Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
• • 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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • 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
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
  • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S525/902—Core-shell

Definitions

• This invention relates to epoxy compounds, and in particular, to epoxy resins which contain polymeric materials contained therein.
• Epoxy compounds, and in particular epoxy resins comprise a well-ki.own class of thermosettable resins. Such epoxy compounds possess excellent physical and chemical properties, and are particularly useful in a wide variety of applications.
• epoxy resins are useful as coatings for a variety of substrates, laminates, moldings, adhesives, and in numerous other applications where a material exhibiting good heat resistance, hardness, electrical properties, dimensional stability, corroaion resistance and chemical resistance is desirable.
• toughened epoxy compounds typically exhibit poor heat resistance.
• toughened epoxy compounds can exhibit varying physical properties because commonly used elastomeric materials can vary in size and/or behavior.
• the elastomeric materials which are incorporated into the epoxy compounds can act as plasticizers which in turn provide undesirable stability problems to the toughened compound.
• the present invention is a composition
• a continuous phase which is an epoxy compound and (2) a discontinuous phase dispersed in said continuous phase which is an elastomeric particle in the form of a grafted rubber concentrate which contains a functionally effective amount of crosslinking and which further is grafted such that a functionally effective amount of a functional group is capable of reacting along with a functionality of the continuous phase.
• the present invention is a process for preparing a toughened epoxy compound, which process comprises contacting (1) a continuous phase which is an epoxy compound and (2) an amount of an elasto eric particle composition wherein said elasto ⁇ meric particle composition is in the form of a grafted rubber concentrate which grafted rubber concentrate contains a functionally effective amount of crosslinking and which further is grafted such that a functionally effective amount of a functional group is capable of reacting along with a functionality of the continuous phase and which amount is sufficient to provide a dispersed phase in the epoxy compound and sufficient to provide toughness to the epoxy compound when cured, and wherein said contact is in a manner sufficient to provide a dispersion of said grafted rubber concentrate in said epoxy compound such that functionalities of the epoxy compound can react with the reactive functional groups of the grafted rubber concentrate.
• compositions of this invention can be broadly described as rubber-modified epoxy compounds.
• the compositions of this invention are stable dispersions of polymer in the epoxy compound.
• stable is meant to refer to dispersions which remain substantially constant (i.e., do not undergo substantial reprecipitation or redis- persion) under conditions of preparation .as well as conditions of thermal cure.
• ⁇ _i_2 dispersion of grafted rubber concentrate remains- stable (e.g., insoluble and noncoagulating) under normal preparation, handling and processing (e.g., curing) conditions by maintaining a substantially constant morphology (e.g., size and distribution) in the continuous phase at some temperature, normally above 60°C.
• compositions of this invention find a wide variety of uses in numerous applications where high performance engineering plastics are required.
• the compositions of this invention are useful in all appli ⁇ cations in which epoxy resins are useful.
• the compo ⁇ sitions of this invention can exhibit improved toughness and can maintain hardness at high application tempera- tures.
• stable dispersions are used as coatings (e.g., solution, high solids or powder coatings); fiber-reinforced laminates; advanced composites including aerospace, fiberglass reinforced plastics tooling, casting and molding resins; bonding agents; adhesives; encapsulants of electrical components which are exposed to wide temperature fluctuations; and the like.
• Epoxy compounds useful in this invention include a wide variety of epoxy compounds.
• the epoxy compounds are epoxy resins which are also re erred to as polyepoxides.
• Polyepoxides useful herein can be monomeric (e.g., the diglycidyl ether of bisphenol A), higher molecular weight advanced resins or polymerized unsaturated monoepoxides (e.g., glycidyl acrylates, glycidyl methacrylate, allyl glycidyl ether, etc.) to homopolymers or copolymers.
• ep ⁇ __y compounds contain, on the average, at least one pe dan or terminal 1,2-epoxy group (i.e., vicinal epoxy grour- ) per molecule.
• polyepoxides examples include the polyglycidyl ethers of both polyhydric alcohols and polyhydric phenols; polyglycidyl amines, polyglycidyl amides, polyglycidyl imides, polyglycidyl hydantoins, polyglycidyl thioethers, epoxidized fatty acids or drying oils, epoxidized polyolefins, epoxidized di-
• polyepoxides prepared from polyhydric phenols include those which are disclosed, for example, in U.S. Patent 4,431,782.
• Poly ⁇ epoxides can be prepared from mono-, di- and tri-hydric phenols, and can include the novolac resins.
• Poly ⁇ epoxides can include the epoxidized cycloolefins; as well as the polymeric polyepoxides which are polymers and copolymers of glycidyl acrylate, glycidyl methacrylate and allylglycidyl ether.
• Suitable poly ⁇ epoxides are disclosed in U.S. Patent 3,804,735; 3,892,819; 3,948,698; 4,014,771 and 4,119,609; and Lee and Neville, Handbook of Epoxy Resins, Chapter 2, McGraw Hill, New York (1967).
• polyepoxides While the invention is applicable to poly- ⁇ epoxides, generally preferred polyepoxides are glycidyl polyethers of polyhydric alcohols or polyhydric phenols having weights per epoxide group of 150 to 2,000. These polyepoxides are usually made by reacting at least about two moles of an epihalohydrin or glycerol dihalohydrin with one mole of the polyhydric alcohol or polyhydric phenol, and a sufficient amount of a caustic alkali to combine with the halohydrin. The products are charac ⁇ terized by the presence of more than one epoxide group, i.e., a 1,2-epoxy equivalency greater than one.
• the polyepoxide may also include a minor amount of a monoepoxide, such as butyl glycidyl ether, phenyl glycidyl ether, or cresyl glycidyl ether, as a reactive diluent.
• a monoepoxide such as butyl glycidyl ether, phenyl glycidyl ether, or cresyl glycidyl ether
• reactive diluents are commonly added to polyepoxide formulations to reduce the working viscosity thereof, and to give better wetting to the formulation.
• a monoepoxide affects the stoichiometry of the polyepoxide formulation and adjustments are made in the amount of curing agent and other parameters to reflect that change.
• elastomeric particle compositions useful in this invention which are in the form of grafted rubber concentrates are those types of particles as are described in U.S. Patent 4,419,496.
• Other elastomeric particles are disclosed in U.S. Patent 3,830,878.
• particles are composed of aliphatic conjugated dienes such as 1,3-butadiene or acrylate ho opolymers or interpolymers such as the esters of o o acrylic acid, and range in size from 300 A to 20,000 A in diameter.
• the amount of elastomeric material typically ranges from 15 to 90, preferably from 25 to 80, weight percent in the form of polymerized butadiene, isoprene and acrylate monomers such as 2-ethylhexyl acrylate and butylaerylate, and poly- sulfides, silicone -rubbers, and the like; which is grafted with a polymer containing a functionally reactive group.
• the elastomeric particles of this invention are those which can have a functionally effective amount of crosslinking.
• the elastomeric or rubbery component is -not completely soluble in a suitable solvent _or the elastomeric or rubbery component. That is, the elastomeric or rubbery component of the gr?fte ⁇ rubbex concentrate forms a gel and swells in the solvents, but does not dissolve. Typically, in such a situation, the percent gel ranges from 50 to 95 percent, and- he swelling index ranges from 3 to 50.
• the elastomeric particles are those particles which comprise a graft polymer having a substrate of an elastomeric or rubbery component and having grafted thereto a vinyl polymer component.
• the vinyl polymer component can be described as a polymer containing a functional monomer.
• the amount of vinyl polymer attached phase which is grafted to the elasto ⁇ meric or rubbery component is bonded to the surface region of the elastomeric or rubbery component and ranges from 10 to 90 weight percent of the total attached phase which is polymerized in the presence of the elastomeric or rubbery component.
• the elastomeric or rubbery component comprise an adequate amount of attached phase grafted thereto, such that there be enough attached phase present to effectively stabilize the elastomeric particles in the epoxy phase.
• at least 0.05 to 0.1 parts by weight of attached phase per 1 part by weight of elastomeric or rubbery component will effectively stabilize the elastomeric particles in the epoxy phase.
• as much as 0.5 parts by weight of attached phase per 1 part by weight of elasto ⁇ meric or rubbery component can stabilize the elastomeric particles in the epoxy phase.
• the amount of graft which is employed in such effective amount which is that amount sufficient to stabilize the elastomeric particles in the epoxy phase will vary depending upon factors such as the particle size of the dispersed phase particles. For example, the use of smaller size will typically require the use of greater amounts of graft.
• the graft molecular weight can vary and generally ranges from 10,000 to 250,000. Lower molecular weight grafts typically result in dispersions with low viscosity, while higher molecular weight grafts result in dispersions with high viscosity. When cross- linked, high molecular weight grafts provide improved toughness to the composition.
• the graft weight average molecular weight can be determined using techniques such as gel permeation chromotography on the nonattached phase in the grafted rubber concentrate.
• the elastomeric or rubbery components include conjugated dienes, acrylate rubbers and interpolymers of the type disclosed in U. S. Patent 4,419,496.
• the grafted or vinyl polymer attached phase polymers provide a compatibilizing interface which allows for dispersion of rubber particles in the epoxy compound.
• Preferred attached phase polymers are soluble in the epoxy compound.
• grafted or attached phase polymers comprise copolymerized styrenics, acrylates and methacrylates, acrylonitrile monomers, acrylic acids, methacrylic acids, hydroxypropyl acrylate, hydroxyethyl acrylate, vinylized glycidyl ethers such as glycidyl methacrylate, and combinations thereof.
• the grafted or attached phase can comprise a functionality which reacts along with functionalities of the epoxy compound.
• the grafted or attached phase can comprise a functionality which is capable of reacting along with functionalities of the hardening agent or curing agent.
• the amount of monomer which contains such a functionality and which is polymerized in the attached polymer phase ranges from 1 to 20 weight percent based on tLe polymerized monomer having said functional group and t e polymerized graft monomer in the outer region of J i ⁇ e grafted rubber concentrate.
• Preferred combinations of monomers which polymerize to form attached phase polymers include styrene/acrylonitrile/glycidyl methacrylate; styrene/- acrylonitrile/acrylic acid; and ethyl acrylate/- methacrylic acid.
• the elastomeric particle composition can be incorporated into the epoxy compound continuous phase using a variety of techniques.
• the grafted rubber concentrate in the form of a latex in an aqueous phase is contacted with the epoxy compound, and the aqueous phase is removed.
• the aqueous phase latex, epoxy compound, and suitable organic solvent can be contacted, and the aqueous phase and organic solvent can be removed.
• a dried grafted rubber concentrate can be contacted with the epoxy compound and an optional organic solvent; and the solvent (if employed) can be removed.
• the elastomeric particles are dispersed in the epoxy compound, preferably using a mixing or shearing device. After solvent and/or aqueous phase is removed the composition can be cured.
• the dispersed phase can be in an amount which varies and which is typically of from 2 to 45 weight percent of the total dispersion (i.e., epoxy resin plus dispersed phase).
• the optimum concentration of dispersed phase can and will be varied depending upon the materials employed and the end use that is envisaged.
• the dispersions are usually made at a solids level at which the dispersions are to be used. However, it is possible to prepare higher dispersed phase volume dispersions and dilute to the final dispersed phase level.
• the properties of the dispersion are influenced by a variety of factors including the identity of the components, the particle size and concentration of the disperse phase, the hardness or softness of the particles of the disperse phase, the concentration and nature of the graft phase, and many other factors.
• the dispersions typically exhibit moderately low viscosities, which provides a viscosity control which is desirable in epoxy compound appli ⁇ cations.
• the stability of the dispersion and the property enhancement due to the dispersed phase will be optimized with particles that are less than some critical particle size which is 20 microns.
• the elastomeric particles range o o in size from 300 A to 20,000 A, more desirably from o o
• the bimodai mixture is particularly desired, and the small size o o particles preferably range from 900 A to 1,500 A" in diameter, while the large size particles range from o o
• the dispersions are solidified by curing the polyepoxide.
• the choice of curing agent can influence the cure rate, the exotherm and resultant properties of the finished product.
• Curing agents or hardening agents a ⁇ _ ⁇ their influence are known in the literature as, for example, in the book, Handbook of Epoxy Resins, (supra) a d in Chemical Reactions of Polymers, Interscience T ⁇ blishers, New York, pages 912-926, (1967) and in other reference works. Some of these influences are illustrated in Modern Plastics Encyclopedia, pages 33-34, (1982-1983).
• the hardening agent can be added to the composition , after the dispersion of grafted rubber concentrate in epoxy compound is formed.
• the hardening agent can be contacted with the grafted rubber concen ⁇ trate' prior to the time that said grafted rubber concen ⁇ trate is added to the continuous phase.
• the cured products have improved toughness over those without the dispersed phase.
• the heat distortion temperatures are improved over those exhibited by the products obtained by curing a poly- epoxide containing dissolved carboxylated rubbers as, for example, carboxy-terminated diene elastomers.
• Example 1- Into a 1-gallon (3.8 x 10 -3 m3) glass reactor was charged 2689 g of a dispersion of a rubber latex.
• the latex dispersion contained 890 g rubber solids which solids represented 5 percent styrene, 93 percent butadiene and 2 percent acrylonitrile polymerized to o yield a mixture of 56 percent diameter 8000 A and o
• the resulting dispersion contained 42.8 percent polymer solids, and the polymer contained 53.6 percent rubber in polymerized form.
• the polymer contained 36.4 percent grafted rigid phase and 10 percent nongrafted rigid phase.
• the grafted rubber resin so formed was isolated using freeze coagulation techniques and air dried.
• a dispersion of the grafted rubber concentrate with an epoxy resin was prepared as follows: 81.3 g of an epoxy resin which is a diglycidyl ether of bisphenol A (a liquid epoxy resin sold commercially by The Dow Chemical Company as D.E.R. 383 epoxy resin, having an epoxy equivalent weight of from 178 to 186 and a viscosity at 25°C of between 9,000 and 11,500 centi- poise [9 and 11.5 Pa*s]) is dissolved in 50 g of methyl ethyl ketone by mixing said components together at room temperature. To this solution was added 18.7 g of the dry grafted rubber concentrate which has been described hereinbefore. This mixture was sheared at room tempera- ture for 5 minutes using a Tekmar _ high shear device.
• an epoxy resin which is a diglycidyl ether of bisphenol A (a liquid epoxy resin sold commercially by The Dow Chemical Company as D.E.R. 383 epoxy resin, having an epoxy equivalent weight of from 178 to 186 and a vis
• the solvent and water are removed from the mixture by rotary evaporation under vacuum to yield a toughened epoxy dispersion having uniform disperion and good stability.
• the viscosity of the toughened epoxy dispersion was low enough such that the sample was pourable at room temperature.
• the dispersion was cross- linked using a, stoichiometric amount of methylene dianiline. The sample is designated as Sample No. 1.
• Sample No. 2 was provided as follows: A grafted rubber concentrate was provided by polymerizing 319 g of the monomer mixture described hereinbefore in the presence of 108 g of rubber latex solids.
• the o rubber latex solids had 80 percent 12,000 A diameter o and 20 percent 1,300 A diameter solid particles.
• the grafted rubber concentrate had 13.1 percent attached rigid phase and 9.7 percent nonattached rigid phase; and the nonattached rigid phase had a molecular weight of 22,000.
• the dispersion of the grafted rubber concen ⁇ trate in epoxy resin was provided by shearing 63.7 g of the grafted rubber latex dispersion (19.4 g of polymer solids) and 13.6 g of the previously described epoxy resin, and then removing water by rotary evaporation techniques.
• the dispersion of grafted rubber concen ⁇ trate in epoxy resin was crosslinked using a stoichio- metric amount of methylene dianiline.
• Fracture energy is determined using a double-edged notched tensile bar which is 0.125 inch (0.319 cm) thick and drawn at 0.2 inch/minute (0.5 cm/minute) .
• the data in Table I indicate that the samples of this invention exhibit excellent fracture energies with little, if any, lowering of the glass transition temperature.
• a grafted rubber concentrate was prepared by polymerizing 20 parts of a 92 percent ethyl acrylate, 8 percent methacrylic acid mixture in the presence of 80 parts of a latex containing butadiene type rubber o particle.
• the rubber particles had a 1,000 ' A diameter and were comprised of, in polymerized form, 92 parts butadiene, 5 parts styrene and 3 parts acrylonitrile.
• the polymerization was carried out in an agitated reactor outfitted for nitrogen blanketing whereby there was charged into the reactor 1,009 parts of the afore ⁇ mentioned rubber particles in the form of a 35 percent solids latex dispersion, 360 parts water, 1 part acetic acid in order to provide a reaction mass pH of 4, 0.085 part of the bisodium salt of ethylenediamine tetraacetic acid, and 1.05 part potassium persulfate.
• the reaction mass was heated to 65°C. At this point, 2 continuous additions were simultaneously fed into the reactor.
• the first feed contained 68 parts of an aqueous solution containing 0.125 percent potassium persulfate and 2.5 percent sodium dodecylbenzene sulfonate; and said feed was added over a 1.25 hour period.
• the second feed contained 85 parts of a mixture containing 92 percent ethyl acrylate and 8 percent methacrylic acid; and said feed was added ove a 1 hour period. After addition of the continuous feeds were completed, the reaction mass was maintained at 65°C, with stirring for an additional 3 hours.
• a dispersion of the ethyl acrylate/methacrylic acid grafted rubber concentrate in epoxy resin was provided as follows: To 80 parts of epoxy resin maintained at 50°C was added dropwise with agitation over a 15 minute period, 64.7 parts of a latex dispersion containing 20 parts of the previously described grafted rubber concentrate.
• the epoxy resin was a diglycidyl ether of bisphenol A. Water is removed from the uniform dispersion by evaporation in order to yield a viscous adhesive product.
• the sample was cured with triethylene tetraamine in order to provide a toughened resin exhibiting a glass transition tempera ⁇ ture of 108°C.
• Example 3 Into a thermostatically controlled 500 ml round-bottomed flask equipped with _a stirrer, reflux condenser and feed ports was charged 131.6 g deionized water, 0.45 g of an azobisisobutyronitrile initiator, sold commercially as Vazo 64 by E. I. duPont de Nemours and Co., and 346.8 of a partially coalesced latex.
• the latex was 34.6 percent solids in an- queous medium, and the solids comprised 50 percent by volume particles having an average diameter of 0.1 ⁇ m and 50 percent by volume particles having an average diameter of 0.8 ⁇ m.
• the latex comprised in polymerized form 5 percent styrene, 92 percent butadiene and 3 percent acrylo ⁇ nitrile.
• the mixture which was charged into the flask was heated to 70°C under nitrogen atmosphere.
• a monomer stream containing 27 g styrene, 11.25 g acrylonitrile and 6.75 g glycidyl methacrylate was added to the heated mixture over a 1.5 hour period.
• the resulting mixture was continued to be heated at 70°C for 2 hours in order to yield a latex dispersion of grafted rubber concentrate solids having 30.8 percent solids, and an average o particle size of 1,390 A as determined by light scattering.
• the dispersion of latex particles in the epoxy resin continuous phase was provided as follows: Into a 1-liter container was charged 100 g of an epoxy resin which is a diglycidyl ether of bisphenol A having an epoxy equivalent weight of from 182 to 190 and a viscosity at 25°C of between 11,000 and 14,000 centi- poise (11 and 14 Pa-s) and sold commercially as D.E.R. _ 331 epoxy resin by The Dow Chemical Company.
• an epoxy resin which is a diglycidyl ether of bisphenol A having an epoxy equivalent weight of from 182 to 190 and a viscosity at 25°C of between 11,000 and 14,000 centi- poise (11 and 14 Pa-s) and sold commercially as D.E.R. _ 331 epoxy resin by The Dow Chemical Company.
• o solids particles had an average diameter of 1,140 A.
• the latex comprised, in polymerized form, 92 percent butadiene, 5 percent styrene and 3 percent acrylo ⁇ nitrile.
• the polymer phase was 91 percent gel and the swelling index of the particles was 19.
• the mixture which was charged into the flask is heated to 70°C under nitrogen atmosphere.
• 90 g of a monomer stream containing 60 g styrene, 25 g acrylonitrile and 15 g glycidyl methacrylate was added to the heated mixture over a 1.5 hour period.
• the resulting mixture was continued to be heated at 70°C for 1.5 hours in order to yield a latex dispersion of grafted rubber concen ⁇ trate solids having 31.3 percent solids, and an average o particle size of 1,410 A as determined by light scattering.
• methyl ethyl ketone To 1,000 g of methyl ethyl ketone was added 250 g of the previously described latex dispersion. The mixture was allowed to phase separate overnight. To 1,185 g of the r upper phase (i.e., methyl ethyl ketone phase) which was separated from the aqueous phase was added a mixture containing 275 g of the previously described D.E.R. ® 331 epoxy resin and 275 g of methyl ethyl ketone. The mixture was subjected to vacuum distillation at 60°C to 80°C.
• the product which contained 25 percent grafted rubber concentrate and 75 percent epoxy resin was gel- free and pourable, having a viscosity of 24,000 cps (24 Pa-s).
• a coating provided by mixing 5.4 g of the previously desc ibed product and 2 g of polyamide resin which is comm rcially available as Versamid ® 140 from

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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)
• Epoxy Resins (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Epoxy Compounds (AREA)
• Graft Or Block Polymers (AREA)

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• 1986
  • 1986-06-23 DE DE8686904553T patent/DE3674902D1/de not_active Expired - Fee Related
  • 1986-06-23 JP JP61503734A patent/JPS62501299A/ja active Granted
  • 1986-06-23 WO PCT/US1986/001339 patent/WO1987000188A1/en active IP Right Grant
  • 1986-06-23 KR KR1019870700169A patent/KR900007766B1/ko not_active Expired
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• 1987
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• 1988
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