CN101171296A - Crosslinkable polytetrafluoroethylene composition, cross-linked polytetrafluoroethylene powder, polytetrafluoro-ethylene moldings, resin blend compositions, and resin blend moldings - Google Patents
Crosslinkable polytetrafluoroethylene composition, cross-linked polytetrafluoroethylene powder, polytetrafluoro-ethylene moldings, resin blend compositions, and resin blend moldings Download PDFInfo
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Abstract
The invention aims at providing a PTFE resin which can be molded by a conventional process such as compression molding without expensive equipment or hot-coining of low productivity and little generates toxic substance during the molding and which retains the strength, crystallinity and surface characteristics inherent in conventional PTFE resins and exhibits isotropy, uniformity, and less deformation than those of conventional PTFE resins. The crosslinkable polytetrafluoroethylene composition comprises a polytetrafluoroethylene and a crosslinking agent. The polytetrafluoroethylene has at least one reactive functional group selected from the group consisting of cyano (-CN), carboxyl (-COOH), alkoxycarbonyl (-COOR (wherein R is a monovalent organic group)), and acid halide groups (-COX (wherein X is halogen)) at the end of at least either of the backbone chain and the side chain. The crosslinking agent can react with one or more of the reactive functional groups to form a ring structure.
Description
Technical field
The present invention relates to form the polyetetrafluoroethycomposition composition of crosslinking structure and teflon resin with crosslinking structure.And, the invention still further relates to the mixed with resin composition of the teflon resin that contains polyetetrafluoroethycomposition composition or have crosslinking structure.And, the present invention also relates to the mixed with resin formed body that obtains by the mixed with resin composition.
Background technology
Tetrafluoroethylene (hereafter is PTFE) resin is widely used as sliding material, flame-retardant additives, low-k mould material etc. at aspect excellent performances such as chemical resistant properties, rub resistance, weathering resistance, electric insulating quality, flame retardant resistances.But the PTFE resin exists abrasion and the big such problem of creep under the slip environment or under the pyritous compression environment.Therefore, the wear characteristic of expectation PTFE resin and creep properties etc. improve further in the industry.As the method that addresses this problem, the method for the method of " mixed additive in the PTFE resin " as well known to those skilled in the art and " shining the ionization radioactive rays so that PTFE resin crosslinksization (for example, referring to patent documentation 1 and 2) " etc. to the PTFE resin.And, also have report disclose method, " behind the mixed fluoride pitch and the PTFE resin; " of " having the PTFE resin of carboxyl etc. to heat-treat to importing; to make PTFE resin crosslinks (for example ;) thus " referring to patent documentation 3 by heating or the irradiation of ionization radioactive rays makes PTFE resin crosslinks (for example, referring to patent documentation 4) method, " the ratio of mixture surface-area is 1.0～2.0m in the PTFE resin
2The carbon fiber of/g (for example, referring to patent documentation 5) " method etc.
Patent documentation 1: the spy opens flat 7-118423 communique
Patent documentation 2: the spy opens the 2001-329069 communique
Patent documentation 3: the spy opens flat 3-234753 communique
Patent documentation 4: the spy opens flat 2003-119293 communique
Patent documentation 5: the spy opens the 2003-41083 communique
But, in the method for " mixed additive or carbon fiber ", aspect many rerum naturas of the formed body of PTFE resin, not only anisotropy may appear, also may bring detrimentally affect to the surface property (low frictional properties etc.) of PTFE resin.And, it is reported, the PTFE resin that can obtain having low abradability according to the method for " PTFE resin irradiation ionization radioactive rays are made its crosslinkedization ", but the problem that exists in the PTFE resin-formed body that is obtained by this method is, owing to cutting off, being ionized property of PTFE main chain radioactive rays cause intensity to reduce and the crystallinity reduction, and have following problem: cause crosslinked unhomogeneity owing to noncrystalline part is earlier crosslinked, this is the problem that is derived from radioactive rays cross-linking agent itself.And, this method need be carried out the thermal treatment of PTFE formed body under the high temperature more than the fusing point of PTFE, and temperature need be controlled at 20 ℃ up and down of this temperature, preferably this temperature temperature control of 5 ℃ of such precisions up and down, in addition, need under low oxygen concentration, heat-treat in order to obtain good cross-linking efficiency.Therefore there is the problem that to use expensive device in order to adopt this method.And, in this method, on the structure of device, because it is difficult shining the ionization radioactive rays equably to the PTFE formed body, under the situation of powder, the problem that will exist crosslinking structure to import unevenly, under the situation of film, will there be the problem that fold etc. occurs.In addition, utilizing heat to carry out under the crosslinked situation, lack the effect of improving performance.
And, in the method for " pitch is fluoridized in utilization makes the PTFE crosslinked ", exist in and produce deleterious HF gas and F in the crosslinking reaction
2The problem of gas etc.And, as the spy open flat 2001-240682 communique, the spy opens as shown in 2002-114883 communique etc., in the compressed moulding of the above-mentioned crosslinked PTFE powder that obtains (hereinafter being called crosslinked PTFE powder), it is difficult only crosslinked PTFE powder being carried out compressed moulding, therefore exist need be before compressed moulding with uncrosslinked PTFE blended problem, if improved the content of crosslinked PTFE then be difficult to compressed moulding problem and since need be when the compressed moulding temperature of use more than the fusing point refrigerative hot-coining method of pressurizeing cause the problem etc. of productivity difference.
Summary of the invention
The object of the present invention is to provide a kind of PTFE resin, this resin can utilize common forming method such as compressed moulding to make and not need the expensive device and the hot-coining method of productivity difference etc., and can not produce deleterious material in the mill and can keep original intensity, crystallinity and surface property etc.; And this resin do not exist anisotropy and unhomogeneity, compares not yielding with existing P TFE resin.
The bridging property polyetetrafluoroethycomposition composition that the present invention relates to contains tetrafluoroethylene and linking agent.Tetrafluoroethylene has at least one side of main chain and side chain terminal and is selected from by cyano group (CN), carboxyl (COOH), at least a reactive functional groups in the group formed of alkoxy carbonyl (COOR (R represents the organic group of 1 valency)) and acid halide group (COX (X represents halogen atom)).Linking agent can react with the reactive functional groups more than 1 or 2, forms ring texture.
Described linking agent is preferably at least a linking agent that is selected from the group of being made up of amidoxim class linking agent, amidrazone class linking agent, aminophenols linking agent, aminothiophenol class linking agent and amino-benzene base class linking agent.
And, described linking agent be preferably be selected from by contain at least two compounds with the bridging property reactive group of general formula (1) expression, with at least a compound in the compound of general formula (2) expression, the group formed with the compound of general formula (3) expression with the compound of general formula (4) expression;
In the general formula (1), R
1Identical or different, expression-NH
2,-NHR
2,-OH or-SH, R
2The organic group of expression fluorine atom or 1 valency;
In the general formula (2), R
3Expression-SO
2-,-O-,-CO-, carbonatoms are that 1～6 alkylidene group, carbonatoms are 1～10 perfluorinated alkylidene or singly-bound, R
4Expression
Or
In the general formula (3), R
f 1The expression carbonatoms is 1～10 perfluorinated alkylidene;
In the general formula (4), n represents 1～10 integer.
And described linking agent can be the compound with general formula (5) expression,
In the general formula (5), R
1With above-mentioned R
1Identical, R
5Expression-SO
2-,-O-,-CO-, carbonatoms be 1～6 alkylidene group, carbonatoms be 1～10 perfluorinated alkylidene, singly-bound or with
The group of expression.
And, make it that crosslinking reaction take place by heating above-mentioned bridging property polyetetrafluoroethycomposition composition, just can access polytetrafluoroethylmolded molded article and the crosslinked body powder of tetrafluoroethylene as the application's purpose.
And,, also can access polytetrafluoroethylmolded molded article as the application's purpose by the crosslinked body powder of above-mentioned tetrafluoroethylene is carried out compressed moulding, plunger extrusion moulding, paste extrusion moulding etc.
In addition, above-mentioned bridging property polyetetrafluoroethycomposition composition and the crosslinked body powder of tetrafluoroethylene also can be used as modification with dispersion of materials or be mixed in other resins such as molding resin or elastomerics or the resin precursor.As the method for this acquisition mixing moulding body, can enumerate, with above-mentioned bridging property polyetetrafluoroethycomposition composition with after resin or resin precursor mix, to the method for mixture heating up moulding; The crosslinked body powder of above-mentioned tetrafluoroethylene is mixed with other resin or resin precursor, mixture is carried out the method for moulding etc.In addition, in the former method, in hot briquetting, linking agent in the bridging property polyetetrafluoroethycomposition composition and polytetrafluoroethyl-ne alkene reaction form crosslinking structure.In addition, be not particularly limited for said " resin " herein, can enumerate: polyvinyl resin, acrylic resin, ethylene-vinyl acetate copolymer resin, the ethylene-ethyl acrylate copolymer resin, the ethylene-vinyl alcohol copolymer resin, poly-cyclic olefin resins, the polyisobutene resin, polyolefin resin, the polymethylpentene resin, polyvinyl chloride (PVC) RESINS, polystyrene resin, acrylonitrile-styrene copolymerized resin (AS resin), the styrene-methylmethacrylate copolymer resin, acrylic nitrile-butadiene-alkene-styrene copolymer resin (ABS resin), acrylonitrile acryloid styrene resin (AAS resin), vinyl cyanide-ethylene-propylene rubber-styrene-alkene copolymer resin (AES resin), acrylonitrile-styrene-acrylic ester copolymer resin (ASA resin), silicone-acrylonitritrile-styrene resin resin (SAS resin), acrylic resin, methacrylic resin, polyamide resin, polycarbonate resin, polyacetal resin, modified polyphenylene ether resin, the polybutylene terephthalate resin, pet resin, the PEN resin, polyphenylene sulfide, polysulfone resin, fluoro-resin, polyethersulfone resin, polyetherimide resin, polyether ketone resin, polyether-ether-ketone resin, polyimide resin, polyacrylate resin, silicone resin, polylactic resin, urethane resin, vibrin, the aromatic polyester amide resins, aromatic series azomethine resin, polyarylene sulfide resin, the polyketone resin, polyamide-imide resin and polyethers nitrile resin etc.And,, comprise tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and voltalef etc. in the fluoro-resin herein.And, said herein " resin precursor " is not particularly limited, and can enumerate liquid before the curing of Resins, epoxy, phenol resins, urea resin, melamine resin, unsaturated polyester resin, Synolac and diallyl phthalate resin etc., solution, pressed powder etc.
Make bridging property polyetetrafluoroethycomposition composition generation crosslinking reaction of the present invention, just can provide following teflon resin, this teflon resin has been kept original intensity, crystallinity and surface property, and this resin does not exist anisotropy and unhomogeneity, compares not yielding with existing P TFE resin.And when carrying out this crosslinking reaction, common forming methods such as employing compressed moulding just are enough to finish reaction, and do not need the expensive device and the hot-coining method of productivity difference etc.And, can not produce deleterious material in this crosslinking reaction.
And,, when mixing, also can carry out moulding with high weight ratio with other fluoro-resin such as for example tetrafluoroethylene even separately use also can moulding for the crosslinked body powder of above-mentioned bridging property polyetetrafluoroethycomposition composition and tetrafluoroethylene.In addition, the crosslinked body powder of above-mentioned bridging property polyetetrafluoroethycomposition composition and tetrafluoroethylene has the feature that can carry out moulding when compressed moulding with the prebake method.And the formed body that obtains thus can be kept existing surface property, does not possess anisotropy simultaneously, compares more not yielding with existing teflon resin.
And then, except disperseing or being mixed in molding resin or the elastomerics, the modification that crosslinked body powder of tetrafluoroethylene of the present invention or bridging property polyetetrafluoroethycomposition composition can also conduct be used for improving flame retardant resistance, non-binding property, sliding, water and oil-resistant, electrical specification, resistance to soiling, erosion resistance, weathering resistance etc. disperses with material or is mixed to other materials.
Embodiment
[bridging property polyetetrafluoroethycomposition composition]
The bridging property polyetetrafluoroethycomposition composition of embodiments of the present invention contains tetrafluoroethylene and linking agent.Respectively tetrafluoroethylene and the linking agent that adopts in the present embodiment described below.In addition, hereinafter abbreviate tetrafluoroethylene as PTFE.
[PTFE]
As the PTFE of present embodiment, can preferably enumerate at main chain and/or side chain terminal and have cyano group (CN yl), carboxyl (COOH yl), alkoxy carbonyl (COOR
7Base, R
7Be the univalent organic group), acid halide group (COX:X is a halogen) is as the PTFE of the cross-linking part that can react with linking agent.Wherein, consider reactivity, more preferably have cyano group or acid halide group.And, consider to be easy to make more preferably have carboxyl or alkoxy carbonyl, especially preferably have carboxyl.
The cross-linking part that can react with linking agent both can be the cross-linking part that is directed into PTFE by high molecular weight reactive, also can be the cross-linking part that the copolymerization of monomer by cross-linking part is provided and tetrafluoroethylene (hereafter is TFE) imports.As the method that in PTFE, imports functional group by high molecular weight reactive, known so far have utilize radioactive rays, laser, electronics line, plasma body, corona discharge etc. that PTFE is handled and import the dry method of functional group; Utilize electrochemical method or utilize Li metal/naphthalene coordination compound to carry out reductive wet method etc.In addition, from the aspect that is easy to make, preferably adopt the latter's method.
In the PTFE of present embodiment, with respect to as necessary monomeric TFE, provide the monomeric content of cross-linking part to be preferably 0.01 mole more than the %, more preferably 0.03 mole more than the %, more preferably 0.06 mole more than the %; Be preferably 50 moles below the %, more preferably 20 moles below the %, more preferably 5 moles below the %.This be because, be 0.01 mole below the % if the monomeric content of cross-linking part is provided, then can't obtain effect of sufficient; If monomeric content is 50 moles more than the %, then be difficult to obtain polymkeric substance.
In the present embodiment,, can use compound arbitrarily,, and have cyano group, carboxyl, alkoxy carbonyl or acid halide group as functional group and have copolymerization with TFE and get final product as long as this compound has the ethylenic unsaturated link(age) as the monomer that cross-linking part is provided.As monomer, can use chain and cyclic compound arbitrarily.If monomer is ring compound, the compound that the part or all of hydrogen atom that then can enumerate cyclopentenes and derivative, norbornylene and derivative thereof with above-mentioned functional group, encircles norbornylene and derivative, vinylcarbazole and derivative thereof and these compounds is replaced by halogen atom (particularly fluorine atom, contain fluoroalkyl) more etc. as an example.In addition, consider polymerizability, preferred monomers is a chain compound.And, in the chain compound, the preferred especially monomer of representing with following general formula.
CY
1Y
2＝CY
3(O)
m(R
8)
n-Z
1 (7)
In the general formula (7), Y
1～Y
3Represent independently of one another hydrogen atom, halogen atom ,-CH
3Or-CF
3, R
8The organic group of expression divalent, n represents 0 or 1, m is to represent 0 at 0 o'clock at n, is to represent 0 or 1, Z at 1 o'clock at n
1Expression cyano group (CN yl), carboxyl (COOH), alkoxy carbonyl (COOR
9Base, R
9Be the organic group of 1 valency), acid halide group (COX base, X are halogen group).
In above-mentioned, consider polymerizability, preferred Y
1～Y
3Be hydrogen atom or halogen atom, preferred especially fluorine atom in the halogen atom.Specifically, can enumerate CH
2=CH-, CH
2=CF-, CFH=CF-, CFH=CH-, CF
2=CF-is as preferred structure.Especially, more preferably CH
2=CH-, CH
2=CF-, CF
2The structure of=CF-.In addition, when n=0, can enumerate CH
2=CHCN, CH
2=CHCOOR, CF
2=CFCN, CF
2The such compound of=CFCOOR is as crosslinkable monomer.
During n=0, m=0; During n=1, m both can be 0, also can be 1.M is 1 o'clock, can enumerate CH
2=CHO-, CH
2=CFO-, CFH=CFO-, CFH=CHO-, CF
2=CFO-is as preferred structure.Especially, can enumerate CH
2=CHO-, CH
2=CFO-and CF
2=CFO-is as preferred structure.
As R
8, can from the organic group of divalent, select group arbitrarily, to consider synthetic and the polymeric easiness, preferred carbonatoms is 1～100 to have or do not have the alkylidene group of ehter bond.In addition, more preferably carbonatoms is 1～50, and further preferred carbon atom is 1～20.The part or all of hydrogen atom of this alkylidene group can be replaced by halogen atom (particularly fluorine atom).This be because, if carbonatoms is more than 100, then be difficult to polymerization, crosslinkedly also can't obtain preferred characteristic even carry out.Above-mentioned alkylidene group can be the alkylidene group of straight chain type or branched chain type.The minimal structure unit example of alkylidene group that constitutes this straight chain type or branched chain type is as follows.
(i) the minimal structure unit of straight chain type:
-CH
2-、-CHF-、-CF
2-、-CHCl-、-CFCl-、-CCl
2-
The (ii) minimal structure unit of branched chain type:
With R
8The alkylidene group of expression does not contain under the situation of ether group, with R
8The alkylidene group of expression is made of a kind of in these minimal structure unit, or is constituted each other or (ii) be made of each other branched chain type by straight chain type (i), or constitutes by appropriate combination is above-mentioned.And, when with R
8The alkylidene group of expression contains under the situation of ether group, with R
8The alkylidene group of expression can be made of a kind of and Sauerstoffatom in these minimal structure unit, or by straight chain type (i) each other, branched chain type (ii) constitutes with Sauerstoffatom each other, or constitute, but Sauerstoffatom bonding each other by appropriate combination is above-mentioned.In addition, for R
8The alkylidene group of expression, in above example, because the group that is made of the structural unit that does not contain Cl can not take place to take off the HCl reaction and more stable by what alkali caused, thereby preferably it is made of the structural unit that does not contain Cl.
And, further preferred R
8Have with-R
10-,-(OR
10)-or-(R
10O)-(R
10Be that carbonatoms is 1～6 fluorine-containing or not fluorine-containing alkylidene group) expression structure.As R
10Preferred concrete example, can enumerate the following straight chain type or the group of branched chain type.
As the group of straight chain type, can enumerate-CH
2-,-CHF-,-CF
2-,-CH
2CH
2-,-CF
2CH
2-,-CF
2CF
2-,-CH
2CF
2-,-CH
2CH
2CH
2-,-CH
2CH
2CF
2-,-CH
2CF
2CH
2-,-CH
2CF
2CF
2-,-CF
2CH
2CH
2-,-CF
2CF
2CH
2-,-CF
2CH
2CF
2-,-CF
2CF
2CF
2-,-CH
2CF
2CH
2CF
2-,-CH
2CF
2CF
2CF
2-,-CH
2CH
2CF
2CF
2-,-CH
2CH
2CH
2CH
2-,-CH
2CF
2CH
2CF
2CH
2-,-CH
2CF
2CF
2CF
2CH
2-,-CH
2CF
2CF
2CH
2CH
2-,-CH
2CH
2CF
2CF
2CH
2-,-CH
2CF
2CH
2CF
2CH
2-,-CH
2CF
2CH
2CF
2CH
2CH
2-,-CH
2CH
2CF
2CF
2CH
2CH
2-,-CH
2CF
2CH
2CF
2CH
2CH
2-etc., as the group of branched chain type, can enumerate,
By above-mentioned constitute can enumerate following compound as example.
CH
2＝CH-(CF
2)
n-Z
2 (8)
(in the formula, n is 2～8 integer)
CY
4 2＝CY
4(CF
2)
n-Z
2 (9)
(in the formula, Y
4Be hydrogen atom or fluorine atom, n is 1～8 integer)
CF
2＝CFCF
2R
f 4-Z
2 (10)
(in the formula, R
f 4Expression OCF
2
nOr OCF (CF
3)
n, n is 0～5 integer)
CF
2＝CFCF
2(OCF(CF
3)CF
2)
m(OCH
2CF
2CF
2)
nOCH
2CF
2-Z
2 (11)
(in the formula, m is 0～5 integer, and n is 0～5 integer)
CF
2＝CFCF
2(OCH
2 CF
2 CF
2)
m(OCF(CF
3)CF
2)
nOCF(CF
3)-Z
2 (12)
(in the formula, m is 0～5 integer, and n is 0～5 integer)
CF
2＝CF(OCF
2 CF(CF
3))
mO(CF
2)
n-Z
2 (13)
(in the formula, m is 0～5 integer, and n is 1～8 integer)
CF
2＝CF(OCF
2CF(CF
3))
m-Z
2 (14)
(in the formula, m is 1～5 integer)
CF
2＝CFOCF
2(CF(CF
3)OCF
2)
nCF(-Z
2)CF
3 (15)
(in the formula, n is 1～4 integer)
CF
2＝CFO(CF
2)
nOCF(CF
3)-Z
2 (16)
(in the formula, n is 2～5 integer)
CF
2＝CFO(CF
2)
n-(C
6H
4)-Z
2 (17)
(in the formula, n is 1～6 integer)
CF
2＝CF(OCF
2CF(CF
3))
nOCF
2CF(CF
3)-Z
2 (18)
(in the formula, n is 1～2 integer)
CH
2＝CFCF
2O(CF(CF
3)CF
2 O)
nCF(CF
3)-Z
2 (19)
(in the formula, n is 0～5 integer)
CF
2＝CFO(CF
2 CF(CF
3)O)
m(CF
2)
n-Z
2 (20)
(in the formula, m is 0～5 integer, and n is 1～3 integer)
CH
2＝CFCF
2 OCF(CF
3)OCF(CF
3)-Z
2 (21)
CH
2＝CFCF
2 OCH
2 CF
2-Z
2 (22)
CF
2＝CFO(CF
2CF(CF
3)O)
mCF
2CF(CF
3)-Z
2 (23)
(in the formula, m is the integer more than 0)
CF
2＝CFOCF(CF
3)CF
2 O(CF
2)
n-Z
2 (24)
(in the formula, n is the integer more than 1)
CF
2＝CFOCF
2OCF
2 CF(CF
3)OCF
2-Z
2 (25)
CF
2＝CF-(CF
2 C(CF
3)F)
n-Z
2 (26)
(in the formula, n is 1～5 integer),
CF
2＝CFO-(CFY
5)
n-Z
2 (27)
(in the formula, Y
5For F or-CF
3, n is 1～10 integer)
CF
2＝CFO-(CF
2 CFY
6O)
m-(CF
2)
n-Z
2 (28)
(in the formula, Y
6For F or-CF
3, m is 1～10 integer, n is 1～3 integer)
CH
2＝CFCF
2 O-(CF(CF
3)CF
3 O)
n-CF(CF
3)-Z
2 (29)
(in the formula, n is 0～10 integer)
CF
2＝CFCF
2O-(CF(CF
3)CF
2O)
n-CF(CF
3)-Z
2 (30)
(in the formula, n is 1～10 integer)
In general formula (8)～(30), Z
2Be cyano group (CN yl), carboxyl (COOH), alkoxy carbonyl (COOR
11Base, R
11Be 1 valency organic group), acid halide group (COX base, X are halogen group).
In addition, above-mentioned R
11Be hydrogen atom or univalent organic group, but in order to make-COOR
11Group plays the effect of cross-linking part, and is preferred-COOR
11Group is to be easy to the structure that the reactive functional groups with linking agent reacts.That is preferred R,
11Be easy to break away from.As this R
11, can enumerate sulfonyl ester, phosphoric acid ester and the organophosphate etc. of toluenesulphonic acids, nitrotoluene sulfonic acid and fluoroform alkyl sulfonic acid etc.But, for sulfonyl ester, because the acid degree height of the sulfonic acid that broken away from, may corroding metal (for example mould of former), thereby not preferred.And, for phosphoric acid ester and organophosphate, because the phosphoric acid and the organic phosphoric acid that are broken away from may produce detrimentally affect to environment, thereby not preferred.Therefore, preferred R
11For having or not having the alkyl of ehter bond or aromatic nucleus.In this case, preferred carbonatoms is 1～20, more preferably 1～10, more preferably 1～6.And, if the part hydrogen atom is replaced then detachment height by halogen atom, thus preferred.Work as R
11Under the situation for the alkyl that has or do not have ehter bond or aromatic nucleus, as R
11, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, phenyl, 1,1 particularly, 1-trifluoroethyl, 1,1,1,2,2-seven fluoropropyls, 1,1,1,3,3,3-hexafluoro sec.-propyl etc.And, consider from the high angle of reactivity, preferably with-acid halide group that COX represents.But, when PTFE carries out polymerization in water-based system, because acid halide group is unstable and not preferred in water.In addition, when being aggregated under the situation of carrying out in the non-aqueous solution system of PTFE, preferred acid halide group.
In the monomer with general formula (8)～(30) expression, its cyano group, carboxyl, alkoxy carbonyl or acid halide group become cross-linking part, carry out crosslinking reaction with linking agent.
As monomer with general formula (9) expression, can enumerate particularly,
CF
2＝CF-CF
2-CN、CF
2＝CF-CF
2CF
2-CN、
CF
2＝CF-CF
2-COOH、CF
2＝CF-CF
2CF
2-COOH、
CF
2=CF-CF
2-COOCH
3, CF
2=CF-CF
2CF
2-COOCH
3Deng,
But consider the aspect of crosslinking reaction, be preferably
CF
2＝CF-CF
2-CN、CF
2＝CF-CF
2CF
2-CN，
Consider the aspect of polymerisation reactivity excellence, be preferably
CF
2＝CF-CF
2-COOH、CF
2＝CF-CF
2CF
2-COOH、
CF
2＝CF-CF
2-COOCH
3、CF
2＝CF-CF
2CF
2-COOCH
3。
As monomer, can enumerate particularly with general formula (26) expression
CF
2＝CFCF
2 C(CF
3)FCN、CF
2＝CF(CF
2C(CF
3)F)
2 CN、
CF
2＝CFCF
2 C(CF
3)FCOOH、
CF
2＝CF(CF
2 C(CF
3)F)
2 COOH、
CF
2＝CFCF
2C(CF
3)FCOOCH
3、
CF
2=CF (CF
2C (CF
3) F)
2COOCH
3Deng,
But consider the aspect of polymerisation reactivity, be preferably
CF
2＝CFCF
2C(CF
3)FCOOH。
As monomer, can enumerate particularly with general formula (27) expression
CF
2＝CFOCF
2CF
2CF
2CN、CF
2＝CFOCF
2CF
2 CN、
CF
2＝CFOCF
2 CN、
CF
2＝CFOCF
2CF
2CF
2COOH、CF
2＝CFOCF
2CF
2COOH、
CF
2＝CFOCF
2COOH、
CF
2＝CFOCF
2CF
2CF
2COOCH
3、
CF
2=CFOCF
2CF
2COOCH
3, CF
2=CFOCF
2COOCH
3Deng,
But consider the aspect of crosslinking reaction and polymerisation reactivity, preferred
CF
2＝CFOCF
2CF
2CF
2COOH、CF
2＝CFOCF
2CF
2COOH、
CF
2＝CFOCF
2CF
2CF
2COOCH
3、
CF
2＝CFOCF
2CF
2COOCH
3。
As monomer with general formula (28) expression, can enumerate particularly,
CF
2＝CFOCF
2 CF(CF
3)OCF
2CF
2 CN、
CF
2＝CFOCF
2CF(CF
3)OCF
2CF
2COOH、
CF
2=CFOCF
2CF (CF
3) OCF
2CF
2COOCH
3Deng,
But consider reactive aspect, preferred
CF
2＝CFOCF
2 CF(CF
3)OCF
2 CF
2 CN，
Consider the aspect that is easy to make, preferred
CF
2＝CFOCF
2CF(CF
3)OCF
2CF
2COOH、
CF
2＝CFOCF
2CF(CF
3)OCF
2CF
2COOCH
3。
As monomer, can enumerate particularly with general formula (29) expression
CH
2＝CFCF
2 OCF(CF
3)CN、
CH
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)CN、
CH
2＝CFCF
2O(CF(CF
3)CF
2O)
2CF(CF
3)CN、
CH
2＝CFCF
2OCF(CF
3)COOH、
CH
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)COOH、
CH
2＝CFCF
2O(CF(CF
3)CF
2O)
2CF(CF
3)COOH、
CH
2＝CFCF
2OCF(CF
3)COOCH
3、
CH
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)COOCH
3、
CH
2=CFCF
2O (CF (CF
3) CF
2O)
2CF (CF
3) COOCH
3Deng,
But consider the aspect of polymerisation reactivity, preferred
CH
2＝CFCF
2OCF(CF
3)CN、
CH
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)CN、
CH
2＝CFCF
2OCF(CF
3)COOH、
CH
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)COOH、
CH
2＝CFCF
2OCF(CF
3)COOCH
3、
CH
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)COOCH
3。
As monomer, can enumerate particularly with general formula (30) expression
CF
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)CN、
CF
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)COOH、
CF
2=CFCF
2OCF (CF
3) CF
2OCF (CF
3) COOCH
3Deng,
But consider reactive aspect, preferred
CF
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)CN，
Consider the aspect that is easy to make, preferred
CF
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)COOH、
CF
2＝CFCF
2OCF(CF
3)CF
2OCF(CF
3)COOCH
3。
And, and be combined in-CF (CF
3)-CN or-CF (CF
3Compare on the such branched alkylidene of)-COOR, above-mentioned reactive functional groups preferably with-CF
2-CN or-CF
2The such straight-chain alkyl-sub-of-COOR combines, because can demonstrate hyperergy like this.
In addition, among the PTFE of present embodiment, can use the monomer that contains above-mentioned reactive functional groups, also can use simultaneously arbitrarily monomer as copolymer composition as copolymer composition.
Be not particularly limited for the monomer beyond the monomer that cross-linking part is provided, for example can enumerate fluorochemical monomer beyond the TFE and non-fluorochemical monomer etc.But the monomer of this copolymerization also can have not the functional group with the linking agent reaction.As not with the functional group of linking agent reaction, can enumerate hydroxyl, sulfonic group, phosphate, sulfonic acid imide, sulfonic acid amides base, phosphoric acid imide, phosphoamide base, carboxylic acyloxy amido and carboxylic acyloxy imido grpup etc.Use has not under the situation of monomer as copolymer composition with the functional group of linking agent reaction, can expect close-burning improvement and dispersed effects such as improvement.And, import and do not contain under the situation of monomer as copolymer composition of such functional group, can carry out the adjustment of particle diameter, the adjustment of fusing point and the adjustment of mechanical characteristic etc.And,, for example can enumerate the fluorinated monomer of fluoroolefins, ring type and fluorinated alkyl vinyl ether etc. as above-mentioned " fluorochemical monomer ".As above-mentioned fluoroolefins, for example can enumerate R 1216 (HFP), vinyl fluoride, vinylidene fluoride (VDF), trifluoro-ethylene, hexafluoro-isobutene, perfluorobutyl ethylene etc.And, as the fluorinated monomer of above-mentioned ring type, can enumerate perfluor-2,2-dimethyl-1,3-dioxole (PDD), perfluor-2-methylene radical-4-methyl isophthalic acid, 3-dioxolane (PMD) etc.And, as above-mentioned fluorinated alkyl vinyl ether, for example can enumerate, with general formula CY
7 2=CY
8OR
12Or CY
7 2=CY
8(OR
13)
nOR
12The compound of expression, wherein, Y
7Identical or different, expression H or F, Y
8Expression H or F, R
12Represent that carbonatoms that part or all of hydrogen atom can be replaced by fluorine atom is 1～8 alkyl or terminal alkyl with functional group, R
13Identical or different, represent that carbonatoms that part or all of hydrogen atom can be replaced by fluorine atom is 1～8 alkylidene group, n is 0～10 integer.In addition, as above-mentioned fluorinated alkyl vinyl ether, for example preferred perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE).And, be not particularly limited as above-mentioned " non-fluorochemical monomer ", as long as have copolymerization, for example can enumerate hydro carbons monomer etc. with above-mentioned TFE.Above-mentioned hydro carbons monomer also can have element such as halogen atom beyond the fluorine, Sauerstoffatom, nitrogen-atoms and various substituting groups etc.As above-mentioned hydro carbons monomer, can enumerate for example olefines, alkyl vinyl ethers, vinyl ester, alkyl allyl ether series, alkyl allyl ester class etc.
Employed TFE can utilize common polymerization manufacturings such as emulsion polymerization, suspension polymerization, solution polymerization process among the present invention.Polymerizing conditions such as the temperature during as polymerization, time can suitably be determined according to monomeric kind etc.
As employed emulsifying agent in the letex polymerization, can use range emulsifying agent widely, consider and suppress the chain transfer reaction that takes place in the polymerization preferably have the salt of the carboxylic acid of fluoro carbochain or fluoro polyether chain to the emulsifying agent molecule.
As polymerization starter, for example can use organo-peroxides such as ammonium persulphate persulphates such as (APS), disuccinic acid superoxide (DSP) and diamyl diacid peroxilde separately, perhaps use their mixture.And, as above-mentioned polymerization starter, can also be shared with reductive agents such as S-WATs, become redox system and used afterwards.Preferably can make the main chain end have carboxyl maybe can generate carboxyl group (for example can enumerate acyl fluorides, acyl chlorides ,-CF
2OH etc., these all can generate carboxyl in the presence of water) polymerization starter.As concrete example, can enumerate ammonium persulphate (APS), Potassium Persulphate (KPS) etc.
And, also can use the chain-transfer agent that is generally used for adjusting molecular weight.This compound that plays a role as chain-transfer agent constitutes by a kind in hydrocarbon, halon and the water-soluble organic compounds at least.Above-mentioned chain-transfer agent can be contain hydrocarbon and do not contain halohydrocarbon material, contain halohydrocarbon and do not contain the material of hydrocarbon and contain hydrocarbon and the material of hydrofluoric ether in any, and hydrocarbon, halohydrocarbon and water-soluble organic compounds can use respectively more than a kind or 2 kinds or 2 kinds.As above-mentioned chain-transfer agent, consider dispersiveness in reaction system and homogeneity good aspect, preferably contain at least a kind that is selected from the group of forming by methane, ethane, butane, HFC-134a, HFC-32, methyl alcohol and ethanol.
And, further, contain the compound of iodine or bromine atoms by utilization, can obtain the product of narrow molecular weight distribution, be easy to adjust molecular weight.As this chain-transfer agent, can enumerate following compound with general formula (31)～(39) expression with iodine atom.
I(CF
2CF
2)
nI (31)
ICH
2CF
2CF
2(OCF(CF
3)CF
2)
mOCF(CF
3)-Z
3 (32)
ICH
2CF
2CF
2(OCH
2CF
2CF
2)
mOCH
2CF
2-Z
3 (33)
I(CF
2)
nZ
3 (34)
I(CH
2CF
2)
nZ
3 (35)
ICF
2CF
2OCF
2CF(CF
3)OCF
2CF
2-Z
3 (36)
ICH
2CF
2CF
2OCH
2CF
2-Z
3 (37)
ICF
2CF
2OCF
2CF
2-Z
3 (38)
ICF
2CF
2O(CF
2)
nOCF
2CF
2-Z
3 (39)
Can use the compound of representing with above-mentioned general formula, in the above-mentioned general formula, Z
3Expression cyano group (CN yl), carboxyl (COOH yl), alkoxy carbonyl (COOR
14Base, R
14The expression carbonatoms is 1～10 the alkyl that contains or do not contain fluorine atom), m is 0～5 integer, n is the integer more than 1.Wherein, can consider with the aspect of the cross-linking part of linking agent reaction, preferably with the chain-transfer agent of general formula (32)～(39) expression from having.
As from method by separation of polymeric resultant the resulting polymerization reaction mixture of letex polymerization, can adopt the method for utilizing acid treatment to carry out condensation, utilize lyophilize or ultrasonic wave etc. to carry out method of condensation etc., but consider from the aspect of simplifying working process, preferably utilize mechanical force to carry out the method for condensation.Utilizing mechanical force to carry out in the method for condensation, diluting aqueous liquid dispersion usually, can according to circumstances adjust pH down, in having the container of stirrer, carrying out vigorous stirring then so that polymer concentration reaches 10～20 weight %.And, also can use series connection agitator etc. to carry out condensation continuously.Before condensation or in the condensation, if add the weighting agent that is used for painted pigment or is used for improved mechanical properties, the PTFE fine powder of can be uniformly mixed pigment or weighting agent.
Keeping not making through the drying of the PTFE of condensation under the state of moistening flow of powder and carrying out, preferably keeping utilizing means such as decompression, high frequency, hot blast to carry out under the state that leaves standstill.Friction between the powder (particularly friction at high temperature) generally can bring bad influence to the PTFE fine powder.This be because, even thereby this PTFE particle have be subjected to little shearing force also easily fibrillation lose the character of the state of original stable particle structure.Drying temperature is 10～250 ℃, is preferably 100～200 ℃.
Employed PTFE can be converted to carboxyl with groups such as the metal-salt of the carboxylic acid that exists in the product of polymerization or ammonium salts by product of polymerization being carried out acid treatment among the present invention.As acidic treatment, following method suits, for example clean with hydrochloric acid, sulfuric acid, nitric acid etc., or the mixture system after utilizing these acid with polyreaction to transfer to pH be below 3.
And, also can import carboxyl by utilizing the PTFE that the nitrosonitric acid oxidation contains iodine or bromine.
And then, as the method that imports cyano group, carboxyl, alkoxy carbonyl, can also use the international method that discloses No. 00/05959 brochure is put down in writing.
[linking agent]
Linking agent related in the embodiments of the present invention can react with the above-mentioned reactive functional groups more than 1 or 2, forms ring texture.Can carry out in the functional group of crosslinking reaction, preferably this linking agent and the above-mentioned reactive functional groups reaction more than 1 or 2 form heterocycle.In addition, as this linking agent, especially preferably can cause the linking agent of πDian Zi shortage type heterocyclic cyclization.Thus, in this case, will in crosslinking reaction, form excellent πDian Zi shortage type heterocycle (azoles, triazole, azine, diazine, triazine etc.) such as scale resistance and chemical resistant properties.Can form the firm crosslinking structure that the past does not have thus.As this formation πDian Zi shortage type heterocyclic crosslinking reaction, for example can utilize the known reactions of record in " a newly organized heterogeneous ring compound basis piece of writing, an application piece of writing " (mountain is medium, the talk サ イ エ of society Application テ イ Off イ Star Network, 2004).As the crosslinking structure of final formation, for example can enumerate: contain the PTFE of cyano group and contain the linking agent of 2 above cyano group through the formed crosslinking structure of triazine cyclization; Contain the PTFE of cyano group and contain the linking agent of 2 above diazanyls through the formed crosslinking structure of triazole cyclization; Contain the PTFE of acid halide group, carboxyl or alkoxy carbonyl and contain the linking agent of 2 above guanidine radicals through the formed crosslinking structure of triazole cyclization; The PTFE that contains acid halide group, carboxyl or alkoxy carbonyl and the linking agent that contains amino hydrazone group more than 2 are through the formed crosslinking structure of triazole cyclisation etc.Wherein, as crosslinking reaction, especially preferably utilize 1, the cyclization of 3-azoles becomes reaction, and this reaction has utilized the ring-closure reaction that forms based on 1,2 bonding.And,, also have the effect of the adherence that improves PTFE and other materials by importing heterocycle as cross-linking set.
As such linking agent, be preferably and be selected from by containing at least two two diamino-phenyl compounds, diaminophenol compounds and two aminothiophenol compounds with the bridging property reactive group of general formula (1) expression; Two amidrazone compounds and two amidoxim compounds with general formula (2) expression; With two amidrazone compounds of general formula (3) expression with at least a compound in the group of two amidoxim compounds compositions of general formula (4) expression.
In the general formula (1), R
1Identical or different, expression-NH
2,-NHR
2,-OH or-SH, R
2The organic group of expression fluorine atom or 1 valency;
In the general formula (2), R
3Expression-SO
2-,-O-,-CO-, carbonatoms are that 1～6 alkylidene group, carbonatoms are 1～10 perfluorinated alkylidene or singly-bound, R
4Expression
Or
In the general formula (3), R
f 1The expression carbonatoms is 1～10 perfluorinated alkylidene;
In the general formula (4), n represents 1～10 integer.
Have at least 2 compounds and preferably have 2～3 bridging property reactive groups, more preferably have 2 bridging property reactive groups with the bridging property reactive group of general formula (1) expression.As if 2 of the bridging property reactive group less thaies of representing with general formula (1), then can't carry out crosslinked.
With the substituent R in the bridging property reactive group of general formula (1) expression
2Be 1 valency organic group or fluorine atom beyond the hydrogen atom.Because N-R
2The scale resistance of key is higher than the N-H key, thereby preferred N-R
2Key.
Organic group as 1 valency is not particularly limited, and can enumerate aliphatic alkyl, phenyl or benzyl.For example can enumerate particularly: R
2In at least 1 be-CH
3,-C
2H
5,-C
3H
7Deng carbonatoms be 1～10 low alkyl group of (particularly 1～6);-CF
3,-C
2F
5,-CH
2F ,-CH
2CF
3,-CH
2C
2F
5Deng carbonatoms be 1～10 low alkyl group that contains fluorine atom of (particularly 1～6); Phenyl; Benzyl;-C
6F
5,-CH
2C
2F
5The phenyl or the benzyl that have been replaced by fluorine atom Deng 1～5 hydrogen atom;-C
6H
5-n(CF
3)
n,-CH
2C
6H
5-n(CF
3)
n1～5 hydrogen atom quilt-CF such as (n are 1～5 integer)
3The phenyl that has replaced or benzyl etc.
In the middle of these, the aspect excellent especially from thermotolerance, that crosslinking reaction is good and synthetic relatively easy considers, preferred phenyl and-CH
3
And, consider preferably that from being easy to the synthetic aspect compound with following general formula (5) expression is as linking agent.
In the general formula (5), R
1With above-mentioned R
1Identical, R
5Expression-SO
2-,-O-,-CO-, carbonatoms be 1～6 alkylidene group, carbonatoms be 1～10 perfluorinated alkylidene, singly-bound or with
Being the preferred concrete example of 1～6 alkylidene group as carbonatoms, can enumerating methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene etc., is 1～10 perfluorinated alkylidene as carbonatoms, can enumerate
Deng.In addition, these linking agents are opened in the flat 8-120146 communique etc. as the example of two diaminobenzene based compounds and known the fair 2-59177 communique of spy, spy.
Wherein, preferred linking agent is the compound with general formula (6) expression.
In the general formula (6), R
6Identical or different, represent separately hydrogen atom, carbonatoms be 1～10 alkyl, the carbonatoms that contains fluorine atom be 1～10 alkyl, phenyl, benzyl, 1～5 hydrogen atom by fluorine atom and/or-CF
3Phenyl that is replaced or benzyl.
In addition, as the linking agent of present embodiment, the linking agent that can utilize the cyclization one-tenth reaction of 1,3 benzothiazole preferred as described above especially as crosslinking reaction, described cyclization becomes reaction to utilize the ring-closure reaction that forms based on 1,2 bonding.This is because by importing benzothiazole and aromatic nucleus, can improve the adherence of PTFE and other materials.
Unqualified to concrete example, for example can enumerate: 2,2-two (3, the 4-diamino-phenyl) HFC-236fa, 2, two [3-amino-4-(N-methylamino) phenyl] HFC-236fa, 2 of 2-, two [3-amino-4-(N-ethylamino) phenyl] HFC-236fa, 2 of 2-, two [3-amino-4-(the N-propyl group amino) phenyl] HFC-236fa, 2 of 2-, two [3-amino-4-(N-phenyl amino) phenyl] HFC-236fa, 2 of 2-, two [3-amino-4-(the N-perfluorophenyl amino) phenyl] HFC-236fa, 2 of 2-, two [3-amino-4-(N-benzylamino) phenyl] HFC-236fa of 2-etc.Wherein, consider from the good especially aspect of excellent heat resistance, crosslinking reaction, further preferred 2, two (3, the 4-diamino-phenyl) HFC-236fa of 2-.
The cyano group that PTFE had, carboxyl, alkoxy carbonyl, the acid halide group used among these pairs amidoxim class linking agent, two amidrazone class linking agent, two aminophenols linking agent, two aminothiophenol class linking agent and two diaminobenzene base class linking agents etc. and the present invention react; shape becomes oxazole ring, thiazole ring, imidazole ring, and PTFE is provided crosslinked body.
The linking agent of above-mentioned explanation can provide the crosslinked body of following PTFE: this crosslinked body has been kept existing intensity, crystallinity and surface property etc., and does not have anisotropy and unhomogeneity, and, compare not yielding with existing P TFE resin.And, in the present embodiment,, also have the effect of the adherence that improves PTFE and other materials by adopting above-mentioned linking agent.
For the addition of linking agent, with respect to the PTFE of 100 weight parts, preferably add 0.01～20 weight part, more preferably add 0.03～10 weight part.This be because, if linking agent less than 0.01 weight part then has physical strength, thermotolerance, the chemical-resistant tendency that can't obtain to be enough to practicality, if linking agent surpasses 20 weight parts, then needing to expend the plenty of time is used for crosslinkedly, and has the tendency that the crosslinked body of PTFE becomes fragile.And,, can change the rerum natura of PTFE formed body by adjusting the addition of linking agent.For example, both can add can with the linking agent of the amount that imports to the total overall reaction functional group reactions among the above-mentioned PTFE, the linking agent that also can add the amount of not exclusively reserving uncrosslinked position with importing to the total overall reaction functional group reactions among the above-mentioned PTFE improves the effect that comes from functional group with the adherence of other materials etc. with expectation.
[modulator approach of bridging property PTFE composition]
Bridging property PTFE composition of the present invention can prepare by utilizing above-mentioned each dry type blending meanss that become to grade of mixing such as internal mixer.And this bridging property PTFE composition can also prepare by following wet mixing method: with linking agent dissolving or be dispersed in water or the organic solvent, in the liquid that obtains dipping PTFE or after dipping stirred solution; Perhaps, the PTFE dispersion liquid that is dispersed in water or the organic solvent is mixed with linking agent, stir.In addition, adopt in the situation of wet mixing method,, preferably utilize ultrasonic vibration in order further to improve the contact of linking agent and PTFE.And, can after polymerization, stir the dispersion soln that maintains primary particle, drip the cross-linking agent solution be dissolved in the high organic solvent of NMP, DMF or this polarity of DMSO simultaneously, improve cross-linking density thus.
[preparation method of the crosslinked body powder of PTFE]
Can obtain the crosslinked body powder of PTFE of the present invention it is believed that to handle under the suitable suitable condition.For example, under the crosslinked situation of the Hang oxazole of Jin, bridging property PTFE composition or the crosslinked body powder of PTFE are dropped in the air circulating oven, kept 1～300 minute in 120～320 ℃, can obtain the crosslinked body of PTFE thus.And, carry out under the crosslinked situation of imidazoles, can access the crosslinked body of the PTFE with good rerum natura at low relatively crosslinking temperature (for example 120～280 ℃ are preferably 120～250 ℃).In addition, can be not yet fixing Heating temperature and carry out interim variation.Also can consider for example following method: linking agent is remained near the temperature the fusing point of linking agent, linking agent is fully infiltrated heat up behind the PTFE, carry out crosslinking reaction.And, can be by the impurity such as by product that the crosslinked body powder of the PTFE that is generated is produced when keeping certain hour to remove unreacted linking agent of intrinsic and crosslinking reaction more than 100 ℃.In this case, preferably keeping more than 1 hour more than 200 ℃.
[preparation method of formed body]
The method that is obtained formed body by bridging property PTFE composition or the crosslinked body powder of PTFE can be used usual method, for example can enumerate: known method such as compressed moulding method, plunger extrusion moulding, paste extrusion moulding.Utilize the compressed moulding method to obtain to carry out moulding with the hot-coining method, but the prebake method that also can utilize productivity to be higher than the hot-coining method to be carried out moulding under the situation of formed body.Above-mentioned bridging property PTFE composition or the crosslinked body powder of PTFE can be filled into mould, (be preferably under 10～70MPa) the pressure and compress at 2～100MPa, obtain preform, then in air circulating oven, under the temperature of fusing point～420 ℃ (be preferably fusing point～380 ℃), resulting preform is fired 10 minutes～10 days (being preferably 30 minutes～5 hours).At this moment, heat-up rate and speed of cooling can be for arbitrarily, but preferred 10～100 ℃/hour, more preferably 20～60 ℃/hour.And, also can adopt interim method for regulating temperature, for example, before being raised to 300 ℃, improve heat-up rate, be raised to reduction heat-up rate in back more than 300 ℃; Before dropping to 300 ℃, reduce speed of cooling, dropping to the raising of back below 300 ℃ speed of cooling.
By bridging property PTFE composition of the present invention is carried out cross moulding, can obtain PTFE formed body of the present invention.PTFE formed body of the present invention is kept existing intensity, crystallinity and surface property etc., and does not have anisotropy and unhomogeneity, and compares not yielding with existing P TFE resin.And the thermotolerance of this PTFE formed body and chemical resistant properties are also excellent.
The crosslinked body of PTFE of the present invention can be used as powder or formed body utilizes.As concrete example, can enumerate the modification material as powder.The PTFE powder is added in the resins for universal use (particularly engineering plastics, fluoro-resin, viton) into the content utilized with material as modification to be opened clear 60-110749 communique, spy the spy and opens that clear 62-72751 communique, spy are opened the 2000-109668 communique, the spy opens in the patent documentations such as 11-269350 communique and Te Kai 10-9270 communique open, be known, but the crosslinked body powder of PTFE of the present invention also can come as the modification material according to suitable purposes.The crosslinked body of PTFE is used under the situation of material as modification with powder type, and preferred PTFE is a lower molecular weight.
And, by the crosslinked body powder of PTFE of the present invention being disperseed or being mixed in the other materials such as molding resin or elastomerics, can improve flame retardant resistance, non-binding property, sliding, water and oil-resistant, electrical specification, resistance to soiling, erosion resistance, weathering resistance, mechanical characteristic etc.And, also can adopt bridging property PTFE composition to replace the crosslinked body powder of PTFE, after the dispersion of bridging property PTFE composition or being mixed in the other materials, this dispersion thing or mixture are heated next crosslinked PTFE.
Concrete example as other materials is unqualified, can enumerate: general-purpose plastics such as polyvinyl resin, acrylic resin, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-vinyl alcohol copolymer resin, poly-cyclic olefin resins, polyisobutene resin, polyolefin resin, polyvinyl chloride (PVC) RESINS and polystyrene resin; The polymethylpentene resin, acrylonitrile-styrene copolymerized resin (AS resin), the styrene-methylmethacrylate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile acryloid styrene resin (AAS resin), vinyl cyanide-ethylene-propylene rubber-styrene-alkene copolymer resin (AES resin), acrylonitrile-styrene-acrylic ester copolymer resin (ASA resin), silicone-acrylonitritrile-styrene resin resin (SAS resin), acrylic resin, methacrylic resin, polyamide resin, polycarbonate resin, polyacetal resin, polyphenylene oxide resin, the polybutylene terephthalate resin, pet resin, the PEN resin, polyphenylene sulfide, fluoro-resin, polyethersulfone resin, polyetherimide resin, polyether ketone resin, polyether-ether-ketone resin, polyimide resin, polyacrylate resin, aromatic polyester resins, polyphenylene sulfide, polysulfone resin, the aromatic polyester amide resins, aromatic series azomethine resin, polyarylene sulfide resin, the polyketone resin, engineering plastics such as polyamide-imide resin and polyethers nitrile resin; PTFE, voltalef, tetrafluoroethylene-perfluor (alkyl vinyl ether) analog copolymer (PFA), hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) analog copolymer fluoro-resin such as (FEP); Tetrafluoroethylene-perfluor (alkyl vinyl ether) class copolymer elastomer, vinylidene fluoride-R 1216 copolymer elastomer, vinylidene fluoride-viton such as hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymer elastomer.And other materials also can be that Resins, epoxy, phenol resins, urea resin, melamine resin, unsaturated polyester resin, Synolac and diallyl phthalate resin etc. solidify preceding liquid, solution, pressed powder etc.In this case, can obtain formed body by solidification process (for example curing process).The crosslinked body powder of PTFE of the present invention is used in the situation of material as modification, and preferred addition is 1～80 weight % with respect to subject material, more preferably 5～50 weight %.
In addition, among the present invention,, can preferably enumerate crystalline melt point or second-order transition temperature and be the thermoplastic resin more than 150 ℃ as the crosslinked body powder of PTFE or the dispersion object of bridging property PTFE composition or the resin of blending objects.As thermoplastic resin, for example can enumerate polyacetal resin, polyamide resin, polycarbonate resin, poly (phenylene ether) resin, aromatic polyester resins, aromatic polyester amide resins, aromatic series azomethine resin, polyarylene sulfide resin, polysulfone resin, polyethersulfone resin, polyketone resin, polyether ketone resin, polyetherimide resin, polyamide-imide resin, polymethylpentene resin and polyethers nitrile resin etc.
Wherein, preferred resin is: the high resin of (1) thermotolerance, promptly, during with the crosslinked body powder mixes of PTFE, must not can reduce the thermostability of mixture, and, because the thermotolerance height of thermoplastic resin itself, if the improvement shock-resistance of thermoplastic resin and chemical resistant properties and use general properties-correcting agent and additive, then the thermotolerance of mixture reduces, the therefore preferred high fluorine resin of thermotolerance that adds; (2) physical strength and dimensional stability aspect excellence, can carry out modified resins to these rerum naturas of fluoro-resin; (3) the formability excellence, can give with the mixture of fluorine resin with resin of the processibility of excellence etc., for example wherein can enumerate aromatic polyester resins, polyamide resin, polyamide-imide resin, polyarylene sulfide resin, polyketone resin, polyethers nitrile resin, polycarbonate resin, polyphenylene oxide resin, polysulfone resin, polyetherimide resin, polyimide resin etc. as the preferred object among the present invention.
Further specifically, can enumerate as preferred object: strong expectation improves shock-resistance and generally can not destroy thermotolerance, chemical-resistant polyarylene sulfide resin; As the polyamide resin of trolley part with material time expectation improvement solvent resistance, particularly ethanol petrol resistant (gasohol) property etc.; Can expect to improve the formability of fluoro-resin and the aromatic polyester resins of mechanical properties by adding; Wherein, because forming process and excellent in dimensional stability under high elastic coefficient, especially preferably by improving and the consistency of fluoro-resin forms the anisotropy fusion liquid-crystal polyester resin mutually of the mechanical properties that can expect to improve significantly fluoro-resin, formability, dimensional stability, load flexure temperature.
On the other hand, consider under the situation of affinity of crosslinked body powder of PTFE of the present invention and thermoplastic resin, because polyphenylene sulfide has thiol group (or thiol), polyamide resin has amino and carboxyl and amido linkage, aromatic polyester resins has hydroxyl and carboxyl and ester bond, thereby with the crosslinked body powder of PTFE of the present invention in the affinity height of functional group, from this angle, also can be described as preferred object.
In addition, it is believed that the surface of the crosslinked body powder of PTFE of the present invention has functional group to expose, therefore can infer: the part main chain or the end of this functional group and thermoplastic resin react; Chemical reaction takes place in the part functional group of this functional group and thermoplastic resin, and this reaction product plays the effect of the consistency properties-correcting agent of the consistency of improving the mixture that contains unreacted reactant; And have interface affinity and interface adhesion between this functional group and the thermoplastic resin; Deng.In addition, when the crosslinked body powder of PTFE is under the situation of bridging property PTFE composition, infer that this tendency can strengthen.
So to obtain the mechanism of good mutually dispersiveness still indeterminate by mixing crosslinked body powder of PTFE and thermoplastic resin, but the present invention is not limited.
In order to improve affinity or the reactivity with the crosslinked body powder of PTFE of the present invention, the present invention does not get rid of yet and utilizes usual method that thermoplastic resin is carried out modification.And, can also contain the resinous principle except that crosslinked body powder of PTFE and thermoplastic resin in the resin compound of the present invention.
Polyphenylene sulfide as the blending objects of the crosslinked body powder of PTFE is not particularly limited, can be the polyphenylene sulfide that obtains with the known method described in the public clear 45-3368 communique of spy, but preferably contain the above repeating unit of 70 moles of % with following general formula (40) expression.
And then, especially preferably contain 70 moles of % above to the polyphenylene sulfide of diphenyl sulfide unit as repeating unit.At this moment, for remaining repeating unit without limits, so long as unit that can copolymerization gets final product, can enumerate for example adjacent diphenyl sulfide unit, a diphenyl sulfide unit, diphenyl sulfide ether unit, diphenyl sulfide sulfone unit, diphenyl sulfide ketone unit, biphenyl thio-ether units, naphthalene thio-ether units, 3 officials can the diphenyl sulfide unit etc.These multipolymers both can block copolymerization also can random copolymerization.
As the concrete example of preferred polyphenylene sulfide, can enumerate poly-(to diphenyl sulfide) resin, poly-(to diphenyl sulfide)-poly-(diphenyl sulfide) block copolymer resin, poly-(to diphenyl sulfide)-polysulfones block copolymer resin, poly-(to diphenyl sulfide)-PPSS copolymer resin etc.
And, no matter be straight catenate resin, under the coexistence of oxygen, carried out the crosslinked resin of oxygen, still under inert gas atmosphere, carried out the resin of heat treated, all be fine, and also can be the mixture of these structures.
And,, can the functional group that reactivity is high be directed in the polyphenylene sulfide for the consistency of further raising with the crosslinked body powder of PTFE of the present invention.As the functional group that imports, amino, carboxylic acid group and hydroxyl etc. suit, as this introduction method, can enumerate the method that imports with the method that contains the halogenated aromatic compound copolymerization of these functional groups, by polyphenylene sulfide and the high molecular weight reactive that contains the low-molecular weight compound of described functional group etc.
And polyphenylene sulfide also can be by breaking away from the product after son processing (pickling or hot water cleaning etc.) reduces sodium ion.
The resin compound that is made of polyphenylene sulfide that as above obtains and the crosslinked body powder of PTFE can provide excellent mechanical characteristics, particularly shock-resistance to formed body, can not obtain this excellent mechanical characteristics and only mix the fluorine resin that does not have functional group.
And this resin compound can also have thermotolerance, chemical resistant properties, sliding that fluorine resin has originally concurrently; The thermotolerance that polyphenylene sulfide has originally, mechanical characteristics, so this resin compound is useful especially as following formed material: the electrical/electronic components of having utilized thermotolerance, electrical specification; The automobile parts of sliding have been utilized; Utilized chemical-resistant chemical plant conduit; The valve pump is with geared parts etc.
In addition, polyamide resin is excellence aspect high strength, high tenacity, processibility, oil-proofness, is widely used in flexible pipe, pipe, conduit etc.But polyamide resin is low to alcoholic solvent patience, contains under the situation of gasoline of lower alcohol in use especially, and ethanol petrol resistant is poor, volume swelling or fuel perviousness occur and becomes the material degradation that causes intensity reduction etc. greatly, and this is also needed to improve.In addition, also require the reduction of wear factor.
But, by the crosslinked body powder of PTFE of the present invention is mixed with this polyamide resin, or by add crosslinked body powder of PTFE of the present invention or bridging property PTFE composition in the mixture of fluoro-resin that does not contain functional group and polyamide resin, solvent resistance, the ethanol petrol resistant that can access polyamide resin have obtained improved resins.
Polyamide resin can use usually by with general formula H
2N-(CH
2)
P "-NH
2The straight chain shape diamines of (in the formula, p " be 3～12 integer) expression and with general formula HO
2C-(CH
2)
Q "-CO
2The product that the condensation of the straight chain shape carboxylic acid of H (in the formula, q " be 2～12 integer) expression manufactures, or the product that uses the ring-opening polymerization by lactan to manufacture.As the preference of these polyamide resins, can enumerate nylon 6,6, nylon 6,10, nylon 6,12, nylon 4,6, nylon 3,4, nylon 6,9, nylon 6, nylon 12, Ni Long11, nylon 4 etc.And, can also use nylon 6/6,10, nylon 6/6,12, nylon 6/4,6, nylon 6/12, nylon 6/6,6, nylon 6/6,6/6, and 10, nylon 6/4,6/6,6, nylon 6/6,6/6,12, nylon 6/4,6/6, and 10, nylon 6/4,6/12 class such as copolyamide such as grade.
And then, can also enumerate nylon 6/6, T (T is the terephthalic acid composition); The semiaromatic polyamide composition class that obtains by the aromatic dicarboxylic acid of terephthalic acid, m-phthalic acid and so on and m-xylene diamine or alicyclic diamine; By m-xylene diamine and straight chain shape carboxylic acid obtain polyamide-based.
The resin compound that constitutes by crosslinked body powder of PTFE and polyamide resin as described above or in the mixture of the fluoro-resin that does not contain functional group and polyamide resin, be added with the crosslinked body powder of PTFE resin compound can to the moulding product only provide with mix the fluoro-resin that do not contain functional group the chemical resistant properties that can not obtain, low temperature shock-resistance and mechanical characteristics, special in for containing alcohol (methyl alcohol for example, ethanol etc.), the modified gasoline of methyl tertiary butyl ether etc., acid etc. have excellent chemical resistant properties and the material of impermeability is useful, at formed body (for example, flexible pipe, pipe, conduit, gasket, packing ring, liner, sheet, films etc.) aspect is useful.And, can become especially at trolley part (for example, fuel distribution tube flexible pipe, pipe, packing ring etc.) the useful material in aspect that requires for the chemical resistant properties and the impermeability of gasoline, methanol mixed gasoline.
The crosslinked body powder of the PTFE of the application of the invention replaces existing fluorine resin, mix with thermotolerance thermoplastic resin, particularly aromatic polyester resins or polycarbonate resin, or, can obtain mechanical characteristics, the flexure temperature of loading, dimensional stability that fluoro-resin itself had and obtain the improved resins mixture by when mixing existing fluorine resin, adding the crosslinked body powder of PTFE with aromatic polyester resins or polycarbonate resin.
But though polycarbonate is widely used in automobile or building field with characteristics such as its physical strength, shock-resistance and weathering resistancies, it has the shortcoming of chemical resistant properties (particularly alkali resistance and solvent resistance) difference.
Use the identical method of chemical resistant properties with the improvement polyamide resin, in polycarbonate resin, mix the crosslinked body powder of the PTFE with hydroxyl in the crosslinked body powder of PTFE of the present invention, can access the resin compound of further having improved chemical resistant properties effectively and not had significantly to reduce mechanical properties thus.
As the aromatic polyester resins that uses in the resin compound of the present invention, for example can enumerate: hexanodioic acid, terephthalic acid, 2, the 6-naphthalene dicarboxylic acids, 4, diprotic acid and ethylene glycol such as 4 '-diphenyl dicarboxylic acid, trimethylene, tetramethylene glycol, the pentamethylene glycol, hexamethylene glycol, 1, the 4-cyclohexanedimethanol, the condenses of the dibasic alcohol of dihydroxyphenyl propane etc. (for example, pet resin, the polybutylene terephthalate resin, poly-terephthalic acid 1,4-cyclohexanedimethanoester ester resin, poly-[2,2-propane two (4-phenyl right/isophthalic acid ester)] resin etc.) and the aromatic polyester (liquid crystal copolyester) that forms mutually by the anisotropy fusion etc.
And the polycarbonate resin that uses in the resin compound of the present invention can obtain by the reaction of bisphenol cpd and phosgene or carbonic diester.As bisphenol cpd, preferred especially 2, two (4-hydroxy phenyl) propane (hereafter is a dihydroxyphenyl propane) of 2-also can replace part or all of dihydroxyphenyl propane with other bisphenol cpds.As the bisphenol cpd beyond the dihydroxyphenyl propane, for example can enumerate: quinhydrones, Resorcinol, 4,4 '-dihydroxyl phenylbenzene, two (4-hydroxy phenyl) alkane, two (4-hydroxy phenyl) naphthenic hydrocarbon, two (4-hydroxy phenyl) thioether, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ketone, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide or their alkyl substituent, aryl substituent, halogen substituent etc.
In addition, in the middle of these, liquid crystal polyester is because the orientation of itself and have the most excellent performance at aspects such as thermal properties, dimensional stability such as mechanical characteristics such as intensity, Young's modulus and load flexure temperatures demonstrates high workability when fusion.Further, liquid crystal polyester can be by being orientated in resin compound with the melting mixing of other resins, give resin compound with excellent specific property same as described above, can become the mechanical characteristics that is used to obtain fluoro-resin, the improved composition or the most preferred object of composition for thermoplastic elastomer of load flexure temperature, dimensional stability and formability.As being used for liquid crystal polyester of the present invention, for example can enumerate by be selected from aromatic dicarboxylic acid, the ester ring type dicarboxylic acid more than a kind or 2 kinds, in the aromatic diol, ester ring type glycol, aliphatic diol more than a kind or 2 kinds, the liquid crystal copolyester that constitutes of the composition more than a kind or 2 kinds of aromatic hydroxy-carboxylic.As representational combination, for example can enumerate: with P-hydroxybenzoic acid, biphenyl glycol, terephthalic acid be main component combination (for example, Econol E2000, E6000, E7000 that Sumitomo Chemical Company Ltd makes, the Xydar RC/FC400,300 that Nippon Petrochemicals Company, Limited makes, the bright dipping LCP300 that the UENO LCP2000 that the Vectra C series that Polyplastics Co., Ltd. makes, Ueno Seiyaku K.K. make, Idemitsu Petrochemical Co., Ltd. make); With P-hydroxybenzoic acid, 6-hydroxynaphthoic acid is the combination (for example, the UENO LCP1000 of the VICTREX SRP of ICI Japan Co., Ltd. manufacturing, Ueno Seiyaku K.K.'s manufacturing, the Vectra A series that Polyplastics Co., Ltd. makes, Novaculate E324, the bright dipping LCP300 that Idemitsu Petrochemical Co., Ltd. makes, the Rodran LC-5000 of Unitika Co., Ltd. manufacturing that Mitsubishi Kasei Corp makes) of main component; It with P-hydroxybenzoic acid, terephthalic acid, aliphatic diol the combination (for example, Mitsubishi Kasei Corp make Novaculate E310, bright dipping LCP100, the Rodran LC-3000 that Unitika Co., Ltd. makes, the X7G that Eastman Kodak Co., Ltd. makes that Idemitsu Petrochemical Co., Ltd. makes) etc. of main component.
As above in the resin compound that contains aromatic polyester resins or polycarbonate resin of gained, described resin compound has the mechanical characteristics of fluorine resin through improvement, the load flexure temperature, dimensional stability and formability, except above-mentioned characteristic, the thermotolerance that also has the original excellence of fluorine resin simultaneously, chemical resistant properties and electrical specification, its result, can become as inferior aspect useful especially material: require dimensional stability, thermotolerance and electrical specification electric, electronic unit, for example, junctor, chip, carrier, socket, printed circuit board (PCB), wire covering materials; Require the relevant product of chemical-resistant semi-conductor, especially under the condition of formability, undercapacity, be difficult to the large-scale wafer frame (wafer baskets) that obtains separately by fluoro-resin; Or valve, chemical pumping parts; Require machinery relevant product, for example automobile fuel round-robin parts, gear, the bearing of thermotolerance, sliding etc.And this resin compound has formability and the recirculation based on injection molding etc. as thermoplastic elastomer certainly.
Therefore, resin compound of the present invention is in medical treatment/biochemical fields such as pipe, chemical plug, packing ring, syringes; Semi-conductor industry fields such as pipe, annulus, sealing material; Electrical/electronic fields such as heatproof wire coating material, sealing material; Field of food industry such as flexible pipe, sealing material; Automobile association areas such as fuel-based flexible pipe, pipe, packing ring, constant velocity cardan joint cover, rack-and-pinion case; Chemical industry fields such as pressure hose, barrier film, liner, packing ring, flexible pipe; Be useful material in the purposes such as building materials field such as sealing material.
In addition, resin compound of the present invention can also contain for example fibrous tougheners such as glass fibre, carbon fiber, aramid fiber, graphite whisker, potassium titanate crystal whisker, basic magnesium sulfate whisker, magnesium whisker, magnesium borate crystal whisker, calcium carbonate crystal whisker, calcium sulfate crystal whiskers, ZnOw, aluminium borate whisker, alumina whisker, silicon carbide whisker, silicon nitride crystal whisker, wollastonite, burning vermiculite, sepiolite, gypsum fiber, slag fibre in the scope that does not influence its effect; Inorganic fillers such as carbon dust, powdered graphite, calcium carbonate powders, talcum, mica, clay, glass microballon; Heat-resistant resins such as polyimide resin; And the solid lubricant of molybdenumdisulphide and so on or other tinting material, fire retardant etc. employed inorganic or organic filler usually, its combined amount is generally 1～30 all weight % of composition.At this moment, because the existence of the unreacted functional group that resin compound of the present invention contained, thereby their filling effect may be further enhanced.
And, compare with the formed body that uses existing P TFE, by independent use bridging property PTFE of the present invention composition or the crosslinked body powder of PTFE, the PTFE formed body that can easily obtain mechanical characteristic, sliding, thermotolerance and have excellent weather resistance.And this PTFE formed body can be used for purposes widely such as eaves film, gas-liquid separating film, spacer, supported film of liner, packing ring, pipe, lining, coating, insulating tape, bearing, air dome.Shape for formed body has no particular limits, and can enumerate shapes such as pipe, film, sheet, fiber, porous-film.As the forming method that is shaped to this shape, can use known method.Specifically, can enumerate and behind moulding bridging property PTFE composition, make crosslinked method of PTFE or direct method of the crosslinked body powder of PTFE being carried out moulding etc., can according to circumstances suitably select these methods.For example, for the situation that is shaped to fiber, then both can be and it is shaped to carry out crosslinking Treatment after fibrous, also can stretch fibrosis to the PTFE formed body after the crosslinking Treatment at the formed body of stretching bridging property PTFE composition.And, for using this bridging property PTFE composition to be used for the situation of other materials, then can adopt the method for the PTFE dispersion after carrying out crosslinked method, coating crosslinking Treatment after the uncrosslinked PTFE dispersion of coating, bridging property PTFE composition carried out lining/be coated with the crosslinked method of the laggard row of stratification, the PTFE formed body after using crosslinking Treatment carries out lining/be coated with the method for stratification etc. as lining/coated material.But, general preferably carry out after the moulding crosslinked again to uncrosslinked body.
Among the present invention, special in the field that requires high purity and nonstaining property, can in the PTFE formed body, mix common additive as required, for example weighting agent, processing aid, softening agent, tinting material, stablizer and adhesive aid etc. also can use a kind or be mixed with two or more commonly used linking agent or the crosslinking coagent different with above-mentioned substance.
As required, bridging property PTFE composition of the present invention can also further apply other processing after crosslinking Treatment.Handle existing a lot of introduction of the method that improves specified property by the PTFE after the crosslinking Treatment is applied further, also can improve its performance by suitably utilizing known various gimmick for the crosslinked body of PTFE of the present invention.For example, want to give the crosslinked body of PTFE of the present invention with hydrophilic situation under, can followingly operate: (1) is to the crosslinked body irradiation of PTFE radioactive rays, laser, electronics line, plasma body, corona discharge etc.; (2) with electrochemical method or utilize the crosslinked body of Li metal/naphthalene coordination compound reduction PTFE; (3) in the crosslinked body of PTFE, add tensio-active agent; (4) hydrophilic macromolecules such as infiltration polyvinyl alcohol or polyoxyethylene glycol in the crosslinked body of PTFE; (5) metal oxide is attached to the crosslinked body of PTFE; (6) the inorganic powder mixing is filled in the crosslinked body of PTFE.
Below the actual example of implementing among the present invention is described.
[embodiment]
(1) has the manufacture method of the PTFE of reactive functional groups
(synthesis example 1)
Be 6L, have and add 3560g deionized water, 94g paraffin and 5.4g ammonium perfluorocaprylate dispersion agent in the stainless steel reactor of stirrer to inner capacities.Next the content with reactor is heated to 70 ℃, bleeds simultaneously, meanwhile, purifies with the TFE monomer, removes the oxygen in the reactor.Then, in reactor, add 0.17g ethane gas and 16.6g perfluorobuttene acid (PFBA), with the speed stirring content of 280rpm.Adding the TFE monomer in reactor is 0.73MPa until pressure.0.36g ammonium persulphate (APS) initiator that is dissolved in the 20g deionized water is injected in the reactor, and the pressure that makes reactor is 0.83MPa.After injecting initiator, observe pressure and reduce, polymerization begins.The TFE monomer is added in the reactor, continued polymerization to keep-up pressure and finish until the TFE of about 1.1Kg monomer reaction.Then, with the reactor exhaust, content is taken out by reactor and cool off.The paraffin of supernatant is removed from the PTFE aqueous liquid dispersion.
The solid component concentration of resulting PTFE aqueous liquid dispersion is 23.7 weight %, and average primary particle diameter is 0.22 μ m.In addition, this average primary particle diameter is following to be obtained: the light that shines 550nm to the cuvette of the regulation that is injected with PTFE aqueous liquid dispersion (solids component of this PTFE aqueous liquid dispersion is adjusted to 0.15 weight %), obtain transmitance, utilize the transmission electron microscope photo to measure unidirectional particle diameter, calculate the number average primary particle size, obtain the correlationship of number average primary particle size and transmitance thus, then, in the described correlationship of above-mentioned transmitance substitution that will measure for resulting sample, obtain average primary particle diameter (calibration curve) thus.
Dilute resulting PTFE aqueous liquid dispersion with deionized water,, under the high-speed stirring condition, it is solidified so that solid component concentration is about 15 weight %.Powder after will solidifying was in 145 ℃ of dryings 18 hours.The PFBA modification amount of the PTFE powder of this moment is 0.28 mole of %.In addition, modification amount is following to be obtained: according to having adopted probe diameter: 4.0mm, rotating speed: 13～15KHz when measuring, having measured atmosphere: nitrogen, measure temperature: 150 ℃ condition determination
19F-MAS-NMR (manufacturing of BRUKER society) assay method, detection resources from the peak of TFE and be derived from properties-correcting agent the peak (under the situation of PFBA for-179～-peak of 190ppm, under the situation of CBVE and CNVE be-77～-peak of 88ppm), obtain the modification amount by their ratio of peak area.
(synthesis example 2)
Except the amount with PFBA in the synthesis example 1 changes 6.6g into, similarly carry out polymerization with synthesis example 1.
The solid component concentration of the PTFE aqueous liquid dispersion that obtain this moment is 23.8 weight %, and average primary particle diameter is 0.20 μ m.And this moment, the PFBA modification amount of PTFE powder was 0.14 mole of %.
(synthesis example 3)
Except the amount with PFBA in the synthesis example 1 changes 6.6g into, the amount of ethane is changed into the 3.0ml, similarly carry out polymerization with synthesis example 1.
The solid component concentration of the PTFE aqueous liquid dispersion that obtain this moment is 23.7 weight %, and average primary particle diameter is 0.23 μ m.And this moment, the PFBA modification amount of PTFE powder was 0.12 mole of %.
In addition, in this synthesis example, owing to be less than addition in synthesis example 1 and 2 as the addition of the ethane of chain-transfer agent, thereby the molecular weight of resulting PTFE is higher than the molecular weight of resulting PTFE in synthesis example 1 and 2 in this synthesis example.Point out in passing, this point by use according to ASTMD 4895-89 manufactured samples utilize substitution method is measured in the water standard specific gravity [SSG] obtained really with.
(synthesis example 4)
Except the amount with PFBA in the synthesis example 1 changes 1.7g into, the amount of ethane is changed into the 3.0ml, similarly carry out polymerization with synthesis example 1.
The solid component concentration of the PTFE aqueous liquid dispersion that obtain this moment is 23.2 weight %, and average primary particle diameter is 0.20 μ m.And this moment, the PFBA modification amount of PTFE powder was 0.03 mole of %.
(synthesis example 5)
Be 6L, have and add the 3380g deionized water in the stainless steel reactor of stirrer to inner capacities.Next the content with reactor is heated to 70 ℃, bleeds simultaneously, meanwhile, purifies with the TFE monomer, removes the oxygen in the reactor.Then, in reactor, add 0.51g ethane gas and 6.6g PFBA, with the speed stirring content of 700rpm.Adding the TFE monomer in reactor is 0.73MPa until pressure.The 0.68g APS initiator that is dissolved in the 20g deionized water is injected in the reactor, and the pressure that makes reactor is 0.83MPa.After injecting initiator, observe pressure and reduce, polymerization begins.The TFE monomer is added in the reactor, and the lasting polymerization that keep-ups pressure finishes until the TFE of about 0.8Kg monomer reaction.Then, with the reactor exhaust, be cooled to room temperature after, with washed with de-ionized water resulting PTFE powder, filter then.
Resulting PTFE powder was in 145 ℃ of dryings 18 hours.This moment, the PFBA modification amount of PTFE powder was 0.20 mole of %.
(synthesis example 6)
Except the 6.6g PFBA in the synthesis example 5 being changed into 15.2g CBVE, similarly carry out polymerization with synthesis example 5.
This moment, the PTFE powder that obtains was in 145 ℃ of dryings 18 hours.And the CBVE modification amount of the PTFE powder of this moment is 0.45 mole of %.
(synthesis example 7)
Except the 6.6g PFBA in the synthesis example 5 being changed into 15.2g CBVE, changing the amount of APS initiator into 0.07g and do not use the ethane, similarly carry out polymerization with synthesis example 5.
After this moment, the PTFE powder that obtains carried out coarse reduction, in 145 ℃ of dryings 18 hours.Using pulverising mill to pulverize until median size then is 10～150 μ m, obtains the PTFE powder that moulding is used.The CBVE modification amount of the PTFE powder of this moment is 0.35 mole of %.
(synthesis example 8)
Except the 16.6g PFBA in the synthesis example 1 being changed into 14.6g perfluor [3-(1-methyl-2-vinyl oxygen-oxyethyl group) propionitrile] (hereafter is CNVE), similarly carry out polymerization with synthesis example 1.
The solid component concentration of the PTFE aqueous liquid dispersion that obtain this moment is 23.1 weight %, and average primary particle diameter is 0.17 μ m.And this moment, the CNVE modification amount of PTFE powder was 0.14 mole of %.
(synthesis example 9)
Except the 16.6g PFBA in the synthesis example 1 being changed into 15.7g perfluor [3-(1-methyl-2-vinyl oxygen-oxyethyl group) methyl propionate] (hereafter is RVEE) and the amount of ethane gas being changed into the 0.07g by 0.17g, similarly carry out polymerization with synthesis example 1.
The solid component concentration of the PTFE aqueous liquid dispersion that obtain this moment is 23.5 weight %, and average primary particle diameter is 0.18 μ m.And this moment, the RVEE modification amount of PTFE powder was 0.25 mole of %.
(2) preparation and the physical property measurement of bridging property PTFE composition, the crosslinked body powder of PTFE and PTFE formed body
Embodiment 1
With resulting PTFE powder and 0.12g 2 in the 100g synthesis example 1, two (3, the 4-diamino-phenyl) HFC-236fa (hereafter is BDHF) of 2-are mixed in 200g THF solvent, at room temperature fully stir.Removed the THF solvent in 7 hours by under the condition of decompression, leaving standstill, prepare bridging property PTFE composition at 30 ℃.
The bridging property PTFE composition that obtains is inserted in the air circulating oven, after 2 hours, slowly cool to room temperature, obtain the crosslinked body powder of PTFE in 220 ℃ of heat treated.
(mensuration of wear resistant)
At room temperature the crosslinked body powder of 42g PTFE is filled in the cylindrical mold of diameter 32mm.Pressurization at leisure after 19.6MPa keeps 5 minutes, by taking out in the mould, obtains preform then.This preform is put into 200 ℃ air circulating oven, is heated to 380 ℃ with 25 ℃/hour heat-up rates, carry out 1 hour sintering after, be cooled to 200 ℃ with 60 ℃/hour speed of cooling, after taking out in the stove, be cooled to room temperature lentamente.Cut down the sliding test sheet of external diameter 25.6mm, internal diameter 20.0mm, height 1 5.0mm by resulting formed body.
The EFM-III-F that uses Orientec (strain) society to make uses the subject material made from SUS304, carries out the friction wear test under pressure 0.4MPa, speed 1m/sec, 7 hours condition of test period, measures frictional coefficient and compares wear loss.The results are shown in table 1.
(mensuration of creep resistant)
At room temperature the crosslinked body powder of 15g PTFE is filled in the cylindrical mold of diameter 29.0mm.Pressurization at leisure after 14.0MPa keeps 2 minutes, by taking out in the mould, obtains preform then.This preform is put into 290 ℃ air circulating oven, is heated to 380 ℃ with 120 ℃/hour heat-up rates, carry out 30 minutes sintering after, be cooled to 294 ℃ with 60 ℃/hour speed of cooling, after 24 minutes,, be cooled to room temperature lentamente 294 ℃ of maintenances by taking out in the stove.Cut down the cylindric compression creep test sheet of diameter 11.0mm, height 10.0mm by resulting formed body.
Compressive creep when resulting test film being measured room temperature (23 ± 2 ℃) according to ASTM D621-64.The deflection that increases the weight of when being located at pressure for 13.7MPa after 24 hours is full distortion.Discharge load then, establishing through the deformation rate after 24 hours is tension set.The results are shown in table 1.
(tension test)
At room temperature the crosslinked body powder of 12g PTFE is filled in the cylindrical mold of diameter 29.0mm.Pressurization at leisure after 14.0MPa keeps 2 minutes, by taking out in the mould, obtains preform then.This preform is put into 290 ℃ air circulating oven, is heated to 380 ℃ with 120 ℃/hour heat-up rates, carry out 30 minutes sintering after, be cooled to 294 ℃ with 60 ℃/hour speed of cooling, after 24 minutes,, be cooled to room temperature lentamente 294 ℃ of maintenances by taking out in the stove.After resulting formed body machining is thickness 0.5mm membranaceous, in air circulating oven,, be cooled to 250 ℃, keep after 5 minutes being cooled to room temperature by taking out in the stove with 60 ℃/hour speed of cooling in 380 ℃ of anneal of carrying out 5 minutes.Punch out as the described little dumb-bell shape of ASTMD4895-94 (microdumbell) by resulting film, make the tension test sheet.
The Autograph AG-300kNI that tension test uses society of (strain) Shimadzu Seisakusho Ltd. to make tests with 50mm/ minute draw speed, obtains yield strength and Young's modulus.The results are shown in table 1.
(cementation test)
After the moulding of the crosslinked body powders compression of PTFE made sheet, this sheet-like formed body is clipped in 2 aluminium foils, is installed on the pressing machine that is set at 350 ℃, in 3MPa pressurization 10 minutes.It is wide that resulting duplexer is cut to 1cm, carries out the stripping test of T word.The results are shown in table 1.
Embodiment 2
The amount of BDHF is that 0.24g prepares the bridging property PTFE composition in establishing embodiment 1, prepares the crosslinked body powder of PTFE similarly to Example 1, tests.The results are shown in table 1.
Embodiment 3
The amount of BDHF is that 0.48g prepares the bridging property PTFE composition in establishing embodiment 1, prepares the crosslinked body powder of PTFE similarly to Example 1, tests.The results are shown in table 1.
Embodiment 4
Except the PTFE powder with embodiment 1 replaces with in the synthesis example 2 the resulting PTFE powder, prepare the crosslinked body powder of PTFE similarly to Example 1, test.The results are shown in table 2.
Embodiment 5
The amount that replaces with resulting PTFE powder in the synthesis example 2 and establish BDHF except the PTFE powder with embodiment 1 is that 0.24g prepares the bridging property PTFE composition, prepares the crosslinked body powder of PTFE similarly to Example 1, tests.The results are shown in table 2.
Embodiment 6
The amount that replaces with resulting PTFE powder in the synthesis example 2 and establish BDHF except the PTFE powder with embodiment 1 is that 0.48g prepares the bridging property PTFE composition, prepares the crosslinked body powder of PTFE similarly to Example 1, tests.The results are shown in table 2.
Embodiment 7
The amount that replaces with resulting PTFE powder in the synthesis example 3 and establish BDHF except the PTFE powder with embodiment 1 is that 0.24g prepares the bridging property PTFE composition, prepares the crosslinked body powder of PTFE similarly to Example 1, tests.The results are shown in table 3.
Embodiment 8
The amount that replaces with resulting PTFE powder in the synthesis example 4 and establish BDHF except the PTFE powder with embodiment 1 is that 0.24g prepares the bridging property PTFE composition, prepares the crosslinked body powder of PTFE similarly to Example 1, tests.The results are shown in table 3.
(3) the preparation transitivity of the mixing moulding body of PTFE and bridging property PTFE composition is measured
Embodiment 9
PTFE powder (F-104) with respect to the manufacturing of 100 weight part Daikin Industries societies, add the crosslinked body powder of resulting PTFE among the 4.7 weight part embodiment 2, after utilizing the Rocking Mixer thorough mixing, make the test film of respectively measuring usefulness in the same manner, test with embodiment 1.The results are shown in table 4.
Embodiment 10
PTFE powder (F-104) with respect to the manufacturing of 100 weight part Daikin Industries societies, add the crosslinked body powder of resulting PTFE among the 25.0 weight part embodiment 2, after utilizing the Rocking Mixer thorough mixing, make the test film of respectively measuring usefulness in the same manner, test with embodiment 1.The results are shown in table 4.
Embodiment 11
PTFE powder (F-104) with respect to the manufacturing of 100 weight part Daikin Industries societies, add the crosslinked body powder of resulting PTFE among the 42.9 weight part embodiment 2, after utilizing the Rocking Mixer thorough mixing, make the test film of respectively measuring usefulness in the same manner, test with embodiment 1.The results are shown in table 4.
(comparative example 1)
Except the PTFE powder (F-104) that the crosslinked body powder of the PTFE among the embodiment 1 is changed into the manufacturing of Daikin Industries society, make the test film of respectively measuring usefulness in the same manner with embodiment 1, test.The results are shown in table 5.
(comparative example 2)
Change the crosslinked body powder of the PTFE among the embodiment 1 into PTFE powder (F-104) that Daikin Industries society makes, with embodiment 1 make in the same manner respectively measure the test film of usefulness after, the gained test film is shone the gamma ray of 1 00kGy under vacuum.Then, test in the same manner with embodiment 1.The results are shown in table 5.
(comparative example 3)
Change the crosslinked body powder of the PTFE among the embodiment 1 into PTFE powder (F-104) that Daikin Industries society makes, with embodiment 1 make in the same manner respectively measure the test film of usefulness after, the gained test film is shone the gamma ray of 1000kGy under vacuum.Then, test in the same manner with embodiment 1.The results are shown in table 5.
Embodiment 12
The crosslinked body powder of resulting PTFE among the 210g embodiment 3 being filled in the mould of diameter 50mm, exerting pressure at leisure, is 29.4MPa until forming pressure, further keeps 5 minutes under this pressure, produces preform.Resulting preform put into electric furnace by taking out in the mould, be warming up to 300 ℃ by room temperature, to be warming up to 340 ℃ with 25 ℃/hour heat-up rate then with 50 ℃/hour heat-up rates.After 5 hours, be cooled to 300 ℃ in 340 ℃ of maintenances, cool off with 50 ℃/hour cooling rate then with 25 ℃/hour cooling rates.Make the test film of respectively measuring usefulness in the same manner with resulting formed body and embodiment 1, test.The results are shown in table 6.
Embodiment 13
PTFE powder (M-111) with respect to the manufacturing of 100 weight part Daikin Industries societies, add the crosslinked body powder of the PTFE that obtains among the 100 weight part embodiment 3, use cutting stirrer (liking that the worker's dormitory makes the K-55 type that society of institute makes) with 3000 rev/mins speed thorough mixing 1 minute.The resulting mixed powder of 210g being filled in the mould of diameter 50mm, exerting pressure at leisure, is 29.4MPa until forming pressure, further keeps 5 minutes under this pressure, produces preform.Resulting preform put into electric furnace by taking out in the mould, be warming up to 300 ℃ by room temperature, to be warming up to 365 ℃ with 25 ℃/hour heat-up rate then with 50 ℃/hour heat-up rates.After 5 hours, be cooled to 300 ℃ in 365 ℃ of maintenances, cool off with 50 ℃/hour cooling rate then with 25 ℃/hour cooling rates.Make the test film of respectively measuring usefulness in the same manner with resulting formed body and embodiment 1, test.The results are shown in table 6.
Embodiment 14
PTFE powder (M-111) with respect to 100 weight part Daikin Industries societies make adds the crosslinked body powder of the PTFE that obtains among the 400 weight part embodiment 3, is prepared similarly to Example 13 in addition.Make the test film of respectively measuring usefulness in the same manner with resulting formed body and embodiment 1, test.The results are shown in table 6.
Embodiment 15
PTFE powder among the embodiment 1 is replaced with resulting PTFE powder in the synthesis example 5, and then change the amount of BDHF into 0.35g, prepare bridging property PTFE composition thus, in addition, prepare the crosslinked body powder of PTFE similarly to Example 1.
Embodiment 16
PTFE powder among the embodiment 1 is replaced with resulting PTFE powder in the synthesis example 6, and then change the amount of BDHF into 0.80g, prepare bridging property PTFE composition thus, in addition, prepare the crosslinked body powder of PTFE similarly to Example 1.
Embodiment 17
PTFE powder among the embodiment 1 is replaced with resulting PTFE powder in the synthesis example 7, and then change the amount of BDHF into 0.62g, prepare bridging property PTFE composition thus, prepare the crosslinked body powder of PTFE then similarly to Example 1.
(comparative example 4)
The PTFE powder (M-111) that 210g Daikin Industries society is made is filled in the mould of diameter 50mm, exerts pressure at leisure, and be 29.4MPa until forming pressure, further under this pressure, kept 5 minutes, produce preform.Resulting preform is put into electric furnace by taking out in the mould, be warming up to 365 ℃ by room temperature with 50 ℃/hour heat-up rates.Then,, cool off after 5 hours in 365 ℃ of maintenances with 50 ℃/hour cooling rate.Make the test film of respectively measuring usefulness in the same manner with resulting formed body and embodiment 1, test.The results are shown in table 6.
Embodiment 18
After using cutting stirrer (liking that the worker's dormitory makes the K-55 type that society of institute makes) the bridging property PTFE composition that obtains among the 500g embodiment 3 fully to be pulverized 1 minute with 3000 rev/mins rotating speeds, sieve with 300 microns mesh, remove sieve and go up residual powder, prepare bridging property PTFE composition.
Then, the resulting bridging property PTFE of 210g composition being filled in the mould of diameter 50mm, exerting pressure at leisure, is 29.4MPa until forming pressure, further keeps 5 minutes under this pressure, produces preform.Then, resulting preform is put into electric furnace by taking out in the mould, be warming up to 220 ℃ by room temperature with 50 ℃/hour heat-up rates.Next, in 220 ℃ keep 2 hours after, be warming up to 300 ℃ with 50 ℃/hour heat-up rates, be warming up to 365 ℃ with 25 ℃/hour heat-up rate then.Then, after 5 hours, be cooled to 300 ℃, cool off with 50 ℃/hour cooling rate then with 25 ℃/hour cooling rates in 365 ℃ of maintenances.Make the test film of respectively measuring usefulness in the same manner with resulting formed body and embodiment 1, test.The results are shown in table 7.
Embodiment 19
Except the forming pressure among the embodiment 18 being changed into 49.0MPa, make preform similarly to Example 18, test.The results are shown in table 7.
Embodiment 20
PTFE powder among the embodiment 1 is replaced with the PTFE powder that obtains in the synthesis example 8, and then changes the amount of BDHF into 0.25g, prepare bridging property PTFE composition thus after, prepare the crosslinked body powder of PTFE similarly to Example 1.
Embodiment 21
PTFE powder among the embodiment 1 is replaced with the PTFE powder that obtains in the synthesis example 9, and then changes the amount of BDHF into 0.44g, prepare bridging property PTFE composition thus after, prepare the crosslinked body powder of PTFE similarly to Example 1.
Embodiment 22
Change the 0.12g BDHF among the embodiment 1 into 0.72g 6,6-hexichol amido-3,3-[2,2,2-three fluoro-1-(trifluoromethyl) ethylidene] pentanoic, preparation bridging property PTFE composition prepares the crosslinked body powder of PTFE in addition similarly to Example 1.
Embodiment 23
Change the 0.12g BDHF among the embodiment 1 into 0.50g 2, two (the 3-amino-4-hydroxy phenyl) HFC-236fa of 2-, preparation bridging property PTFE composition prepares the crosslinked body powder of PTFE in addition similarly to Example 1.
Embodiment 24
Change the 0.12g BDHF among the embodiment 1 into 0.30g 3,3 '-diaminobenzidine, preparation bridging property PTFE composition prepares the crosslinked body powder of PTFE in addition similarly to Example 1.
Embodiment 25
Change the 0.12g BDHF among the embodiment 1 into 0.26g 2,3,6,7-tetramino naphthalene, preparation bridging property PTFE composition prepares the crosslinked body powder of PTFE in addition similarly to Example 1.
Embodiment 26
55.0g polycarbonate resin (Teijin Chemicals, Ltd. make Panlite L-1125WP) is fed into temperature, and to be set at 280 ℃, internal volume be 60cm
3Brabender mixing machine (the LABO PLASTOMILL that Japan smart machine Co., Ltd. makes) in, with the rotating speed fusion of 50rpm after 5 minutes, add the bridging property PTFE composition that obtains among the 6.0g embodiment 3, with the rotating speed of 50rpm mixing 10 minutes, obtain the mixed with resin composition.
Embodiment 27
Except the 55.0g polycarbonate resin among the embodiment being replaced with 57.0g nylon 66 (the Leona 1300S that Asahi Kasei Corporation makes), mixing similarly to Example 26, obtain the mixed with resin composition.
Embodiment 28
55.0g polycarbonate resin among the embodiment is replaced with 72.0g liquid crystal polyester (PolyplasticsCo., Ltd. make, VectraA130), and then change bridging property PTFE composition into 7.9g by 6.0g, change design temperature into 320 ℃ by 280 ℃, in addition, mixing similarly to Example 26, obtain the mixed with resin composition.
Embodiment 29
55.0g polycarbonate resin among the embodiment is replaced with the 77.0g fluoro-resin, and (Daikin Ind Ltd makes, Neoflon EFEP RP-5000), and then changes bridging property PTFE composition into 8.5g by 6.0g, in addition, mixing similarly to Example 26, obtain the mixed with resin composition.
Embodiment 30
55.0g polycarbonate resin among the embodiment is replaced with the 93.0g tetrafluoraoethylene-hexafluoropropylene copolymer, and (Daikin Ind Ltd makes, Neoflon FEP NP-30), and then change bridging property PTFE composition into 10.3g by 6.0g, change design temperature into 300 ℃ by 280 ℃, in addition, mixing similarly to Example 26, obtain the mixed with resin composition.
Embodiment 31
55.0g polycarbonate resin among the embodiment is replaced with the 93.0g tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and (Daikin Ind Ltd makes, Neoflon PFA AP-231), and then change bridging property PTFE composition into 10.3g by 6.0g, change design temperature into 320 ℃ by 280 ℃, in addition, mixing similarly to Example 26, obtain the mixed with resin composition.
Embodiment 32
55.0g polycarbonate resin among the embodiment is replaced with the 92.0g voltalef, and (Daikin Ind Ltd makes, Neoflon PCTFE M-300), and then change bridging property PTFE composition into 10.3g by 6.0g, change design temperature into 320 ℃ by 280 ℃, in addition, mixing similarly to Example 26, obtain the mixed with resin composition.
Embodiment 33
55.0g polycarbonate resin among the embodiment is replaced with the 82.0g tetrafluoroethylene-ethylene copolymer, and (Daikin Ind Ltd makes, Neoflon ETFE EP-610), and then change bridging property PTFE composition into 9.1g by 6.0g, in addition, mixing similarly to Example 26, obtain the mixed with resin composition.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | ||
| Resin is formed | Modified ptfe | Synthesis example 1 | Synthesis example 1 | Synthesis example 1 |
| BDHF (annotating 1) | 0.2 | 0.5 | 1.0 | |
| The friction wear test | Than wear loss (10 -8×mm 3/N·m) | 1.47×10 4 | 1.20×10 4 | 8.93×10 3 |
| Frictional coefficient | 0.19～0.21 | 0.19～0.21 | 0.19～0.21 | |
| Compression creep test | Compressive creep (%) | 6.6 | 4.2 | 3.6 |
| Tension set (%) | 3.6 | 2.0 | 2.0 | |
| Tension test | Young's modulus (MPa) | 756 | 686 | 657 |
| Yield strength (MPa) | 13.1 | 13.2 | 13.3 | |
| Cementation test | Well | Well | Well | |
(annotating 1) is with respect to the amino equivalent number of the carboxyl of PFBA
[table 2]
| Embodiment 4 | Embodiment 5 | Embodiment 6 | ||
| Resin is formed | Modified ptfe | Synthesis example 2 | Synthesis example 2 | Synthesis example 2 |
| BDHF (annotating 1) | 0.3 | 0.5 | 1.0 | |
| The friction wear test | Than wear loss (10 -8×mm 3/N·m) | 1.23×10 5 | 9.48×10 4 | 6.92×10 4 |
| Frictional coefficient | 0.17～0.19 | 0.17～0.19 | 0.17～0.19 | |
| Compression creep test | Compressive creep (%) | 7.4 | 6.7 | 4.7 |
| Tension set (%) | 9.8 | 4.9 | 3.9 | |
| Tension test | Young's modulus (MPa) | 662 | 597 | 581 |
| Yield strength (MPa) | 12.4 | 12.5 | 12.5 | |
| Cementation test | Well | Well | Well | |
(annotating 1) is with respect to the amino equivalent number of the carboxyl of PFBA
[table 3]
| Embodiment 7 | Embodiment 8 | ||
| Resin is formed | Modified ptfe | Synthesis example 3 | Synthesis example 4 |
| BDHF (annotating 1) | 0.5 | 0.5 | |
| The friction wear test | Than wear loss (10 -8×mm 3/N·m) | 8.64×10 5 | 6.57×10 6 |
| Frictional coefficient | 0.27～0.37 | 0.27～0.34 | |
| Compression creep test | Compressive creep (%) | 9.2 | 10.5 |
| Tension set (%) | 6.6 | 11.2 | |
| Tension test | Young's modulus (MPa) | 809 | 921 |
| Yield strength (MPa) | 13.7 | 14.3 | |
| Cementation test | Well | Well | |
(annotating 1) is with respect to the amino equivalent number of the carboxyl of PFBA
[table 4]
| Embodiment 9 | Embodiment 10 | Embodiment 11 | ||
| Resin is formed | The crosslinked body powder of PTFE (embodiment 2) (weight %) | 4.5 | 20 | 30 |
| PTFE powder (F-104) (weight %) | 95.5 | 80 | 70 | |
| The friction wear test | Than wear loss (10 -8×mm 3/N·m) | 8.77×10 5 | 7.68×10 4 | 2.68×10 4 |
| Frictional coefficient | 0.22～0.32 | 0.26～0.36 | 0.27～0.48 | |
| Compression creep test | Compressive creep (%) | 13.2 | 12.2 | 10.6 |
| Tension set (%) | 9.5 | 8.8 | 8.6 | |
| Tension test | Young's modulus (MPa) | 440 | 528 | 528 |
| Yield strength (MPa) | 8.8 | 10.5 | 10.5 | |
| Cementation test | Well | Well | Well | |
[table 5]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | ||
| The friction wear test | Than wear loss (10 -8×mm 3/N·m) | 2.38×10 6 | 9.14×10 3 | 4.59×10 3 |
| Frictional coefficient | 0.22～0.30 | 0.15～0.25 | 0.17～0.19 | |
| Compression creep test | Compressive creep (%) | 14.0 | 4.0 | 1.3 |
| Tension set (%) | 10.1 | 2.7 | 1.0 | |
| Tension test | Young's modulus (MPa) | 453 | 507 | 578 |
| Yield strength (MPa) | 9.8 | 10.7 | 11.8 | |
| Cementation test | Bad | Bad | Bad | |
[table 6]
| Embodiment 12 | Embodiment 13 | Embodiment 14 | Comparative example 4 | ||
| Resin is formed | The crosslinked body powder of PTFE (embodiment 3) (weight %) | 100 | 50 | 80 | 0 |
| PTFE powder (M-111) (weight %) | 0 | 50 | 20 | 100 | |
| The friction wear test | Than wear loss (10 -8×mm 3/N·m) | 1.05×10 3 | 4.95×10 3 | 1.97×10 3 | 1.18×10 6 |
| Frictional coefficient | 0.20～0.24 | 0.12～0.19 | 0.13～0.19 | 0.10～0.16 | |
| Compression creep test | Compressive creep (%) | 1.8 | 2.8 | 1.6 | 5.7 |
| Tension set (%) | 2.2 | 2.6 | 1.9 | 3.6 | |
| Tension test | Young's modulus (MPa) | 743 | 694 | 626 | 469 |
| Yield strength (MPa) | 12.8 | 12.1 | 11.2 | 9.3 | |
| Cementation test | Well | Well | Well | Bad | |
[table 7]
| Embodiment 18 | Embodiment 19 | ||
| Resin is formed | Modified ptfe | Synthesis example 1 | Synthesis example 1 |
| BDHF (annotating 1) | 1 | 1 | |
| The friction wear test | Than wear loss (10 -8×mm 3/N·m) | 1.28×10 3 | 5.91×10 2 |
| Frictional coefficient | 0.19～0.23 | 0.19～0.22 | |
| Compression creep test | Compressive creep (%) | 1.8 | 1.5 |
| Tension set (%) | 1.8 | 2.0 | |
| Tension test | Young's modulus (MPa) | 721 | 732 |
| Yield strength (MPa) | 12.6 | 12.7 | |
| Cementation test | Well | Well | |
(annotating 1) is with respect to the amino equivalent number of the carboxyl of PFBA
Table 1～5 show that PTFE formed body of the present invention has been kept existing surface property.And can find that compare with existing P TFE resin, PTFE formed body of the present invention has improved modulus in tension and creep properties, and is not yielding.
In addition, table 5 has also been put down in writing in the lump and has been utilized the ionization radioactive rays to carry out many rerum naturas (referring to comparative example 2 and 3) of the tetrafluoroethylene of crosslinking Treatment, utilize exist in the cross-linking treatment method of ionization radioactive rays the problem that needs to use expensive isolated plant, can't big area or make powder carry out crosslinked problem equably, through the part of crosslinking Treatment problem, a kind of preferred cross-linking treatment method of can not saying so to the surface arrangement inequality.
And by table 6 and table 7 as can be known, the crosslinked body powder of PTFE of the present invention plays effective function as the properties-correcting agent that unmodified PTFE is carried out modification.
Industrial applicibility
Bridging property polyetetrafluoroethycomposition composition of the present invention can provide a kind of polyflon, this resin can be kept original intensity, crystallinity and surface characteristic etc., and this resin does not exist anisotropy and inhomogeneity, and is more yielding than not with existing PTFE resin-phase. Be useful as modification with material etc. by the resulting crosslinked polytetrafluoroethylpowder body of crosslinked this bridging property polyetetrafluoroethycomposition composition powder, polytetrafluoroethylmolded molded article is useful as sliding material etc.
Claims (13)
1. bridging property polyetetrafluoroethycomposition composition, said composition contains tetrafluoroethylene and linking agent, described tetrafluoroethylene has at least one side of main chain and side chain terminal and is selected from that (CN), (COOH), alkoxy carbonyl (COOR) and acid halide group (at least a reactive functional groups in the group of COX) forming for carboxyl by cyano group, among-the COOR, R represents the organic group of 1 valency, among-the COX, X represents halogen atom; Described linking agent can react with the above-mentioned reactive functional groups more than 1 or 2, forms ring texture.
2. bridging property polyetetrafluoroethycomposition composition as claimed in claim 1, wherein, described linking agent is at least a linking agent that is selected from the group of being made up of amidoxim class linking agent, amidrazone class linking agent, aminophenols linking agent, aminothiophenol class linking agent and amino-benzene base class linking agent.
3. bridging property polyetetrafluoroethycomposition composition as claimed in claim 2, wherein, described linking agent for be selected from by contain at least two compounds with the bridging property reactive group of general formula (1) expression, with at least a compound in the compound of general formula (2) expression, the group formed with the compound of general formula (3) expression with the compound of general formula (4) expression;
In the general formula (1), R
1Identical or different, expression-NH
2,-NHR
2,-OH or-SH, R
2The organic group of expression fluorine atom or 1 valency;
In the general formula (2), R
3Expression-SO
2-,-O-,-CO-, carbonatoms are that 1～6 alkylidene group, carbonatoms are 1～10 perfluorinated alkylidene or singly-bound, R
4Expression
Or
In the general formula (3), R
f 1The expression carbonatoms is 1～10 perfluorinated alkylidene;
In the general formula (4), n represents 1～10 integer.
4. bridging property polyetetrafluoroethycomposition composition as claimed in claim 3, wherein, described linking agent is the compound with general formula (5) expression;
In the general formula (5), R
1With above-mentioned R
1Identical, R
5Expression-SO
2-,-O-,-CO-, carbonatoms be 1～6 alkylidene group, carbonatoms be 1～10 perfluorinated alkylidene, singly-bound or with
5. polytetrafluoroethylmolded molded article, it obtains by making each described bridging property polyetetrafluoroethycomposition composition generation crosslinking reaction of claim 1～4.
6. crosslinked body powder of tetrafluoroethylene, it obtains by making each described bridging property polyetetrafluoroethycomposition composition generation crosslinking reaction of claim 1～4.
7. polytetrafluoroethylmolded molded article, it forms by the crosslinked body powder of the described tetrafluoroethylene of claim 6 is carried out moulding.
8. mixed with resin composition, it contains each described bridging property polyetetrafluoroethycomposition composition of claim 1～4, and contains resin or resin precursor.
9. mixed with resin composition as claimed in claim 8, wherein, described resin is at least a fluoro-resin that is selected from the group of being made up of tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, voltalef.
10. mixed with resin formed body, it forms by claim 8 or 9 described mixed with resin compositions are carried out moulding.
11. a mixed with resin composition, it contains the crosslinked body powder of the described tetrafluoroethylene of claim 6, and contains resin or resin precursor.
12. mixed with resin composition as claimed in claim 11, wherein, described resin is at least a fluoro-resin that is selected from the group of being made up of tetrafluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, voltalef.
13. a mixed with resin formed body, it forms by claim 11 or 12 described mixed with resin compositions are carried out moulding.
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|---|---|---|---|
| JP134020/2005 | 2005-05-02 | ||
| JP2005134020 | 2005-05-02 | ||
| JP233919/2005 | 2005-08-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113388296A (en) * | 2021-07-07 | 2021-09-14 | 滁州中氟环保科技有限公司 | Production method of special fluorine material capable of being roll-formed |
| CN114729257A (en) * | 2019-11-27 | 2022-07-08 | 美国圣戈班性能塑料公司 | Seal and method of forming same |
| CN114989547A (en) * | 2022-06-24 | 2022-09-02 | 佛山科学技术学院 | Polymer composite material with abrasion in-situ repair function and preparation method and application thereof |
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2006
- 2006-04-24 CN CNA2006800151109A patent/CN101171296A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030907A (en) * | 2012-12-20 | 2013-04-10 | 常熟市董浜镇徐市盛峰液压配件厂 | Large and high-performance O-shaped sealing ring |
| CN114729257A (en) * | 2019-11-27 | 2022-07-08 | 美国圣戈班性能塑料公司 | Seal and method of forming same |
| CN114729257B (en) * | 2019-11-27 | 2024-06-07 | 美国圣戈班性能塑料公司 | Seal and method of forming the same |
| CN113388296A (en) * | 2021-07-07 | 2021-09-14 | 滁州中氟环保科技有限公司 | Production method of special fluorine material capable of being roll-formed |
| CN114989547A (en) * | 2022-06-24 | 2022-09-02 | 佛山科学技术学院 | Polymer composite material with abrasion in-situ repair function and preparation method and application thereof |
| CN114989547B (en) * | 2022-06-24 | 2024-01-02 | 佛山科学技术学院 | Polymer composite material with abrasion in-situ repair function and preparation method and application thereof |
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