CN100441605C - Perfluoroelastomer compsns. - Google Patents
Perfluoroelastomer compsns. Download PDFInfo
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- CN100441605C CN100441605C CNB998043354A CN99804335A CN100441605C CN 100441605 C CN100441605 C CN 100441605C CN B998043354 A CNB998043354 A CN B998043354A CN 99804335 A CN99804335 A CN 99804335A CN 100441605 C CN100441605 C CN 100441605C
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- Prior art keywords
- perfluoroelastomer
- group
- sizing material
- vinyl ether
- ether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
Abstract
A perfluoroelastomer compound having improved processability comprising a perfluoroolefin, a perfluorovinyl ether and a halogen-containing cure site, where the polymer contains substantially no ionizable moieties; and processes for making such copolymers; and articles made therefrom.
Description
FIELD OF THE INVENTION
The present invention relates to have good processibility and when sulfuration, have the perfluoroelastomer composition of the peroxide curable of good physicals.
The background of invention
Perfluoroelastomer (elasticity (per) fluoropolymer) is to have outstanding high-temperature durable and chemical-resistant polymeric material.Therefore, this composition particularly suitable work can run into sealing and the packing ring in the system of high temperature and/or eroding chemical.They can be used for such as industrial circles such as chemical process, semi-conductor, aerospace, oil.
The outstanding properties major part of (per) fluoropolymer is attributable to constitute the unitary stability of copolymerization perfluorinated monomers and the inertia of most of main polymer chain (as tetrafluoroethylene and perfluor (alkyl vinyl) ether).In order to reach elasticity fully, general as making (per) fluoropolymer crosslinked through sulfuration.For this reason, with a spot of sulfide site monomer (cure site monomer) and the copolymerization of perfluorinated monomers unit.The sulfide site monomer that contains at least one bromo or iodo group is known.When this sulfide site monomer and superoxide and coagent combination, it can provide suitable sulfurized composition.
Perfluoroelastomer is very expensive material, thereby it is not only having other material can finish just use under the situation of above-mentioned work.Because the expense of raw material is very high, so the scrap stock rate in the molded operation process must be kept minimum.Yet known Perfluoroelastomer is because mixing, the flow characteristics and the demoulding and be difficult to very much processing.When using conventional initiator to prepare polymkeric substance (as persulphate), the end group of polymkeric substance generally has the feature of ion and/or acid.These general ionizable polymer terminal groups that exist are easy to some additive (as acid acceptor) commonly used undesirable reaction take place.The example of acid acceptor commonly used is zinc oxide, calcium hydroxide, lime carbonate, magnesium oxide etc.They are used to prepare burden prescription with issuable any HF or other acid under the high temperature that is strapped in Perfluoroelastomer and must works.
WO-A-97/02300 has described a kind of method for preparing fluoropolymer, this method comprises the water-based emulsion or the suspension of polymerization Fluorine containing olefine, wherein initiator is fluorine-containing aliphatic sulfinic acid salt or-sulfinic acid and the mixture that is selected from chloranion, bromate ion and hypochlorite ion's oxygenant, and condition is that described fluorine-containing aliphatic sulfinic acid salt or fluorine-containing aliphatic sulfinic acid and described oxygenant are water miscible.
FR-A-2 305 462 has disclosed the fluoropolymer that makes by the monomer mixture copolymerization that a spot of bromotrifluoethylene or bromine tetrafluoro butylene and some is selected from fluorochemicals.The fluoro-containing copolymer composition that is used to make the sulfuration fluoropolymer article can be by mixing gained fluoropolymer or closely-related fluoropolymer with organo-peroxide such as dialkyl, better also add bivalent metal oxide and/or oxyhydroxide and suitable coagent such as triallyl isocyanurate and make.
US-A-5; 285; 002 has disclosed a kind of method for preparing fluoropolymer, and the water-based emulsion or the suspension of polymerizable mixture that it is included in the-sulfinate that will comprise fluorine-containing aliphatic group under the condition of free radical and described-sulfinate can be oxidized to the oxygenant of alkylsulfonyl carries out polymerization.
Be starved of Perfluoroelastomer sizing material with good processing characteristics.Because many application of these polymkeric substance also require good sealing property, preferably can disadvantageous effect not arranged to key physical performance such as incompressible set (compression set resistance) so improve the step of processibility.
The general introduction of invention
Perfluoroelastomer sizing material of the present invention adopts a kind of Perfluoroelastomer, and this elastomerics is to use oxygenant and R
fSO
2The initiator mixture of Na type perfluoroalkyl-sulfinate makes.The multipolymer that makes by this way can be processed as other elastomer precursor gum astoundingly.They are easy to promptly not need to be heated above in the mill of room temperature or the mixing equipment in the mill of routine or at mixing equipment process.When adding acid acceptor such as Ca (OH)
2The time, their compound viscosity (compound viscosity) can not improve.This Perfluoroelastomer also has improved physicals (as incompressible set).
An example of the present invention provides a kind of Perfluoroelastomer sizing material that is easy to process and be substantially free of the peroxide curable of ionizable end group.Be preferably Perfluoroelastomer and be substantially free of ionizable end group, described end group is selected from carboxylate salt or carboxylic end group and sulfonate or sulfonic acid end group." be substantially free of " this end group and be meant in these end groups less than 10% it is ionizable group.The sizing material of this example comprises:
A) comprise derive from following 1), 2) and 3) the Perfluoroelastomer of copolymerization units, 1) perfluoroolefine, 2) be selected from perfluor (alkyl vinyl) ether, the perfluoroalkyl vinyl ether of perfluor (alkoxy vinyl) ether and their mixtures, with 3) can participate in the sulfide site component (cure site component) of the halogen-containing group of peroxide cure reaction, this component is selected from the fluorinated olefin that contains at least one this halogen group, the fluorinated vinyl ether that contains at least one this halogen group, contain the chain-transfer agent of at least one this halogen group and contain the initiator of at least one this halogen group and their mixture; Condition be the sulfide site component be substantially free of itrile group and
B) peroxide vulcanizing agent.
In another example, the invention provides a kind of Perfluoroelastomer sizing material of the peroxide curable that is easy to process, it comprises:
A) be substantially free of the Perfluoroelastomer of ionizable end group, wherein this Perfluoroelastomer comprise derive from following 1), 2) and 3) copolymerization units, 1) perfluoroolefine, 2) be selected from perfluor (alkyl vinyl) ether, the perfluoroalkyl vinyl ether of perfluor (alkoxy vinyl) ether and their mixtures, with 3) can participate in the sulfide site component that contains the bromine or iodine atom that peroxide cure reacts, this component is selected from bromination or the iodate alkene that contains at least one this atom, the bromination or the ethylene iodide base ether that contain at least one this atom, bromination or iodinated chain transfer agents, bromination or iodate initiator and their mixture; With
B) peroxide vulcanizing agent.
The present invention also provides a kind of method of improving the processibility of Perfluoroelastomer; the water-based emulsion or the suspension of polymerizable mixture that this method is included in will comprise perfluoroolefine and perfluoroalkyl vinyl ether or perfluorinated alkoxy vinyl ether and composition thereof under the condition of free radical, can participate in the-sulfinate of the Halogen sulfide site component of peroxide cure reaction, fluorine-containing aliphatic group and described-sulfinate can be oxidized to the oxygenant of alkylsulfonyl carries out polymerization, and condition is that the sulfide site component is substantially free of itrile group.
The present invention also provides a kind of method of improving the processibility of Perfluoroelastomer, and this method is included in will comprise perfluoroolefine and perfluoroalkyl vinyl ether or perfluorinated alkoxy vinyl ether and composition thereof under the condition of free radical, the water-based emulsion or the suspension of polymerizable mixture brominated or that contain the-sulfinate of the sulfide site component of iodine, fluorine-containing aliphatic group and described-sulfinate can be oxidized to the oxygenant of alkylsulfonyl carries out polymerization.
But the invention still further relates to sulfuration and the unvulcanized goods made by this vulcanized rubber.
Describe in detail
Composition of the present invention comprises the Perfluoroelastomer of peroxide curable, and this is elastomeric to be characterised in that to have improved processibility and less and reactivity alkali.These compositions comprise a) Perfluoroelastomer, and it comprises perfluoroolefine, perfluoroalkyl vinyl ether and contains the copolymerization units that at least one contains the sulfide site component of bromine or iodine part, and b) as the compound of the vulcanizing agent of Perfluoroelastomer.Perfluoroelastomer is substantially free of ionizable end group, as those can with the end group of alkali reaction.This also is not precluded within and has crosslinked required sulfide site in the Perfluoroelastomer.
The example of the suitable perfluoroolefine that the present invention is useful comprises tetrafluoroethylene and R 1216.
The example of suitable perfluoroalkyl vinyl ether is the ether of those following structural formula:
CF
2＝CFO(R
fO)
n(R’
fO)
mR
f (I)
R wherein
fAnd R '
fBe different line style that contains 2-6 carbon atom or branching perfluorinated alkylidenes, m and n are 0-10 independently, R
fIt is the perfluoroalkyl that contains 1-6 carbon atom.
Better perfluor (alkyl vinyl) ether of kind comprises the following formula composition:
CF
2＝CFO(CF
2CFXO)
nR
f (II)
Wherein X is F or CF
3, n is 0-5, R
fIt is the perfluoroalkyl that contains 1-6 carbon atom.
Best perfluor (alkyl vinyl) ether be those wherein n be 0 or 1 and R
fThe ether that contains 1-3 carbon atom.The example of this perfluor ether comprises perfluor (methyl ethylene) ether, perfluor (ethyl vinyl) ether and perfluor (propyl ethylene base) ether.Other useful monomer comprises following formula: compound:
CF
2＝CFO[(CF
2)
mCF
2CFZO]
nR
f (III)
R wherein
fBe the perfluoroalkyl that contains 1-6 carbon atom, m=0 or 1, n=0-5, Z=F or CF
3
The better example of this type ether is R wherein
fBe C
3F
7, m=0 and n=1 ether.Useful other perfluor (alkyl vinyl) ether monomer of the present invention comprises following formula: compound:
CF
2＝CFO[(CF
2CFCF
3O)
n(CF
2CF
2CF
2O)
m(CF
2)
p]C
xF
2x+1 (IV)
Wherein m and n=1-10, p=0-3, and x=1-5.
The better example of this type ether comprises wherein n=0-1, the compound of m=0-1 and x=1.
The example of perfluor (alkoxy vinyl) ether that the present invention is useful comprises:
CF
2＝CFOCF
2CF(CF
3)O(CF
2O)
mC
nF
2n+1 (V)
N=1-5 wherein, m=1-3, and be preferably n=1.
The object lesson of the perfluoroalkyl vinyl ether that the present invention is useful comprises CF
2=CFOCF
2OCF
2CF
2CF
3, CF
2=CFOCF
2CF
3, CF
2=CFO (CF
2)
3OCF
3And CF
2=CFOCF
2CF
2OCF
3
Also can use the mixture of perfluor (alkyl vinyl) ether and perfluor (alkoxy vinyl) ether.
Multipolymer is made up of as the principal monomer unit tetrafluoroethylene and at least a perfluor (alkyl vinyl) ether preferably.In this multipolymer, copolymerization perfluor ether unit accounts for about 15-50 mole % of monomeric unit total amount in the polymkeric substance.
The used sulfide site component of the present invention is the halogen-containing materials that can participate in the peroxide cure reaction.Halogen is typically bromine or iodine.Suitable sulfide site component comprises terminal unsaturation monoolefine such as bromine difluoroethylene, bromotrifluoethylene, iodine trifluoro-ethylene and the 4-bromo-3,3,4 that contains 2-4 carbon atom, 4-tetrafluoro butene-1.The example of the sulfide site component that other is suitable comprises CF
2=CFOCF
2CF
2Br, CF
2=CFOCF
2CF
2CF
2Br and CF
2=CFOCF
2CF
2CF
2OCF
2CF
2Br.Be preferably all or basically all these components all be ethylenically unsaturated monomer.
Other useful sulfide site component is bromination or iodinated chain transfer agents and initiator.The example of useful chain-transfer agent comprises perfluoroalkyl bromides or perfluoroalkyl iodides.The example of useful initiator comprises NaO
2SC
2F
4OF
4X (wherein X is Br or I).
The used suitable peroxide vulcanizing agent of the present invention is those vulcanizing agents that can produce free radical under curing temperature.Being higher than dialkyl or two (dialkyl) of decomposing under 50 ℃ the temperature is good especially.In many cases, should use the di-t-butyl peroxide that contains the tertiary carbon atom on the oxygen that is connected to peroxy.The most useful such superoxide is 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3 and 2,5-2.Other superoxide can be selected from following these compounds, as dicumyl peroxide, dibenzoyl peroxide, t-butylperoxyl benzoate, α, α ' two (t-butylperoxy-diisopropylbenzene(DIPB)) and two [1,3-dimethyl-3-(t-butylperoxy)-butyl] carbonic ether.In general, per 100 parts of Perfluoroelastomers use about 1-3 part superoxide.
Usually be coagent with another kind of material as the composition blend of a vulcanizing agent system part, this coagent is formed by providing with the sulfurized polyunsaturated compounds with superoxide.Per 100 parts of Perfluoroelastomers, the add-on of these coagents can be 0.1-10 part, better is per 100 parts of Perfluoroelastomers, and described add-on is 2-5 part.The example of useful coagent comprises triallyl cyanurate; Triallyl isocyanurate; Isocyanuric acid three (methyl allyl) ester; Three (diallylamine)-s-triazines; Triallyl phosphite; N, N-diallyl acrylamide; Six allyl group phosphamides; N, N, N ', N '-tetraalkyl tetraphthalamide; N, N, N ', N '-tetraallyl Malonamide; Isocyanuric acid triethylene ester; 2,4,6-trivinyl methyl trisiloxanes; With three (5-norbornylene-2-methylene radical) cyanurate.Useful especially is triallyl isocyanurate.
Other useful coagent is included in the alkadiene that discloses among EPA 0 661 304 A1, EPA 0 784 064 A1 and EPA 0 769521 A1.
General additive such as carbon black, stablizer, softening agent, lubricant, filler and the processing aid that uses in Perfluoroelastomer is mixing can be added in the composition of the present invention, and needing only them has suitable stability to the condition of required application.Especially can improve low-temperature performance (referring to United States Patent (USP) 5,268,405) by adding PFPE.
Carbon black filler can be used in the elastomerics means as a kind of modulus, tensile strength, elongation, hardness, wear resistance, specific conductivity and processibility of balanced combination thing.Suitable example comprises that the trade mark is the MT carbon black (MT medium thermal black) of N-991, N-990, N-908 and N-907 and the furnace treated black of volume particle size.When using this volume particle size carbon black, its amount is just enough usually during for 1-70phr.
In addition, in composition, also can there be fluoropolymer fillers.In general, per 100 parts of Perfluoroelastomers, the consumption of fluoropolymer fillers is 1-50 part.Fluoropolymer fillers can be trickle, be easy to dispersive plastics fluoropolymer, it is a solid under the used top temperature of preparation and sulfuration perfluoroelastomer composition.Solid means the crystalline melting temperature that fluoro-containing plastic (if words of partial crystallization) has the processing temperature that is higher than Perfluoroelastomer.This trickle, be easy to the dispersive fluoro-containing plastic and be commonly referred to fine powder or fluorochemical additive.Fine powder is the polymkeric substance of partial crystallization normally.
Method of the present invention is included in and uses perfluor-sulfinate and oxygenant in the radical polymerization process.Polymerization process comprises that each monomer carries out radical polymerization separately or with the form of the solution in organic solvent or water, emulsion or dispersion.Because fast and conversion of monomer almost completely, be easy to remove heat of polymerization and separate easily polymkeric substance, so polymerization is normally preferably in water-based emulsion or suspension.Emulsion or suspension polymerization generally comprise in the presence of inorganic free radical initiator system and tensio-active agent or suspension agent polymerization single polymerization monomer in aqueous medium.
Aqueous emulsion polymerization can carry out under the condition of stable state continuously, for example under the pressure and temperature condition of the best, monomer, water, tensio-active agent, buffer reagent and catalyzer are sent in the stirred reactor continuously, discharged the emulsion or the suspension of gained simultaneously continuously.Another kind method is in batches or semi-batch polymerization, it is that each component is sent in the stirred reactor, makes them react specific time under the temperature of setting, and perhaps each component is added in the reactor, again monomer is added in the reactor, to keep constant compression force up to the polymkeric substance that forms aequum.
A kind of useful fluorine-containing aliphatic sulfinic acid salt of the present invention is disclosed in United States Patent (USP) 5,285, and in 002, with reference to quoting, can represent with following general formula by this-sulfinate at this for the content of this patent:
R
3 fSO
2M
1/x (VI)
Or
R
2 f[SO
2M
1/x]
n (VII)
R wherein
3 fRepresentative contains as 1-20 carbon atom, better contains the fluorine-containing aliphatic group of monovalence of 4-10 carbon atom, R
2 fRepresentative contains as 1-20 carbon atom, better contains the multivalence of 2-10 carbon atom, better is the fluorine-containing aliphatic group of divalence, and it is the positively charged ion of x that M represents hydrogen or valency, and described x is 1-2, is preferably 1, and n is 1-4, is preferably 1 or 2.
The fluorine-containing aliphatic group R of monovalence
3 fBe fluoridize, stablize, inertia, nonpolar saturated part.It can be straight chain, side chain, and it is if enough greatly, then can be ring-type or its combination, as the alkyl cycloaliphatic groups.In general, R
3 fComprise 1-20 carbon atom, better contain 4-10 carbon atom, and it comprises 40-83 weight %, be preferably the fluorine of 50-78 weight %.Compound is those wherein R preferably
3 fGroup is fluorizated compound, R wherein in this case fully all or basically
3 fBe perfluoroalkyl, i.e. C
nF
2n+1, wherein n is 1-20.
Multivalence better is the fluorine-containing aliphatic group R of divalence
2 fBe fluoridize, stablize, inertia, nonpolar saturated part.It can be straight chain, side chain, and it is if enough greatly, then can be ring-type or its combination, as alkyl cyclic aliphatic two groups.In general, R
2 fComprise 1-20 carbon atom, better contain 2-10 carbon atom.Compound is those wherein R preferably
2 fGroup is a perfluorinated alkylidene, i.e. C
nF
2n(wherein n is 1-20), or perfluor cycloalkyl, i.e. C
nF
2nThe compound of (wherein n is 5-20).
About R
3 fOr R
2 f, can insert divalence oxygen, sexavalence sulphur or trivalent nitrogen heteroatoms in the skeletal chain of carbon atom, each heteroatoms only is connected on the carbon atom, but better is when having this heteroatoms, does not contain the described heteroatoms more than in this skeletal chain on per two carbon atoms.Hydrogen atom, iodine atom, bromine atoms or the chlorine atom on the carbon of being connected that can have a chance; Yet, when there being these atomic time, their suitable no more than one of amounts on per two carbon atoms in chain.Work as R
3 fOr R
2 fBe or when comprising ring texture, this structure better comprises 6 yuan of annular atomses that wherein 1 or 2 atoms can be described heteroatomss, as oxygen and/or nitrogen-atoms.R
3 fThe example of group is a fluorinated alkyl, as C
4F
9--, C
6F
13--, C
8F
17--, alkoxyalkyl such as C
3F
7OCF
2--.R
2 fExample be to fluoridize alkylidene group, as--C
4F
8--,--C
8F
16--.When indicating R
3 fBe specific group such as C
8F
17--the time, what should understand is that this group can be represented such as C
6F
13--to C
10F
21--the average structure of mixed group, described mixed group also can comprise branched structure.
The useful representative fluorine-containing aliphatic sulfinic acid salt compound of the inventive method comprises following each material:
CF
3SO
2Na
C
4F
9SO
2H
C
8F
17SO
2Na
CF
3C(Cl)
2CF
2SO
2K
Cl(CF
2)
8OC
2F
4SO
2Na
Cl (CF
2)
xCF
2SO
2Na, wherein x is 0,1,3,4,7,9
NaO
2SC
8F
16SO
2Na
NaO
2SC
6F
12SO
2Na
NaO
2SC
2F
4OC
2F
4SO
2Na
NaO
2SC
2F
4OC
2F4X, wherein X is Br or I
NaO
2S[C
4F
8O]
nC
3F
6SO
2Na
NaO
2SCF
2O(CF
2CF
2O)
m(CF
2O)
nCF
2SO
2Na
(CF
3)
2NCF
2CF
2SO
2Na
(C
2F
5)
2NCF
2CF
2SO
2Na
N(C
2F
4SO
2Na)
3
NaO
2SC
8F
16SO
2F
NaO
2SC
3F
6O (C
4F
8O)
nC
3F
6SO
2Na, wherein n is 4 to 8.
Whether need use-sulfinate as initiator, monomer or not only as initiator but also as monomer, can use the mixture of a-sulfinate, two-sulfinates and three-sulfinates if looking.When the-sulfinate that uses multivalence-sulfinate such as those to be represented by formula VII,-sulfinate is a monomer, and will fluoridize part and be added on the main polymer chain.When using a-sulfinate, add and fluoridize part as polymer terminal group.
The amount of the fluorine-containing aliphatic sulfinic acid salt that the inventive method is used for example can be looked the molecular weight of required polymkeric substance and be become.The amount of fluorine-containing aliphatic sulfinic acid salt better is in monomer total amount 0.01-50 mole %, preferably the-sulfinate compound of 0.05-10 mole %.
Except-sulfinate, can there be other reductive agent, as the sodium salt in sulphite, hydrosulphite, metabisulphite, hyposulfite, thiosulfite, the phosphite, sylvite or ammonium salt, formaldehyde closes sodium salt or the sylvite in sulfoxylic acid hydrogen salt or the hypophosphite.Also can there be activator such as ferrous salt, cuprous salt and silver salt.
The used oxygenant of the inventive method is water miscible, and it can be transformed into-sulfinate the alkylsulfonyl part.Be sure of that the alkylsulfonyl that the inventive method makes can eliminate SO
2, and form and can cause ethylenically unsaturated monomer and carry out the polymeric fluorinated groups.
Many useful oxygenants are known, and they are at United States Patent (USP) 5,285, disclose in 002.The representative example of this useful oxygenant is persulfuric acid, peroxophosphoric acid, peroxyboric acid, percarbonic acid, bromic acid, chloric acid and hypochlorous sodium salt, sylvite and ammonium salt.Other useful oxygenant comprises cerium (IV) compound, as (NH
4)
2Ce (NO
3)
6What should understand is that these oxygenant table look-ups only are usefulness for example.Those of ordinary skill in the art will understand that the present invention also has other useful oxygenant based on foregoing.
Visual used concrete oxygenant of the consumption of oxygenant and-sulfinate and become.General use equimolar amount or still less (amount in-sulfinate is benchmark).
Vulcanisable compound of the present invention can make by Perfluoroelastomer, peroxide vulcanizing agent and other additive are mixed in conventional rubber tooling.This equipment comprises rubber mixing mill, Banbury mixer such as Banbury mixer and mixes forcing machine.
Before the present invention, people are difficult to prepare the composition that contains Perfluoroelastomer.In general, this composition need use the processing units of heating, prevents that composition from forming frangible material.Perfluoroelastomer sizing material of the present invention does not need to use the roller or the processing units of heating in mixing process.They can prepare at ambient temperature, and can not form frangible material.Basically not having reactive terminal group on Perfluoroelastomer is the partly cause that causes this situation at least.Basically do not exist these groups can reduce reactive problem to greatest extent, obviously improve as heat release or the viscosity that in the process that adds acid acceptor, is taken place.Compound viscosity can not improve the problem that can prevent mobile and loading mould cavity.Mixing at a lower temperature ability makes and begins too early to vulcanize or the problem of crosslinking reaction is reduced to minimum.
Vulcanisable compound of the present invention can be used for making the goods such as packing ring, flexible pipe and sealing.This goods make through following method, carry out molding adding the batching prescription of depressing vulcanisable compound and various additives, vulcanize this parts, then it are carried out the postcure circulation.In the process of molding step, Perfluoroelastomer of the present invention also demonstrates other advantage.Very fast or the required pressure of mold filling is lower, shows that viscosity is less.When removing moulded parts (press cured part) from mould or when articles injection-moulded, seeing that obviously the demoulding improves.Vulcanising composition has good thermostability and chemical resistant properties.They are particularly useful for following purposes, for example make sealing and the packing ring that semiconductor devices uses and are used for the sealing that high temperature automotive is used.
Following embodiment will further specify the present invention.In these embodiments, test performance as follows.
Measure mooney viscosity with ASTM D 1646-96 (ML 1+10 121 ℃ the time).The result is with the mooney unit record.
Press ASTM D 5289-95 in the time of 177 ℃, not preheating, process time is that use Monsanto Moving Die Rheometer (MDR) model is that 2000 pairs of mixing mixtures vulcanize rheometric test under 12 minutes (except as otherwise noted outer) and the 0.5 ° of radian.Measure minimal torque (ML), peak torque (MH) value, i.e. the highest moment of torsion that does not have flat-top or reach in the peaked time of regulation.Also record: t
S2 (moment of torsion is brought up to the time that is higher than 2 units of ML), t ' 50 (moment of torsion reaches ML+0.5[MH-ML] time) and t ' 90 (moment of torsion reaches ML+0.9[MH-ML] time).Moment of torsion is represented with a minute Newton meter (dNm).
Come the mold pressing sample (the outer except as otherwise noted sheet that is 150 * 150 * 2.0mm) of formation determination physicals with about 6.9 megapascal (MPa)s (MPA) specified time of compacting and temperature.
The mold pressing sample is placed on prepares the postcure sample in the circulated air oven.Make baking oven remain on specified temperature, to the specified time of sample preparation.
Write down power on the per unit area with megapascal (MPa) (MPa).
Measure physicals by ASTM D-412, measure hardness by ASTM D2240.
Press with the O shape circle of 0.139 inch (3.5 millimeters) 200 ℃ the time by ASTM D 395-89 method B and to measure compression set in 70 hours.The result represents with %.
Embodiment 1
Except used monomer and other component are gram is expressed as follows with weight, all the other are all by United States Patent (USP) 5,285, and embodiment 1 similar mode prepares some fluoropolymers in 002.Used monomer is tetrafluoroethylene (TFE), perfluoro methyl vinyl ether (PMVE) and bromotrifluoethylene (BTFE).With (NH
4)
2S
2O
8Be designated as APS.Press United States Patent (USP) 5,285, the method described in 002 prepares fluorochemical-sulfinate (C
4F
9SO
2Na).
Comparative polymer A polymer A
Deionization (DI) water 2,777 2,774
C
7F
15COONH
4： 15.9 15.9
K
2HPO
4： 10 10
C
4F
9SO
2Na： ---- 4
The pre-monomer that adds:
TFE： 142 140
PMVE： 342 331
BTFE： 3.9 3
The APS:2 3 that injects
The monomer of sending in reaction times
TFE： 662 664
PMVE： 496 497
BTFE： 9.7 9.9
For comparative polymer A, polymerization is 651 minutes in the time of 60 ℃, and for polymer A, polymerization is 262 minutes in the time of 71 ℃.Two kinds of polymerizations are to carry out under 16 crust at pressure all.
All obtain the transparent polymer latex of clarification of water in both cases.The 30 gram Als of use in 1000 milliliters of DI water
2(SO
4)
318H
2O condenses latex.Filter polymkeric substance,, spend the night, obtain polymer latex at 100 ℃ circulated air oven inner dryings with hot DI water washing several times.
The mooney viscosity of comparative polymer A (ML 1+10 in the time of 121 ℃) is 76, and polymer A is 96.
Mixing each polymer latex of 100 weight parts, its way are to add 15 weight parts (phr) N990 carbon black, 5phr zinc oxide, the 1.5phr Luperco available from Atochem in each polymer latex
TM101 XL organo-peroxides and 2phr are available from isocyanic acid triallyl-dry liquids concentrate (TAIC-DLC of Harwick; 72% activity).
Polymer A is carried out mixing in mill in a usual manner.Comparative polymer A must carry out mixing in (50-70 ℃) mill of heating because if in a usual manner (condition of promptly using standard or not heating) mixing words it can become fragile and powder.
Table 1 has been listed the rheological data that obtain from the MDR test.
Table 1
MDR (177 ℃) contrast sizing material A sizing material A
ML(dNm)： 5.1 3.0
MH(dNm)： 26 20
t
S2 (minute): 0.44 0.48
T ' 50 (minute): 0.65 0.68
T ' 90 (minute): 1.51 1.76
From the MDR data as can be seen, A compares with sizing material, and the ML (a kind of tolerance of compound viscosity) of contrast sizing material A obviously improves, even the mooney viscosity of comparative polymer A is lower than the polymer A.In other words, even the stock polymer viscosity ratio polymer A of comparative polymer A is low, adds filler, acid acceptor and vulcanizing agent and also make the compound viscosity of contrast sizing material A bring up to the compound viscosity that is higher than sizing material A.
Behind the rubber vulcanization, obtain the listed data of table 2.Vulcanizing press sulfuration contrast sizing material A is 10 minutes in the time of 150 ℃, postcure 16 hours in the time of 150 ℃ subsequently, further postcure 8 hours in the time of 200 ℃ again.Vulcanizing press vulcanized rubber A is 10 minutes in the time of 177 ℃, postcure 20 hours in the time of 200 ℃ subsequently.Attempt to vulcanize and postcure contrast sizing material A, but this trial fail by the identical mode of sizing material A because in test sample generation warpage and form crackle.
Table 2
Contrast sizing material A sizing material A
Tensile strength (MPa) 24.5 19.6
Extension at break (%) 165 136
100% modulus (MPa) 14.1 12.7
Hardness (Shore A) 87 80
Compression set O shape circle, in the time of 200 ℃ 70 hours 42% 30%
The incompressible set of sizing material A is significantly better than the incompressible set of contrast sizing material A.Contrast sizing material A also needs mixing, lower vulcanizing press curing temperature of hot-rolling and two step postcure.
Embodiment 2
Prepare these samples, be used for illustrating when the reactivity of polymkeric substance when mixing with alkali or acid acceptor.
Except not using BTFE, and use 4 gram APS and 5.4 gram C
4F
9SO
2Na and 11.6 the crust pressure under carry out outside the polymerization, all the other all prepare polymer B by the similar mode of polymer A.
Except not using-sulfinate, only use 1 the gram APS and 11.0 the crust pressure under carry out outside the polymerization, all the other all prepare comparative polymer B by the similar mode of polymer B.
The mooney viscosity of polymer B (ML 1+10 in the time of 121 ℃) is 38, and comparative polymer B is 73.
Ca (OH) 2 of the MT N990 carbon black of comparative polymer B and 15phr and 6phr is mixing.In mixing process, each component is mixed the beginning heat release, and forms easily crisp sizing material.When MDR tested the control compounds B of gained, the moment of torsion of easy crisp sizing material was brought up to 17dNm from the 3.4dNm of beginning in 30 seconds, and continues to be elevated to 20dNm in 10 minutes when at 177 ℃.
It is mixing that polymer B uses the additive identical with contrasting sizing material B to carry out.Each component is blended in and remains the viscosity sheet in the mill, and it raises less than 1.1dNm at 8 minutes internal torques on 177 ℃ MDR.
These results show that the reactivity of sizing material of the present invention when adding basic component such as acid acceptor is obviously lower.Even it is also apparent when there is not the sulfide site component in this species diversity in sizing material.
Claims (8)
1. the Perfluoroelastomer sizing material of a peroxide curable that is easy to process, it comprises:
A) be substantially free of the Perfluoroelastomer of ionizable end group, described Perfluoroelastomer comprise derive from following 1), 2) and 3) copolymerization units, 1) perfluoroolefine, 2) be selected from perfluor (alkyl vinyl) ether, the perfluoroalkyl vinyl ether of perfluor (alkoxy vinyl) ether and their mixtures, with 3) can participate in the sulfide site component of the halogen-containing group of peroxide cure reaction, described halogen is iodine or bromine, described sulfide site component is selected from the fluorinated olefin that contains at least one this halogen group, the fluorinated vinyl ether that contains at least one this halogen group, contain the chain-transfer agent of at least one this halogen group and contain the initiator of at least one this halogen group and their mixture; Condition be the sulfide site component be substantially free of itrile group and
B) peroxide vulcanizing agent.
2. the Perfluoroelastomer sizing material of peroxide curable as claimed in claim 1, wherein perfluoroalkyl vinyl ether is selected from perfluoro methyl vinyl ether, perfluoroethylvinyl ether and perfluoro propyl vinyl ether.
3. the Perfluoroelastomer sizing material of peroxide curable as claimed in claim 1, wherein Perfluoroelastomer is substantially free of ionizable end group, and described end group is selected from carboxylate salt or carboxylic end group and sulfonate or sulfonic acid end group.
4. the Perfluoroelastomer sizing material of peroxide curable as claimed in claim 1, wherein said Perfluoroelastomer prepares through following method, and water-based emulsion or suspension that described method is included in the polymerizable mixture that will comprise following component under the condition of free radical carry out polymerization: perfluoroolefine and perfluoroalkyl vinyl ether or perfluorinated alkoxy vinyl ether and composition thereof; Can participate in the halogen-containing sulfide site component of peroxide cure reaction, described halogen is iodine or bromine; The-sulfinate of fluorine-containing aliphatic group and the oxygenant that described-sulfinate can be oxidized to alkylsulfonyl, condition is that the sulfide site component is substantially free of itrile group.
5. molded article, it comprises the Perfluoroelastomer sizing material of peroxide curable as claimed in claim 1.
6. the Perfluoroelastomer sizing material of peroxide curable as claimed in claim 1, wherein perfluoroolefine is a tetrafluoroethylene, perfluoroalkyl vinyl ether is a perfluoro methyl vinyl ether.
7. the Perfluoroelastomer sizing material of peroxide curable as claimed in claim 1, wherein the sulfide site component is described chain-transfer agent.
8. the Perfluoroelastomer sizing material of peroxide curable as claimed in claim 1, wherein the sulfide site component is described initiator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7906198P | 1998-03-23 | 1998-03-23 | |
| US60/079,061 | 1998-03-23 |
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| Publication Number | Publication Date |
|---|---|
| CN1294601A CN1294601A (en) | 2001-05-09 |
| CN100441605C true CN100441605C (en) | 2008-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998043354A Expired - Fee Related CN100441605C (en) | 1998-03-23 | 1999-02-18 | Perfluoroelastomer compsns. |
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| Country | Link |
|---|---|
| EP (1) | EP1068248A1 (en) |
| JP (1) | JP2002507640A (en) |
| KR (1) | KR100612706B1 (en) |
| CN (1) | CN100441605C (en) |
| BR (1) | BR9908975A (en) |
| CA (1) | CA2324954A1 (en) |
| WO (1) | WO1999048939A1 (en) |
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| US6465576B1 (en) | 1999-07-02 | 2002-10-15 | Dyneon Llc | Fluoroelastomer compositions and articles made therefrom |
| US6255536B1 (en) † | 1999-12-22 | 2001-07-03 | Dyneon Llc | Fluorine containing vinyl ethers |
| US6720360B1 (en) | 2000-02-01 | 2004-04-13 | 3M Innovative Properties Company | Ultra-clean fluoropolymers |
| US6593416B2 (en) | 2000-02-01 | 2003-07-15 | 3M Innovative Properties Company | Fluoropolymers |
| IT1318488B1 (en) * | 2000-04-21 | 2003-08-25 | Ausimont Spa | FLUOROVINYLETERS AND POLYMERS THAT CAN BE OBTAINED. |
| IT1318487B1 (en) * | 2000-04-21 | 2003-08-25 | Ausimont Spa | FLUORO-ELASTOMERS. |
| US7067564B2 (en) | 2000-11-22 | 2006-06-27 | Dsm Ip Assets B.V. | Coated optical fibers |
| US6916855B2 (en) | 2000-11-22 | 2005-07-12 | Dsm Ip Assets B.V. | Radiation curable compositions |
| US7706659B2 (en) | 2000-11-22 | 2010-04-27 | Dsm Ip Assets B.V. | Coated optical fibers |
| US6890995B2 (en) | 2001-01-31 | 2005-05-10 | 3M Innovative Properties Company | Fluoropolymer compositions |
| US6730760B2 (en) | 2001-01-31 | 2004-05-04 | 3M Innovative Properties Company | Perfluoroelastomers having a low glass transition temperature and method of making them |
| US6803425B2 (en) | 2001-04-12 | 2004-10-12 | 3M Innovative Properties Company | Fluoropolymers having pendant imidate structures |
| US6844388B2 (en) | 2001-04-12 | 2005-01-18 | 3M Innovative Properties Company | Fluoropolymer compositions containing a nitrogen cure site monomer |
| US6794457B2 (en) | 2001-04-30 | 2004-09-21 | 3M Innovative Properties Company | Fluoropolymer curing system containing a nitrogen cure site monomer |
| US6916887B2 (en) * | 2002-05-02 | 2005-07-12 | Dupont Dow Elastomers Llc | Curable base-resistant fluoroelastomers |
| US6803435B2 (en) | 2002-07-18 | 2004-10-12 | 3M Innovative Properties Company | Curable fluoropolymers containing bromine groups having improved compression set |
| CN100354323C (en) * | 2002-09-12 | 2007-12-12 | 3M创新有限公司 | Fluoroelastomers with improved permeation resistance and method for making the same |
| US6846880B2 (en) | 2002-10-11 | 2005-01-25 | 3M Innovative Properties Company | Fluoropolymer compositions |
| US6734254B1 (en) | 2003-01-13 | 2004-05-11 | 3M Innovative Properties Company | Co-curable blends featuring bromine-and iodine-containing fluoroplastic polymers |
| US6956085B2 (en) | 2003-02-14 | 2005-10-18 | 3M Innovative Properties Company | Fluoroelastomer compositions |
| ITMI20041573A1 (en) | 2004-07-30 | 2006-01-31 | Solvay Solexis Spa | FLUORO-ELASTOMERS |
| ITMI20041571A1 (en) | 2004-07-30 | 2004-10-30 | Solvay Solexis Spa | perfluoroelastomers |
| EP1630179B1 (en) | 2004-08-25 | 2007-10-31 | Asahi Glass Company Ltd. | Fluorocopolymer |
| US7402630B2 (en) | 2004-12-16 | 2008-07-22 | 3M Innovative Properties Company | Curing compositions for fluoropolymers |
| JP2012505948A (en) | 2008-10-22 | 2012-03-08 | ダイキン工業株式会社 | Perfluoroelastomer composition |
| WO2010076876A1 (en) | 2008-12-29 | 2010-07-08 | Daikin Industries, Ltd. | Perfluoroelastomer composition and crosslinked molded article made by crosslinking and molding said perfluoroelastomer composition |
| EP2445939B1 (en) | 2009-06-25 | 2020-09-23 | 3M Innovative Properties Company | Curing compositions for fluoropolymers |
| JP5986102B2 (en) | 2010-12-17 | 2016-09-06 | スリーエム イノベイティブ プロパティズ カンパニー | Microemulsions and fluoropolymers made using microemulsions |
| CN103582627B (en) * | 2011-06-03 | 2016-08-31 | 3M创新有限公司 | The fluoro-alkyl sulfinic acid of allyl ether end-blocking and salt thereof |
| CN103833874B (en) * | 2014-03-07 | 2016-08-17 | 中昊晨光化工研究院有限公司 | A kind of fluorubber and synthetic method thereof |
| CN114621383B (en) * | 2020-12-14 | 2023-12-12 | 中昊晨光化工研究院有限公司 | Perfluoroether elastomer emulsion, preparation method and perfluoroether elastomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4035565A (en) * | 1975-03-27 | 1977-07-12 | E. I. Du Pont De Nemours And Company | Fluoropolymer containing a small amount of bromine-containing olefin units |
| CN1119870A (en) * | 1993-03-23 | 1996-04-03 | 明尼苏达矿产制造公司 | Fluorine-containing polymers and preparation and use thereof |
| US5639837A (en) * | 1996-06-04 | 1997-06-17 | E. I. Du Pont De Nemours And Company | Process for making fluoropolymers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69610099T2 (en) * | 1995-06-30 | 2001-05-10 | Du Pont | METHOD FOR PRODUCING FLUOR-CONTAINING POLYMERS |
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1999
- 1999-02-18 JP JP2000537917A patent/JP2002507640A/en active Pending
- 1999-02-18 WO PCT/US1999/003490 patent/WO1999048939A1/en not_active Application Discontinuation
- 1999-02-18 BR BR9908975-0A patent/BR9908975A/en not_active Application Discontinuation
- 1999-02-18 CN CNB998043354A patent/CN100441605C/en not_active Expired - Fee Related
- 1999-02-18 EP EP99908238A patent/EP1068248A1/en not_active Withdrawn
- 1999-02-18 KR KR1020007010508A patent/KR100612706B1/en not_active IP Right Cessation
- 1999-02-18 CA CA002324954A patent/CA2324954A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4035565A (en) * | 1975-03-27 | 1977-07-12 | E. I. Du Pont De Nemours And Company | Fluoropolymer containing a small amount of bromine-containing olefin units |
| CN1119870A (en) * | 1993-03-23 | 1996-04-03 | 明尼苏达矿产制造公司 | Fluorine-containing polymers and preparation and use thereof |
| US5639837A (en) * | 1996-06-04 | 1997-06-17 | E. I. Du Pont De Nemours And Company | Process for making fluoropolymers |
Also Published As
| Publication number | Publication date |
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| JP2002507640A (en) | 2002-03-12 |
| CA2324954A1 (en) | 1999-09-30 |
| WO1999048939A1 (en) | 1999-09-30 |
| KR100612706B1 (en) | 2006-08-16 |
| BR9908975A (en) | 2000-12-05 |
| EP1068248A1 (en) | 2001-01-17 |
| CN1294601A (en) | 2001-05-09 |
| KR20010034623A (en) | 2001-04-25 |
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