water redispersible epoxy polymer powder, method for preparing water dispersible epoxy polymer powde

专利摘要:
water-dispersible epoxy polymer powder, method for preparing water-dispersible epoxy polymer powder, and, dispersion of the water-dispersible epoxy polymer powder, an aqueous dispersion of epoxy resin and a redispersible epoxy polymer contains particles of 50 to 90 weight percent epoxy resin with 10 to 50 weight percent alkali-soluble wrap around the particles and 2 to 25 weight percent dispersion aid, with the weight percentage based on the total combined weight of epoxy resin, polymer shell soluble in alkali and dispersion aid.
公开号:BR112013031811B1
申请号:R112013031811
申请日:2012-06-13
公开日:2020-05-19
发明作者:Chen Liang；Hong Liang；N Sekharan Manesh；J Radler Michael
申请人:Dow Global Technologies Llc；
IPC主号:

专利说明:

“WATER REDISPERSABLE EPOXY POLYMER POWDER, METHOD FOR PREPARING THE WATER DISPERSIBLE EPOXY POLYMER DUST, AND, DISPERSION OF THE REDISPERSABLE EPOXY POLYMER POWDER IN WATER”
BACKGROUND OF THE INVENTION
Field of invention
[01] The present invention relates to a method for making a water redispersible epoxy polymer powder and the resulting water redispersible epoxy polymer powder and dispersions of epoxy polymer particles.
Description of the Related Art
[02] Redispersible polymer powders (PRD, redispersible polymer) in water are dry powders of polymeric particles that dissolve during mixing with an aqueous fluid and form a polymeric dispersion in the aqueous fluid. PRD powders in water from polymeric binders are valuable additives in dry formulations of cement materials such as mortar, plaster and concrete for the purpose of improving the final properties of the resulting material. Epoxides, for example, are desirable additives in cement formulation to increase toughness, reduce water permeability and / or increase chemical and stain resistance in cement materials. Epoxides can be added to a cement formulation as a liquid dispersion. However, it is desirable to include epoxy additives in the form of a PRD powder in water in dry cement formulations to facilitate shipping, formulation and handling. PRD powders from epoxy resins are not well known despite a desire for such a material. Those PRD powders that contain epoxy resins that contain epoxy polymer comprise a lesser amount (50% by weight or less) of epoxy resin mixed in another polymer (typically emulsion polymerized polymer).
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[03] United States published patent application No. 20100197831A1 describes a water redispersible powder of a combination of polymers that comprises up to 50% by weight of epoxy polymer. The polymer powder is prepared by emulsion polymerization of a non-epoxy polymer, then addition of epoxy resin to the emulsion polymer and isolation of the particles of the polymer blend as a powder.
[04] United States patent application published No. 2001/0024644 describes a method for manufacturing a dispersion of polymeric particles by emulsion polymerization of monomers, up to 10 weight percent of which may contain epoxide functionality, and incorporation into the particles in emulsion of up to 50% by weight of a non-copolymerizable difunctional epoxide. The emulsion particles can be isolated to form water-redispersible polymer powder.
[05] European patent application No. EP723975A1 describes a water redispersible polymer powder comprising a copolymer containing up to 50 weight percent ethylenically unsaturated comonomer containing epoxide group.
[06] The aforementioned references do not mention a method for forming a PRD powder that contains more than 50% by weight of epoxy resin based on the PRD particle weight. Such a PRD powder would be desirable for the concentrated delivery of epoxy resin in the form of dry powder. The aforementioned references additionally do not mention a method for forming a PRD powder that contains more than 50% by weight of epoxy resin based on the weight of PRD powder particles where the epoxy resin has a glass transition temperature below temperatures in which it is isolated as a PRD powder or even below the temperatures at which it is used, or a method for making such a PRD powder. Such PRD powders would be highly desirable for concentrated delivery and rapid epoxide dissociation in cement formulations.
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BRIEF SUMMARY OF THE INVENTION
[07] The present invention provides an improvement over the technique known for surprisingly providing a process for making an epoxy PRD powder (or simply "epoxy PRD") that has the above desirable characteristics. In particular, the process of the present invention has overcome the process challenges related to the manufacture of an epoxy PRD that contains more than 50% by weight of epoxy resin based on the total weight of epoxy PRD particles, for example, by discovery of suitable combinations of types and concentrations of dispersion aids and shell-forming polymer to allow the formation of PRD. In addition, a desirable embodiment of the present invention further provides a process that enables the formation of such an epoxy PRD in which the epoxide is a liquid at the temperatures at which it is isolated as a PRD. Furthermore, the process of the present invention provides a method for making such epoxy PRDs so that they are stable during isolation and redispersion but that they readily release the epoxide for use as a binder when formulated in a cement formulation. These achievements are partly due to a surprising discovery that it is possible to produce an alkali-soluble wrap around the resin particles without the need to first form emulsion polymerized seed latex to dissolve the epoxy resin for the purpose of obtaining the dispersed resin particles. Another discovery is how to produce an alkali-soluble wrap around the epoxy particles that is able to protect the epoxy resin from diffusion between the particles during spray drying and storage as a PRD powder but that is able to release the epoxide when formulated in an alkaline environment such as a cement formulation.
[08] In a first aspect, the present invention is a water-redispersible epoxy polymer powder comprising resin particles
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4/45 epoxy, epoxy resin particles comprising: (a) epoxy resin;
(b) an alkali-soluble polymeric shell around each of the epoxy resin particles, the alkali-soluble polymeric shell comprising a polymer made up of at least five weight percent to forty weight percent or less of monomers selected from monomers of carboxylic acid and anhydride monomers based on the total weight of polymerized monomers to form the alkali-soluble polymeric shell and the alkali-soluble polymeric shell having a glass transition temperature of at least 60 degrees Celsius as calculated by the Fox formula; and (c) a dispersion aid; being that the epoxy resin is present in a concentration greater than fifty percent by weight to ninety percent by weight or less, the alkali-soluble polymeric shell is present in a concentration in a range of ten to fifty percent by weight and the auxiliary dispersion is present in a concentration of two to twenty-five percent by weight with the weight percentages of epoxy resin, alkali-soluble polymeric shell and dispersion aid being based on the combined total weight of epoxy resin, polymer-soluble shell in alkali and dispersion aid such that the total combined weight percentages of each of these three components is 100 percent by weight.
[09] In a second aspect, the present invention is a method for making the water-dispersible epoxy polymer powder of the first aspect, the method comprising: (a) dispersing an epoxy resin in an aqueous phase to form a dispersion of initial epoxy resin of epoxy resin particles that contain more than 50 weight percent epoxy resin by weight of the epoxy resin particles; (b) introducing a selection of unsaturated monomers at any point or combinations of points prior to or simultaneously with the next polymerization step (c) in the initial epoxide dispersion during the polymerization step (c),
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5/45 with at least five weight percent to 40 weight percent or less of unsaturated monomers are selected from carboxylic acid monomers and anhydride monomers; (c) feeding a free radical initiator into the initial epoxy resin dispersion and subjecting the dispersion, free radical initiator and monomers to conditions that result in free radical polymerization while maintaining agitation in order to polymerize the unsaturated monomers in an alkali-soluble polymeric shell around each particle of epoxy resin; and (d) removing the aqueous phase from the epoxy resin particles that have an alkali-soluble polymeric shell to obtain a water-redispersible epoxy polymer powder; where: (i) a dispersion aid is added to the epoxy resin or dispersion at one or more points before or during any of the steps (a) - (d); (ii) the unsaturated monomers in step (b) are selected so that the resulting polymer that forms the alkali-soluble polymeric shell has a glass transition temperature as calculated by the Fox equation of at least 60 degrees Celsius; and (iii) the amounts of epoxy resin, unsaturated monomers and dispersion aid are selected so that the resulting water redispersible epoxy polymer powder has a concentration of epoxy resin that is greater than 50 weight percent at 90 percent in weight or less; a concentration of alkali-soluble polymeric shell in a range of ten to fifty percent by weight; and a total of two to 25 percent by weight of a dispersion aid with the concentration of each epoxy resin, alkali-soluble polymeric shell and dispersion aid being in relation to the total combined weight of epoxy resin, soluble polymeric shell in alkali and dispersion aid such that the total combined weight percentages of epoxy resin, alkali-soluble polymeric shell and dispersion aid is 100 percent by weight.
[10] In a third aspect, the present invention is a dispersion
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6/45 of the water redispersible epoxy polymer powder of the first aspect, the dispersion comprising epoxy particles comprising epoxy resin particles dispersed in an aqueous solution, the epoxy resin particles comprising: (a) resin epoxy; (b) an alkali-soluble polymeric shell around each of the epoxy resin particles, the alkali-soluble polymeric shell comprising a polymer made up of at least five weight percent to forty weight percent or less of monomers selected from monomers of carboxylic acid and anhydride monomers based on the total weight of polymerized monomers to form the alkali-soluble polymeric shell and the alkali-soluble polymeric shell having a glass transition temperature of at least 60 degrees Celsius as calculated by the Fox formula; and (c) a dispersion aid; being that the epoxy resin is present in a concentration greater than fifty percent by weight to ninety percent by weight or less, the alkali-soluble polymeric shell is present in a concentration in a range of ten to fifty percent by weight and the auxiliary dispersion is present in a concentration of two to twenty-five percent by weight with the weight percentages of epoxy resin, alkali-soluble polymeric shell and dispersion aid being based on the combined total weight of epoxy resin, polymer-soluble shell in alkali and dispersion aid such that the total combined weight percentages of each of these components is 100 percent by weight.
[11] The process of the present invention is useful for making epoxy PRDs of the present invention. The epoxy PRD of the present invention is useful for formulating non-epoxy binder in cement formulations as a dry-mixable component. The dispersions of the present invention are useful both as an intermediate step in the epoxy PRD manufacturing method
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7/45 of the present invention as, more generally, as binder compositions.
DETAILED DESCRIPTION OF THE INVENTION
[12] “ASTM” refers to ASTM International and is used to designate a test method by number as published by ASTM. “ISO” refers to the International Organization for Standardization and is used to identify numbers of ISO test methods. The test number refers to the most recent test published before the priority date of this document unless otherwise specified by a date that uses a hyphenated suffix after the test number. "Multiple" means two or more. "And / or" means "and, or as an alternative". All ranges include maximum and minimum values unless otherwise indicated.
[13] “Glass transition temperature” or “Tg” of a material refers to the glass transition temperature value as determined by ASTM D7426-08 using a heating and cooling speed of 10 ° C per minute.
[14] The particle size of the particles in a dispersion here are presented in terms of average particle size by volume as determined by laser diffraction according to ISO 13320-2009 using coulter particle size and counting analyzers. Counter.
[15] Here, "total epoxy PRD particle weight" is interchangeable with "combined epoxy resin weight, alkali-soluble polymeric shell and dispersion aid in an epoxy PRD particle".
Water redispersible epoxy polymer powder (“epoxy PRD”)
[16] The present invention provides a new epoxy PRD that satisfies a need in that it provides a high concentration of epoxy resin in the form of redispersible dry powder. Epoxy PRD is designed to be particularly useful as a binder additive for cement formulations. The design of the epoxy PRD is to have an alkali-soluble polymeric protective wrap around each epoxy particle to protect
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8/45 the epoxy particles from the irreversible agglomeration resulting from the epoxy resin from the diffusion between the particles even in an alkaline formulation. The epoxy PRD comprises epoxy resin particles that comprise epoxy resin, an alkali-soluble polymeric wrap around each particle and a dispersion aid.
[17] The epoxy resin is present in a concentration greater than 50 weight percent (% by weight), preferably 65 weight% or greater, even more preferably 75 weight% or greater and may be present in a concentration of 85 % by weight or greater and be at a concentration of 90% by weight or less based on the total weight of epoxy PRD particle. Such a high concentration of epoxy resin is unprecedented in any PRD powder known to the inventors of the present epoxy PRD.
[18] The glass transition temperature (Tg) of the epoxy resin is not a restriction on the broader scope of the present invention. However, the epoxy resin will typically have a Tg of 100 degrees Celsius (° C) or less, preferably 90 ° C or less, even more preferably 75 ° C or less, much more preferably 50 ° C or less. Lower Tg epoxy resins are desirable because they diffuse more quickly when distributed in a formulation as a binder and because they are film-forming at lower temperatures, even at room temperature or lower, than more Tg epoxy resins high. However, lower Tg resins are more challenging to isolate than a PRD because they tend to diffuse more easily between the PRD particles and cause irreversible particle agglomeration which prevents the effective redispersibility of the non-epoxy powder. This is a specific challenge for epoxy resins that are in liquid form during the formation of the PRD, during the storage of the PRD, and the most challenging is when the epoxy resin is liquid both during formation and during the storage of the PRD. The challenge is heightened in the epoxy PRDs of
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9/45 present invention by the relatively high concentration of epoxy resin in the epoxy PRD particles. It is believed that the diffusion of epoxy resin between the particles is one of the reasons why the concentrations of epoxy resin in the range of the present invention are unknown in the form of PRD. One of the surprising aspects of the present invention is that the epoxy resin in the epoxy PRD can have a Tg of 25 ° C or less, even 20 ° C or less, even 0 ° C or less and as such be a liquid epoxy resin during the formation of the epoxy PRD and also during the storage of the epoxy PRD while maintaining the redispersibility of the particles even at the high concentration of epoxy resin of the present epoxy PRD particles. In general, the Tg of the epoxy resin is - 40 ° C or higher mainly because commercially available epoxy resins have a Tg above this value.
[19] Epoxy resins suitable for use in the present invention include aliphatic, araliphatic and aromatic epoxy compounds. Aromatic epoxy resins are particularly desirable because they are more readily available and tend to have more desirable chemical and physical properties. Epoxy resins are free of ethylenic unsaturation which would cause free radical polymerization of the resin. Epoxy resins have at least two epoxide groups per molecule. Epoxy resins particularly desirable for use in the present invention include condensates of bisphenol A and epichlorohydrin or methylpichlorohydrin ("resins of the type Bisphenol A") and epoxy resins based on bisphenol F which generally contain a mixture of bisglycidyloxyphenylmethanes ("resins of Bisphenol F type ”). The epoxy resin can and is desirably sulfur-free.
[20] The epoxy resin particles in the epoxy PRD additionally comprise an alkali-soluble polymeric shell around the epoxy resin. The alkali-soluble casing is believed to serve multiple purposes. The alkali-soluble casing is believed to protect
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10/45 the epoxy resin against diffusion from one particle to another and thereby prevent the irreversible agglomeration of the particles. Due to the fact that the wrapper is strategically located around the particle rather than mixed with the epoxy resin in the particle, the particles may contain a much lower coating concentration (and, consequently, a much higher concentration of epoxy resin) than than the epoxy PRD particles of the current art which comprise epoxy resin mixed into emulsion polymerized particles. The alkali-soluble polymeric shell additionally serves as a means to release the epoxide when the epoxide is desired for use as a binder in a cement formulation (or other alkaline formulation). During the dispersion of the epoxy PRD particles of the present invention in an alkaline aqueous composition, the alkali-soluble envelope weakens in order to release the epoxy resin to diffuse into the composition.
[21] The alkali-soluble shell is a polymeric shell around the particle's epoxy resin core that forms a barrier against the dissociation or diffusion of the epoxy resin out of the particle until the particles are exposed to the base (alkali) . The alkali-soluble casing has acid functionality when it acts as a barrier against the diffusion of epoxide. During exposure to the base, the acid functionality is neutralized causing the swelling of the polymer of the shell in aqueous solution and the desired dissolution to some extent thereby weakening the barrier properties of the polymer of the shell that protects the epoxy resin core. As a result, exposure to the base weakens or even eliminates the barrier properties of the shell and can cause the epoxy resin to release into the core, for example, to act as a binder in the alkaline solution. Preferably 0.8 to 1.5 equivalents of base are used to sufficiently neutralize the acid functionalities in the shell and cause swelling and / or dissolution of the shell polymer in solution
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Aqueous 11/45.
[22] For the purpose of achieving its alkali-soluble property, the alkali-soluble polymeric wrapper comprises a polymer made of at least five wt%, preferably ten wt% or more, even more preferably 15 wt% or more and even more preferably 20% by weight or more of monomers selected from monomers of carboxylic acid and anhydride monomers based on the total weight of polymerized monomers to form the alkali-soluble polymeric shell. At the same time, the alkali-soluble polymeric shell has 40% by weight or less, preferably 30% by weight or less, of copolymerized monomer selected from carboxylic acid and anhydride monomers based on the total weight of polymerized monomers to form the polymeric shell. soluble in alkali. Suitable carboxylic acid monomers include methacrylic acid, acrylic acid, itaconic acid, maleic acid and fumaric acid although methacrylic acid is more preferable. Suitable anhydride monomers include methacrylic anhydride, maleic anhydride and itaconic anhydride. Desirably, the selection of carboxylic acid monomers and anhydride monomers includes or consists of carboxylic acid monomers and much more preferably includes or consists of methacrylic acid.
[23] The remaining monomers copolymerized to form the alkali-soluble polymeric shell are desirably selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, styrene, substituted styrene, acrylonitrile, vinyl acetate, other alkyl acrylates of one to twelve carbon atoms in the alkyl group. Monomers are selected to form an alkali-soluble polymeric shell that has a transition temperature
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12/45 glass (Tg) of 60 ° C or higher, preferably 75 ° C or higher, even more preferably 90 ° C or higher, much more preferably 100 ° C or higher as calculated by Fox's equation. It is desirable for the alkali-soluble polymeric shell to have a high Tg to resist irreversible particle agglomeration during the isolation of epoxy PRD particles, particularly in the presence of components such as dispersion aids that can plasticize the alkali-soluble polymeric shell to some degree . The Tg of the alkali-soluble polymeric shell is calculated using the Fox equation:
where Tg _CO polymer is the Tg of the alkali-soluble polymeric shell copolymer, wfi is the weight fraction of monomer “i in the alkali-soluble polymeric shell copolymer and Tgi is the glass transition temperature of a homopolymer made of monomer” ie the sum is of all monomers “i.
[24] The alkali-soluble polymeric shell desirably has an average molecular weight of 2,500 grams per mol (g / mol) or greater, preferably 5,000 g / mol or greater and at the same time desirably has an average molecular weight of 500,000 g / mol or less, generally 250,000 g / mol or less and typically 100,000 g / mol or less. The average molecular weight of the alkali-soluble polymeric shell is determined by gel permeation chromatography.
[25] An alkali-soluble polymeric shell desirably is a copolymer of 5 to 40% by weight of monomers selected from carboxylic acids and carboxylic anhydrides, 30 to 95% by weight of monomers selected from alkyl acrylate, alkyl methacrylate and styrene, and zero to 30% by weight of a hydroxyalkyl ester of a carboxylic acid or acrylamide or methacrylamide with% by weight based on the total copolymers monomers to form the soluble polymeric shell copolymer.
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13/45 in alkali.
[26] Particularly desirable alkali-soluble polymeric casings comprise, even consist of methacrylic acid and methyl methacrylate. In such a copolymer, the concentration of copolymerized methacrylic acid is desirably 5% by weight or greater, preferably 10% by weight or greater, still more preferably 15% by weight or greater and much more preferably 20% by weight or greater while at the same time desirably it is 60% by weight or less, preferably 50% by weight or less and typically 40% by weight or less. The remainder of the copolymer is copolymerized methyl methacrylate.
[27] The alkali-soluble shell is mainly located around the surface of the epoxy PRD particles and as such efficiently protects the epoxy resin within the particles. As such, the concentration of the alkali-soluble shell can be equal to or less than the concentration of epoxy resin and still prevent irreversible agglomeration of the epoxy PRD particles. The alkali-soluble shell is typically present in a concentration of less than 50% by weight, preferably 40% by weight or less, more preferably 30% by weight or less, much more preferably 25% by weight or less and at the same time it is desirably present in a concentration of ten% by weight or greater, preferably 15% by weight or greater and even more preferably 20% by weight or greater relative to the total weight of the epoxy PRD particle.
[28] A dispersion aid has epoxy PRD. Dispersion aids are materials that facilitate the dispersion of one or more materials into another material. In the case of the present invention, the dispersion aid facilitates the dispersion of an oil phase in an aqueous phase. In particular, the dispersion aid facilitates the dispersion of epoxy resin particles in an aqueous phase. Dispersion aids can be useful in the process of the present invention for making epoxy PRD.
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Alternatively, or in addition, dispersion aids can be useful as an additive with the epoxy PRD to facilitate the redispersion of the epoxy particles in an aqueous solution. Suitable dispersion aids include surfactants (anionic, cationic and / or non-ionic). The most desirable dispersion aid is poly (vinyl alcohol) (PVOH), preferably a partially hydrolyzed PVOH. Other dispersion aids that are suitable in addition to PVOH or as an alternative to PVOH include cellulose derivatives such as hydroxypropyl cellulose; methylvinylether polymers; polyvinylpyrrolidone; and copolymers of monomeric acids such as acrylic acid. Desirably, the dispersion aid contains less than 5% by weight of surfactants containing ethylene oxide groups because such surfactants can interfere with the protective nature of the alkali-soluble shell.
[29] The dispersion aid is present in the epoxy PRD at a concentration of 2% by weight or greater, preferably 5% by weight or greater, even more preferably 7% by weight or greater and may be present at a concentration of 10 % by weight or greater while at the same time it is generally present in a concentration of 25% by weight or less, preferably 20% by weight or less, and more preferably 15% by weight or less with% by weight in relation to weight total epoxy PRD particle.
[30] The particularly preferred PRD of the present invention comprises, or even consists of PVOH as a dispersion aid in a concentration of 5% by weight or greater, preferably 7% by weight or greater and may be present in a concentration of 10% by weight or greater while at the same time it is desirably present at a concentration of 20% by weight or less, preferably 15% by weight or less in relation to the total weight of epoxy PRD particle.
[31] The redispersible characteristic of a polymer powder
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15/45 redispersible in water means that the epoxy PRD is capable of dispersing in an aqueous medium to form a dispersion of fine particles, which is also a dispersion of the present invention. This contrasts, for example, with a powder of irreversibly agglomerated particles that are unable to redispersize into fine particles. The epoxy PRD of the present invention forms a dispersion of epoxy particles that have a particle size of five micrometers or smaller, preferably two micrometers or smaller, even more preferably one micrometer or smaller, much more preferably smaller than one micrometer, and with even greater preferably 750 nanometers or less and can be 500 nanometers or less when dispersed in an aqueous medium (preferably water) at a pH in the range of 9-11. Notably, the pH of the dispersion formed does not necessarily fall within a pH range of 9-11 but instead there must be sufficient base present in the initial aqueous medium to neutralize the acid in the alkali-soluble envelope of the epoxy PRD particles to ensure efficient redispersion. There is no known lower limit on the epoxy particle size for the redispersed epoxy PRD particles of the present invention yet the particles in general have a particle size larger than one nanometer and more typically 10 nanometers or larger.
[32] Notably, the epoxy PRD of the present invention in its non-redispersed dry form may have an epoxy particle size that appears to be larger than the epoxy particle size of the redispersed epoxy particles. In powder form, epoxy particles tend to associate with each other to form clusters of particles. A beneficial feature of the present invention is that these clusters of particles dissociate in an aqueous solution to allow redispersion in a dispersion of fine particles instead of remaining irreversibly agglomerated together.
[33] An anti-cake agent is often dispersed
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16/45 with the epoxy PRD of the present invention. Pie anti-forming agents are useful when spraying an epoxy dispersion to isolate the epoxy particles. Typical pie-forming agents include mineral fillers such as calcium carbonate, kaolin, barium sulfate, titanium oxide, talc, hydrated alumina, bentonite, calcium sulfoaluminate and silica. The concentration of anti-cake agent in the epoxy PRD is typically 50% by weight or less, preferably 20% by weight or less, more preferably 15% by weight or less, even more preferably 10% by weight or less and much more preferably 5% by weight or less in relation to the total weight of epoxy PRD. The epoxy PRD may be free of pie anti-forming agent, but in general it contains 0.5% by weight or greater, preferably 2% by weight or greater and more preferably 5% by weight or greater relative to the total weight of PRD of epoxy.
[34] A particularly desirable epoxy PRD of the present invention is characterized by the fact that it comprises an epoxy resin that has a glass transition temperature of -40 ° C to 50 ° C (which may include or exclude the value of 50 ° C ), an alkali-soluble polymeric shell comprising a polymer consisting of polymerized monomers selected from the group consisting of acrylates, ethyl acrylate, butyl acrylates, 2-ethylhexyl acrylate, decyl acrylates, methyl methacrylate, methacrylate ethyl, butyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid and selected in such a way that the alkali-soluble envelope polymer has a glass transition temperature above 100 ° C as calculated by the equation of Fox and the dispersion aid comprising poly (vinyl alcohol) in a concentration of at least 5% by weight based on the total weight of epoxy PRD. In an especially desirable embodiment of this epoxy PRD the alkali-soluble polymeric envelope is a copolymer of methacrylate and methyl methacrylate.
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[35] The epoxy PRD of the present invention is particularly useful for formulation with cement components to form epoxy modified cement. Dry epoxy PRD can be mixed dry with cement components to ensure easy mixing before adding water, which tends to result in an increase in viscosity and a concomitant increase in difficulty in combining and mixing. During the addition of water, the epoxy particles in the epoxy PRD redisperse around the cement components and the alkaline environment of the solution causes the alkali-soluble polymeric envelope around the particles to release the epoxide to serve as a binder throughout the cement formulation.
[36] A particularly desirable use for the epoxy PRD of the present invention is as a dry component mixing system comprising the epoxy, cement and sand PRD for use in mortar preparation. The preparation of mortar from the dry component system simply requires the addition of water to the dry component system. No additional or separate hardener is required either in the dry mix system or in the mortar. The total alkali content of the hydrated cement promotes crosslinking of the epoxide groups in the epoxy PRD, which in turn provides the resulting flexural strength to the mortar that is comparable to that of the known three-part systems that require a separate hardening additive.
Method for making epoxy redispersible polymer powder
[37] The method of the present invention makes the epoxy PRD of the present invention. A characteristic aspect of the process of the present invention is the direct formation of a dispersion of epoxy resin in an aqueous phase, which contrasts with the other methods that need to disperse the epoxy resin in latex particles during or after emulsion polymerization with the purpose of obtaining epoxy resin particles small enough to form an epoxy PRD. As a result,
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18/45 the epoxy PRD particle of the present method and the epoxy PRD contain higher concentrations of epoxy resin than those of the prior art emulsion polymerization methods.
[38] The process of the present invention needs to disperse the epoxy resin in an aqueous phase to form an initial aqueous dispersion of epoxy resin particles ("initial epoxy resin dispersion"). Unlike other epoxy dispersions in the art that are precursors to forming epoxy resin PRDs, dispersed epoxy resin particles are dispersed directly in an aqueous phase to form dispersed epoxy resin particles. The dispersed epoxy resin particles may be free of emulsion polymerized polymers during the step of forming the epoxy resin dispersion. In fact, the epoxy resin particles in the initial epoxy resin dispersion are more than 50% by weight, preferably 65% by weight or greater, even more preferably 75% by weight or greater and can be 85% by weight or greater , 90% by weight or greater, and up to 95% by weight or greater of epoxy resin based on the total weight of the epoxy resin particles. The aqueous phase can be simply water.
[39] Epoxy resins suitable for use in the method of the present invention are the same as those previously described here as suitable for the epoxy PRD of the present invention.
[40] It is not critical to the broader scope of the present invention how to disperse the epoxy resin in the aqueous phase to form the initial epoxy resin dispersion. It is appropriate to grind or comminute (for example, cryogenically grind) the epoxy resin into a fine powder and disperse that fine powder in an aqueous phase. However, it is desirable to avoid having to grind or comminute the epoxy resin prior to dispersion and to directly disintegrate the epoxy resin into small particles while it is dispersed in an aqueous phase (ie directly to disperse the epoxy resin in one phase
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Aqueous 19/45). The direct dispersion of the epoxy resin in an aqueous phase is generally accomplished by obtaining the epoxy resin in a softened state and combining it with an aqueous phase under shear. The shear serves to disintegrate the particulate epoxy resin because it disperses those particles in the aqueous phase. Obtaining the epoxy resin in a softened state facilitates the disintegration of the resin into particles under shear. An epoxy resin is in a "softened state" if its molecules are able to flow in relation to each other. The softer, the greater the flow capacity of the epoxy resin and the easier it is to disintegrate while it is dispersed.
[41] One way to obtain an epoxy resin in a softened state is to obtain it at a temperature higher than its Tg. Consequently, it is desirable to obtain the epoxy resin at a temperature higher than its Tg when it is dispersed in the aqueous phase during the method of the present invention. Furthermore, it may be desirable to obtain and even maintain the aqueous phase at a temperature above the Tg of the epoxy resin when the epoxy resin is dispersed into the aqueous phase to keep the epoxide in a soft state throughout the dispersion step. . Since it is easier to disperse epoxy resins in a softened state, liquid epoxy resins are desirable to form the dispersion of epoxy resin, particularly resins that are liquid at temperature in order to avoid cost and complexity application of heat to soften the epoxy resin. As such, epoxy resins that have a Tg of 50 ° C or less, especially those with a Tg of 25 ° C or less, 20 ° C or less and up to 0 ° C or less are particularly desirable to form the dispersion of epoxy resin in the first stage of the present method because they are typically inherently in a softened state without the need for additional heating or softening of any other type.
[42] Another way to get epoxy resin in a state
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20/45 softened is to add a plasticizer to the epoxy resin. A plasticizer is any molecule that increases the fluidity of a polymer by solvating the molecules in the polymer. Consequently, the epoxy resin may be accompanied by a plasticizer when it is dispersed in an aqueous phase during the method of the present invention. Desirably, the plasticizer is a "fleeting plasticizer", which means that it ceases its plasticizer effect from before or during, preferably before the isolation of epoxy particles as an epoxy PRD. A plasticizer can be a fleeting plasticizer by escaping the epoxy resin (for example, by evaporation).
[43] Another particularly desirable fleeting plasticizer is a monomeric plasticizer that serves as a comonomer during polymerization of the alkali-soluble shell and that becomes less effective as a plasticizer during polymerization. The epoxy resin may contain a fleeting plasticizer, non-fleeting plasticizer, a combination of fleeting and non-fleeting plasticizer or be completely free of plasticizer when the epoxy resin is dispersed to form an initial epoxy dispersion.
[44] The concentration of plasticizer added in an epoxy resin before forming an initial epoxy dispersion is desirably 50% by weight or less, preferably 40% by weight or less, more preferably 20% by weight or less, even more preferably 10% by weight or less, still preferably maximum 5% by weight or less and much more preferably 2% by weight or less or even one% by weight or less. The epoxy resin can be completely free of plasticizer. The fleeting plasticizers can generally be present at a higher concentration than that of the non-fleeting plasticizers. Non-fugitive plasticizers have a potential to soften the epoxy resin and / or the alkali-soluble polymeric shell to an undesirable extent such that the epoxy particles will irreversibly agglomerate when isolated from a dispersion.
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Consequently, non-fugitive plasticizers are desirably present in a concentration of 5% by weight or less, preferably 2% by weight or less, much more preferably 1% by weight or less. Much more desirably, the epoxy resin is free of non-fleeting plasticizers before forming an initial dispersion.
[45] The dispersion of the epoxy resin in the aqueous phase is carried out using a batch, semi-continuous or continuous process. Batch processes include preparing the dispersion of epoxy resin in a single container by adding the aqueous phase and epoxy resin together while maintaining agitation to mix. It is common to add the epoxy resin to the aqueous phase while maintaining agitation to mix, however both the aqueous phase and the epoxy resin can be added together in the container while maintaining agitation to mix or the epoxy resin can be added first and the aqueous phase is added keeping stirring to mix. It is also possible to add the epoxy resin and the aqueous phase together without stirring and, once the two components have been combined, they are then mixed together to form a dispersion. It is desirable to form the epoxy resin dispersion by a continuous method in which both the aqueous phase and the epoxy resin are mixed together in a direct stream to produce an epoxy resin dispersion.
[46] A desirable method for continuously producing the initial epoxy resin dispersion is by mechanical dispersion, as taught in United States Patent No. 4123403. In a mechanical dispersion process, an aqueous phase and an organic phase are fed together through a high shear mixer that disperses one phase within the other, typically forming a high internal emulsion or a high internal phase dispersion. High internal phase emulsions and dispersions have more than 74 percent by volume of internal phase dispersed within a continuous phase where the volume percentage is in relation to the total volume of the
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22/45 emulsion or dispersion. In the context of the method of the present invention an epoxy resin (typically either as a ground powder or as a resin in a softened state) an aqueous phase can be fed into a high shear mixer to produce an epoxy resin dispersion in the aqueous phase. A high-internal dispersion of epoxy resin in aqueous phase is commonly produced, which can be diluted with additional aqueous phase if desired to, for example, reduce the viscosity of the dispersion. A particularly desirable benefit of mechanical dispersion is that it can produce dispersions with dispersed particles that have a highly uniform particle size (narrow particle size distribution). In addition, the highly uniform particle size can be two micrometers or smaller, one micrometer or smaller. It is desirable to use a mechanical dispersion process with a softened epoxy resin (for example, by processing above the Tg of the epoxy resin, with addition of a plasticizer as a monomeric plasticizer, or a combination of processing above the Tg of the resin epoxy and with the addition of a plasticizer) to prepare the initial epoxy resin dispersion.
[47] Small epoxy particle sizes are desirable in the initial epoxy resin dispersion. The method finally produces the epoxy PRD of the present invention. Therefore, it is desirable for the resulting epoxy PRD to redisperse into the aqueous phase to produce an epoxy dispersion that has an epoxy particle size as described for the epoxy PRD of the present invention (five micrometers or less, preferably two micrometers or smaller, even more preferably one micrometer or smaller, much more preferably smaller than one micrometer, and most preferably maximum of 750 nanometers or smaller and can be 500 nanometers or smaller). Therefore, the epoxy resin particles in the initial epoxy resin dispersion must be no larger than the
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23/45 particle size of epoxy resin particles in the dispersion formed by the redispersion of the epoxy PRD, prepared by the process, into an aqueous phase. As such, the epoxy particles in the initial epoxy resin dispersion desirably have a particle size of five micrometers or smaller, preferably two micrometers or smaller, even more preferably one micrometer or smaller, much more preferably smaller than one micrometer, and yet preferably maximum 750 nanometers or less and can be 500 nanometers or less. The initial epoxy resin is produced by applying sufficient shear to fragment the epoxide into particle sizes small enough to produce the desired particle size. In general, higher shear is required for the formation of smaller particles.
[48] It is often necessary to use a dispersion aid to prepare the initial epoxy resin dispersion. A dispersion aid can serve to stabilize the epoxy resin particles in the aqueous phase. A dispersion aid can be added to the epoxy resin before dispersing, to the aqueous phase before dispersing the epoxy resin, or added to the initial epoxy dispersion when the epoxy resin and the aqueous phase are being mixed. Suitable dispersion aids to stabilize the initial epoxy resin dispersion include those dispersion aids taught above with respect to the epoxy PRD. Desirably, any dispersion aid added before or during the formation of the initial epoxy resin dispersion comprises or consists of PVOH. If added before or during the formation of the initial epoxy resin dispersion, the dispersion aid is typically present in a concentration of 15% by weight or less, preferably ten% by weight or less and can be present in a concentration of six % by weight or less, up to five% by weight or less, four% by weight or less in relation to the total weight of the epoxy resin A desirable embodiment uses 7.5% by weight PVOH to form
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24/45 an initial epoxy resin dispersion, with% by weight relative to the total weight of epoxy resin.
[49] An alkali-soluble polymeric shell as previously described with respect to the epoxy PRD is polymerized around the epoxy resin particles by polymerizing the monomers in the initial epoxy dispersion. Therefore, the method needs to introduce, in order to be present in the initial epoxy dispersion during the polymerization of the alkali-soluble polymeric shell, a selection of unsaturated monomers. The addition of the unsaturated monomers can occur at any point or combination of points before or at the same time as the polymerization of the monomers to form the alkali-soluble polymeric shell.
[50] All unsaturated monomers, or a portion of the unsaturated monomers, can be mixed with the epoxy resin prior to the initial epoxy dispersion formation. It is desirable that the unsaturated monomers added in the epoxy resin before the formation of the initial epoxy dispersion are miscible with the epoxy resin and even plasticize the epoxy resin to facilitate the formation of the initial epoxy dispersion. When unsaturated monomers are present in the epoxy resin particles of the initial epoxy dispersion, the polymerization of the unsaturated monomers to form an alkali-soluble polymeric shell is of the type of microemulsion polymerization in which the monomer being polymerized is present in a particle. dispersed that has a particle size of one micrometer or smaller. A characteristic aspect of this microemulsion polymerization is that most of the material in the particles is epoxy resin instead of the monomers being polymerized in emulsion. Mixing a plasticizer unsaturated monomer with epoxide provides at least two benefits. First, it softens the epoxy resin to facilitate the direct dispersion of the epoxy resin into the aqueous phase. Second, it provides a means to distribute the
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25/45 alkali-soluble casing monomer to a highly uniform extent throughout the resulting epoxy resin dispersion, which is believed to result in a more uniform alkali-soluble casing formation around the more epoxy resin particles further on in the method. The plasticizer unsaturated monomer is selected from the group consisting of acrylate and methacrylate monomers that plasticize the epoxy resin. A particularly desirable plasticizer monomer is methyl methacrylate.
[51] All unsaturated monomers, or a portion of the unsaturated monomers, can (m) be mixed (mixed) in the initial epoxy dispersion after the formation of the initial epoxy dispersion. In this regard, the unsaturated monomers can be mixed in the initial epoxy dispersion prior to or during the polymerization of the unsaturated monomers to form the alkali-soluble envelope around the epoxy particles. Therefore, unsaturated monomers for polymerization to form the alkali-soluble polymeric shell can be added before the formation of the initial epoxy dispersion, after the formation of the initial epoxy dispersion but before the initiation of polymerization, after the formation of the initial epoxy dispersion. and while polymerizing, or any combination of these addition options.
[52] The total amount of polymerized unsaturated monomer in an alkali-soluble polymeric shell, including any monomer combined with the epoxy resin in the formation of the initial epoxy resin dispersion and monomer fed into the initial epoxy resin dispersion, comprises at least minus five wt%, preferably ten wt% or greater, even more preferably 15 wt% or greater and most preferably maximum 20 wt% or greater of monomers selected from carboxylic acid monomers and anhydride monomers based on weight total polymerized monomers to form the alkali-soluble polymeric shell. At the same time, the
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26/45 alkali-soluble polymer has 40% by weight or less, preferably 30% by weight or less of copolymerized monomer selected from monomers of carboxylic acid and carboxylic anhydride based on the total weight of polymerized monomers to form the polymer soluble shell in alkali. The remaining monomers copolymerized to form the alkali-soluble polymeric shell are desirably selected from a group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, methacrylate ethyl, butyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, styrene, substituted styrene, acrylonitrile, vinyl acetate, other alkyl acrylates that have one to twelve carbon atoms in the alkyl group. The monomers are selected to form an alkali-soluble polymeric shell that has a Tg of at least 60 ° C, preferably at least 75 ° C, even more preferably at least 90 ° C, much more preferably at least 100 ° C as calculated by Fox equation. A desirable combination of unsaturated monomers consists of five to 40% by weight of monomers selected from carboxylic acids and anhydrides, 30 to 95% by weight of monomers selected from alkyl acrylate, alkyl methacrylate and styrene, and zero to zero. 30% by weight of a hydroxyalkyl ester of a carboxylic acid or acrylamide or methacrylamide with% by weight based on the total copolymers monomers to form the alkali-soluble polymeric shell copolymer.
[53] The unsaturated monomers used to form the alkali-soluble polymeric shell (including any unsaturated monomer added before or during the formation of the initial epoxy resin dispersion and also added in the initial epoxy resin dispersion) desirably comprise, until they consist of in methacrylic acid and methyl methacrylate. The concentration of methacrylic acid is desirably five% in
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27/45 weight or greater, preferably ten% by weight or greater, even more preferably fifteen% by weight or greater and much more preferably twenty% by weight or greater while at the same time it is desirable to be sixty% by weight or less preferably fifty wt% or less and typically 40 wt% or less based on the total weight of the unsaturated monomers. The rest of the unsaturated monomers are desirably methyl methacrylate. A portion of or all of the methyl methacrylate is desirably included with the epoxy resin before or during the formation of the initial epoxy resin dispersion, preferably before the formation of the initial epoxy dispersion. Typically, the unsaturated monomers that are added in the initial epoxy dispersion are added gradually over the course of the polymerization of the alkali-soluble polymeric shell.
[54] The method desirably includes the addition of methyl methacrylate as an unsaturated monomer in the epoxy resin prior to or during the formation of the initial epoxy dispersion. At the same time, the method desirably includes the addition of methacrylic acid as an unsaturated monomer, preferably after the formation of the initial epoxy dispersion and during or after the addition of a free radical initiator and the polymerization of the alkali-soluble polymeric shell. Unsaturated monomers can consist of just these two monomers added in this way. For example, methyl methacrylate can be added prior to the formation of the initial epoxy dispersion while methyl methacrylate can be added during polymerization of the alkali-soluble polymeric shell.
[55] A free radical initiator is fed into the initial epoxy resin dispersion prior to, during or after the addition of the unsaturated monomers and the mixture is subjected to conditions that result in free radical polymerization while stirring to polymerize the
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28/45 unsaturated monomers in an alkali-soluble polymeric shell around each epoxy resin particle. The free radical initiator serves to initiate the polymerization of the unsaturated monomers around the dispersed epoxy resin particles from the initial epoxy resin dispersion. Suitable primers and free radicals include thermally activated and / or redox primers, preferably those that are soluble in water. Examples of thermally activated initiators include the persulfate salts (for example, sodium persulfate and ammonium persulfate). Suitable redox initiators include combinations of an oxidizing agent (such as persulfate salt and organic peroxides) and reducing agents (such as sodium formaldehyde-sulfoxylate) and a redox catalyst such as iron (II) sulfate. The "conditions that result in free radical polymerization" depend on the type of the free radical initiator added. For example, thermally activated initiators will decompose and initiate free radical polymerization in the presence of unsaturated monomers at a temperature above their free radical decomposition temperature (initiation temperature). Thermally activated initiators may require heating of the initial epoxy dispersion mixture, unsaturated monomers and initiators to achieve the conditions that result in free radical polymerization depending on the initiator initiation temperature and the ambient temperature of the mixture. Redox initiators require the presence of an appropriate pair of oxidizing agent and reducing agent which, when mixed with each other, react to form the polymerization initiating free radicals.
[56] The amount of free radical initiator is generally 0.01% by weight or greater, preferably 0.1% by weight or greater while at the same time it is generally two% by weight or less, with% by weight in relation to the weight of unsaturated monomers.
[57] The resulting epoxy resin dispersion comprising
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29/45 epoxy particles having an alkali-soluble shell is a dispersion of the present invention.
[58] The isolation of the resulting epoxy resin particles that have an alkali-soluble polymeric shell such as an epoxy PRD is accomplished by removing a continuous aqueous phase. The removal of the aqueous phase can be done in any of a number of ways including freeze drying or spray drying (atomization), or a combination of both. It is preferable to isolate the epoxy PRD by spray drying the dispersion containing the epoxy particles with the alkali-soluble envelope. In order to help prevent irreversible agglomeration of epoxy resin particles, it is common to introduce a pie anti-forming agent in the epoxy resin particles during the spray drying step. The pie anti-forming agent can be added in any manner which includes mixing with the dispersion prior to spray drying or mixing with the dispersion during spray drying, for example, by blowing into a chamber with the dispersion. Suitable pie-forming agents include mineral fillers such as calcium carbonate, kaolin, barium sulfate, titanium oxide, talc, hydrated alumina, bentonite, calcium sulfoaluminate and silica. In general the concentration of the anti-cake agent added in the epoxy resin particles is 0.5% by weight or greater, preferably 2% by weight or greater, much more preferably 5% by weight or greater and at the same time it is generally 50% by weight or less, preferably 20% by weight or less and more preferably 15% by weight or less with% by weight relative to the weight of solids of the dispersion.
[59] A dispersion aid can also be added while feeding and polymerizing the monomers of the alkali-soluble polymeric shell, while spraying the epoxy resin particles, or both. Desirably, a dispersion aid is added when
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30/45 spray-dried the epoxy resin particles. The dispersion aid added when spray-dried should facilitate the redispersion of the epoxy resin particles when the epoxy PRD particles are added in an aqueous solution. Suitable dispersion aids that can be added during spray drying include those already identified for the epoxy PRD. It is particularly desirable to add PVOH to the epoxy resin particles during the spray drying process. The desired concentration of PVOH added during the spray drying process is desirably 10-15% by weight relative to the total weight of epoxy resin.
[60] The total amount of dispersion aid added during the entire process of the present invention is as described for the epoxy PRD of the present invention. In particular, the total amount of dispersion aid is two wt% or greater, preferably 5 wt% or greater, even more preferably 10 wt% or greater and is generally present at a concentration of 25 wt% or less , preferably 20% by weight or less, and more preferably 15% by weight or less with% by weight with respect to the combined total weight of epoxy resin, alkali-soluble polymeric shell and dispersion aid. The process of the present invention desirably includes the addition of a total amount of PVOH as one, or even as only, dispersion aid in a concentration of 5% by weight or greater, preferably 10% by weight or greater and desirably 20% in weight or less, preferably 15% by weight or less in relation to the total weight of epoxy PRD particles.
[61] The resulting epoxy PRD isolated during the spray drying process is an epoxy PRD of the present invention.
[62] The process of the present invention is desirably characterized by an epoxy resin that has a glass transition temperature in a range of -40 ° C to 50 ° C (including or excluding 50 ° C), the monomers used
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31/45 to form the alkali-soluble polymeric shell being selected from the group consisting of acrylates, ethyl acrylate, butyl acrylates,
2-ethylhexyl, decyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid so that the resulting alkali-soluble polymeric envelope has a temperature glass transition above 100 ° C as calculated by the Fox equation, and the dispersion aid comprises poly (vinyl alcohol) in a concentration of at least five wt.% based on the total weight of epoxy resin, polymeric soluble shell in alkali and dispersion aid. In a particularly desirable embodiment of this process, the monomers used to form the alkali-soluble envelope are a combination of methacrylic acid and methyl methacrylate.
[63] The present invention is additionally a dispersion of epoxy particles comprising epoxy resin particles dispersed in an aqueous solution, the epoxy resin particles comprising epoxy resin and an alkali-soluble polymeric shell around the particles individual epoxy resin. The epoxy resin and the alkali-soluble polymeric shell are as described for the epoxy PRD of the present invention. The dispersion of epoxy particles that fall within the scope of the present invention include the dispersion of epoxy particles that comprise an alkali-soluble shell before removing the aqueous phase that is formed during the method of the present invention. Dispersions formed by redispersing the epoxy PRD of the present invention into the aqueous phase also qualify as dispersions of the present invention.
[64] The following examples further describe embodiments of the present invention.
Example 1
Preparation of initial epoxy dispersion
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[65] In a 300 milliliter PARR reactor equipped with a Cowles-type spreading disc add 50.0 grams of an epoxy resin that has an epoxide equivalent weight of 500-560 determined by ASTM D1652, an epoxide percentage of 7 , 7-8,6 determined by ASTM D1652, an epoxide content of 1,780-2,000 millimoles per kilogram determined by ASTM D-1652, a Tg of 41 ° C (for example, Dow Epoxy Resin (DER) 661) and 18, 5 grams of a 27% by weight aqueous solution of a PVOH that has an average molecular weight of approximately 31,000 grams per mol (eg poly (vinyl alcohol) Mowiol ™ 4-88, Mowiol is a trademark of Hoechst Aktiengesellschaft ). Close the reactor and heat to 100 ° C then stir for 10 minutes at 1,830 revolutions per minute. Using a high performance liquid chromatography (HPLC) pump, add 30 milliliters (mL) of water to the solution in the reactor at a flow rate of one milliliter per minute (mL / min). Stop heating and increase the flow rate of water addition to 10 mL / min for five minutes and add another 50 mL of water while the reactor and solution are cooled. Stop stirring when the solution reaches 50 ° C and isolate the resulting initial epoxy dispersion through a 190 micrometer filter. The resulting initial epoxy dispersion has 91% by weight of epoxy resin based on the total weight of epoxy resin and dispersion aid and has a particle size of 298 nanometers and has 33% by weight of solids based on the total weight. dispersion.
Polymerization of the alkali-soluble polymeric shell and spray drying
[66] In a round-bottom flask add 100 grams of the initial epoxy dispersion and purge with nitrogen gas while maintaining 60 ° C. While stirring, add 2.5 milligrams of ferrous sulphate as a 1% by weight aqueous solution. Pre-mix 6.60 grams of methyl methacrylate and 1.65 grams of methacrylic acid and inject the mixture into
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33/45 reactor for 30 minutes. At the same time feeding a five wt% aqueous solution of tert-butyl peroxide and a five wt% aqueous solution of sodium hydroxymethanesulfinate in order to add one wt% of each component to the weight of the monomers inside of the reactor as a free radical initiator for 45 minutes. Keep the reaction at 60 ° C for 60-90 minutes and then allow to cool to 25 ° C and filter through a 190 micrometer filter. The resulting dispersion comprises epoxy resin particles that contain 77% by weight of epoxy resin, 8% by weight of dispersion aid (PVOH) and 15% by weight of an alkali-soluble shell comprising a copolymer of methacrylic acid and methacrylate of methyl, with the weight% in relation to the total combination of epoxy resin, dispersion aid and polymeric casing soluble in alkali. The resulting dispersion has a particle size of 307 nanometers.
[67] Pump the resulting dispersion into a two-fluid nozzle atomizer equipped in a Mobile Minor spray dryer. Fix the air pressure in the nozzle at 100 kilopascals with 50% of the flow, which is equivalent to 6 kilograms per hour of air flow. Spray the epoxy dispersion in a nitrogen gas environment with an inlet temperature set at 120-140 ° C and an outlet temperature set at 50 ° C. Add kaolin clay powder (eg, Kamin ™ HG-90, Kamin is a trademark of Kamin LLC) as a pie anti-forming agent at a concentration of eight% by weight relative to the weight of solids in the dispersion. Dry the resulting epoxy PRD at 40 ° C.
[68] Redispersing the resulting epoxy PRD in water at a pH of 911 by adding 0.1 gram of PRD in ten milliliters of water and adding 1-2 drops of one molar sodium hydroxide solution and swirling for one minute . The epoxy particles redisperse to form a dispersion that has a particle size of 310 nm.
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[69] Tg analysis of the epoxy PRD describes an epoxy Tg at about 5 ° C of the pure epoxy resin that confirms a core-shell structure with an essentially unmodified epoxy resin. Furthermore, the isolation of the epoxy resin particle via the spray drying process without irreversible agglomeration of the particles together confirms that there is a wrap around the epoxy resin particles that prevents the epoxy resin from mixing between the particles when particles contact each other. The epoxy particles readily re-disperse in aqueous alkaline solution, much more readily than in acidic aqueous solutions, which is consistent with the solubilization of the casing in the alkaline aqueous solution and is indicative of an alkali-soluble casing around the resin core. of epoxy.
[70] Example 1 illustrates a method of the present invention that produces the epoxy PRD of the present invention. The process directly disperses epoxy resin into an aqueous phase with the use of a non-ionic dispersion aid. The dispersion aid is only introduced during the formation of the initial epoxy resin dispersion. The epoxy PRD has an epoxy resin concentration of 77% by weight, an alkali-soluble polymeric shell concentration of 15% by weight and a dispersion aid concentration of 8% by weight relative to the total combined weight of epoxy resin. , polymeric shell soluble in alkali and dispersion aid.
Example 2 Preparation of initial epoxy dispersion
[71] In a 300 milliliter PARR reactor equipped with a Cowles-type spreading disc add 50.0 grams of an epoxy resin blend: 25.0 grams of an epoxy resin as in Example 1 and 25.0 grams of a liquid epoxy resin having an epoxide equivalent weight of 82-192 determined by ASTM D-1652, an epoxide percentage of 22.4-23.6 determined by ASTM D-1652, an epoxide content of
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5,200-5,500 millimoles per kilogram determined by ASTM D-1652, a glass transition temperature of -19 ° C (for example, Dow Epoxy Resin (DER) 331). The resulting blend of epoxy resins has a Tg of 7 ° C. Add 3.5 grams of anionic dispersion aid to the reactor (ESPERSE ™ 100, 60% by weight of solids in aqueous solution; E-Sperse is a trademark of Ethox Chemicals, LLC). Close the reactor and heat to 100 ° C then stir for 10 minutes at 1,830 revolutions per minute. Using a high performance liquid chromatography (HPLC) pump add 20 milliliters (mL) of water to the solution in the reactor at a flow rate of one milliliter per minute (mL / min). Stop heating and increase the flow rate of water addition to 10 mL / min during your minutes to add an additional 60 mL of water while the reactor and solution are cooled. Stop stirring when the solution reaches 50 ° C and isolate the resulting initial epoxy dispersion through a 190 micrometer filter. The resulting initial epoxy dispersion is 96% by weight of epoxy resin based on the total weight of epoxy resin and dispersion aid and has a particle size of 330 nanometers. The dispersion is 36% by weight of solids based on the total weight of the dispersion.
Polymerization of alkali-soluble polymeric shell and spray drying
[72] In a round-bottom flask add 50 grams of the initial epoxy dispersion and purge with nitrogen gas while maintaining 50 ° C. While mixing, add 2.5 milligrams of ferrous sulfate as an aqueous solution. Pre-mix 3.27 grams of methyl methacrylate and 0.82 grams of methacrylic acid and inject the mixture into the reactor for 30 minutes. At the same time feeding an aqueous solution of tert-butyl peroxide and sodium hydroxymethanesulfinate into the reactor as a free radical initiator for 45 minutes as described in Example 1. Keep the reaction at 50 ° C for 120 minutes and then allow to cool to 25 ° C and filter
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36/45 through a 190 micrometer filter. The resulting dispersion comprises epoxy resin particles that contain 78% by weight of epoxy resin, 3% by weight of dispersion aid and 19% by weight of an alkali-soluble shell comprising a copolymer of methacrylic acid and methyl methacrylate, with% by weight in relation to the total combination of epoxy resin, dispersion aid and alkali-soluble polymeric shell. The resulting dispersion has a particle size of 335 nanometers.
[73] Before spray drying add solid PVOH dispersion aid (10% by weight based on epoxide weight). The PVOH is the same as that described for Example 1. Pump the resulting dispersion into a two-fluid nozzle atomizer equipped in a Mobile Minor spray dryer. Fix the air pressure in the nozzle at 100 kilopascals with 50% of the flow, which is equivalent to 6 kilograms per hour of air flow. Spray the epoxy dispersion in a nitrogen gas environment with an inlet temperature set at 120-140 ° C and an outlet temperature set at 40 ° C. Add kaolin clay powder (for example, Kamin ™ HG-90, Kamin is a trademark of Kamin EEC) as an anti-cake agent in a concentration of eight weight% relative to the weight of solids in the dispersion. Dry the resulting epoxy PRD at 40 ° C.
[74] Redispersing the resulting PRD in water at pH 11 in a manner similar to that described in Example 1. The epoxy particles redispersate to form a dispersion that has a particle size of 330 nanometers.
[75] Tg analysis of the epoxy PRD describes an epoxy Tg at about 5 ° C of the pure epoxy resin that confirms a core-shell structure with an essentially unmodified epoxy resin. In addition, the isolation of the epoxy resin particle via the spray drying process without irreversible agglomeration of the particles together confirms that there is a wrap around the epoxy resin particles that prevents the
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37/45 intermixing of epoxy resin between the particles when the particles contact each other. The epoxy particles readily re-disperse in aqueous alkaline solution, much more readily than in acidic aqueous solutions, which is consistent with the solubilization of the casing in the alkaline aqueous solution and is indicative of an alkali-soluble casing around the resin core. of epoxy.
[76] Example 2 illustrates a method of the present invention that produces an epoxy PRD of the present invention using an epoxy resin composition that has an average Tg Tg of seven ° C. The process directly disperses epoxy resin into an aqueous phase using an anionic dispersion aid. Dispersion aids are added both during the formation of the initial epoxy resin dispersion and during spray drying to isolate the final epoxy PRD. The epoxy PRD has an epoxy resin concentration of 72% by weight, 18% by weight alkali-soluble polymeric shell concentration and 10% by weight dispersion aid concentration (PVOH + E-Sperse 100) the total combined weight of epoxy resin, polymeric shell soluble in alkali and dispersion aid.
Example 3
Preparation of initial epoxy dispersion
[77] Dissolve 150 grams of epoxy resin as used in Example 1 in 40 grams of methyl methacrylate. Add 100 grams of the resulting solution in a polyethylene beaker and add 18 grams of aqueous PVOH solution (28% by weight of solids, PVOH is as used in Example 1) and 0.5 grams of Hitenol BC-10 polymerizable anionic surfactant ( 100% active agent; Hitenol BC available from Montellow, Inc.). Mix with a serrated disk at 3,000 revolutions per minute for approximately two minutes. While mixing, add 15-20 ml of water at a flow rate of 3 ml / minute to obtain a thick gel / paste (a). Continue mixing
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38/45 for another three minutes. Continue adding water at a flow rate of 20 mL / minute until a total of 175 mL of water has been added. The resulting mixture is an initial dispersion which is an oil-in-water dispersion in which the oil phase is a combination of epoxy resin and methyl methacrylate monomer. Prepare the initial dispersion at approximately 25 ° C. The initial dispersion has a particle size of 406 nanometers.
Polymerization of alkali-soluble polymeric shell and spray drying
[78] Transfer the initial dispersion into a polymerization flask equipped with a nitrogen purge, reflux condenser, thermometer and stirrer. While stirring, add 5 grams of methacrylic acid to the initial dispersion. Then while stirring, add 0.6 ml of 1% by weight aqueous ferrous sulphate solution and heat the resulting mixture to 60 ° C. Add 10 ml of 2.6% by weight aqueous solution of sodium formaldehyde sulfoxylate and 10 ml of tert-butyl peroxide aqueous solution (0.5 gram of 70% by weight solution in 10 ml of water) during a one hour time frame. Continue to mix at 60 ° C for 45 minutes after the complete addition of one hour to form an epoxy resin dispersion that has an alkali-soluble shell. The resulting dispersion has a particle size of 406 nanometers.
[79] Pump the epoxy resin dispersion that has an alkali-soluble casing through a two-fluid nozzle atomizer equipped in a Mobile Minor spray dryer. Fix the air pressure in the nozzle at 100 kilopascals with 50% of the flow, which is equivalent to 6 kilograms per hour of air flow. Spray the epoxy dispersion in a nitrogen gas environment with an inlet temperature set at 140 ° C and an outlet temperature set at 50 ° C. Add kaolin clay powder (eg Kamin ™ HG-90, Kamin is a trademark of Kamin LLC)
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39/45 as a pie anti-forming agent in a concentration that corresponds to 10% by weight of the total solids weight. Dry the resulting epoxy PRD at 40 ° C.
[80] The resulting epoxy PRD has an average powder particle size of 10-20 micrometers due to the reversible agglomeration of the particles. During the dispersion of the epoxy PRD powder in water at a pH of 11 in a 1% by weight solution and swirling twice for 30 seconds the epoxy PRD redispersed to have a dispersed epoxy particle size of 410 nanometers.
[81] Tg analysis of the epoxy PRD describes an epoxy Tg at about 5 ° C of the pure epoxy resin that confirms a core-shell structure with an essentially unmodified epoxy resin. Furthermore, the isolation of the epoxy resin particle via the spray drying process without irreversible agglomeration of the particles together confirms that there is a wrap around the epoxy resin particles that prevents the epoxy resin from mixing between the particles when particles contact each other. The epoxy particles readily re-disperse in aqueous alkaline solution, much more readily than in acidic aqueous solutions, which is consistent with the solubilization of the casing in the alkaline aqueous solution and is indicative of an alkali-soluble casing around the resin core. of epoxy.
[82] Example 3 illustrates a method of the present invention which comprises mixing a monomer with the epoxy resin before dispersing the resin directly into an aqueous phase. The dispersion aid is added only during the formation of the initial epoxy resin dispersion. Example 3 further illustrates an epoxy PRD of the present invention that has a composition of 76% by weight of epoxy resin, 19% by weight polymeric shell soluble in alkali and 5% by weight of dispersion aid, and a particle size 410 nanometers when redispersed in water.
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Example 4
Preparation of initial epoxy dispersion
[83] Mix 75 grams of a liquid epoxy resin that has an epoxide equivalent weight of 82-192 determined by ASTM D-1652, an epoxide percentage of 22.4-23.6 determined by ASTM D-1652, a epoxide content of 5,200-5,500 millimoles per kilogram determined by ASTM D-1652, a glass transition temperature of -18 ° C determined by ASTM D-3104 (eg DER 331 epoxy resin) with 18 grams of methyl methacrylate in a polyethylene beaker. Add 35 grams of 28% by weight aqueous solution of PVOH (PVOH is as used in Example 1) and 0.5 grams of polymerizable anionic surfactant Hitenol BC-10 (100% active agent; Hitenol BC available from Montellow, Inc .). Mix with a serrated disk at 3,000 revolutions per minute for approximately two minutes. While mixing, add 15-20 mL of water at a flow rate of 3 mL / minute to obtain a thick paste / gel (o). Continue mixing for another three minutes. Continue adding water at a rate of 20 mL / minute until a total of 175 mL of water has been added. The resulting mixture is an initial dispersion which is an oil-in-water dispersion in which the oil phase is a combination of epoxy resin and methyl methacrylate monomer. Prepare the dispersion at approximately 25 ° C. The resulting dispersion has a particle size of 720 nanometers.
Polymerization of alkali-soluble polymeric shell and spray drying
[84] Transfer the initial dispersion into a polymerization vial equipped with a nitrogen purge, reflux condenser, thermometer and stirrer. While stirring, add 7 grams of methacrylic acid to the initial dispersion. Add 1 ml of 1% by weight aqueous ferrous sulphate solution and heat the resulting mixture to 70 ° C. Add 10 mL of 5% by weight aqueous solution of formaldehyde sulfoxylate
Petition 870190139502, of 12/26/2019, p. 54/66
41/45 sodium and 10 mL of a solution of 0.5 grams of 70% by weight aqueous tert-butyl hydroperoxide in 10 mL of water over a period of one hour. Continue to mix at 60 ° C for 45 minutes after the complete addition of one hour to form an epoxy resin dispersion that has an alkali-soluble shell. The resulting dispersion has a particle size of 720 nanometers. The dispersed particle composition has 68 wt.% Epoxy resin, 23 wt.% Alkali soluble casing and 9 wt.% Dispersion aid based on the total weight of epoxy PRD particles.
[85] Mix the resulting dispersion of epoxy resin that has an alkali-soluble shell with solid PVOH (10% by weight relative to the epoxide weight; the same PVOH used in Example 2) and pump the resulting mixture through an atomizer two-fluid nozzle fitted in a Mobile Minor spray dryer. Fix the air pressure in the nozzle at 100 kilopascals with 50% of the flow, which is equivalent to 6 kilograms per hour of air flow. Spray the epoxy dispersion in a nitrogen gas environment with an inlet temperature set at 140 ° C and an outlet temperature set at 40 ° C. Add kaolin clay powder (eg, Kamin ™ HG-90, Kamin is a trademark of Kamin LLC) as a pie anti-forming agent in a concentration that corresponds to 10% by weight of the total solids weight. Dry the resulting epoxy PRD at 40 ° C.
[86] The resulting epoxy PRD has an average powder particle size of 10-20 micrometers due to the reversible agglomeration of the particles. During the redispersion of the epoxy PRD powder in water at a pH of 9-11 in a 1% by weight solution and swirling twice for 30 seconds the epoxy PRD is redispersed to have a dispersed epoxide particle size 1600 nm or less.
[87] Tg analysis of epoxy PRD describes an epoxy Tg at
Petition 870190139502, of 12/26/2019, p. 55/66
42/45 about 5 ° C of the pure epoxy resin that confirms a core-shell structure with an essentially unmodified epoxy resin. Furthermore, the isolation of the epoxy resin particle via the spray drying process without irreversible agglomeration of the particles together confirms that there is a wrap around the epoxy resin particles that prevents the epoxy resin from mixing between the particles when particles contact each other. The epoxy particles readily re-disperse in aqueous alkaline solution, much more readily than in acidic aqueous solutions, which is consistent with the solubilization of the casing in the alkaline aqueous solution and is indicative of an alkali-soluble casing around the resin core. of epoxy.
[88] Example 4 illustrates a method of the present invention which comprises mixing a monomer with the epoxy resin before dispersing the resin directly into an aqueous phase. Dispersion aids are added both during the formation of the initial epoxy resin dispersion and during spray drying to isolate the final epoxy PRD. Example 4 further illustrates the epoxy PRD of the present invention which has a composition of 66% by weight of epoxy resin, 17% by weight of alkali-soluble shell and 17% by weight of dispersion aid, and an average size of particle of 1,600 nanometers or less when redispersed in water having a pH of 9-11 as Example 1. Furthermore, Example 4 illustrates a process for preparing an epoxy PRD and an epoxy PRD that comprises more than 50% by weight of epoxy resin that is liquid at 20 ° C, with% by weight in relation to the total weight of epoxy resin, alkali-soluble casing and dispersion aid.
Example 5: Dry mixing of a component and mortar of the same
[89] Example 5 is a dry component mixing system comprising the PRD of Example 1. Comparative Examples (Exs. Comps.) A-C provide alternative systems. The Ex. Comp. A is a typical
Petition 870190139502, of 12/26/2019, p. 56/66
43/45 three-part system with a separate hardener available under the trade name of Sika Armatec 110 EpoCem ™ (EPOCEM is a trademark of Sika Ag) comprising Part A (liquid bisphenol A epoxide dispersion (average molecular weight) of epoxide <700 g / mol), Part B (isophorone-diamines solution) and Part C (dry mix of amorphous silica and cement) Prepare the four mortars according to the descriptions in Table 1:
Table 1
Example 5 Ex. Comp. THE Ex. Comp. B Ex. Comp. Ç Polymer Ex. PRD 1 Sika Parts A &B Ex. 1 initial epoxy dispersion ASR powder ^a Tg (° C) 39 <0 39 > 100 EEW (gram / equivalent) 500-600 <200 500-560 AT Sand and cement Sika C Sika C Sika C Sika C Defoamer ^b (% by weight based on the weight of Sika C) 0.047 0.047 0.047 0.047 Kaolin clay ^c (% by weight based on polymer weight) None None 14 14 Final water load (% by weight in relation to sand and cement) 15.66 15.66 15.66 15.66
^a ASR Powder is a copolymer of poly (methyl methacrylate) poly (methacrylic acid) (4: 1) that has a dispersed state particle size of 400 nanometers that is spray-dried with 40% Mowiol ™ 488 as a colloidal stabilizer to match the ratio of PVOH / ASR to that of the PRD of Example 1.
^b Kaolin clay defoamer modified by propylene oxide (40% clay by weight).
^c Kamin ™ HG-90
[90] Prepare the dry mixing systems by combining sand, cement and polymer together in a plastic bag, close the bag and then mix well for two minutes. Prepare mortars from the
Petition 870190139502, of 12/26/2019, p. 57/66
44/45 dry mixes by slowly adding the dry mix in water to the mixing bowl of a Hobart mixer (model N-50 at speed 1) for two minutes. Allow the mortar to mix for 30 seconds. Remove the mixing paddle and mix by hand with a spatula for one minute, then reattach the mixing paddle and mix for one minute with the Hobart mixer. Hydrate the mortar with a uniformly moistened trowel and leave it covered for ten minutes. Then mix with the Hobart mixer for an additional 15 seconds and characterize the viscosity of the mortar as Thin, Good, or Thick.
[91] Characterize the flexural strength of mortars according to ASTM C580-02 (2008). Assemble standard molds (51 mm x 51 mm x 254 mm) available from Humboldt Test Equipment, Schiller Park, Illinois, USA). Half fill the molds with mortar and then force the air bubbles out with a rubber compound foot (152 mm x 13 mm x 25 mm; available from Humboldt Test Equipment). Finish filling the molds and cover again. Produce a flat, uniform surface over the mortar with the use of a metal spatula. Cover the molds with a polyester film and allow to harden for 72 hours and then demould the samples and allow to harden for another four days. Characterize flexural strength using a United Floor Model Smart-1 Machines Model SFTM-150 KN (United Testing Systems, Inc.) using a one kilonewton load cell and a 229 mm extension. Apply the load to the sample to achieve a deflection rate of 3.429 mm per minute (0.135 inch / minute) until rupture.
[92] Table 2 describes the characterization of Example 5 and Exs. Comps. B.C. A comparison of the properties of the mortars of Example 5 and Comparative Examples A-C illustrates the surprisingly desirable performance of a mortar prepared from a dry component mixing system using a PRD of the present invention without a
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45/45 additional hardener.
Table 2
Sample Flexural Strength (MPa) Standard Deviation for Flexural Strength(MPa) Viscosity Assessment Example 5 8.16 2.04 Good Ex. Comp. THE 8.59 1.61 Slim Ex. Comp. B 6.57 2.02 Thick Ex. Comp. Ç <1.00 AT Slim
[93] The two-component mortar of Example 5 has a flexural strength similar to that of the Ex-Comp three-part mortar. Although it has good feasibility (viscosity) without rheology modifiers. To observe, Example 5 and Ex. Comp. A also demonstrated similar retractions during hardening over 7 days. In contrast, Ex. Comp. B showed lower practicality due to the higher viscosity and lower flexural strength. The Ex. Comp. C did not harden or cure, indicating that flexural strength is attributed to the epoxy phase. Examples 5 and Exs. Comps. A-C described the ability and value of using an epoxy PRD of the present invention in mortar applications.

权利要求:
Claims (15)
[1]
1. Water-redispersible epoxy polymer powder comprising epoxy resin particles, characterized by the fact that epoxy resin particles comprise:
(a) epoxy resin;
(b) an alkali-soluble polymeric shell around each of the epoxy resin particles, the alkali-soluble polymeric shell comprising a polymer made up of at least five weight percent and forty weight percent or less of monomers selected from monomers of carboxylic acid and anhydride monomers based on the total weight of polymerized monomers to form the alkali-soluble polymeric shell and the alkali-soluble polymeric shell having a glass transition temperature of at least 60 degrees Celsius as calculated by the Fox formula; and (c) a dispersion aid;
where the epoxy resin is present in a concentration greater than fifty percent by weight and ninety percent by weight or less, the alkali-soluble polymeric shell is present in a concentration in a range of ten to fifty percent by weight and the auxiliary dispersion is present in a concentration of two to twenty-five percent by weight with the weight percentages of epoxy resin, alkali-soluble polymeric shell and dispersion aid being based on the combined total weight of epoxy resin, polymer-soluble shell in alkali and dispersion aid such that the total combined weight percentages of each of these components is 100 percent by weight.
[2]
2. Water-redispersible epoxy polymer powder according to claim 1, characterized in that in addition the epoxy resin particles have an average particle size of two micrometers or less as measured by laser diffraction according to
Petition 870190139502, of 12/26/2019, p. 60/66
2/6
ISO 13320-2009 with the use of Coulter Counter particle size and counting analyzers when the water redispersible polymer powder is dispersed in an aqueous liquid that has a pH in the range of 9 to 11.
[3]
3. Water redispersible epoxy polymer powder according to claim 1, characterized in that the epoxy resin is present in a concentration of at least 75 weight percent based on the total combined weight of the epoxy resin, wrapper polymeric soluble in alkali and dispersion aid.
[4]
4. Water redispersible polymer powder according to claim 1, characterized by the fact that the epoxy resin has a glass transition temperature of 20 degrees Celsius or less as measured by ASTM D7426-08 using a speed of heating and cooling to 10 ° C per minute.
[5]
5. Water redispersible epoxy polymer powder according to claim 1, characterized in that the alkali-soluble polymeric shell comprises a methyl methacrylate and methacrylic acid copolymer and has a glass transition temperature of at least 100 degrees Celsius as calculated using Fox's formula.
[6]
6. Water-redispersible epoxy polymer powder according to claim 1, characterized in that the dispersion aid comprises poly (vinyl alcohol) in a concentration of at least five percent by weight based on the total weight of resin epoxy, polymeric shell soluble in alkali and dispersion aid.
[7]
7. Water redispersible epoxy polymer powder according to claim 1, characterized by the fact that the epoxy resin has a glass transition temperature in the range of -40 degrees Celsius to 50 degrees Celsius, the polymeric soluble coating in alkali comprising a polymer consisting of polymerized monomer selected from the group consisting of acrylate, ethyl acrylate, butyl acrylate, 2-ethyl acrylate
Petition 870190139502, of 12/26/2019, p. 61/66
3/6 hexyl, decyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid and selected so that the alkali-soluble polymeric casing has a temperature glass transition above 100 degrees Celsius as calculated by the Fox equation and the dispersion aid comprises poly (vinyl alcohol) in a concentration of at least five weight percent based on the total weight of the epoxy resin, soluble polymeric shell in alkali and dispersion aid.
[8]
8. Method for preparing the water dispersible epoxy polymer powder as defined in claim 1, characterized in that it comprises:
(a) dispersing an epoxy resin in an aqueous phase to form an initial epoxy resin dispersion of epoxy resin particles that contain more than 50 weight percent epoxy resin by weight of the epoxy resin particles;
(b) introducing, in order to be present in the initial epoxy dispersion during the polymerization step (c), a selection of unsaturated monomers at any point or combinations of points before or simultaneously with the next polymerization step (c), being whereas at least five weight percent and 40 weight percent or less of unsaturated monomers are selected from carboxylic acid monomers and anhydride monomers;
(c) feeding a free radical initiator into the initial epoxy resin dispersion and subjecting the dispersion, free radical initiator and monomers to conditions that result in free radical polymerization while stirring in order to polymerize the unsaturated monomers in one alkali-soluble polymeric shell around each particle of epoxy resin; and (d) removing the aqueous phase from the epoxy resin particles that
Petition 870190139502, of 12/26/2019, p. 62/66
4/6 have an alkali-soluble polymeric shell to obtain a water-redispersible epoxy polymer powder;
being that:
(i) a dispersion aid is added to the epoxy resin or dispersion at one or more points before or during any of the steps (a) - (d);
(ii) the unsaturated monomers in step (b) are selected so that the resulting polymer that forms the alkali-soluble polymeric shell has a glass transition temperature as calculated by the Fox equation of at least 60 degrees Celsius; and (iii) the amounts of epoxy resin, unsaturated monomers and dispersion aid are selected so that the resulting water redispersible epoxy polymer powder has a concentration of epoxy resin that is greater than 50 weight percent and 90 percent in weight or less; a concentration of alkali-soluble polymeric shell in a range of ten to fifty percent by weight; and a total of two to 25 percent by weight of a dispersion aid with the concentration of each epoxy resin, alkali-soluble polymeric shell and dispersion aid being in relation to the total combined weight of epoxy resin, soluble polymeric shell in alkali and dispersion aid such that the total combined weight percentages of epoxy resin, alkali-soluble polymeric shell and dispersion aid is 100 percent by weight.
[9]
Method according to claim 8, characterized in that at least a portion of the unsaturated monomers is mixed with the epoxy resin before step (a).
[10]
Method according to claim 8, characterized in that at least a portion of the unsaturated monomers is fed into the initial epoxy dispersion during step (c).
[11]
11. Method according to claim 8, characterized
Petition 870190139502, of 12/26/2019, p. 63/66
5/6 by the fact that methyl methacrylate is added to the epoxy resin before step (a) and methacrylic acid is added as an unsaturated monomer after step (a) and during or before step (c).
[12]
Method according to claim 8, characterized in that step (a) includes providing an epoxy resin in a softened state and feeding the softened epoxy resin to an aqueous phase while shearing to disperse the epoxy .
[13]
Method according to claim 8, characterized in that it additionally forms in step (d) water-redispersible epoxy polymer powder which, during redispersion in an aqueous medium that has a pH in the range of 9 to 11, produces a dispersion of epoxy particles that have an average particle size of two micrometers or less.
[14]
Method according to claim 8, characterized in that step (d) requires spray drying of the epoxy resin particles while introducing an anti-cake agent.
[15]
15. Dispersion of the redispersible epoxy polymer powder in water as defined in claim 1, characterized in that it comprises epoxy particles that comprise epoxy resin particles dispersed in an aqueous solution, the epoxy resin particles comprising:
(a) epoxy resin; and (b) an alkali-soluble polymeric shell around each of the epoxy resin particles, the alkali-soluble polymeric shell comprising a polymer made up of at least five weight percent and forty weight percent or less of monomers selected from among carboxylic acid monomers and anhydride monomers based on the total weight of polymerized monomers to form the alkali-soluble polymeric shell and the alkali-soluble polymeric shell having a glass transition temperature of at least 60 degrees Celsius as
Petition 870190139502, of 12/26/2019, p. 64/66
6/6 calculated using Fox's formula; and (c) a dispersion aid;
wherein the epoxy resin is present in a concentration greater than fifty percent by weight and ninety percent by weight or less, the alkali-soluble polymeric shell being present in a concentration in a range of ten to fifty percent by weight and the auxiliary dispersion being present in a concentration of two to twenty-five percent by weight with the percentages by weight of epoxy resin, alkali-soluble polymeric shell and dispersion aid being based on the combined total weight of epoxy resin, polymer-soluble shell in alkali and dispersion aid such that the total combined weight percentages of each of these components is 100 percent by weight.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-03-17| B09A| Decision: intention to grant|

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2020-05-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201161500167P| true| 2011-06-23|2011-06-23|

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PCT/US2012/042114|WO2012177448A1|2011-06-23|2012-06-13|Water redispersible epoxy polymer powder and method for making the same|

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