CN1336938A - Fluoropolymers containing organo-silanes and methods of making the same - Google Patents
Fluoropolymers containing organo-silanes and methods of making the same Download PDFInfo
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- CN1336938A CN1336938A CN00802612A CN00802612A CN1336938A CN 1336938 A CN1336938 A CN 1336938A CN 00802612 A CN00802612 A CN 00802612A CN 00802612 A CN00802612 A CN 00802612A CN 1336938 A CN1336938 A CN 1336938A
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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Abstract
A fluoropolymer is described which is a polymer reaction product of a fluoropolymer comprising a polymer reaction product of: a) at least one first alkylene co-monomer containing at least one fluorine atom; b) optionally at least one monomer selected from: 1) at least one second alkylene containing at least one fluorine atom; 2) at least one alkyl alkenyl ether containing at least one fluorine atom; 3) at least one aliphatic or cyclic ketone containing at least one fluorinated alpha-alpha position; or 4) non-fluorinated alkene, alkyl alkenyl ether, or alkenyl ester; and c) at least one sterically hindered alkenyl or alkenyl ether organo silane co-monomer with or without at least one fluorine substituent. The fluoropolymer can be subsequently cross-linked or further reacted. Methods of making the fluoropolymer are further disclosed as well as applications of the fluoropolymers.
Description
The background of invention
The present invention relates to the purposes of fluoropolymer and these fluoropolymers.More particularly, the present invention relates to comprise the fluoropolymer of organic silane functional.The invention still further relates to the method for preparing fluoropolymer.
For various reasons, once do various trials and prepared fluoropolymer.Fluoropolymer need to be used to the application of property traditionally, described property such as low surface energy, high chemical resistance, low dielectric loss or to the extreme requirement of ageing resistance.Yet these particular performances itself are exactly problem in the process of using fluoropolymer sometimes.For example, lack the binding property that can promote to base material, be convenient to the position crosslinked, that chemical modification subsequently is provided, application that the functional group that introduces ion-exchange capacity or ionic conductivity has seriously limited conventional fluoropolymer.Like this, have the modification performance in searching all the time, for example contain the fluorinated polymer of the reactive functional groups that can be modified.Yet just known to the inventor, the fluoropolymer with reactive complete organosilane part still prepares in aqueous medium.
For example, Buning etc. [chemical abstracts 72:101262 and Die Ang.Mak.Chemie13 (1970) pp.89-96] has described (foundation english abstract) at dilauroyl peroxide or Bz
2O
2Exist down vinyl (three tert.-butoxies) silane and vinylchlorid or vinylbenzene are carried out copolymerization in emulsion or suspension, obtain uncrosslinked multipolymer.This summary has also illustrated when replacing vinyl (three tert.-butoxies) silane with vinyl (trimethoxy) silane, has obtained to contain soluble, the crosslinked copolymers of poly-(vinylchlorid).In this english abstract, do not address fluoropolymer, not in the suspension polymerization process, using the pH control agent to make any explanation yet.
Piotrowski etc. [chemical abstracts 102:167808] have described in the presence of superoxide with alkenyl organoalkoxysilane grafted CH
2: CF
2Polymkeric substance, acquisition can be by silanol condensation catalyst and the crosslinked resin of moisture.Do not address aqueous medium used in reaction and in the presence of peroxide initiator, be grafted to the specific hydrolyzable organosilane part of not being obstructed in the fusion poly-(vinylidene fluoride).
European patent application No.0736583 has related generally to the aqueous dispersion of fluoropolymer, and it carries out silicoorganic compound in fluoropolymer dispersive waterborne compositions the back is mixed to get.Addressed the copolymerization that comprises organosilane, but it is as midbody product.Like this, by this public publication, after fluoropolymer dispersions is made in polymerization, silicoorganic compound are mixed with fluoropolymer dispersions.
In addition, the United States Patent (USP) 5,621,038 of Chen etc. has disclosed curable composition, and it comprises the organo-metallic catalyst and the water of hydrolysis-stable of curable polymer, water-dispersion or the water soluble of the water-dispersion that contains sterically hindered alkoxylate silane group.Chen etc. have illustrated that these compositions can be used as tackiness agent, sealing agent and paint.Chen etc. have pointed out that also said composition has improved performance, comprises solvent resistance, binding property, hardness, wear resistance and scuff resistance.Chen etc. do not address the organo-metallic catalyst that uses fluoropolymer and require to exist hydrolysis-stable.The United States Patent (USP) 5,686,523 of Chen etc. similarly but does not need the organo-metallic catalyst of hydrolysis-stable.
Before had fluoropolymer such as useful performances such as chemical resistant properties, high-temperature stability, high tensile and/or low-refractions and had the shortcoming that such as the back crosslinked or back chemical modification etc. can't be carried out with post-modification, may damage these useful performances because do like this.Therefore, need to obtain such fluoropolymer, it can carry out crosslinked and/or chemical modification well, and can not influence the general useful performance relevant with fluoropolymer basically.
The general introduction of invention
But a feature of the present invention provides crosslinkable and/or chemical modification and can not influence general relevant with the fluoropolymer useful performance such as the fluoropolymer of chemical resistant properties, high-temperature stability, high tensile and/or low-refraction basically.
Another feature of the present invention provides the fluoropolymer that can be chemically bonded on the various base materials.
Another feature of the present invention provides the fluoropolymer that can functionalised.
Another feature of the present invention provides the method for these fluoropolymers of preparation.
Supplementary features of the present invention and advantage part will be illustrated in following description, and part will clearly from describe be found out, or can be learnt from the practice of the present invention.Feature of the present invention and other advantage will be understood and received by the content that this paper illustrates, and described content comprises the combination of each main points of especially pointing out in written description and appended claims.
In order to reach these and other advantage and according to purpose of the present invention, embody and roughly description as this paper, the present invention relates to a kind of fluoropolymer that comprises following polymeric reaction products a)-c), a) at least a first alkene (alkylene) comonomer that contains at least one fluorine atom; B) randomly at least aly be selected from 1) at least a second alkene that contains at least one fluorine atom, 2) at least a alkyl chain alkene ether that contains at least one fluorine atom, 3) at least aly contain aliphatic series or the cyclic ketone that at least one fluoridizes α-α position, or 4) monomer of nonfluorinated alkene, alkyl chain alkene ether or alkenyl ester; And c) at least a sterically hindered alkenyl or the alkenyl ether organosilane comonomer that contains or do not contain at least one fluoro substituents.
The invention still further relates to the above-mentioned fluoropolymer that can be crosslinked and/or contain one or more functional groups.
The present invention also relates to prepare the method for above-mentioned polymkeric substance, it is to adopt the radical polymerization technique that oneself knows in the prior art, as suspension polymerization, letex polymerization, interfacial polymerization, solution polymerization or non-aqueous polymerization system, wherein one or more liquid or supercritical co, liquid or overcritical SF6, liquid or postcritical contain 1 to about 6 carbon atoms fluoridize or perfluorinated hydrocarbon can be used as polymerisation medium.
The invention still further relates to the method for the above-mentioned fluoropolymer of preparation, it is included under enough pressure and temperatures above-mentioned each comonomer polymerization time enough, makes fluoropolymer.Polymerization better is radical polymerization, is more preferably letex polymerization.
In addition, the invention still further relates to fluoropolymer, described application include, but are not limited to foam crosslinked fluoropolymer, fluoroelastomer, tackiness agent, coating etc. in various Application for Field.Fluoropolymer of the present invention also can be used as membrane component and other application.
What should understand is that top summary description and following detailed only is to enumerate with illustrative, and is used for desired the present invention is described further.
Detailed description of the present invention is described
The present invention relates to contain the fluoropolymer of one or more organosilane functionality or functional group.Organosilane functionality or part better are at least one space steric hindrance groups.Space steric hindrance group on the organosilane part can prevent that better the silane group of copolymerization from hydrolyzing taking place too early.At least one organosilane partly is kept perfectly when polymerization is finished, and then is present in the fluoropolymer, thereby just can obtain the former additional properties that can't obtain with fluoropolymer of the present invention.In addition, complete organosilane part can be reactive, can carry out chemical modification to it like this when the performance of application-specific is satisfied in the needs acquisition, and can not lose the outstanding properties relevant with fluoropolymer usually.
Fluoropolymer better is a kind of following polymeric reaction products a)-c), a) at least a first olefin comonomer that contains at least one fluorine atom; B) randomly at least aly be selected from 1) at least a second alkene that contains at least one fluorine atom, this second alkene is if the words that exist are different from first olefin comonomer, 2) at least a alkyl chain alkene ether that contains at least one fluorine atom, 3) at least aly contain aliphatic series or the cyclic ketone that at least one fluoridizes α-α position, or 4) comonomer of nonfluorinated alkene, alkyl chain alkene ether or alkenyl ester; And c) at least a sterically hindered alkenyl or the alkenyl ether organosilane comonomer that contains or do not contain at least one fluoro substituents.
About above-mentioned fluoropolymer, look the desired properties of fluoropolymer, the olefin comonomer that contains at least one fluorine atom can be any amount.The amount of at least a olefin comonomer better is about 50-99.9 mole %, better is about 80-99.9 mole %, preferably is about 90-95.5 mole %.Olefin comonomer better is an ethylene comonomer, well contains 1-4 fluorine atom approximately.Those keys between two carbon atoms that occupied by fluorine better do not have hydrogen or chlorine or both and have.The example of ethylene fluoride includes, but are not limited to vinylidene fluoride (VF
2), tetrafluoroethylene (TFE), trifluoro-ethylene, trifluorochloroethylene (CTFE) and vinyl fluoride.These ethylene fluorides can be separately or are mixed use mutually.These comonomers can be purchased certainly such as ATOFINA Chemicals and DuPont.The ethylene comonomer that comprises at least one fluorine atom is VF2, CTFE and TFE preferably.Mole % used herein is meant the whole monomeric percentage ratio of existence.
About second comonomer of any existence, this comonomer can be any amount when existing, and this amount better is about 0.1-50 mole %, better is about 0.1-40 mole %, preferably is about 0.1-30 mole %.Second comonomer better is the propylene that contains 1-6 fluorine atom approximately; The alkyl vinyl ether that contains at least one fluorine atom; The aliphatic series of fluorinated α-α position or ring-type C
3-C
6Ketone; Or fluorizated C not
2-C
4Alkene, alkyl vinyl ether or vinyl ester.
The example that contains the alkene of at least one fluorine atom includes, but are not limited to R 1216 (HFP), perfluoroisobutylene etc.The example that contains the alkyl chain alkene ether of at least one fluorine atom includes, but are not limited to perfluorovinyl sulfide methyl ether (PVME).Other example comprises the line style that contains at least one fluorine atom or the C of side chain
3-8Alkene, R 1216,2-hydrogen five fluorine propylene, 3,3,3-trifluoro propene, list or polyfluorizated butane (as hexafluoro-isobutene), pentane, hexene or octane.Except at least one fluorine atom, these comonomers can also comprise the chlorine atom.The comonomer of these types better is the C that contains at least one fluorine atom
3-6Alkene is more preferably the C that contains at least one fluorine atom
3-4Alkene.
Other example of optional comonomer comprises the alkyl vinyl ether that contains at least one fluorine atom, as perfluoro propyl perfluoroalkyl vinyl ether, perfluoro-methyl perfluoroalkyl vinyl ether, perfluoro propyl vinyl ether, normal-butyl perfluoroalkyl vinyl ether etc.The example that also has of optional comonomer comprises the open chain and the ring-type C of fluorinated α-α ' position that the copolymerization by the C=O key gets
3-6Ketone is as Perfluoroacetone, perfluor cyclopentanone etc.Other comonomer comprises not fluorizated C
2-4Alkene is as ethene, propylene, 1-butylene, iso-butylene, C
3-6Alkyl vinyl ether, as methylvinylether, ethyl vinyl ether etc., and C
4-6Vinyl ester is as vinyl-acetic ester, propionate etc.
About comonomer c), the alkenyl or the alkenyl ether organosilane comonomer that contain or do not contain at least one fluoro substituents are the sterically hindered that has living space.As mentioned above, sterically hindered organosilane comonomer can prevent or prevent basically that the copolymerization group that forms fluoropolymer from hydrolyzing taking place prematurely.In other words, the space steric hindrance group on fluoropolymer of the present invention is to prevent or to postpone the spatial disposition that reacts with another molecule.For the present invention, sterically hindered organosilane comonomer better is to can be any amount.The amount of sterically hindered organosilane comonomer better is about 0.1-50 mole %, better is about 0.1-20 mole %, preferably is about 0.1-10 mole %.
Sterically hindered organosilane comonomer better has following structural formula:
R
2R
3 nSi (OR
1)
3-n(I) wherein n is the integer of 0-2, or has following structural formula:
R
2[Si (R
3)
k(--OR
1)
2-k(O)]
mR
3(II) wherein m is the integer of about 2-10, and k is 0 or 1; R
1Represent at least one to contain or do not contain the C of at least one fluoro substituents
3Or more senior branched-chain alkyl, cycloalkyl or heterocyclic group; R
2Representative contains at least one alkenyl or allylic group; R
3Represent at least one positive alkyl, at least one C
3Or more senior branched-chain alkyl, at least one C
3Or higher grade naphthenic base or heterocycle (as aromatics) group.
Be preferably R
1Represent at least one C
3-C
6Branched-chain alkyl or cycloalkyl; R
2Representative contains or does not contain the group that contains at least one vinyl, allyl group or vinyl ether of at least one fluoro substituents; And/or R
3Represent at least one C
1-C
6Positive alkyl, C
3-C
6Branched-chain alkyl, C
3-C
6Cycloalkyl or C
6-C
9Aryl.
About above-mentioned formula I and II, n is preferably 0, and m is preferably the integer of 2-5.The example of branched-chain alkyl or cycloalkyl comprises, but be not limited to cyclopentyl, cyclohexyl, suberyl, ring octyl group, two suberyl, iso-octyl, 3-methyl amyl, isopentyl, amyl group, amyl group, isopentyl, 2,5-dimethyl hexyl, 4-methyl-2-amyl group, sec.-propyl, sec-butyl, isobutyl-, the tertiary butyl, isopentyl and sec.-amyl sec-pentyl secondary amyl etc.The example of positive alkyl, branched-chain alkyl and heterocyclic group includes, but are not limited to normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl etc.To R
3The substituting group of group can comprise that the atom of using such as oxygen, nitrogen or sulphur comes alternate c atoms, is not substituted but condition is a carbon atom near silicon.Other substituting group comprises with halogen atom, nitrogen, sulphur, oxygen and organo-functional group such as cyano group, urea, ester, acid amides, oxo and waits and replace the hydrogen atom that is connected on the carbon.
The used alkenyl organosilane comonomer of the present invention can also comprise at least one functional group.About formula I and II, one or more this functional groups better are R
3The part of group.This functional group still can form fluoropolymer of the present invention and required fluoropolymer performance better can be provided or provide any group with post-modification or crosslinked reflecting point for fluoropolymer.The example of functional group includes, but are not limited to halogen, hydroxyl, nitrogen, amino, epoxy, carboxylate salt, ester, sulphur, oxygen, cyano group, urea, acid amides, oxo etc.
As previously mentioned, fluoropolymer can be uncrosslinked or crosslinked.In addition, fluoropolymer of the present invention can also comprise at least a metal oxide, silane, siloxanes or their combination.Metal oxide, silane or siloxanes better and the silane in the fluoropolymer react.Any material that contains silanol functional group all can react with fluoropolymer of the present invention.Fluoropolymer of the present invention better is the reaction product of a kind of radical polymerization product such as emulsion polymeric product.
An advantage of the invention is that the organo-metallic catalyst that does not need hydrolysis-stable just can carry out polymerization and prepare fluoropolymer of the present invention.
Prepare the used sterically hindered organosilane monomer of fluoropolymer of the present invention directly copolymerization go in the polymer chain of fluoropolymer of the present invention.
About the preparation method of fluoropolymer, fluoropolymer prepares so usually, with each comonomer polymerization time enough, makes fluoropolymer under enough pressure and temperatures.As previously mentioned, this polymerization better is radical polymerization, is more preferably the letex polymerization that should carry out in aqueous medium.
Better method about preparation fluoropolymer of the present invention adds deionized water, Di-Sodium Phosphate and at least a fluorinated surfactant in a reactor during beginning, carry out deoxidation then.Then, adding initiator emulsion and vinyl silanes solution or emulsion under the situation of solvent can be with or without, so that in reactor, begin reaction.Reaction medium better is an aqueous medium.In case reaction beginning or with begin reaction simultaneously, each comonomer randomly is added in the reactor continuously together with buffer reagent.After the polymkeric substance that makes reaches required amount of solid, can stop to add monomer, but should keep adding initiator, to consume existing any residual monomers.In case when the pressure drop of reactor is lower than about 300psi and cooling reactor, then just should stop the adding of initiator.Can discharge unreacted monomer, collect fluoropolymer by leakage fluid dram or other collection device.Can adopt the standard isolation technique then, solid such as, but be not limited to salt/acid cure, freeze molten, shearing is solidified or spraying drying is come isolating polymer.
In more detail, about the temperature of reactor, any temperature of reactor all can adopt, as long as this temperature is enough to polymerization and forms fluoropolymer of the present invention.The example of suitable temp includes, but are not limited to from about 30 ℃ to about 120 ℃, better from about 60 ℃ to about 100 ℃.
About pressure used in polymerization process, same, any pressure all can adopt, as long as this pressure is enough to polymerization and forms fluoropolymer of the present invention.This pressure better from about 40 to about 50atm.Although better be that comonomer is added in the reactor continuously, the form that comonomer can mixture or add successively by the feeding line that separates or by any order.
Reactor better is a kind of pressure polymerization reactor that agitator and heating control apparatus are housed.Polymerization temperature can be looked the characteristic of used initiator and become, but it generally is about 30-120 ℃, better is about 60-105 ℃.Yet temperature is not limited thereto scope, if use high temperature or low temperature initiators, this temperature can be higher or lower.The ratio of used VDF/HFP depends on the selected temperature of reaction in polymerization.Polymerization pressure generally is about the 20-80 crust, but if equipment is allowed under higher pressure to be operated, then this pressure can be higher.Pressure most suitably is about the 30-60 crust.
The tensio-active agent that can use in polymerization process is water miscible halogenation tensio-active agent, especially fluorinated surfactant, ammonium, replacement ammonium, quaternary ammonium or an alkali metal salt as perfluorination or partially fluorinated alkyl carboxylic acid, perfluorination or partially fluorinated monoalkyl phosphoric acid esters, perfluorination or partially fluorinated alkyl oxide or polyether carboxylation, perfluorination or partially fluorinated alkylsulfonate and perfluorination or partially fluorinated alkyl-sulphate.Some specific but unrestricted example is a United States Patent (USP) 2,559, formula X (CF described in 752 (its full content is quoted in this reference)
2)
nThe salt of the acid of COOM, wherein X is hydrogen or fluorine, and M is basic metal, ammonium, replacement ammonium (alkylamine that for example contains 1-4 carbon atom) or quaternary ammonium ion, and n is the integer of 6-20; Formula X (CF
2)
nCH
2OSO
3The sulfuric ester of the multi-fluoride chain triacontanol of M, wherein X and M are as mentioned above; With formula CF
3(CF
2)
n(CX
2)
mSO
3The salt of the acid of M, wherein X and M as mentioned above, n is the integer of 3-7, m is the integer of 0-2, as perfluoro octyl sulfonic acid potassium.In used monomeric gross weight, the consumption of tensio-active agent is about 0.05-5 weight %, and the consumption of tensio-active agent preferably is about 0.1-2.0 weight %.
Paraffin antifoulant is conventional, and any long-chain, saturated chloroflo are all or part ofly fluoridized wax or oil can use.In used monomeric gross weight, the reactor consumption of paraffin is about 0.01-0.3 weight %.
After in reactor, adding deionized water, tensio-active agent and paraffin antifoulant, vacuumize to remove oxygen with the nitrogen purging reactor or to reactor.Make reactor reach certain temperature, randomly can add chain-transfer agent.Mixture with fluorochemical monomer makes the reactor pressurization then.
Can begin reaction, then keep reaction by adding the known any initiator appropriate of fluorinated monomers polymerize (" redox " combination and the organo-peroxide that comprise inorganic peroxide, Oxidizing and Reducing Agents).The example of typical inorganic peroxide is the ammonium or an alkali metal salt of persulfuric acid, and it has useful activity in 65-105 ℃ temperature range." redox " system can be operated under lower temperature, its example comprises that oxygenant (as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide or persulphate) and reductive agent are (as the reductive metal-salt, its object lesson has iron (II) salt) combination, randomly can also add activator such as rongalite or xitix.Can be used for the polymeric organo-peroxide dialkyl peroxide class, peroxyesters and peroxy dicarbonates are arranged.The example of dialkyl peroxide has di-t-butyl peroxide, the example of peroxyester has the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester and peroxidation PIVALIC ACID CRUDE (25) tert-pentyl ester, and the example of peroxy dicarbonate has peroxy dicarbonate two (n-propyl), di-isopropyl peroxydicarbonate, peroxy dicarbonate two (secondary butyl ester) and peroxy dicarbonate two (2-ethylhexyl).Di-isopropyl peroxydicarbonate is disclosed in United States Patent (USP) 3 in the vinylidene fluoride polymerization with use in other fluorinated monomer copolymerization, in 475,396, its use in the preparation vinylidene fluoride/hexafluoropropylene copolymer is disclosed in United States Patent (USP) 4 further, in 360,652.The use of peroxy dicarbonate two (n-propyl) in the vinylidene fluoride polymerization is described among open not examination of appeal (Kokai) JP 58065711.The temperature that the amount of the initiator that polymerization is required is active with it and polymerization is used is relevant.In used monomeric gross weight, the total amount of used initiator is about 0.05-2.5 weight % usually.In general, add enough initiators so that begin reaction during beginning, randomly add extra initiator then, so that keep polymerization with suitable speed.Look selected initiator, the initiator of adding can be the form of pure, solution, suspension or emulsion.As a concrete example, the suitable form with water-based emulsion of peroxy dicarbonate adds.
Water-soluble inorganic is crossed compound such as persulphate, perborate, percarbonate etc., generally is the initiator that its sylvite, sodium salt or ammonium salt also can be used as letex polymerization.
Look the dissociation constant of polymerization temperature and initiator, can add the decomposition accelerator in addition when carrying out polymerization under adopting cryogenic situation, it is a reductive agent usually.Suitable decomposition accelerator is a sulphur compound, as S-WAT, Sodium Pyrosulfite or Rongalit C (formamidine sulfinic acid sodium) with equally also be organic reducing agent such as xitix, metal-salt such as iron (II) or cobalt (II) salt, organometallic compound etc.
The temperature of reaction of copolymerization is preferably 20 to 115 ℃ in-15 to+120 ℃ scope, more preferably 30 to 110 ℃.
If need, can use chain-transfer agent such as methyl alcohol, Virahol, iso-pentane, ethyl acetate, diethyl malonate and tetracol phenixin, to regulate the molecular weight of obtained polymkeric substance.
Method of the present invention can be carried out copolymerization under elevated pressure.This pressure should be at least 5 crust, but needn't surpass 100 crust.
The better pressure range that is used for the inventive method is the 5-65 crust.
Multipolymer of the present invention can mode intermittently make, and makes with semicontinuous or successive mode although better be.
In one of the inventive method better changes, amount of component b) Css (stationary concentration) of free monomers keeps lower concentration.This reaches by following manner, add the vinyl silanes that accounts for question response comonomer total mole number 0.02-15 mole % during beginning, it be randomly together with component a) and b) other comonomer add, along with the carrying out of copolymerization with intermittently or semicontinuous and add remaining amount of component b equably).Remaining amount of component b) yes with component a) and b) residuum add simultaneously.
As a rule, finishing the polymeric time is the amount according to existing comonomer, the amount of initiator and the condition of reactor.Better be to finish the time that the polymeric time is the solids content that reaches required.
The fluoropolymer that the present invention collects should be made powder, and can adopt such as the mode of washing and further remove any unreacted comonomer with methyl alcohol or other suitable solvent.
It is crosslinking reaction can not take place too early basically between silane functionality that the present invention especially adopts letex polymerization to carry out advantage of polymeric.Compare with conventional fluoropolymer, keep reactive silane group has been expanded these fluoropolymers as the part of fluoropolymer range of application.Like this, fluoropolymer of the present invention can through after crosslinked and any other required back chemical modification, and can not damage the excellent properties such as chemical resistant properties, high-temperature stability, high tensile, low-refraction of fluoropolymer.
Be used for silane emulsion, especially those examples of buffer reagent that comprise the emulsion of biocide are organic and inorganic bronsted lowry acids and bases bronsted lowries, comprise its salt, better are carbonic acid, phosphoric acid, sulfuric acid, hydrofluoric acid, C
1-C
6Organic, list or poly carboxylic acid or C
2-C
30List or polyamine/alkali salt, alkaline earth salt or the amine salt of alkylideneimino poly carboxylic acid (alkyleniminopolycarboxylic acid), ammonia, C
1-C
30Organic bases, or the mixture of above-mentioned any material.Its example has: sodium bicarbonate, yellow soda ash, volatile salt, Sodium Tetraborate, phosphoric acid single, two or trisodium, phosphoric acid single, two or tripotassium, sodium ammonium phosphate, vitriolic list or disodium, sodium acetate, potassium acetate, ammonium acetate, lime acetate, sodium formiate, sulfuration list or disodium, ammonia, single, two or triethylamine, single, two or trolamine, (ethylene nitrilo) tetraacethyl sodium salt (E.D.T.A. sodium), pyridine, aniline and water glass.These only are several examples of suitable buffer reagent.The combination of these materials and other buffer reagent, acid or alkali also is effective as ammonium hydroxide and acetate are used together.
Tertiary sodium phosphate (Na
3PO
4), Di-Sodium Phosphate (Na
2HPO
4) and ammonium hydroxide (NH
4OH) better, but especially with sodium bicarbonate (NaHCO
3) good especially, because it is easy to dispose, can obtain the pH value consistently and be 7.5 emulsion, environmentally safe and inexpensive.
The consumption of buffer reagent can change in very wide scope.Yet, as a rule, can be not enough to reach useful less than 0.01% in the gross weight of composition, will be non-remunerative greater than 5 weight %.
Fluoropolymer of the present invention can be used in various fields, as is applied to polymer foams, elastic composition, binder composition, film and other polymer composition.Fluoropolymer of the present invention should have various physics and/or chemical property.For example, fluoropolymer of the present invention can make low density, as less than about 1.8g/ml, and better less than about 1.0g/ml, good again foaming cross-linked polymer less than 0.6g/ml.In addition, fluoropolymer of the present invention has the heat deflection temperature (HDT) of improvement or raising.And fluoropolymer of the present invention has improved solvent resistance.In addition, this fluoropolymer can be have improve and/or with the fluoroelastomer that is purchased Viton and Fluorel elastomerics different performance.
In addition, the response capacity of fluoropolymer can be improved the chemical adhesion to base material, as the binding property of improvement with inorganic substrate such as glass and metal oxide and other base material.In addition, fluoropolymer of the present invention can be used as the precursor of nano composite material (nano-composites) as clay/fluoropolymer, sol-gel organosilane/fluoropolymer or the functional nano particle/fluoropolymer of organosilane.In addition, this fluoropolymer can be used as coating and maybe can be added in the coating, better is to avoid using priming paint.
And the chemical adhesion ability of fluoropolymer of the present invention can bonding silicon rubber, so just can be between fluoropolymer and silicon rubber alloying and IPN.
Fluoropolymer of the present invention can be used as a component in the blend polymer.Any compatible polymers all can add, and makes blend.Fluoropolymer for example can be added to acrylate, methacrylic ester, polyacetal, polyacrylic ester, polymeric amide, polyamine, polyhutadiene, polycarbonate, polyester, polyalkylene, polyimide, polyolefine, polystyrene, urethane and gather in (vinyl alcohol).Fluoropolymer also can with other polymkeric substance copolymerization.
Other application of fluoropolymer of the present invention includes, but are not limited to as a composition in the Nafion type film that can be applicable to electrode such as Li ionization cell and fuel cell etc.This fluoropolymer also can have controlled functionality, and as articulamentum and multiple layer polymer matrix material.This fluoropolymer also can be used as the compatilizer with other polymkeric substance.
All patents of this paper reference and the full content of other publication are all with reference to quoting.Further illustrate the present invention with following embodiment, these embodiment only are used to illustrate the present invention.
Embodiment
Embodiment 1
1 gram Di-Sodium Phosphate is dissolved in the mixture solution of 900 gram 2/3 weight % perfluoroalkane carboxylate salts in deionized water.Then this mixture is added in 2.0 liters of autoclaves.Then the autoclave of cutting out is heated to 80 ℃, then is vented to normal pressure.Then, the liquid VF2 of 132 milliliters-6.5 ℃ of addings, 650psia in autoclave, then reaction mixture is heated to 100 ℃, then add 45 milliliters and be dispersed in the initiator emulsion that the mixture in the deionized water is formed, the beginning polymerization by 3 weight % peroxy dicarbonate di-n-propyl esters and 2/3 weight % perfluoroalkane carboxylate salt.Pressure descends in elicitation procedure, in 78 minutes time, add described initiator emulsion continuously and add VF2 and the mixture of 25 weight % vinyl, three tert.-butoxy silane in methyl alcohol then, thereby pressure is remained on 600psia with the ratio of 120 milliliters of VF2:41.8 milliliter vinyl three tert.-butoxy solution with the speed of 2 ml/min.Stop to add monomer, keep to add initiator emulsion 50 minutes, stirred reaction mixture 10 minutes in the time of 100 ℃ consumes residual monomers afterwards.After the cooling, the surplus pressure in the time of 32 ℃ is 246psia.With the autoclave exhaust, the latex of turning then.The pH value of latex is 4.6, and the solids content in 90 ℃ baking oven after the dried overnight is 13.25%.
Embodiment 2
0.5 gram tertiary sodium phosphate is dissolved in the mixture solution of 800 gram 2/3 weight % perfluoroalkane carboxylate salts in deionized water.Then this mixture is added in 2.0 liters of autoclaves.Then the autoclave of cutting out is heated to 80 ℃, then is vented to normal pressure.Temperature is risen to 90 ℃.Then, the liquid VF2 of 123.4 milliliters-6.5 ℃ of addings, 550psia in autoclave.Add 55 milliliters and be dispersed in the initiator emulsion that the mixture in the deionized water is formed, the beginning polymerization by 3 weight % peroxy dicarbonate di-n-propyl esters and 2/3 weight % perfluoroalkane carboxylate salt.Pressure at first rises then and to descend in elicitation procedure, speed with 2 ml/min adds described initiator emulsion continuously in 80 minutes time then, with the speed of 1.5 ml/min add continuously 109.5 milliliter of 4.5 weight % Di-Sodium Phosphate in deionized water solution and with 185.4 milliliters of VF2: the ratio of 31.7 milliliters of vinyl three tert.-butoxy solution of silane adds VF2 and the mixture of 25 weight % vinyl silane triisopropoxides in methyl alcohol, thereby pressure is remained on 660psia.Stop to add monomer, keep adding initiator 35 minutes with the speed of 3 ml/min, stirred reaction mixture 35 minutes in the time of 90 ℃ consumes residual monomers afterwards.After the cooling, the surplus pressure in the time of 32 ℃ is 339psia.With the autoclave exhaust, the latex of turning then.The pH value of latex is 6.2, and the solids content in 110 ℃ baking oven after the dried overnight is 17%.
Except difference as described in Table 1, all the other all prepare all the other listed embodiment of following table 1 by embodiment 2 similar modes.
Table 1
| Embodiment # | Silane in MeOH, weight % | Na 3PO 4Initial add-on (gram) | ????T ??(℃) | ????P ??(psia) | Reach the required VF2 of P=550psia (milliliter) |
| ????2 | ??VTiPS?25％ | ????0.5 | ????90 | ????660 | ????123.4 |
| ????3 | ??VTiPS?25％ | ????0 | ????90 | ????640 | ????126.6 |
| ????4* | ??VTiPS?20％ | ????0 | ????100 | ????625 | ????131.9 |
| ????5 | ??VTiPS?25％ | ????0 | ????100 | ????625 | ????127.2 |
| ????6 | ??VTiPS?50％ | ????0.5 | ????90 | ????640 | ????161.8 |
| ????7 | ??VTiPS?50％ | ????0.5 | ????90 | ????650 | ????131.1 |
| ????8 | ??VTiPS?25％ | ????0.5 | ????90 | ????640 | ????130.2 |
| ????9 | ??VTtBS?25％ | ????0 | ????100 | ????645 | ????121.4 |
| ????10 | ??VTtBS?25％ | ????0 | ????90 | ????640 | ????127.8 |
| ????11* | ????0 | ????0 | ????100 | ????630 | ????131.4 |
| ????12* | ????0 | ????0 | ????90 | ????560 | ????130.4 |
| ????13 | ????0 | ????0 | ????100 | ????628 | ????127.7 ??(P＝630psia) |
| ????14 | ??VTtBS?25％ | ????0 | ????80 | ????644 | ????145.8 |
| ????15 | ??VTtBS?35％ | ????0 | ????75 | ????585 | ????158.5 |
| ????16 | ??VTtBS?35％ | ????0.5 | ????70 | ????655 | ????167.7 |
Table 1 (continuing)
| Initial initiator (milliliter) | Na 2HPO 4The aqueous solution (weight %/milliliter) | VF2 add-on (milliliter) | Silane add-on (milliliter) in MeOH | The monomeric joining day (minute) |
| ????55 | ????4.5/109.5 | ????185.4 | ????31.7 | ????80 |
| ????50 | ????5/100 | ????54.9 | ????36.2 | ????140 |
| ????45 | ????5/86.6 | ????200.2 | ????9.7 | ????50 |
| ????43 | ????5/79.5 | ????86.7 | ????26.6 | ????90 |
| ????40 | ????4.5/99.4 | ????136.7 | ????13.5 | ????85 |
| ????46 | ????4.5/75 | ????31.1 | ????13 | ????55 |
| ????44 | ????4/112.5 | ????35.2 | ????15.4 | ????45 |
| ????27.5 | ????5/144 | ????39.6 | ????34.4 | ????126 |
| ????67 | ????5/97.9 | ????62 | ????29.3 | ????120 |
| ????47.5 | ????10/79.9 | ????255.1 | ????0 | ????23 |
| ????37.2 | ????5/99.8 | ????138 | (56.2 pure MeOH) | ????82 |
| ????27 | ????0 | ????244.2 | (70.8 pure MeOH) | ????110 |
| ????25 | ????4/94 | ????57.7 | ????18.6 | ????60 |
| ????39.8 | ????4/108 | ????41.8 | ????28.5 | ????145 |
| ????40.3 | ????4/101 | ????93.1 | ????30.0 | ????155 |
*: partial coagulation; VTiPS: vinyl silane triisopropoxide; VTtBS: vinyl three tert.-butoxy silane
From the content and practice of the present invention of the disclosed specification sheets of this paper, other embodiment of the present invention will be conspicuous concerning the technology skilful person of this area.Want to be pointed out that specification sheets and embodiment only are considered to usefulness as an example, and true scope of the present invention and spirit are limited by following claims.
Claims (21)
1. fluoropolymer, it comprises following polymeric reaction products a)-c):
A) at least a first olefin comonomer that contains at least one fluorine atom;
B) randomly at least aly be selected from 1) at least a second alkene that contains at least one fluorine atom, this second alkene is different from first olefin comonomer; 2) at least a alkyl chain alkene ether that contains at least one fluorine atom; 3) at least aly contain aliphatic series or the cyclic ketone that at least one fluoridizes α-α position; Or 4) monomer of nonfluorinated alkene, alkyl vinyl ether or alkenyl ester; With
C) at least a sterically hindered alkenyl or the alkenyl ether organosilane comonomer that contains or do not contain at least one fluoro substituents.
2. fluoropolymer as claimed in claim 1, wherein said reaction product are the Raolical polymerizable products.
3. fluoropolymer as claimed in claim 1, the amount of wherein said at least a ethylene comonomer are about 40-99.9 mole %.
4. amount fluoropolymer as claimed in claim 1, wherein said at least a comonomer b) is about 0.1-50 mole %.
5. fluoropolymer as claimed in claim 1, the amount of wherein said at least a sterically hindered vinyl organosilicon alkane comonomer is about 0.1-50 mole %.
6. fluoropolymer as claimed in claim 1, wherein said at least a sterically hindered vinyl organosilicon alkane comonomer has following structural formula:
R
2R
3 nSi (OR
1)
3-n(I) wherein n is the integer of 0-2, or has following structural formula:
R
2[Si (R
3)
k(--OR
1)
2-k(O)]
mR
3(II) wherein m is the integer of about 2-10; K is the integer of 0-1; R
1Represent at least one to contain or do not contain branched-chain alkyl, cycloalkyl or the heterocyclic group of at least one fluoro substituents; R
2Representative contains at least one alkenyl or allylic group; R
3Represent at least one positive alkyl, branched-chain alkyl, cycloalkyl or heterocyclic group.
7. fluoropolymer as claimed in claim 6, wherein said R
3Also comprise at least one functional group.
8. fluoropolymer as claimed in claim 7, wherein said at least one functional group is at least one halogen, hydroxyl, nitrogen, amino, epoxy, carboxylate salt, ester, sulphur, oxygen, cyano group, urea, acid amides, oxo or their combination.
9. fluoropolymer as claimed in claim 1, wherein said fluoropolymer is crosslinkable.
10. fluoropolymer as claimed in claim 7, wherein said fluoropolymer is crosslinkable.
11. fluoropolymer as claimed in claim 1, wherein said fluoropolymer also comprise at least a metal oxide, silane, siloxanes or their combination.
12. fluoropolymer as claimed in claim 11, the silane in wherein said at least a metal oxide, silane or siloxanes and the described fluoropolymer reacts.
13. one kind prepares the method for fluoropolymer according to claim 1, it is included under enough pressure and temperatures and in buffer system following a)-c) polymerization time enough is made described fluoropolymer:
A) at least a first olefin comonomer that contains at least one fluorine atom;
B) randomly at least aly be selected from 1) at least a second alkene that contains at least one fluorine atom, this second alkene is different from first olefin comonomer; 2) at least a alkyl chain alkene ether that contains at least one fluorine atom; 3) at least aly contain aliphatic series or the cyclic ketone that at least one fluoridizes α-α position; Or 4) monomer of nonfluorinated alkene, alkyl chain alkene ether or vinyl chain thiazolinyl; With
C) at least a sterically hindered alkenyl or the alkenyl ether organosilane comonomer that contains or do not contain at least one fluoro substituents.
14. method as claimed in claim 13, wherein said polymerization is radical polymerization.
15. method as claimed in claim 13, wherein said polymerization is letex polymerization.
16. method as claimed in claim 13, wherein said polymerization is carried out in aqueous medium.
17. method as claimed in claim 13, wherein said polymerization are to carry out in the pH value is about the scope of 4.5-8.5.
18. method as claimed in claim 13, add deionized water when it also comprises beginning, Di-Sodium Phosphate, tertiary sodium phosphate or both add, and add at least a fluorinated surfactant in reactor, carry out deoxidation, add afterwards comonomer a), optional b) and c).
19. method as claimed in claim 18, it also is included in after the described initial adding step, adds initiator emulsion and the solution of vinyl silanes in solvent, begins reaction.
20. method as claimed in claim 17, it also is included in after described reaction begins, in described reactor, add continuously described comonomer a), optional b) and c).
21. method as claimed in claim 18, it also comprises separates described fluoropolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16512399P | 1999-11-12 | 1999-11-12 | |
| US60/165,123 | 1999-11-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1336938A true CN1336938A (en) | 2002-02-20 |
Family
ID=22597519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00802612A Pending CN1336938A (en) | 1999-11-12 | 2000-11-10 | Fluoropolymers containing organo-silanes and methods of making the same |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1196465A4 (en) |
| JP (1) | JP2003514085A (en) |
| CN (1) | CN1336938A (en) |
| MX (1) | MXPA01007110A (en) |
| RU (1) | RU2001122579A (en) |
| WO (1) | WO2001034670A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210059B (en) * | 2006-12-29 | 2011-06-15 | 北京航空航天大学 | Multipolymer resin water dispersoid containing fluorine and silicon |
| CN102782015A (en) * | 2009-12-08 | 2012-11-14 | 纳幕尔杜邦公司 | Process for preparation of fluorosilicon polymer |
| CN103881030A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Preparation method for fluorine-containing amino silicone oil emulsion |
| CN106496397A (en) * | 2016-10-24 | 2017-03-15 | 内蒙古奥特普氟化学新材料开发有限公司 | Fluoroelastomer, the resin combination with the fluoroelastomer and preparation method |
| CN106632793A (en) * | 2016-10-24 | 2017-05-10 | 内蒙古奥特普氟化学新材料开发有限公司 | A fluoroelastomer resistant to low temperatures and a preparing method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6833414B2 (en) | 2002-02-12 | 2004-12-21 | Arkema Inc. | Cross-linkable aqueous fluoropolymer based dispersions containing silanes |
| JPWO2004007576A1 (en) * | 2002-06-14 | 2005-11-10 | ダイキン工業株式会社 | Fluorine-containing copolymer production method, fluorine-containing copolymer and molded article |
| US7652115B2 (en) * | 2003-09-08 | 2010-01-26 | 3M Innovative Properties Company | Fluorinated polyether isocyanate derived silane compositions |
| US7803894B2 (en) | 2003-12-05 | 2010-09-28 | 3M Innovatie Properties Company | Coating compositions with perfluoropolyetherisocyanate derived silane and alkoxysilanes |
| WO2011014715A2 (en) * | 2009-07-31 | 2011-02-03 | 3M Innovative Properties Company | Fluoropolymer compositions containing a polyol compound and methods of making them |
| CN112759766B (en) * | 2021-01-20 | 2022-07-15 | 新元化学(山东)股份有限公司 | High-vinyl-activity fluorosilicone rubber raw rubber and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4701508A (en) * | 1984-12-14 | 1987-10-20 | Mitsui Sekiyu Kagaku Kogyo Kabushiki Kaisha | Solvent soluble fluorine-containing polymer, coating composition containing the same and coating process thereof |
| JPH0699655B2 (en) * | 1985-10-09 | 1994-12-07 | 大日本インキ化学工業株式会社 | Room temperature curable resin composition |
| US4879345A (en) * | 1988-07-27 | 1989-11-07 | Ppg Industries, Inc. | Fluoropolymer based coating composition for adhesion direct to glass |
| US5179181A (en) * | 1988-12-02 | 1993-01-12 | Mitsui Petrochemical Industries, Ltd. | Process for producing fluorine-containing copolymer and fluorine-containing copolymer composition |
| US5859123A (en) * | 1995-11-15 | 1999-01-12 | Central Glass Company, Limited | Water-based fluorine-containing emulsion |
| US5973090A (en) * | 1997-10-31 | 1999-10-26 | Toagosei Co., Ltd. | Cold-setting coating composition |
| DE60001764T2 (en) * | 1999-05-21 | 2003-11-13 | Jsr Corp | Coating agents and films and glass coated with them |
-
2000
- 2000-11-10 MX MXPA01007110A patent/MXPA01007110A/en unknown
- 2000-11-10 WO PCT/US2000/031040 patent/WO2001034670A1/en not_active Application Discontinuation
- 2000-11-10 CN CN00802612A patent/CN1336938A/en active Pending
- 2000-11-10 EP EP00978536A patent/EP1196465A4/en not_active Withdrawn
- 2000-11-10 RU RU2001122579/04A patent/RU2001122579A/en not_active Application Discontinuation
- 2000-11-10 JP JP2001537381A patent/JP2003514085A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210059B (en) * | 2006-12-29 | 2011-06-15 | 北京航空航天大学 | Multipolymer resin water dispersoid containing fluorine and silicon |
| CN102782015A (en) * | 2009-12-08 | 2012-11-14 | 纳幕尔杜邦公司 | Process for preparation of fluorosilicon polymer |
| CN102782015B (en) * | 2009-12-08 | 2015-08-19 | 纳幕尔杜邦公司 | For the preparation of the method for silicon-fluorine polymer thing |
| CN103881030A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Preparation method for fluorine-containing amino silicone oil emulsion |
| CN103881030B (en) * | 2012-12-19 | 2016-05-18 | 张家港市国泰华荣化工新材料有限公司 | A kind of preparation method of fluorine-containing amino silicon oil emulsion |
| CN106496397A (en) * | 2016-10-24 | 2017-03-15 | 内蒙古奥特普氟化学新材料开发有限公司 | Fluoroelastomer, the resin combination with the fluoroelastomer and preparation method |
| CN106632793A (en) * | 2016-10-24 | 2017-05-10 | 内蒙古奥特普氟化学新材料开发有限公司 | A fluoroelastomer resistant to low temperatures and a preparing method thereof |
| CN106632793B (en) * | 2016-10-24 | 2019-01-08 | 内蒙古奥特普氟化学新材料开发有限公司 | Low-temperature-resistant elastic body containing fluorine and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1196465A1 (en) | 2002-04-17 |
| JP2003514085A (en) | 2003-04-15 |
| WO2001034670A8 (en) | 2001-09-27 |
| MXPA01007110A (en) | 2002-03-20 |
| RU2001122579A (en) | 2003-06-20 |
| EP1196465A4 (en) | 2004-12-29 |
| WO2001034670A1 (en) | 2001-05-17 |
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