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WO1995000560A1 - Polymeres reactifs - Google Patents

Polymeres reactifs Download PDF

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Publication number
WO1995000560A1
WO1995000560A1 PCT/US1994/007000 US9407000W WO9500560A1 WO 1995000560 A1 WO1995000560 A1 WO 1995000560A1 US 9407000 W US9407000 W US 9407000W WO 9500560 A1 WO9500560 A1 WO 9500560A1
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WO
WIPO (PCT)
Prior art keywords
polymer
ethylenically unsaturated
meth
vinyl
epoxide
Prior art date
Application number
PCT/US1994/007000
Other languages
English (en)
Inventor
James Wayne Taylor
Martha Jean Collins
David Robinson Basset
Original Assignee
JOHNSON, Karen, L.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by JOHNSON, Karen, L. filed Critical JOHNSON, Karen, L.
Priority to AU72487/94A priority Critical patent/AU7248794A/en
Publication of WO1995000560A1 publication Critical patent/WO1995000560A1/fr

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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • 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
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages

Definitions

  • This invention relates to reactive polymers, e.g., aqueous emulsion polymers, having pendant flexible or dangling side chains prepared from ethylenically unsaturated epoxides, e.g., epoxide (meth)acrylates, or from imines and ethylenically unsaturated epoxides, e.g., epoxide (meth)acrylates, or from imines and ethylenically unsaturated isocyanates.
  • the reactive polymers contain ethylenic unsaturation near the surface or in the surface area of the particles that form the polymers, the ethylenic unsaturation being connected to the polymer through the pendant flexible or dangling side chains.
  • This invention also relates to the process for preparing the reactive polymers, to crosslinkable formulations based on the reactive polymers, and to thermoplastic and crosslinked films prepared from the reactive polymers.
  • the reactive polymers are useful as decorative and functional coatings, inks, adhesives, textile coatings and sealants.
  • Aqueous emulsion polymers or latexes in both clear and pigmented form are well-known, widely-used articles of commerce. Examples of these uses include interior and exterior architectural coatings, general metal coatings, adhesives, and the like.
  • the latexes are formed by aqueous emulsion polymerization of monoethylenically unsaturated monomers as styrene, butyl acrylate, methyl methacrylate, vinyl acetate, acrylic acid, glycidyl acrylate, 2- hydroxyethyl acrylate, and similar compounds.
  • Illustrative of such techniques is the production of a core and shell latex in which the core of the particles has a given composition that may contain a small amount of the functional groups or be devoid of them and the shell or outer layers of the particle have a different composition which may be rich in the functional groups, and the like.
  • This invention relates in part to a polymer having one or more pendant flexible side chains connected thereto, wherein said pendant flexible side chains contain ethylenic unsaturation and are connected to said polymer by (1) an ester linkage or by (2) an ester linkage and an amine linkage or by (3) an ester linkage and a urea linkage, said ester linkage in (1) formed by the reaction of an ethylenically unsaturated epoxide with a carboxylic acid group on said polymer, said ester linkage in (2) and (3) formed by the reaction of an imine with a carboxylic acid group on said polymer to form an amine group connected to the polymer, said amine linkage in (2) formed by the reaction of an ethylenically unsaturated epoxide with said amine group, and said urea linkage in (3) formed by the reaction of an ethylenically unsaturated isocyanate with said amine group.
  • This invention also relates in part to a process for preparing a polymer having one or more pendant flexible side chains connected thereto comprising:
  • step (c) post reacting the precursor polymer of step (a) with one or more imines;
  • step (d) post reacting the polymer of step (c) with one or more ethylenically unsaturated epoxides or one or more ethylenically unsaturated isocyanates;
  • step (e) optionally recovering the step (b) or (d) polymer and redissolving it in an organic solvent.
  • ethylenic unsaturation of various types can be formed on, in, or near the surface of polymer particles that contain free, reactive carboxylic acid functionality by first preparing a precursor polymer and then post reacting it with one or more ethylenically unsaturated epoxides, e.g., epoxide (meth)acrylates, or one or more suitable imines containing a functional group that will react with all or a portion of the free, reactive carboxyl functionality on the precursor polymer particle and then post reacting the amine group with one or more ethylenically unsaturated epoxides or one or more ethylenically unsaturated isocyanates.
  • ethylenically unsaturated epoxides e.g., epoxide (meth)acrylates
  • suitable imines containing a functional group that will react with all or a portion of the free, reactive carboxyl functionality on the precursor polymer particle and then post reacting the amine
  • Air dry means to cure the liquid coating into a solid film by allowing it to remain under ambient conditions for a period of time sufficient to effect solidification.
  • Force dry means to cure the liquid coating into a solid film by exposing it to a thermal source such as an oven, to an actinic radiation source such as ultraviolet light, as electron beams, as lasers, and the like with or without a predrying step under ambient conditions to remove water, solvent, or other carrier.
  • ethylenic unsaturation shall include all permissible compounds, groups or substituents having at least one carbon-carbon double bond including, for example, (meth)acrylates, vinyls, allyls, alkenes, and the like.
  • the post modified polymer containing ethylenic unsaturation is recovered from the aqueous environment, dissolved in an organic solvent, and applied to a substrate to effect air-cure crosslinking.
  • the water-borne polymer particles can be crosslinked with free radicals generated from an actinic energy source such as an electron beam or by formulation with a free radical-generating photoinitiator and, if necessary, a synergist, and exposed to an ultraviolet light source such as sunlight, mercury vapor lamps, xenon lamps, etc.
  • the polymer precursor containing free, reactive carboxyl functionality can be recovered from the aqueous media and dissolved in an organic solvent or can be prepared in an organic solvent.
  • the polymer in organic solvent can be modified by post reaction with one or more of the above described reactants for aqueous systems to form a polymer with pendant flexible chains having ethylenic unsaturation connected thereto that can be crosslinked under ambient, air-cure conditions or radiation-cure conditions.
  • the post modified polymers containing ethylenic unsaturation neat or formulated with photoinitiator and/or other radiation-reactive chemicals is recovered as a solid, uncrosslinked film by removal of either the aqueous or organic solvent media.
  • the solid film is then used as a photoresist in the manufacture of printed circuit boards or other article by selective exposure to radiation. Selective exposure is provided by a mask through which radiation does not penetrate.
  • the reactive polymers of the invention can be used in a variety of ways including but not limited to clear, colored, filled, or pigmented crosslinked latexes, water-borne alkyds, solvent-borne alkyds, radiation curable systems, and the like.
  • Illustrative of generalized utility areas are coatings for metal, paper, plastics, wood, and masonry; inks; adhesives; binding agents for concrete; photoresists; and the like.
  • interior and exterior architectural coatings can coatings, office and home furniture coatings, pipeline coatings, sign coatings, maintenance coatings, business machine coatings, functional and decorative automotive coatings, textile coatings, conformal coatings, electrical and electronic coatings and the like.
  • Carboxyl group functionalized polymer particles can be reacted with an ethylenically unsaturated epoxide to form a free ethylenically-unsaturated terminated, pendant flexible side chain Hnked to the polymer particle through an ester linkage, or reacted with first an imine, in which case the reaction takes place with a carboxylic acid group to form a free amine group connected to the polymer particle by an ester linkage, and then in a second reaction the amine group is post reacted with:
  • ester linkage is contemplated to include all permissible linkages resulting (i) from the reaction of an ethylenically unsaturated epoxide with a carboxylic acid group on the polymer which links an ethylenically unsaturated terminated, pendant flexible side chain to the polymer or (ii) from the reaction of an imine with a carboxylic acid group on the polymer which forms a free amine group connected to the polymer.
  • amine linkage is contemplated to include all permissible linkages resulting from the reaction of an ethylenically unsaturated epoxide with a free amine group on the polymer which links an ethylenically unsaturated terminated, pendant flexible side chain to the polymer.
  • urea linkage is contemplated to include all permissible linkages resulting from the reaction of an ethylenically unsaturated isocyanate with a free amine group on the polymer which links an ethylenically unsaturated terminated, pendant flexible side chain to the polymer.
  • the polymers having carboxyl group functionality can be prepared from a variety of monoethylenically unsaturated monomers including, for example, acrylates and methacrylates (both referred to herein as (meth)acrylates); vinyl esters; vinyl aromatic, cycloaliphatic, and heterocycles; hydroxyalkyl (meth)acrylates and their derivatives; vinyl halogens and vinylidine halogens; alkenes and substituted alkenes; nitriles; and vinyl ethers. If desired, minor amounts of di- or triethylenically unsaturated monomers can be used if they do not unduly interfere with the polymerization process by causing excessive crosslinking and unusable polymer formation.
  • monoethylenically unsaturated monomers including, for example, acrylates and methacrylates (both referred to herein as (meth)acrylates); vinyl esters; vinyl aromatic, cycloaliphatic, and heterocycles; hydroxyalkyl (meth)acryl
  • Illustrative of the (meth)acrylates are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylates, butyl (meth)acrylates, pentyl (meth)acrylates, hexyl (meth)acrylates, heptyl (meth)acrylates, octyl (meth)acrylates, nonyl (meth)acrylates, decyl (meth)acrylates, and the like.
  • vinyl esters are vinyl acetate, vinyl propionates, vinyl butyrates, vinyl pivalates, vinyl hexanoates, vinyl hepanoates, vinyl octanoates, vinyl isovalerate, vinyl 2-ethylhexanoate, vinyl benzoates, vinyl crotonate, vinyl laurates, vinyl myristate, vinyl linoleate, vinyl Unolenate, vinyl cinnamate, vinyl stearates, vinyl oleate, vinyl napthanoates, vinyl cyclopentanoates, vinyl versatates, vinyl salicylate, monovinyl adducts of difunctional or higher functional carboxylic acids as monovinyl adipate.
  • vinyl aromatic, cycloaliphatic, and heterocycles are styrene, vinyl cyclohexane, vinyl cyclopentane, vinyl toluene, vinyl anthracenes, 3- vinyl benzyl chloride, 4-vinyl biphenyl, 4-vinyl-l-cyclohexene, vinyl cyclooctane, 2-vinyl naphthalene, 5-vinyl-2-norbornene, 1-vinyl imidazole, 2-vinyl pyridine, 4-vinyl pyridine, l-vinyl-2-pyrrolidinone, 9- vinyl carbazole, 3-vinylbenzyl chloride, and the like.
  • the hydroxyalkyl (meth)acrylates and their derivatives include 2-hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), ethylene oxide and propylene derivatives of HEA and HPA containing from 1 to about 20 moles of the alkylene oxide, caprolactone acrylates which are epsilon-caprolactone derivatives of HEA and HPA containing from 1 to about 6 moles of epsilon-caprolactone, carboxylic acid terminated adducts of HEA and HPA and the alkylene oxide and caprolactone derivatives of HEA and HPA, and the like.
  • HPA 2-hydroxyethyl acrylate
  • HPA hydroxypropyl acrylate
  • HPA ethylene oxide and propylene derivatives of HEA and HPA containing from 1 to about 20 moles of the alkylene oxide
  • caprolactone acrylates which are epsilon-caprolactone derivatives of
  • the polymer particles of this invention contain a major quantity of the functional groups in, at or near the surface (i.e., the surface region) of the particles, though it is realized that some of the functional groups may be positioned within the interior of the particles.
  • the number of copolymers in each polymer particle is indeterminate since particle size and copolymer molecular weight will vary, it is important that, on the average, carboxyl functionality exist on a majority of any copolymer molecules and that at least some of the functionahty be found in the surface region or related region so it can react with the post reaction reactants.
  • Other functional groups such as hydroxyl, etc., may also be present in the carboxyl functional polymer, i.e., precursor polymer, used in this invention.
  • Illustrative of the imines that can be used to produce the polymer particles containing amine termination are alkylene imines, such as ethylene imine, propylene imine, butylene imine, hexylene imine, 1,2- dimethylethylene imine, 1,1,2-trimethylethylene imine, cyclohexylene imine, and the like. Mixtures of the various alkylene imines may be used for the purposes of this invention. Both substituted and unsubstituted imines may be used for purposes of this invention.
  • Illustrative of the ethylenically unsaturated epoxides that can be used to react with the carboxyl group functionalized polymers or with the amine-ter inated polymer particles are the epoxide (meth)acrylates such as glycidyl (meth)acrylates, 2,3-epoxypropyl (meth .acrylate, allyl glycidyl (meth)acrylates, and the like.
  • the ami ne-terminated polymer particles are prepared in such a manner that less than an equivalent amount of imine is used so that residual carboxylic acid groups remain, ethylenically unsaturated cycloaliphatic epoxides can be used.
  • the 3,4-epoxycyclohexane (meth)acrylates can be prepared by (1) reacting tetrahydrobenzyl alcohol or tetrahydrobenzyl alcohol that has been first reacted with one or more appropriate alkylene oxide and/or epsilon-caprolactone, (2) reacting the alcohol or alcohol adduct with (meth)acrylic acid in an esterification reaction or with a lower alkyl (meth)acrylate such as methyl (meth)acrylate in a transesterification reaction to form 3- cyclohexene (meth)acrylate, and (3) epoxidizing the 3-cyclohexene (meth)acrylate to the 3,4-epoxycyclohexane (meth)acrylate.
  • the polymer particles are made by reacting 3,4-epoxycyclohexane (meth)acrylates with polymer particles.
  • Mixtures of various ethylenically unsaturated epoxides may be used for purposes of this invention. Both substituted and unsubstituted ethylenically unsaturated epoxides may be used for purposes of this invention.
  • Illustrative of the ethylenically unsaturated isocyanates that can be used to react with either the polymer particles (containing hydroxyl functionality) or the amine-terminated polymer particles are the isocyanato alkyl (meth)acrylates such as 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl methacrylate, and the like; the monoisocyanates prepared from diolefins such as the dialkylidene aryls that produce compounds such as l-(l-isocyanato-l-methyl ethyl )-3-(l- methyl ethenyl) benzene (p-TMI), l-(l-isocyanato-l-methyl ethyl)-4-(l- methyl ethenyl) benzene (m-TMI),l-(l-isocyanato-l-methyl propyl)-3- (1-methyl propenyl) benzene
  • initial aqueous emulsions used to prepare aqueous emulsion polymers of this invention have an initial pH of about 2.0 to 10.5 and contain about 0.05 to 20% or more of carboxylic acid functionality, preferably an initial pH of 3.5 to 9.0 and contain from about 0.1% to 15% carboxylic acid functionahty, and are prepared at about 40°C to about 100°C for about 6 to 48 hours, preferably at about 60 °C to about 90 °C for about 10 to about 24 hours under atmospheric pressure or superatmospheric pressure of about 15 psig to about 100 psig.
  • the post reactions leading to the reactive polymers of this invention are carried out at a temperature of from about 0°C to about 100°C, preferably from about 20°C to about 90° for about 30 minutes to 24 hours or more under atmospheric or superatmospheric pressure of about 15 psig to about 100 psig.
  • Illustrative of other such post reactions include, for example, (1) reaction with a carbodiimide (meth)acrylate wherein reaction takes place with carboxyl groups on the precursor polymer particle; (2) reaction with an ethylenically unsaturated isocyanate wherein reaction takes place with hydroxyl groups on the precursor polymer particle to form free vinyl groups connected to the particle with urethane linkages; (3) reaction with an ethylenically unsaturated aziridine wherein reaction takes place with carboxyl groups on the precursor polymer particle; and the like.
  • Both substituted and unsubstituted post reactants may be used for purposes of this invention.
  • Suitable other post reactions which may be employed herein include those disclosed in U.S. Patent Application Serial No.
  • the reactive polymers e.g., aqueous emulsion polymers, of this invention can be used in a variety of ways illustrative of which are as air-dry coatings that will increase in molecular weight presumably through crosslinking by reaction with atmospheric oxygen and/or incidental radiation under ambient conditions without the use of heavy metal catalysts known as drier salts, though such catalysts may be optionally included in coating formulations if desired; as thermally crosslinkable coatings when formulated with peroxides that will break down and cause crosslinking to take place through the ethylenic unsaturation; as radiation curable coatings, preferably in the presence of free-radical generating photoinitiators of either the homolytic fragmentation type or the hydrogen abstraction type which are usually 12
  • solvent reduced coatings in which relatively large quantities of solvent, i.e., more than flexibilizing or plasticizing quantities, are added to the formulation before application to a substrate; and the like.
  • the reactive polymers of this invention may be used alone or in combination with other systems illustrative of which are aqueous emulsions, water reducible alkyds, solutions of polymers, radiation- curable (meth)acrylates or epoxides, unsaturated fatty acid derivatives, linseed oil, soybean oil, tall oil, and the like.
  • aqueous alkyds having molecular weights of from about 500 to 5000 are prepared by adding chain transfer agents to the emulsion polymers during polymerization.
  • the reactive polymers of this invention are recovered as a solid, redissolved in an organic solvent, and formulated into solvent- borne coatings, particularly high solids alkyd coatings when low molecular weight polymers are formed in the emulsion process.
  • Suitable solvents are polar in nature illustrative of which are esters, ketones, esters of lactic acid; ethylene oxide glycol ethers as ethylene glycol monomethyl ether, ethylene glycol and diethylene glycol monoethyl ethers, ethylene glycol and diethylene glycol monopropyl ethers, ethylene glycol and diethylene glycol monobutyl ethers, and et ylene glycol and diethylene glycol monohexyl ethers; propylene oxide glycol ethers such as propylene glycol and dipropylene glycol monomethyl ethers, propylene glycol and dipropylene glycol monopropyl ethers, propylene glycol and dipropylene glycol monobutyl ethers, propylen glycol monobutyoxyethyl ether; toluene, methyl ethyl ketone, xylene, dimethylfo ⁇ namide, ethyl acetate, butyl acetate
  • these solvents may be used in combination with aliphatic hydrocarbons, aromatic hydrocarbons, super critical carbon dioxide, and the like.
  • film forming agents or plasticizers of various types may be incorporated into the formulations.
  • Optional heavy metal driers that may be incorporated into the coatings to promote curing.
  • These driers are metal salts of organic acids illustrative of which acids are tall oil fatty acids, ethylhexanoic acid, neodecanoic acids, naphthenic adds, and the like.
  • Illustrative of typical metals used for air- or ambient-dry systems are cobalt, zirconium, and manganese, and the like, and for heat-cure coatings are iron, manganese, cobalt, cerium, and the Uke.
  • Auxiliary driers include lead, barium, calcium, zirconyl (ZrO-) , zinc, and the like. If desired, mixtures of the various driers can be used.
  • Illustrative of the peroxides or compounds that will generate oxygen when heated that can be used in the thermally curable coating compositions of this invention are benzoyl peroxide, t-butyl peroxybenzoate, d ⁇ sopropyl peroxide, and the like. These compounds are used in an amount of about 0.05% to about 5%, preferably from about 0.1% to about 2.5%. It is known to those skilled in the art of these compounds that the cure temperature and decomposition temperature of any chosen compound must be properly considered when they are used.
  • hydrogen abstraction-type photoinitiators are benzophenone, benzophenone derivatives, 2-chlorothioxanthone, isopropylthioxanthone, fluorenone, benzil, 9,10-anthraquinone, •camphor quinones, 1,3,5-triacetylbenzene, 3-ketoco ⁇ m ⁇ arines, acridone, bis-(4,4'-d__methyla____ino)benzophenone, and the Hke.
  • amine, amides, urethanes or ureas with a hydrogen- bearing carbon atom in the alpha position to the nitrogen group among which one can mention dimethylethanol amine, triethyl amine; primary, secondary, and tertiary amine-terminated poly (propylene oxide) polyols as well urea and urethane derivatives of such polyols, and the Hke.
  • reactive polymers of this invention can be cured alone with or without added photoinitiator when exposed to ultraviolet light, they may be combined with one or more other radiation-polymerizable ethylenically unsaturated compounds such as substituted and unsubstituted (meth)acrylates.
  • esters of (meth)acrylic acid with monohydric and polyhydric compounds among which one can mention ethyl, butyl, hexyl, octyl, decyl, and the Hke (meth)acrylates; neopentyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate and tetra(meth)acrylate, caprolactone (meth)acrylates which are adducts of 1 to 10 moles of epsilon- caprolactone and a hydroxylalkyl (meth)acrylate, alkoxylated (meth)acrylates, glycerol (meth)acrylates, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)
  • vinyl esters are vinyl 2-ethylhexanoate, vinyl benzoate, vinyl isovalerate, vinyl nonylates, vinyl neononanoate, vinyl neodecanoate, vinyl myristate, vinyl oleate, vinyl linoleate, vinyl abietate, divinyl adipate, divinyl oxalate, divinyl succinate, divinyl fumarate, divinyl maleate, diisopropenyl adipate, trivinyl mellitate, trivinyl citrate, 1, 2, 4-trivinyl benzenetricarboxylate, tetravinyl mellophanate, 3,3',4,4'-tetravinyl benzophenonetetracarboxylate, and the Hke.
  • Such vinyl ester can also be used as reactive flexibizers/plasticizers in other non-photocurable coating compositions of the invention.
  • the photopolymerization is carried out by exposing the uncured - ..m or coating to Hght radiation which is rich in short wave radiation. Particularly useful is radiation of about 200 to 450 nanometers in wavelength.
  • Hght radiation which is rich in short wave radiation. Particularly useful is radiation of about 200 to 450 nanometers in wavelength.
  • lUustrative of appropriate light sources are low-pressure, medium pressure, and high-pressure mercury vapor lamps as weU as lamps of this type that have been doped to exclude selected wavelengths; xenon and other flash-type lamps; lasers operating in the above Hsted wavelength range; sunHght, and the like.
  • Other sources of radiant energy such as electron beams, gamma radiation, X-rays, and so on can also be used.
  • Any permissible conventional additives, processing aids, etc. may be employed in conventional amounts in the compositions and processes of this invention. This invention is not intended to be limited in any manner by any permissible additives, processing aids, and
  • the invention is illustrated by certain of the foU owing examples.
  • Gel Fraction The gel fraction or gel content is the amount of material that is insoluble when a given mass of the cured coating is extracted with tetrahydrofuran (THF) for 18 houre at room temperature. The extracted film is removed from the THF, rinsed with fresh THF, and dried at 110°C for one hour. The gel fraction, expressed as a percentage, is calculated with the foUowing expression.
  • Gel Fraction (1 - ((Weight of original film - Weight extracted film ./(Weight of original film)) x (100%)
  • Surfactant 2 A 70% solution of nonyl phenol-based alkylene oxide nonionic surfactant in water commercially available from Union Carbide Chemicals and Plastics Company Inc. under the designation Tergitol® NP-40.
  • Feed 1 was added over a 190 minute period.
  • an initiator feed composed of 2.20 grams of potassium persulfate dissolved in 107.8 grams of deionized water was begun and continued over a 240 minute period.
  • Feed 2 Table 2, was started and added to the reactor over a 50 minute period.
  • Total time of addition for Feed 1 and 2 was 240 minutes. After the reactants were added to the reactor, the aqueous emulsion was heated for 15 minutes at 80°C. While stirring the aqueous emulsion at 300 rpm, 165 grams of deionized water was added to decrease the emulsion solids to 42%. The pH was then adjusted to 7.2 by slowly adding a solution of triethylamine that contained 1% Surfactant 1 and 0.5% deionized water. Then, a pressure-equalizing dropping funnel equipped with a rubber septum was charged with 33.41 grams of water and 8.36 grams (0.15 mole) of propylenimine.
  • Preparation A The mixture was added to the aqueous emulsion at room temperature, and the mixture was stirred for 1 hour at 60°C to effect reaction of the imine and form amine groups in the surface area of the emulsion.
  • a second emulsion was prepared in the same manner as described above and the two emulsions were combined and designated as Preparation A, which had a total solids content of 41.55%, a pH of 8.6, and a minimum filming temperature of 45.8°C.
  • Gel fraction of the emulsion particles was determined by adding 2.0 grams of emulsion to 35 milUUters of acetone, swirling the mixture for 5 minutes, and then centrifuging for 30 minutes at 18,000 rpm. The Uquid was removed and a second 35 miUiliters of acetone was added to the solid material. The mixture was swirled and centrifuged as previously described. The procedure was repeated again, and then the residue sample was dried in a forced-air oven at 75° C for 2 hours. The film gel fraction was then determined in the usual manner.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention se rapporte à des polymères réactifs, par exemple des polymères formant des émulsions aqueuses, ayant des chaînes latérales flexibles pendantes, préparées à partir d'époxydes à insaturation éthylénique, par exemple des (méth)acrylates d'époxyde, ou à partir d'imines et d'époxyde à insaturation éthylénique, par exemple des (méth)acrylates d'époxyde, ou à partir d'imines et d'isocyanates à insaturation éthylénique. Les polymères réactifs contiennent une insaturation éthylénique près de la surface ou dans la zone de surface des particules qui forment les polymères, l'insaturation éthylénique étant reliée au polymère au moyen des chaînes latérales flexibles pendantes. Cette invention se rapporte également à un procédé de préparation des polymères réactifs, à des formulations réticulables à base des polymères réactifs, et à des films thermoplastiques et réticulés préparés à partir des polymères réactifs. Les polymères réactifs sont utiles comme revêtements décoratifs et fonctionnels, comme encres, adhésifs, revêtements textiles et matériaux d'étanchéité.
PCT/US1994/007000 1993-06-23 1994-06-20 Polymeres reactifs WO1995000560A1 (fr)

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Cited By (7)

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WO1997024378A1 (fr) * 1995-12-29 1997-07-10 Minnesota Mining And Manufacturing Company Utilisation de fragments pendants a polymerisation radicalaire ainsi que de polymeres polaires en vue de la preparation de compositions adhesives hydrophiles et sensibles a la pression
US5780117A (en) * 1996-02-26 1998-07-14 Rohm And Haas Company Dual-cure latex compositions
WO1998028286A3 (fr) * 1996-12-23 1998-08-13 Sartomer Co Inc Esters de (meth)acrylates non satures contenant des groupes cycliques epoxydes et procede de preparation
US5985990A (en) * 1995-12-29 1999-11-16 3M Innovative Properties Company Use of pendant free-radically polymerizable moieties with polar polymers to prepare hydrophilic pressure sensitive adhesive compositions
WO2001096413A1 (fr) * 2000-06-15 2001-12-20 Tesa Ag Procede de production de substances auto-adhesives d'acrylate reticulables
WO2020010069A1 (fr) * 2018-07-02 2020-01-09 Cytec Industries, Inc. Polymère de production de fibres de carbone et fibres de carbone constituées à partir de ce dernier
CN118420892A (zh) * 2024-07-04 2024-08-02 潍坊恒彩数码影像材料有限公司 一种用于偏光片的耐高温光学薄膜材料及其制备方法

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WO1997024378A1 (fr) * 1995-12-29 1997-07-10 Minnesota Mining And Manufacturing Company Utilisation de fragments pendants a polymerisation radicalaire ainsi que de polymeres polaires en vue de la preparation de compositions adhesives hydrophiles et sensibles a la pression
US5985990A (en) * 1995-12-29 1999-11-16 3M Innovative Properties Company Use of pendant free-radically polymerizable moieties with polar polymers to prepare hydrophilic pressure sensitive adhesive compositions
US5780117A (en) * 1996-02-26 1998-07-14 Rohm And Haas Company Dual-cure latex compositions
WO1998028286A3 (fr) * 1996-12-23 1998-08-13 Sartomer Co Inc Esters de (meth)acrylates non satures contenant des groupes cycliques epoxydes et procede de preparation
WO2001096413A1 (fr) * 2000-06-15 2001-12-20 Tesa Ag Procede de production de substances auto-adhesives d'acrylate reticulables
WO2001096414A1 (fr) * 2000-06-15 2001-12-20 Tesa Ag Procede pour la production de matieres adhesives acryliques reticulables
US7084185B2 (en) 2000-06-15 2006-08-01 Tesa Ag Method for the production of cross-linkable acrylate contact adhesive materials
WO2020010069A1 (fr) * 2018-07-02 2020-01-09 Cytec Industries, Inc. Polymère de production de fibres de carbone et fibres de carbone constituées à partir de ce dernier
US12122864B2 (en) 2018-07-02 2024-10-22 Cytec Industries Inc. Polymer for the production of carbon fibers and carbon fibers made therefrom
CN118420892A (zh) * 2024-07-04 2024-08-02 潍坊恒彩数码影像材料有限公司 一种用于偏光片的耐高温光学薄膜材料及其制备方法

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