.
In the polymerization of above-mentioned elastomerics polymkeric substance, consider to select the condition that suits according to the physical properties of subject polymer and to the angle that polymerization velocity is controlled, polymerization temperature is generally-20 ℃～200 ℃, be preferably 5 ℃～150 ℃, polymerization pressure is generally 0.5MpaG～10MpaG, is preferably 1MpaG～7MpaG.In addition, preferably utilize known method, use pH mediator agent described later to make the pH in the polymerisation medium maintain 2.5～9.
Employed monomer in the polymerization as above-mentioned elastomerics polymkeric substance, except that vinylidene, also can enumerate the fluorine-containing vinyl unsaturated monomer that for example has at least with the fluorine atom of carbonatoms similar number, and this fluorine-containing vinyl unsaturated monomer can with the vinylidene copolymerization.As above-mentioned fluorine-containing vinyl unsaturated monomer, can enumerate for example trifluoro propene, five fluorine propylene, hexafluoro butylene, octafluoro butylene etc.Wherein, R 1216 is particularly suitable for because its blocking-up polymkeric substance crystalline growth the time getable elastomeric characteristic.As above-mentioned fluorine-containing vinyl unsaturated monomer, can enumerate for example trifluoro-ethylene, TFE and CTFE etc., and can use a kind or at least 2 kinds fluorochemical monomer with chlorine and/or bromine substituent.Also can use perfluor (alkyl vinyl ether), for example perfluor (methylvinylether).Preferably utilize TFE and HFP during preparation elastomerics polymkeric substance.
It is vinylidene: HFP: TFE=(20～70) that the preferred monomer of elastomerics polymkeric substance is formed (quality %): (20～60): (0～40).The elastomerics polymkeric substance of this composition has good elasticity bulk properties, chemical resistant properties and thermostability.
In the polymerization of above-mentioned elastomerics polymkeric substance, above-mentioned carboxylic acid derivative with carboxylic acid ester bond can use in the preparation method's of described fluoropolymer of the present invention use range, and its addition is generally the 0.0001 quality %～5 quality % of aqueous medium.
In the polymerization of above-mentioned elastomerics polymkeric substance, can use known inorganic radical polymerization initiator as polymerization starter.As above-mentioned inorganic radical polymerization initiator, water-soluble inorganic peroxide commonly known in the art, for example, the persulphate of sodium, potassium and ammonium, superphosphate, perborate, percarbonate or permanganate etc. are particularly useful.Above-mentioned radical polymerization initiator can adopt reductive agent or easy oxidized metallic compound to activate further, and described reductive agent is sulphite, hydrosulphite, metabisulphite, company's sulphite, thiosulphate, phosphite or company's phosphite of sodium, potassium or ammonium for example; Described oxidized easily metallic compound is ferrous salt, cuprous salt or silver salt for example.Ammonium persulphate is the inorganic radical polymerization initiator that suits, and more preferably uses ammonium persulphate and sodium bisulfite jointly.
The interpolation concentration of above-mentioned polymerization starter is suitably determined according to the molecular weight or the polymerization rate of subject polymer, is set at the 0.0001 quality %～10 quality % of monomer total amount, is preferably 0.01 quality %～5 quality %.
In the polymerization of above-mentioned elastomerics polymkeric substance, can use known chain-transfer agent, in the polymerization of PVDF, can use hydro carbons, ester, ether, alcohol, ketone, muriate, carbonate etc. as chain-transfer agent; In the polymerization of thermoplastic elastomer, can use hydro carbons, ester, ether, alcohol, muriate, iodide etc.Wherein, in the polymerization of PVDF, preferably use acetone, Virahol; In the polymerization of thermoplastic elastomer, consider from the viewpoint that speed of response is difficult for reducing, preferred iso-pentane, diethyl malonate and the ethyl acetate used considered from the viewpoint that can make the polymer ends iodate make polymkeric substance become reactive polymer, preferably uses I (CF 2) 4I, I (CF 2) 6I, ICH 2Diiodo-compounds such as I.
With respect to the monomeric total amount of being supplied, the usage quantity of above-mentioned chain-transfer agent is generally 0.5 * 10 -3Mole %～5 * 10 -3Mole % is preferably 1.0 * 10 -3Mole %～3.5 * 10 -3Mole %.
In the polymerization of above-mentioned elastomerics polymkeric substance, the polymerization of PVDF can preferably use paraffin etc. as emulsion stabilizer; The polymerization of thermoplastic elastomer can preferably use phosphoric acid salt, sodium hydroxide, potassium hydroxide etc. as the pH regulator agent.
By the solid component concentration of the resulting elastomerics polymkeric substance of the preparation method of fluoropolymer of the present invention when polymerization finishes is 10 quality %～40 quality %, median size is 0.03 μ m～1 μ m, be preferably 0.05 μ m～0.5 μ m, number-average molecular weight is 1000～2000000.
For by the resulting elastomerics polymkeric substance of the preparation method of fluoropolymer of the present invention, can add dispersion stabilizers such as hydrocarbon-surfactant as required, by step such as concentrating, obtain being suitable for the suspension of rubber-moulding processing.Above-mentioned suspension is handled by regulate pH, solidify, heating etc.Each is handled and carries out as follows.
The adjusting of described pH can be by adding mineral acids such as nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid, and/or add carbonatoms smaller or equal to 5 and pK smaller or equal to 4.2 carboxylic acid, with pH regulator to smaller or equal to 2.
Described solidifying by adding alkali earth metal salt undertaken.As described alkali earth metal salt, can enumerate nitrate, hydrochloride and the acetate of calcium for example or magnesium.
For above-mentioned pH regulator and above-mentioned solidifying, can carry out earlier any step, but the preferred pH that regulates earlier.
After each step operation is finished, wash,, carry out drying then to remove impurity such as a spot of damping fluid that exists in the elastomerics or salt by adding with the water of elastomerics with volume.Dry following carrying out usually: in drying oven, at high temperature make air cycle, under about 70 ℃～200 ℃, carry out drying.
In described each step processing, above-mentioned carboxylic acid derivative with carboxylic acid ester bond is hydrolyzed the generation hydrolysate usually.
Above-mentioned carboxylic acid derivative with carboxylic acid ester bond also is suitable for use as dispersion agent, and the fluoropolymer that is used for obtaining by polymerization is distributed to aqueous medium.
Fluoropolymer aqueous liquid dispersion of the present invention contains the particle that is formed by fluoropolymer, the carboxylic acid derivative with carboxylic acid ester bond and aqueous medium.
In the fluoropolymer aqueous liquid dispersion of the present invention, in the presence of the carboxylic acid derivative with carboxylic acid ester bond, the particle that is formed by fluoropolymer is dispersed in the aqueous medium.
In the fluoropolymer aqueous liquid dispersion of the present invention, the carboxylic acid derivative with carboxylic acid ester bond described in the preparation method of described carboxylic acid derivative with carboxylic acid ester bond and fluoropolymer of the present invention is identical.Above-mentioned carboxylic acid derivative with carboxylic acid ester bond preferably can generate hydrolysate by hydrolysis.
The said hydrolyzed product has volatility usually, can be by adding heat extraction.As the said hydrolyzed product, for example can enumerate material cited in the preparation method of fluoropolymer of the present invention.As above-mentioned heating; can enumerate for example heating in following step, described step for example will be applied to by the coating composition of fluoropolymer aqueous liquid dispersion of the present invention preparation carries out drying behind the base material or fires, the above-mentioned fluoropolymer water-based of condensation is disperseed and the moistening powder that obtains carries out drying or pelletization or utilizes the dried powder or the spherolite that obtain to carry out forming process etc.Above-mentioned heating is preferably carried out under 10 ℃～250 ℃ temperature.
In the fluoropolymer aqueous liquid dispersion among the present invention, as described carboxylic acid derivative with carboxylic acid ester bond, the angle of removing from excellent dispersion and the powder, spherolite, the formed body that obtain from above-mentioned fluoropolymer aqueous liquid dispersion easily, filming considers, the dicarboxylic acid half ester of be preferably 2-acyloxycarboxylic acid derivative with above-mentioned general formula (1) expression, representing with above-mentioned general formula (2) etc.
Above-mentioned carboxylic acid derivative with carboxylic acid ester bond is preferably the 0.0001 quality %～15 quality % of fluoropolymer aqueous liquid dispersion of the present invention.If less than 0.0001 quality % makes the dispersion stabilization variation sometimes; If surpass 15 quality %, can not have the dispersion effect that mates with amount yet, thereby impracticable.The above-mentioned preferred lower limit of carboxylic acid derivative with carboxylic acid ester bond is 0.001 quality %, and the preferred upper limit is 10 quality %, and the further preferred upper limit is 2 quality %.
Fluoropolymer aqueous liquid dispersion among the present invention can be for following any: the aqueous liquid dispersion that obtains by above-mentioned polymerization, this aqueous liquid dispersion concentrated or suspension that decentralized stabilization obtains after handling and will be scattered in the system that forms in the aqueous medium by the powder that fluoropolymer forms in the presence of above-mentioned carboxylic acid derivative with carboxylic acid ester bond.
Above-mentioned concentration method adopts known method, according to the purposes difference, the concentration of fluoropolymer can be concentrated into 40 quality %～60 quality %.Concentrate the stability that may damage suspension, can add some dispersion stabilizers this moment again.Can add above-mentioned carboxylic acid derivative with carboxylic acid ester bond or other various tensio-active agents as above-mentioned dispersion stabilizer.Above-mentioned various dispersion stabilizer can be enumerated for example nonionogenic tenside, particularly polyoxyethylene alkyl phenyl ether (for example, ロ one ム ﹠amp such as polyoxy alkyl oxide; The ト ラ イ ト Application X-100 (trade(brand)name) that Ha one ス company produces), polyethenoxy ether class such as polyoxyethylene isotridecyl ether (the デ イ ス パ ノ one Le TOC (trade(brand)name) that Japanese grease stock company produces), polyoxyethylene propyl group tridecyl ether, be limited to above-mentioned substance but have more than.
With respect to the solid formation branch in the above-mentioned suspension, the total amount of above-mentioned dispersion stabilizer is the concentration of 0.5 quality %～20 quality %.If less than 0.5 quality % then destroys dispersion stabilization sometimes; If surpass 20 quality %, can not obtain the effect with the amount coupling yet, thereby impracticable.The preferred lower limit of above-mentioned dispersion stabilizer is 2 quality %, and the preferred upper limit is 12 quality %.
Aqueous liquid dispersion for above-mentioned polymerization obtains according to the purposes difference, can also not concentrate and just carry out the decentralized stabilization processing, is mixed with long fluoropolymer aqueous liquid dispersion storage period.Employed dispersion stabilizer can with above-mentioned enumerate identical.
The purposes of fluoropolymer aqueous liquid dispersion of the present invention is not particularly limited, and as with the direct applied purposes of the form of aqueous liquid dispersion, for example can enumerate: application, that is, it is applied on the base material, and fire as required after the drying; Dipping promptly, in wherein, after the drying is preferably fired porous support impregnation such as non-woven fabrics, synthetic resin; Casting film promptly, is coated on it on base materials such as glass, after the drying, impregnated in as required in the water, peels off base material and obtains film etc.Its application examples for example can be enumerated water-based dispersing coating, binding agent for electrode, electrode with water-resisting agent etc.
Fluoropolymer aqueous liquid dispersion among the present invention is by cooperating with Synergist S-421 95s such as known pigment, thickening material, dispersion agent, defoamer, frostproofer, film coalescence aid, perhaps further compound with other macromolecular compounds, can be used as coating use coating.
As the purposes of fluoropolymer aqueous liquid dispersion of the present invention, for example also can enumerate the fluoropolymer aqueous liquid dispersion is carried out reclaiming after condensation or the aggegation, drying, carry out granulation as required, utilize the purposes of resulting powder.Above-mentioned condensation or aggegation can directly adopt known method to carry out.
The represented 2-acyloxycarboxylic acid derivative of following general formula (1) also is one of the present invention:
[changing 5]
In the above-mentioned formula, Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; A and b represent 0～2 integer, and d represents 1～3 integer; A, b and d satisfy a+b+d=3; Rf and M are identical with above-mentioned definition; Rf 1, Rf 2And Rf is identical or different.
2-acyloxycarboxylic acid derivative among the present invention can be brought into play some surface active property, and for example, when preparing fluoropolymer by polymerization in aqueous medium, it is fit to as the emulsifying agent that fluoropolymer is present in the aqueous medium; Perhaps, in the particle that will be formed by fluoropolymer was scattered in fluoropolymer aqueous liquid dispersion in the aqueous medium, it was fit to as dispersion agent.2-acyloxycarboxylic acid derivative of the present invention can reclaim after as uses such as mentioned emulsifier, dispersion agents and recycle.
The aftertreatments such as condensation of 2-acyloxycarboxylic acid derivative of the present invention after by above-mentioned polymerization is easy to take place the ester hydrolysis, and the hydrolysate of generation has volatility usually, can be by adding heat extraction.As above-mentioned heating; can enumerate the heating in for example following step, described step for example is applied to above-mentioned coating composition by fluoropolymer aqueous liquid dispersion preparation carries out drying behind the base material or fires, the above-mentioned fluoropolymer water-based of condensation is disperseed and the moistening powder that obtains carries out drying or pelletization or utilizes the dried powder or the spherolite that obtain to carry out forming process etc.
In view of the above, 2-acyloxycarboxylic acid derivative of the present invention can be used as the emulsifying agent of polymerization fluoropolymer or brings into play some surface active property as the dispersion agent in the fluoropolymer aqueous liquid dispersion, can also remove by aftertreatment hydrolysis at an easy rate simultaneously, in can not remaining in the powder, spherolite, the formed body that form by resulting fluoropolymer, filming etc., thus in these finished products, the processing of filming etc., can suppress foaming, improve rerum natura, prevent painted etc.
For preferred substituted, carbonatoms and compound in the 2-acyloxycarboxylic acid derivative of the present invention, identical with narration relevant among the fluoropolymer preparation method of the present invention.
The preparation method of 2-acyloxycarboxylic acid derivative of the present invention is not particularly limited, for example preferred following method: with the 2-alpha-hydroxy carboxylic acid derivatives esterification of following general formula (5) expression, introduce RfCO-(Rf in the 2-hydroxy position 3Identical with above-mentioned definition);
[changing 6]
Figure A20048002047800301
In the following formula, Rf 1, Rf 2, M, a, b and d be identical with above-mentioned definition.
As above-mentioned 2-acyloxycarboxylic acid derivative, for example can be preferably following substances: (CF 3) 2C (OH) COOM, (CF 3) (CF 3CF 2) C (OH) COOM, (CF 3CF 2) 2C (OH) COOM, (CF 3) C (OH) 2COOM, (CF 3CF 2) C (OH) 2COOM, (CF 3) C (OH) 2COOM, wherein M and above-mentioned definition is identical.
Above-mentioned 2-alpha-hydroxy carboxylic acid derivatives for example can be by following method preparation.
(A) during d=1
Prepare the 2-hydroxycarboxylic acid esters by fluoroolefins base ether,, obtain 2-hydroxycarboxylic acid or its salt again with the known method hydrolysis of this ester.
As above-mentioned fluoroolefins base ether, can enumerate for example seven fluorine iso-butylene alkyl oxide [(CF 3) 2C=CFOR 1, R 1The alkyl of expression carbonatoms 1～12], its be with the by product octafluoro of preparation during hexafluoro-propene for iso-butylene as raw material, this raw material is made pure affixture, obtain by dehydrofluorination then.
As the method that obtains above-mentioned 2-hydroxycarboxylic acid esters by above-mentioned fluoroolefins base ether, can enumerate and for example adopt ruthenium compound or osmium compound to carry out the method for oxidizing reaction.
As above-mentioned oxidizing reaction, for example can enumerate, use the RuO that calculates the amount of trying to achieve by stoichiometry 4The oxidizing reaction of carrying out; RuO 2NH 2O or RuCl 3NH 2Precursors such as O obtain RuO in the presence of co-oxidants 4The catalyzed oxidation that oxidizing reaction is quickened; The OsO of the amount of trying to achieve is calculated in use by stoichiometry 4The oxidizing reaction of carrying out; In the presence of co-oxidants, obtain OsO 4Make catalyzed oxidation that oxidizing reaction quickens etc.; Open oxidizing reaction of putting down in writing in the 2002-234860 communique etc. the spy.
(B) during d=2
With CF 3(CF 2) ZCFCF 2(in the formula, z represents 1～17 integer ,-CFCF to O 2O representative ring oxide structure) represented compound is an initiator, and according to J.Org.Chem., the method for 31,2312 (1996) records prepares with CF 3(CF 2) ZC (OH) 2The represented compound of COOH (wherein, z and above-mentioned definition is identical).
The esterification process of above-mentioned 2-alpha-hydroxy carboxylic acid derivatives does not have particular restriction, can adopt such as following method.
(I) utilize the halo acyl group that obtains by RfCOOH (Rf is identical with above-mentioned definition), carry out de-hydrogen halide.
(II) utilize by RfCOOM 1(Rf is identical with above-mentioned definition, M 1Expression H, NH 4, Li, Na or K) carboxylic acid or its esters of expression, carry out dehydration reaction.
(III) utilize by RfCOOR 2(Rf is identical with above-mentioned definition, R 2The expression carbonatoms is 1～12 alkyl) acid esters of expression, carry out transesterification reaction.
(IV) utilize by RfCOOCOR 3(Rf is identical with above-mentioned definition, R 3Expression Rf or carbonatoms are 1～12 alkyl) acid anhydrides of expression reacts.
In the method for above-mentioned (I)-(IV), consider preferred (I) or the method (II) of adopting from aspects such as operability and yields.
In the method for above-mentioned (I),, can use any among RfCOF, RfCOCl, RfCOBr or the RfCOI (Rf is same as described above), but preferably use RfCOF, RfCOCl as described halo acyl group.
Preparation method as 2-acyloxycarboxylic acid derivative of the present invention, the following method of preferred employing: make by the 2-alpha-hydroxy carboxylic acid derivatives of above-mentioned general formula (2) expression and the alkanols compound of representing by following general formula (6) and carry out esterification, prepare described 2-acyloxycarboxylic acid derivative with this:
RfCOZ (6)
In the following formula, Rf is identical with above-mentioned definition, and Z represents-OM 1Perhaps Y, M 1Expression H, NH 4, Li, Na or K, Y represents F or Cl.
This method also is one of the present invention.
This method is that the halogen of halo acyl group described in above-mentioned (I) method is the method for F or Cl and method (II).
Method as above-mentioned (I), can enumerate for example following method: when Y is Cl, in 0 ℃～100 ℃ scopes, in the presence of organic solvents such as benzene, toluene, chloroform, thionyl chloride is splashed among the above-mentioned RfCOOH, with the form generation acyl chlorides [RfCOCl] of above-mentioned alkanols compound; Then, in 0 ℃～100 ℃ scopes, in the presence of acid reinforcing aidss such as pyridine, triethylamine (helping sour drug) and above-mentioned organic solvent, splash into above-mentioned acyl chlorides, the amount of splashing into is 0.8 equivalent～1.2 equivalents with respect to above-mentioned 2-alpha-hydroxy carboxylic acid derivatives, then stirred for several hour.
As the method for above-mentioned (II), can enumerate for example following method: in the presence of dewatering agents such as organic solvents such as hexane, hexanaphthene, benzene, toluene, chloroform and five phosphorus oxide, sulfuric acid, make above-mentioned 2-alpha-hydroxy carboxylic acid derivatives and above-mentioned RfCOOM 1React at 50 ℃～100 ℃.
For the usage quantity of above-mentioned dewatering agent, be 0.7 equivalent～5 equivalents preferably with respect to above-mentioned 2-alpha-hydroxy carboxylic acid derivatives; RfCOOM 1The amount of splashing into be 0.7 equivalent～2 equivalents preferably with respect to above-mentioned 2-alpha-hydroxy carboxylic acid derivatives.
The RfCOOR that uses in the method for above-mentioned (III) 2In, as R 2, can enumerate for example methyl, ethyl, propyl group etc., be preferably methyl.
2-acyloxycarboxylic acid derivative of the present invention can suit as tensio-active agent.
The tensio-active agent that contains above-mentioned 2-acyloxycarboxylic acid derivative also is one of the present invention.
Tensio-active agent of the present invention just can be used as tensio-active agent fully so long as contain at least a kind of 2-acyloxycarboxylic acid derivative of above-mentioned general formula (1) expression, and this tensio-active agent also can contain at least 2 kinds of above-mentioned 2-acyloxycarboxylic acid derivatives.
Tensio-active agent of the present invention also can contain a kind or at least 2 kinds other compound with some surface active property except containing the 2-acyloxycarboxylic acid derivative.
Above-mentioned other compound with some surface active property is not particularly limited, and can be any in positively charged ion, negatively charged ion, nonionic or the betaines tensio-active agent for example, and these tensio-active agents also can be hydro carbons.
Tensio-active agent of the present invention has the compound of some surface active property except containing above-mentioned 2-acyloxycarboxylic acid derivative and used as required other, also can contain additive.Above-mentioned additive is not particularly limited, and for example, can be the materials of using in tensio-active agent usually such as stablizer.
Tensio-active agent of the present invention is owing to contain above-mentioned 2-acyloxycarboxylic acid derivative, thereby can bring into play appropriate some surface active property in various uses.Tensio-active agent of the present invention is blended in such as having the capillary effect of reduction in the various liquid such as water, can suitably determine addition and set surface tension according to application target.
The effect of invention
The preparation method of fluoropolymer of the present invention is owing to have above-mentioned formation, thereby can make in the resin residual quantity of tensio-active agent few, and can effectively prepare painted less, the fluoropolymer of physical properties excellent.In addition, fluoropolymer aqueous liquid dispersion of the present invention is owing to have above-mentioned formation, thereby can make the fluoropolymer stable existence in wherein, and can provide painted less, the fluoropolymer formed body of physical properties excellent and film etc.2-acyloxycarboxylic acid derivative of the present invention is owing to have above-mentioned formation, thereby the applicable tensio-active agent of doing.In addition, tensio-active agent of the present invention is owing to contain above-mentioned 2-acyloxycarboxylic acid derivative, thereby has suitable some surface active property.
Embodiment
The present invention will be described to utilize preparation example and embodiment below, but the present invention is not limited in described preparation example and embodiment.
Preparation example 1 (CF 3) 2C (OCOCF 2CF 2CF 2CF 2H) COONH 4Synthetic
[1] (CF 3) 2C (OH) COOCH 3Synthetic
In three mouthfuls of round-bottomed flasks of the 1000mL with dropping funnel, cooling tube, thermometer and stirrer, add 53.0g (0.25mol) (CF 3) 2C=CFOCH 3, 0.03g (0.25mmol) RuO 2NH 2O, 17.3g (0.13mol) K 2CO 3And 40.0g water, at room temperature stir, splash into the clorox of 1.7mol/L simultaneously, along with the carrying out of reaction by RuO 2NH 2O generates RuO gradually 4When reaction proceeded to 6 hours, the amount of splashing into of the clorox of 1.7mol/L reached 147g (0.25mol), RuO 4Return and be generated as RuO 2NH 2During O, from reaction mixture, cross and filter RuO 2NH 2O, the filtrate that obtains is carried out separatory by separating funnel.The organic layer that obtains is analyzed with gas chromatograph, result (CF 3) 2C=CFOCH 3Transformation efficiency be 99.8%, and obtain (CF with 90.5% selection rate 3) 2C (OH) COOCH 3
[2] (CF 3) 2C (OH) COOCH's is synthetic
In three mouthfuls of round-bottomed flasks of the 100mL with cooling tube, thermometer and stirrer, add 0.9g sodium hydroxide, 20mL methyl alcohol, dissolving under agitation forms homogeneous solution, and the time of using 3 minutes then is with 4.5g (CF 3) 2C (OH) COOCH 3Splash into wherein, then, splash into 2mL water, stirred 1 hour at 20 ℃.Methyl alcohol is heated up in a steamer in decompression, add 10mL water after, splashing into 35% hydrochloric acid, to regulate pH be 2.Add the 20mL chloroform, the Separation and Recovery oil reservoir.It is imitative to heat up in a steamer dechlorination, obtains 3.9g (CF 3) 2C (OH) COOCH.
[3] (CF 3) 2C (OCOCF 2CF 2CF 2CF 2H) COONH 4Synthetic
In having the 100mL there-necked flask of cooling tube, thermometer and stirrer, add 2.1g (CF 3) 2C (OH) COOCH, the 20mL chloroform, the limit was stirred the limit at 20 ℃ and splashed into the 1.6g triethylamine in 5 minute.After being added dropwise to complete, in 10 minutes, splash into 4.1g HCF again 2CF 2CF 2CF 2COCl.Stir after 1 hour, add 20mL water, after stirring is cleaned, separate oil reservoir, it is imitative to heat up in a steamer dechlorination, obtains 3.1g (CF 3) 2C (OCOCF 2CF 2CF 2CF 2H) COOH.This compound is neutralized with ammoniacal liquor, obtain (CF 3) 2C (OCOCF 2CF 2CF 2CF 2H) COONH 4
Preparation example 2 (CF 3) 2C (OCOCF 2CF 2CF 2CF 2H) COOH's is synthetic
In having the 100mL there-necked flask of cooling tube, thermometer and stirrer, add 2.1g (CF 3) 2C (OH) COOCH, the 20mL chloroform, the limit was stirred the limit at 20 ℃ and splashed into the 1.6g triethylamine in 5 minute.Splash into finish after, in 10 minutes, splash into 4.1g HCF again 2CF 2CF 2CF 2COCl.Stir after 1 hour, add 20mL water, after stirring is cleaned, separate oil reservoir, it is imitative to heat up in a steamer dechlorination, obtains 3.1g (CFx) 2C (OCOCF 2CF 2CF 2CF 2H) COOH.This compound is neutralized with ammoniacal liquor.
For the aqueous solution that obtains, with (CF 3) 2C (OCOCF 2CF 2CF 2CF 2H) concentration adjustment of COOH is 0.1% quality, adopts the Wilhelmy method to be determined at 25 ℃ and measures surface tension, and this surface tension is 62Nm/m.
Preparation example 3 CF 3C (OCOCF 2CF 2CF 2CF 2H) 2COOH's is synthetic
In having the 100mL there-necked flask of cooling tube, thermometer and stirrer, add 1.0gCF 3C (OH) 2COOH, the 20mL chloroform, the limit was stirred the limit at 20 ℃ and splashed into the 1.5g triethylamine in 5 minute.Splash into finish after, in 10 minutes, splash into 3.4g HCF again 2CF 2CF 2CF 2COCl.Stir after 1 hour, add 20mL water, after stirring is cleaned, separate oil reservoir, it is imitative to heat up in a steamer dechlorination, obtains 1.3g CF 3C (OCOCF 2CF 2CF 2CF 2H) 2COOH.This compound is neutralized with ammoniacal liquor.
For the aqueous solution that obtains, with CF 3C (OCOCF 2CF 2CF 2CF 2H) 2The concentration adjustment of COOH is 0.1% quality, the surface tension under employing Wilhelmy method is measured 25 ℃, and this surface tension is 56Nm/m.
Preparation example 4 HCF 2CF 2CF 2CF 2CH 2OOCCH=CH-COONH 4Synthetic
In having the 100mL there-necked flask of cooling tube, thermometer and stirrer, add 5.0g maleic anhydride and 40.0g HCF 2CF 2CF 2CF 2CH 2CH 2OH is heated to 70 ℃, then, adds the 0.3mL vitriol oil, in 70 ℃ of reactions 3 hours, adds entry in reactant, cleans, and carries out 3 separatory operations repeatedly, reclaims oil reservoir, heats up in a steamer residual ethanol, obtains 13.7gHCF 2CF 2CF 2CF 2CH 2OOCCH=CH-COOH.This compound is neutralized with ammoniacal liquor, obtain HCF 2CF 2CF 2CF 2CH 2OOCCH=CH-COONH 4
The preparation [1] of embodiment 1 PTFE emulsion (latex)
In inner capacities is the stainless steel autoclave of band stirring arm of 3L, add the 1.5L deionized water, 60g paraffin (60 ℃ of melting points), and 250mg 2-acyloxycarboxylic acid derivative (CF 3) 2C (OCOCF 2CF 2CF 2CF 2H) COONH 4, with tetrafluoroethylene (TFE) to replacing in the system.The control internal temperature is 70 ℃, and being pressed into TFE, to make internal pressure be 0.78Mpa, adds ammonium persulphate [APS] aqueous solution of 5g0.6 weight %, initiation reaction.Along with polymeric carries out, the pressure in the polymerization system can reduce, and appends TFE continuously, presses in keeping to be 0.78Mpa, continues reaction.Be performed until resin in the aqueous liquid dispersion and form branch admittedly and reach about 5 quality %, when appending TFE, stop to stir, make the pressure in the still return normal pressure, termination reaction.This aqueous liquid dispersion is carried out following mensuration.The results are shown in Table 1.
Gu the concentration of form dividing: with the gained aqueous liquid dispersion 150 ℃ dry 1 hour down, reduce to ask with weight and calculate the solid concentration of dividing that forms.
The concentration of residual surfactant: in the aqueous liquid dispersion that 100g obtains, add 1g nitric acid, stirred 15 minutes in 25 ℃, the toner that obtains is clean with the 100g washing once more, in 180 ℃ of dryings 6 hours, obtain the PTFE powder.This powder of 1g is dispersed in the 20mL methyl alcohol, under 50 ℃, stir and carried out extracting in 24 hours, the surfactant concentrations that extracting goes out from methyl alcohol adopts Quattro LC (Micromass corporate system) to utilize liquid chromatography/tandem type mass spectroscopy (LC/MS/MS) to carry out quantitatively, is converted into corresponding resin concentration.
Above-mentioned liquid chromatography adopts Phenomonex Columbus C18 (15cm * 2mm i.d.) post, adopt the 0.02M ammonium acetate: methyl alcohol (60: 40 v: v, mobile phase A) and the 0.02M ammonium acetate: methyl alcohol (10: 90 v: v, Mobile phase B), carry out stripping according to following condition: the concentration gradient of Mobile phase B (100%)-mobile phase A (100%) in 12～13 minutes after Mobile phase B (100%), (3) stripping began in 6～12 minutes after concentration gradient, (2) stripping of mobile phase A (100%)-Mobile phase B (100%) began in 0～6 minute after (1) stripping began.In above-mentioned tandem type mass spectroscopy, carry out negative electricity ejection-type (ESP-) (negtive electrospray) ionization.
The preparation [2] of embodiment 2 PTFE emulsions
As shown in table 1, remove the toxilic acid half ester HCF that obtains in the adding 210mg preparation example 2 2CF 2CF 2CF 2CH 2OOCCH=CH-COONH 4In addition, carry out polymerization and the mensuration identical with embodiment 1.The result is as shown in table 1.
The preparation [3] of comparative example 1 PTFE emulsion
Except that add 240mg per-fluoro octanoate (PFOA) as tensio-active agent, carry out polymerization and the mensuration identical with embodiment 1.The result is as shown in table 1.
Table 1
Embodiment 1 Embodiment 2 Comparative example 1
Divide concentration (quality %) Gu form 5.1 5.3 5.0
Residual surfactant concentration (ppm) 0.1 0.06 28
As can be seen from Table 1, compare, use 2-acyloxycarboxylic acid derivative (CF with the comparative example 1 that uses tensio-active agent PFOA 3) 2C (OCOCF 2CF 2CF 2CF 2H) COONH 4Perhaps toxilic acid half ester HCF 2CF 2CF 2CF 2CH 2OOCCH=CH-COONH 4Embodiment 1～2 in, tensio-active agent residual very low.
Utilizability on the industry
The preparation method of the present invention's fluoropolymer is owing to have above-mentioned formation, thereby can make in the resin the residual amount of surfactant few, and can effectively prepare painted less, the fluoropolymer of physical properties excellent. In addition, the present invention's fluoropolymer aqueous liquid dispersion is owing to have above-mentioned formation, thereby can make the fluoropolymer stable existence in wherein, and can provide painted less, the fluoropolymer moulding body of physical properties excellent and film etc. The present invention's 2-acyloxycarboxylic acid derivative is owing to have above-mentioned formation, thereby the applicable surfactant of doing. In addition, the present invention's surfactant is owing to contain above-mentioned 2-acyloxycarboxylic acid derivative, thereby has suitable some surface active property.

Claims (16)

1, the preparation method of fluoropolymer, it has the preparation method of the carboxylic acid derivative of carboxylic acid ester bond as the fluoropolymer of tensio-active agent polymerization fluoropolymer for using in aqueous medium, it is characterized in that, described carboxylic acid derivative with carboxylic acid ester bond have the carboxylic acid ester bond that replaced by fluorine atom or do not replaced by fluorine atom and-COOM, wherein M represents H, NH 4, Li, Na or K.
2, the preparation method of the described fluoropolymer of claim 1, wherein, the carboxylic acid ester bond is acyloxy of representing with RfCOO-or the carbalkoxy of representing with RfOCO, and wherein Rf represents that carbonatoms is that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen.
3, the preparation method of fluoropolymer as claimed in claim 1 or 2, wherein, the carboxylic acid derivative with carboxylic acid ester bond is the 2-acyloxycarboxylic acid derivative by following general formula (1) expression;
Figure A2004800204780002C1
In the above-mentioned general formula (1), Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; A and b represent 0～2 integer; D represents 1～3 integer; A, b and d satisfy a+b+d=3; Rf and M are with described identical; Rf 1, Rf 2Identical with Rf or inequality.
4, the preparation method of fluoropolymer as claimed in claim 1 or 2, wherein, the carboxylic acid derivative with carboxylic acid ester bond is the dicarboxylic acid half ester (A) by following general formula (3) expression;
RfOCORf 5COOM (3)
In the above-mentioned general formula (3), Rf 5Expression-C fH 2F-or-C gH 2g-2-, f represents 1～6 integer, g represents 2～6 integer; Rf and M are with described identical.
5, the preparation method of fluoropolymer as claimed in claim 1 or 2, wherein, the carboxylic acid derivative with carboxylic acid ester bond is the dicarboxylic acid half ester (B) of following general formula (4) expression;
RfOCO(CH 2) h-T-(CH 2) iCOOM (4)
In the above-mentioned general formula (4), T represents-CRf 4=CH-,-CH=CRf 4-or-CHRf 4-, Rf 4Expression F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; H is identical with i or different, the integer of expression 0～3; Rf and M are with described identical.
6, as the preparation method of claim 1,2,3,4 or 5 described fluoropolymers, wherein, for carboxylic acid derivative with carboxylic acid ester bond, the result who adopts the Wilhelmy method to measure, the surface tension of the 0.1 quality % aqueous solution under 25 ℃ is 30～70Nm/m.
7, as the preparation method of claim 1,2,3,4,5 or 6 described fluoropolymers, wherein, the carboxylic acid derivative with carboxylic acid ester bond generates hydrolyzate by hydrolysis, and the number of carbon atom that is combined with fluorine atom in the described hydrolyzate is smaller or equal to 6.
8, the preparation method of fluoropolymer as claimed in claim 7, wherein, the number of carbon atom that is combined with fluorine atom is smaller or equal to 4.
9, as the preparation method of claim 1,2,3,4,5,6,7 or 8 described fluoropolymers, wherein, the addition with carboxylic acid derivative of carboxylic acid ester bond is the 0.0001 quality %～15 quality % of aqueous medium.
10, fluoropolymer aqueous liquid dispersion, it contains the particle that is formed by fluoropolymer, the carboxylic acid derivative with carboxylic acid ester bond and aqueous medium, it is characterized in that, described carboxylic acid derivative with carboxylic acid ester bond have the carboxylic acid ester bond that replaced by fluorine atom or do not replaced by fluorine atom and-COOM, wherein M is H, NH 4, Li, Na or K.
11, the 2-acyloxycarboxylic acid derivative is characterized in that, it is represented with following general formula (1);
Figure A2004800204780003C1
In the above-mentioned general formula (1), Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; Rf represents that carbonatoms is that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen; M represents H, NH 4, Li, Na or K; A and b represent 0～2 integer; D represents 1～3 integer; A, b and d satisfy a+b+d=3; Rf 1, Rf 2Identical or different with Rf.
12,2-acyloxycarboxylic acid derivative as claimed in claim 11, wherein, Rf 1And Rf 2Identical or different, be A (CF 2) j(CH 2) p-; Wherein, A represents H or F; J represents 1～6 integer; P represents 0～3 integer.
13, as claim 11 or 12 described 2-acyloxycarboxylic acid derivatives, wherein, Rf is A (CF 2) n(CH 2) m-or A (CF 2) q[CFX-CF 2(CH 2) rO] tCFX-; At A (CF 2) n(CH 2) m-in, A represents H or F, and n represents 1～4 integer, and m represents 0～3 integer; At A (CF 2) q[CFX-CF 2(CH 2) rO] tAmong the CFX-, X represents F or CF 3, q represents 0～3 integer, and r represents 0～2 integer, and t represents 1～3 integer, and A is identical with above-mentioned definition.
14,2-acyloxycarboxylic acid derivative as claimed in claim 11, wherein, Rf 1And Rf 2Identical or different, be A (CF 2) u-, wherein A represents H or F, u represents 1～3 integer; Rf is A (CF 2) w(CH 2) y-, wherein A and above-mentioned definition is identical, and W represents 2～4 integer, and y represents 0～1 integer.
15, tensio-active agent is characterized in that, contains claim 11,12,13 or 14 described 2-acyloxycarboxylic acid derivatives.
16, the preparation method of 2-acyloxycarboxylic acid derivative; in described method, the 2-alpha-hydroxy carboxylic acid derivatives by making following general formula (5) expression and the alkanol compounds of following general formula (6) expression are carried out esterification and are prepared claim 11,12,13 or 14 described 2-acyloxycarboxylic acid derivatives:
In the described general formula (5), Rf 1And Rf 2Identical or different, expression H, F, carbonatoms are that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen, and M represents H, NH 4, Li, Na or K, a and b represent 0～2 integer, d represents 1～3 integer, a, b and d satisfy a+b+d=3;
RfCOZ (6)
In the described general formula (6), Rf represents that carbonatoms is that 1～20 fluoro-alkyl or carbonatoms are 1～20 the fluoro-alkyl that contains ether oxygen, and Z represents-OM 1Perhaps Y, M 1Expression H, NH 4, Li, Na or K, Y represents F or Cl.
CN 200480020478 2003-07-16 2004-07-16 Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent Pending CN1823094A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP275581/2003 2003-07-16
JP275582/2003 2003-07-16
JP2003275581 2003-07-16

Publications (1)

Publication Number Publication Date
CN1823094A true CN1823094A (en) 2006-08-23

Family

ID=36923809

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200480020478 Pending CN1823094A (en) 2003-07-16 2004-07-16 Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent

Country Status (1)

Country Link
CN (1) CN1823094A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103124746A (en) * 2010-09-30 2013-05-29 大金工业株式会社 Method for producing fluorine-containing polymer
CN105061640A (en) * 2015-07-22 2015-11-18 陕西科技大学 Fluorine-containing emulsifier as well as anionic fluorine-containing emulsion prepared based on emulsifier and method
CN110446723A (en) * 2017-03-31 2019-11-12 大金工业株式会社 The use of surfactant and surfactant of fluoropolymer-containing manufacturing method, polymerization
CN111514811A (en) * 2020-03-26 2020-08-11 陕西驭腾实业有限公司 Preparation method of asymmetric Gemini fluorocarbon surfactant
CN111533929A (en) * 2019-02-07 2020-08-14 富士施乐株式会社 Fluororesin-containing particles, composition, layered product, electrophotographic photoreceptor, process cartridge, and image forming apparatus
CN111740108A (en) * 2020-06-19 2020-10-02 浙江中科立德新材料有限公司 High-nickel ternary cathode aqueous binder for lithium ion battery and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103124746A (en) * 2010-09-30 2013-05-29 大金工业株式会社 Method for producing fluorine-containing polymer
CN103124746B (en) * 2010-09-30 2015-08-26 大金工业株式会社 The manufacture method of fluoropolymer
US9567413B2 (en) 2010-09-30 2017-02-14 Daikin Industries, Ltd. Method for producing fluorine-containing polymer
CN105061640A (en) * 2015-07-22 2015-11-18 陕西科技大学 Fluorine-containing emulsifier as well as anionic fluorine-containing emulsion prepared based on emulsifier and method
CN105061640B (en) * 2015-07-22 2017-01-11 陕西科技大学 Fluorine-containing emulsifier as well as anionic fluorine-containing emulsion prepared based on emulsifier and method
CN110446723A (en) * 2017-03-31 2019-11-12 大金工业株式会社 The use of surfactant and surfactant of fluoropolymer-containing manufacturing method, polymerization
CN111533929A (en) * 2019-02-07 2020-08-14 富士施乐株式会社 Fluororesin-containing particles, composition, layered product, electrophotographic photoreceptor, process cartridge, and image forming apparatus
CN111514811A (en) * 2020-03-26 2020-08-11 陕西驭腾实业有限公司 Preparation method of asymmetric Gemini fluorocarbon surfactant
CN111740108A (en) * 2020-06-19 2020-10-02 浙江中科立德新材料有限公司 High-nickel ternary cathode aqueous binder for lithium ion battery and preparation method thereof
CN111740108B (en) * 2020-06-19 2022-06-28 浙江中科立德新材料有限公司 High-nickel ternary cathode water-based binder for lithium ion battery and preparation method thereof

Similar Documents

Publication Publication Date Title
CN1871268A (en) Aqueous tetrafluoroethylene polymer dispersion, process for producing the same, tetrafluoroethylene polymer powder, and molded tetrafluoroethylene polymer
CN1096477C (en) Aqueous dispersion of vinylidene fluoride copolymer, aqueous dispersion of vinylidene fluoride seed polymer and its preparing process
CN1875035A (en) Process for producing aqueous fluoropolymer dispersion and aqueous fluoropolymer dispersion
CN1239940A (en) Alpha-branched fluoroalkylcarbonyl fluorides and their derivatives
CN1082965C (en) Allyl chain transfer agent
CN1727368A (en) Perfluoroelastomers
CN1308352C (en) Process for production of living radical polymers and polymers
CN1727369A (en) Fluoroelastomers
CN1742027A (en) Emulsion polymerization of fluorinated monomers
CN85109314A (en) Preparation has the method and the application thereof of the fluorinated telomer of hydrophilic group
CN1108263A (en) New fluoroelastomers comprising monomeric units deriving from a bis-olefin
CN1651642A (en) Treatment comprising water-and oil-repellent agent
CN1164673C (en) Fuoroelastomer composition for crosslinking
CN1239483A (en) Aqueous fluoropolymer compsns. and method of preparing same
CN101065443A (en) Fluorine-containing treatment composition
CN1246281C (en) Method for producing fluorine-containing compound
CN1239897A (en) Aqueous film-forming foam compositions
CN1880347A (en) Process for preparing fluoropolymer dispersions
CN1690093A (en) Curable fluorelastomers
CN1712430A (en) Perfluoroelastomer gels
CN1186799A (en) Production of hydrofluorocarbons
CN1102041A (en) Novel oil and alcohol repellent fluorinated surfactants and intermediates, derivates and uses thereof
CN1273447C (en) Process for producing diphenyl sulfone compound
CN1639210A (en) Method of making alternating copolymers of isobutylene type monomers
CN1823094A (en) Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
AD01 Patent right deemed abandoned

Effective date of abandoning: 20060823

C20 Patent right or utility model deemed to be abandoned or is abandoned