EP0660849A1 - Systemes polymeres fluorochimique - Google Patents

Systemes polymeres fluorochimique

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Publication number
EP0660849A1
EP0660849A1 EP93922213A EP93922213A EP0660849A1 EP 0660849 A1 EP0660849 A1 EP 0660849A1 EP 93922213 A EP93922213 A EP 93922213A EP 93922213 A EP93922213 A EP 93922213A EP 0660849 A1 EP0660849 A1 EP 0660849A1
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EP
European Patent Office
Prior art keywords
weight
monomer
group
mixtures
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP93922213A
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German (de)
English (en)
Inventor
Yvan A. Bogaert
Robert R. Smolders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0660849A1 publication Critical patent/EP0660849A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
    • 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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers

Definitions

  • the present invention relates to compatible polymeric systems comprising fluorocarbon elastomers and non-fluorinated vinyl polymers, a method of making the compatible systems, and materials such as films, sealants, membranes, and adhesives made therefrom.
  • Fluoropolymers which include fluoroelastomers and plastics are known in the art. Fluoropolymers exhibit high temperature performance, good weatherability, solvent resistance, and acid resistance. Fluoropolymers can be effectively used as surface modifiers of various polymeric substrates because they bloom to the surface giving a low energy surface (i.e., oil and water repellant surface which is useful for low adhesion backsizes in tapes). Fluoropolymers are incompatible with most other polymers, resulting in cloudy or hazy coatings upon blending, which is not acceptable in many applications. Another disadvantage is that fluoropolymers exhibit low wettability and poor adhesion to many substrates.
  • composition of the invention comprises a dispersion comprising the reaction product of:
  • (B) about 2 to about 20 percent by weight of a stabilizer based upon the weight of (A) wherein the stabilizer is selected from the group consisting of:
  • amide-containing monomer (a) amide-containing monomer; and (b) a vinyl-reactive endcapping agent selected from the group consisting of isocyanatoethyl methacrylate, alpha,alpha-dimethyl-meta-isopropenyl benzylisocyanate, parachloromethylstyrene, glycidyl methacrylate, vinyl azlactone, and mixtures thereof; (iv) a copolymer macromonomer having a weight average molecular weight ranging from about 3,000 to about 80,000, wherein the copolymer macromonomer comprises:
  • a vinyl-reactive endcapping agent selected from the group consisting of isocyanatoethyl methacrylate, alpha.alpha-dimethyl-meta-isopropenyl benzylisocyanate, parachloromethylstyrene, glycidyl methacrylate, vinyl azlactone, and mixtures thereof; wherein the sum of (iv)(a) plus (iv)(b) equals 100 parts by weight total; and
  • (v) mixtures thereof (C) about 20 to about 90 parts by weight of a solvent capable of dissolving the fluoroelastomer, the (meth)acrylic acid ester monomer(s), the optional ethylenically unsaturated monomer and the stabilizer; and (D) about 0.01 to about 0.5 percent by weight of an initiator, wherein the weight percent of the initiator is based upon the total weight of the (meth)acrylic acid ester monomer and the ethylenically unsaturated monomer(s), if used, in the combination of components (A); wherein the weight of (A) plus (C) equals 100 parts by weight total.
  • the invention also provides the composition comprising the reaction product of the monomers, fluorocarbon elastomer, stabilizer and initiator.
  • the invention also provides powders and polymer beads comprising the reaction product.
  • the invention also provides films prepared from the compositions of the invention.
  • fluoroelastomer refers to fluorinated elastomers. Fluorinated elastomers are a class of synthetic elastomers that are designed for demanding service applications in environments where combinations of extreme temperature ranges, chemicals, fluids, and/or fuels exist. The three basic fluorinated elastomer types are fluorocarbons, fluorosilicones, and fluoroalkoxy phosphazines. This invention involves the use of fluorocarbon elastomers.
  • the FluorelTM Brand fluorocarbon elastomers, which are useful in the present invention are produced using approximately a 4 to 1 (vinylidene fluoride to hexafluoropropylene) ratio of the monomers.
  • the VITONTM fluorocarbon elastomers which are also useful according to the present invention, (available from duPont) are available in similar composition or with increased fluorine content via use of tetrafluoroethylene (C2F ) for improved fluid resistance or with perfluoromethylvinyl ether (C2F4OCF3) for better low temperature properties.
  • the raw fluorocarbon elastomers have a density of 1.80 to 1.86 g/cm 3 .
  • fluorocarbon elastomers which include those selected from the group consisting of poly(vinylidene fluoride-co-hexafluoropropylene) available under the tradenames Fluorel from 3M, Viton A from duPont, Tecnoflon from Montedison, and Dai-El from
  • Daikin poly (vinylidene fluoride-co-hexafluoropropylene-co-tetrafluorethylene) available under the tradenames Viton B from duPont, and Dai-El G-501 from Daikin; poly(vinylidene fluoride-co-hexafluoropropylene-co-tetrafluorethylene) plus cure site monomer available under the tradename Viton G (peroxide curable) from duPont; poly(vinylidene fluoride-co-tertrafluoroethylene-co- perfluoromethyl vinyl ether) plus cure site monomer available under the tradename Viton GLT (peroxide curable) from duPont; poly(tetrafluoroethylene- co-perfluoromethyl vinyl ether) plus cure site monomer available under the trade name Kalrez from duPont; poly(tetrafluoroethylene-co-propylene) available under the trade name Aflas 100 and 150 from Asahi; poly(vinyliden
  • U.S. Patents describe useful fluorocarbon elastomers for the purpose of this invention: U.S. Patent No. 3,051,677 (assigned to E.I. duPont de Nemours & Co., Inc.); U.S. Patent No. 2,968,649 (assigned to E.I. duPont de Nemours & Co., Inc.); U.S. Patent No. 3,331,823 (assigned to Montedison); U.S. Patent N ⁇ .3,335,106 (assigned to Montedison); U.S. Patent No. 3,712,877 (assigned to 3M); U.S. Patent No. 4,866,118 (assigned to 3M); and U.S. Patent No. 4,956,419 (assigned to 3M).
  • the fluorocarbon elastomers used according to the invention comprise monomers selected from the group consisting of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, chlorotrifluoroethylene, 2-chloropentafluoropropene, pentafluoropropene, dichlorodifluoroethylene, trifluoroethylene, 1 , 1-chlorofluoroethylene, l-bromo-2,2-difluoroethylene, perfluoromethylvinyl ether and mixtures thereof, and optionally, in addition, fluoromonomer cure site monomers such as those selected from the group consisting of 3-iodoperfluoropropene, 4-iodoperfluoropentene, bromotrifluoroethylene, bromodifluoroethylene and mixtures thereof, for reasons of commercial availability.
  • the most preferred fluorocarbon elastomer comprises vinylidene fluoride-hexafluoropropylene copolymer having a Mooney viscosity of about 10 to about 120, preferably about 37.
  • the fluorocarbon elastomers selected preferably have a weight average molecular weight between about 15,000 and about 120,000, most preferably about 25,000 to about 80,000, calculated from the corresponding Mooney viscosity.
  • Useful (meth)acrylic acid ester monomers include monofunctional ethylenically-unsaturated esters of (meth)acrylic acid and/or substituted (meth)acrylic acid and alcohols comprising about 1 to about 18 carbon atoms, preferably about 1 to about 8 carbon atoms.
  • Useful monomers include but are not limited to those selected from the group consisting of methyl acrylate, butyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-methylbutyl methacrylate, isooctyl acrylate, dimethylaminoethyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, and mixtures thereof.
  • Preferred (meth)acrylic acid ester monomers include those selected from the group consisting of isooctyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, 2-methyl butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and mixtures thereof.
  • Most preferred (meth)acrylic acid ester monomers include those selected from the group consisting of isooctyl acrylate, methyl methacrylate, and mixtures thereof.
  • composition of the invention may optionally further comprise other ethylenically-unsaturated monomers in admixture with the above-noted (meth)acrylic acid ester monomers.
  • additional monomers include those selected from the group consisting of acrylic acid, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, methacryloyloxy propyltrimethoxy silane, and mixtures thereof.
  • the monomer acrylonitrile is a particularly useful monomer to include. It increases stability due to the strong interaction with the stabilizer and helps provide a more homogeneous coating. Acrylonitrile must be included as a comonomer when a long-chain (meth)acrylic acid ester monomer is used (i.e., greater than about 6 carbon atoms in the chain).
  • the amount of optional ethylenically unsaturated monomer added depends on the (meth)acrylic acid ester monomer(s) and optional ethylenically unsaturated monomers selected. If ethylenically unsaturated monomer is used, the dispersion typically comprises about 0.1 to about 50 percent of ethylenically unsaturated monomer, preferably if added about 20 to about 40 percent, most preferably if added about 25 to about 30 percent, based upon the total weight of (meth)acrylic acid ester and ethylenically unsaturated monomer. The monomer is used in an amount which will give or maintain a stable dispersion if solution or suspension polymerization is employed.
  • a third component of the present invention is a stabilizer for the dispersion.
  • the stabilizer can take on a number of forms, all of which are characterized as homopolymers or copolymers comprising at least one amide-containing monomer.
  • Suitable amide-containing monomers include but are not limited to those selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam, acrylamide, N,N-dimethylacrylamide, and mixtures thereof.
  • the amide-containing monomer is selected from the group consisting of N-vinylpyrrolidone, acrylamide, and mixtures thereof.
  • Suitable ethylenically-unsaturated co-monomers from which copolymeric stabilizers are obtained via copolymerization with amide containing monomers include but are not limited to those selected from the group consisting of vinyl esters of C to Cg monocarboxylic acids and C j to C j g aliphatic alcohol esters of (meth)acrylic acid, and mixtures thereof.
  • Preferred co-monomers are selected from the group consisting of vinyl acetate, vinyl propionate, methyl acrylate, methyl methacrylate, and mixtures thereof.
  • Homopolymeric stabilizers comprise homopolymers having a weight average molecular weight of from about 20,000 to about 200,000, as determined by GPC using polystyrene standards.
  • Copolymeric stabilizers comprise copolymers of amide-containing monomer(s) and ethylenically-unsaturated co-monomer(s) wherein the copolymer has a weight average molecular weight of from about 20,000 to about 200,000.
  • the copolymer comprises from about 10 to about 90 parts by weight of the amide-containing monomer(s) and from about 90 to about 10 parts by weight of the ethylenically-unsaturated co-monomer(s) based upon 100 parts by weight total of the monomer.
  • the copolymer comprises from about 40 to about 60 parts by weight of the amide-containing monomer(s) and from about 60 to about 40 parts by weight of the ethylenically-unsaturated co-monomer(s).
  • the homopolymeric or copolymeric stabilizer may be reacted with a vinyl-reactive endcapping agent to form a macromonomer, the endcapping agent being selected from the group consisting of isocyanatoethyl methacrylate (IEM), alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate (TMI), parachlorodimethylstyrene, glycidyl methacrylate, vinyl azlactone, and mixtures thereof.
  • the endcapping agent is selected from the group consisting of IEM and TMI.
  • Endcapping introduces ethylenically-unsaturated, free-radically polymerizable functional groups into the homopolymer or copolymer stabilizer such that the end-capped macromonomer can be copolymerized with the (meth)acrylic acid ester monomer(s) and optional ethylenically unsaturated monomer of the present invention.
  • the stabilizer comprises a vinyl acetate N-vinylpyrrolidone copolymer endcapped with isocyanatoethyl methacrylate due to its ease of synthesis and the facility with which it is copolymerized with the (meth)acrylic acid ester monomer(s) and optional ethylenically unsaturated monomers.
  • the weight average molecular weight range of the macromenstabilizer is from about 3,000 to about 80,000, preferably about 10,000 to about 70,000. If the molecular weight is too high, the dispersion is too viscous to coat. If the molecular weight is too low, the dispersion is not stable.
  • the stabilizer is an essential part of the formulation of the present invention.
  • the stabilizer is typically present at from about 2 percent to about 20 percent, preferably from about 4 percent to about 8 percent, based on the total weight of the (meth)acrylic acid ester monomer(s) plus fluorocarbon elastomer plus optional ethylenically unsaturated monomers.
  • the copolymer stabilizer can be prepared by combining the desired monomers, initiator (such as those discussed below), a conventional chain transfer agent such as those selected from the group consisting of mercaptans, alcohols, and carbon tetrabromide.
  • chain transfer agents examples include those selected from the group consisting of mercaptoethanol, mercapto acetic acid, isooctyl thioglycolate, and carbon tetrabromide, and a conventional organic solvent such as ethyl acetate (and/or those discussed below) in a reaction vessel.
  • a conventional organic solvent such as ethyl acetate (and/or those discussed below) in a reaction vessel.
  • chain transfer agent typically about 20 to about 50 parts by weight of monomer is used.
  • chain transfer agent Typically about 0.5 to about 5 percent of chain transfer agent is used based on the weight of the monomer charge.
  • about 80 to about 50 parts by weight of solvent is used.
  • Polymerization is conducted under inert atmospheric conditions, with agitation, for about 10 to 24 hours.
  • a macromonomer stabilizer can be prepared by reacting the copolymer with end-capping agent in the presence of a catalytic amount of a catalyst such as those selected from the group consisting of dibutyl tin dilaurate (DBTL) and tin octoate.
  • a catalyst such as those selected from the group consisting of dibutyl tin dilaurate (DBTL) and tin octoate.
  • DBTL dibutyl tin dilaurate
  • tin octoate Preferably about 0.03 to about 0.15 percent of catalyst is used based on the monomer charge.
  • a conventional antioxidant such as IrganoxTM 1010 antioxidant (available from Ciba-Geigy) based on the monomer charge is included.
  • the reaction preferably is conducted under inert atmospheric conditions with agitation for about 1 to about 5 hours.
  • Useful thermal initiators for use in the present invention include, but are not limited to, the following: azo compounds such as 2,2'-azobis-(isobutyronitrile), dimethyl-2,-2'- azo-bis-isobuytrate, azo-bis-(diphenyl methane), 4,4'-azo-bis-(4-cyanopentanoic acid); peroxides such as benzoyl peroxide, cumyl peroxide, tert-butyl peroxide, cyclohexanone peroxide, glutaric acid peroxide, lauroyl peroxide, methyl ethyl ketone peroxide and hydrogen peroxide; hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide; peracid
  • photochemical initiators would also be useful in the compositions of the present invention.
  • photochemical initiators include but are not limited to those selected from the group consisting of benzoin ethers such as diethoxyacetophenone, oximino-ketones, acylphosphine oxides, diaryl ketones such as benzophenone and 2-isopropyl thioxanthone, benzil and quinone derivates, and 3-ketocumarines as described by S.P. Pappas, J. Rad. Cur.. July 1987.
  • the initiator used comprises a thermally decomposed azo or peroxide compound for solubility reasons and in order to control the reaction rate.
  • the initiator used comprises 2,2'-azobis-(iso- butyronitrile) for reasons of cost and appropriate decomposition temperature.
  • a solvent is required in the solution polymerization process of the present invention.
  • the solvent is utilized in order to decrease the viscosity during the reaction to allow for efficient stirring and heat transfer.
  • Suitable solvents include but are not limited to those selected from the group consisting of C j to Cg alcohol esters of acetic acid such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, and acetone; alcohols such as methanol, ethanol, and isopropanol; phthalates such as diooctyl phthalate; propylene glycol ethers, tetrahydro furan; and mixtures thereof.
  • the amount of solvent is generally about 20 to about 90 parts by weight, preferably about 40 to about 80 parts by weight, most preferably about 30 to about 70 parts by weight.
  • composition of the invention can further comprise about 0.1 percent to about 5 percent by weight of a crosslinker based upon the percent solids (i.e., total weight of fluorocarbon elastomer, monomer, initiator, and stabilizer).
  • a crosslinker based upon the percent solids (i.e., total weight of fluorocarbon elastomer, monomer, initiator, and stabilizer).
  • useful crosslinkers include but are not limited to thermally-activated, moisture-activated, and ultraviolet radiation (UV) activated crosslinkers.
  • thermally-activated crosslinkers include but are not limited to those selected from the group consisting of bisamides such as N,N'-bis-l,2-propyleneterephthalamide, metal complexes such as aluminum acetylacetonate, and isocyanates such as H-12MDI (4,4'-methylene-bis- [cyclohexylisocyanate]).
  • moisture-activated crosslinkers include but are not limited to those selected from the group consisting of silanes such as trimethoxysilylpropyl methacrylate (Tris), amino silane, epoxy silane, and mixtures thereof.
  • UV-activated crosslinkers include but are not limited to those selected from the group consisting of chromophore-substituted triazines as described in U.S. Patent No. 4,330,590 (Vesley, 3M) and U.S. Patent No.
  • 4,329,384 (Vesley et al., 3M), such as 2,4-bis(trichloro- methyl)-6-(4-methoxyphenyl)-s-triazine, 2 ,4-bis(trichloromethyl)-6- (3-methoxyphenyl-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4- dimethoxyphenyl)-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4,5- trimethoxyphenyl)-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylene- dioxyphenyl)-s-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxy- naphthyl)-s-triazine, and U.S.
  • Patent No. 4,181,752 (Martens, 3M), e.g., 2,4- bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and copolymerizable aromatic ketone monomers as described in U.S. Patent No. 4,737,559 and U.S. Patent No. 4,847,137 (Kellen et al., 3M), such as acryloxybenzophenone.
  • the homolytic decomposition of the initiator used in the present invention to form free radicals can be induced by heat energy (thermolysis), light energy (photolysis), or the addition of a suitable catalyst.
  • the decomposition rate of the initiator during thermolysis depends upon the chemical nature of the initiator, the reaction temperature, and the solvent (if any) used.
  • the decomposition rate of the initiator during photolysis depends mainly upon the chemical nature of the initiator and the intensity and wavelength of the radiation utilized.
  • Light energy can be supplied to induce the homolytic decomposition of the initiator by means of visible or ultraviolet sources including low intensity fluorescent black light lamps, medium pressure mercury arc lamps, and germicidal mercury lamps. The selection of a preferred light energy source will depend upon the chosen photoinitiator.
  • the decomposition of the initiator can also be accomplished by using a suitable catalyst.
  • Catalyst induced initiator decomposition involves an electron transfer mechanism resulting in a reduction-oxidation (redox) reaction.
  • Initiators such as peroxides and hydroperoxides are more susceptible to this kind of decomposition.
  • Catalysts useful in inducing the homolytic decomposition of the initiator include, but are not limited to, amines and metal ions used in combination with peroxide or hydroperoxide initiators and bisulfite or mercapto compounds used in combination with persulphate initiators.
  • thermolysis which can be readily employed in standard reactors. Thermolysis also provides for ease of control of the reaction rate and exotherm.
  • the copolymerization may be carried out by other well known techniques such as suspension, dispersion, and bulk polymerization.
  • Suspension polymerization is a well-known method of polymerization which results in the formation of polymer beads.
  • the free-radically polymerizable monomers, the initiator, the stabilizer, the fluorocarbon elastomer and solvent employed are charged into an appropriate reaction vessel.
  • fluorocarbon elastomer is added to and dissolved in a monomer/solvent mixture.
  • Previously prepared stabilizer and initiator is added, following which polymerization is initiated. If photolysis is conducted to decompose the initiator, the reactants and the solvent employed are charged into an energy source transparent vessel and therein subjected to the energy source. If the energy source is ultraviolet light radiation, a suitable ultraviolet light-transparent vessel would be utilized.
  • thermolysis is used to decompose the initiator
  • the reactants and the solvent employed are charged into a suitable glass or metal reactor, and therein subjected to the thermal energy source.
  • a glass or metal reactor can also be utilized.
  • the reaction is preferably conducted in a vessel with agitation to permit uniform exposure of the reactants to the energy source. While most of the reactions have been conducted by employing a batch process, it is possible to utilize the same technology in a continuous polymerization operation.
  • a first solution is typically formed comprising fluorocarbon elastomer, chain transfer agent, and monomers by dissolving the fluorocarbon elastomer in the monomer, at room temperature with agitation, following which the chain transfer agent and initiator is added.
  • chain transfer agent typically about 0.5 to about 5 percent by weight of chain transfer agent is used based on the weight of the monomer charge.
  • a second solution comprising stabilizer, deionized water and a suspension agent such as sodium hypophosphite.
  • Suspending agents are those conventionally used in suspension polymerization processes. They may be minimally water-soluble inorganic salts such as tribasic calcium phosphate, calcium carbonate, calcium sulfate, barium sulfate, barium phosphate, hydrophilic silicas, and tribasic calcium phosphate. Water-soluble organic suspending agents may also be used, e.g., polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyacrylic acid, polyacrylamide and hydroxyalkl cellulose. The suspending agent is present in amounts ranging from about 0.01 part to about 5 parts based on 100 parts total monomer content.
  • the two solutions are then combined to form a suspension and are polymerized with agitation for about 2 to 5 hours at a temperature of about 65 to about 85°C, preferably about 70 to about 75°C, to give a suspension which contains the copolymer bead.
  • the beads are then washed and separated from the water by means such as gravity filtration.
  • the filtered product also generally comprises about 15-30 percent water.
  • compositions of the invention can be used to prepare a film by conventional methods.
  • the composition can be coated on a substrate such as a polyester substrate and dried to produce a film. It is proposed that the compositions of the invention may also be used to prepare sealants, membranes and adhesives.
  • the characterization of the molecular weight distribution of the polymers described herein can be by conventional gel permeation chromatography (GPC). GPC analysis is done on the samples, using a Perkin Elmer
  • GLOSSARY Irganox 1010 pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)proprionate], from Ciba Geigy
  • FluorelTM 2230 vinylidene fluoride - hexafluoropropylene copolymer, fro 3M
  • Example 2 Synthesis of Macromonomer Stabilizer with TMI Endcap The procedure of Example 1 was followed, except for the substitution of 2.06 g alpha, alpha-dimethyl-meta-isopropenyl benzylisocyanate (TMI) for the IEM endcapper and the use of a reaction temperature of 65 °C.
  • TMI alpha-dimethyl-meta-isopropenyl benzylisocyanate
  • Example 1 The procedure of Example 1 was followed, except that only 0.2 g of mercapto ethanol was used. In addition, the reaction was stopped at the end of the initial reaction period. The resultant material was not reacted with IEM.
  • a solution of 10 g FluorelTM 2230 and 30 g methyl methacrylate in 40 g methanol was treated with 4 g of the stabilizer from Example 1 and 0.12 g VAZOTM 64, then heated at 55°C for 20 hours.
  • the resultant milky white dispersion was coated on a polyester substrate, dried 15 minutes at 65 °C, resulting in a clear coating.
  • Example 5 Preparation of Fluoroelastomer Composition A in Absence of a Stabilizer The procedure of Example 5 was followed, except that no stabilizer was added. The product thus obtained was a coagulated white polymer which could not be coated or converted into a useable dry polymer.
  • Example 6 Preparation of Fluoroelastomer Composition B
  • Example 6 The procedure of Example 6 was followed except that the acrylonitrile component was omitted. The resulting dispersion settled over time, and gave a nonuniform opaque film when coated and dried according to the procedure of Example 5.
  • This comparative example demonstrates the importance of acrylonitrile as a comonomer when long-chain (meth)acrylic acid esters are used.
  • Example 7 Preparation of Crosslinked Fluoroelastomer Composition C
  • a solution of 10 g stabilizer from Example 4 and 0.8 g sodium hypophosphite in 420 g deionized water was stirred at 550 rpm under nitrogen and heated to 70°C.
  • To the aqueous solution was slowly added a solution of 60 g FluorelTM 2230, 0.4 g isooctylthioglycolate and 0.4 g VAZOTM 64 in 140 g methyl methacrylate.
  • the reaction mixture was stirred and heated at 70-75 °C for 3 hours.
  • the resultant polymer beads were collected on cheesecloth, washed thoroughly with deionized water and dried.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention se rapporte à des compositions comprenant des élastomères de fluorocarbone et des polymères d'acrylate ou vinyliques non fluorés, combinées dans une polymérisation à dispersion ou en suspension utilisant un stabilisateur spécial pour rendre les polymères compatibles. Les revêtements fabriqués avec la composition de l'invention sont clairs et présentent les avantages inhérents aux élastomères de fluorocarbone ainsi qu'une bonne adhérence à de nombreux substrats.
EP93922213A 1992-09-18 1993-09-16 Systemes polymeres fluorochimique Ceased EP0660849A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US94777492A 1992-09-18 1992-09-18
US947774 1992-09-18
PCT/US1993/008746 WO1994006837A1 (fr) 1992-09-18 1993-09-16 Systemes polymeres fluorochimique

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EP0660849A1 true EP0660849A1 (fr) 1995-07-05

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JP (1) JPH08501585A (fr)
WO (1) WO1994006837A1 (fr)

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KR20010041763A (ko) 1998-03-11 2001-05-25 스프레이그 로버트 월터 접착제 층 위에 열가소성 층을 형성하는 형성 방법
DE69940986D1 (de) * 1999-07-15 2009-07-23 Dupont Performance Elastomers UV-vernetzbare Elastomerzusammensetzung
US7351471B2 (en) 2000-12-06 2008-04-01 3M Innovative Properties Company Fluoropolymer coating compositions with multifunctional fluoroalkyl crosslinkers for anti-reflective polymer films
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