TWI298074B - Method of preparing particulate crosslinked polymer - Google Patents

Description

1298074 A7 _____B7 V. INSTRUCTION DESCRIPTION (i) The present invention relates to a process for preparing a particulate crosslinked polymer. In particular, the present invention relates to a process for preparing a particulate polymer wherein the organic phase is suspended in a liquid suspension medium as droplets, followed by polymerization of the droplet suspension to form a particulate crosslinked polymer. The composition of the particular organic phase is (1) a first component comprising a polyisocyanate and a polyepoxide, and optionally a capped polyisocyanate; and (a) a second component comprising a polyamine. Granular crosslinked polymers can be used in a variety of applications such as coatings, adhesives, and cosmetic additives as carrier materials for amusement and agrochemicals, and as spacers for stacked assemblies such as liquid crystal displays. Granular Crosslinked Polyesters Granular crosslinked polyepoxides and polyurethanes can also be used to polish tantalum, which are used to polish and/or planarize various substrates. The polishing crucible can be prepared from a mixture of a particulate crosslinked polymer and a crosslinkable organic binder, which is typically press hardened in a mold. For example, in the computer chip manufacturing process, various substrates such as Shixi wafers are polished, polished and planarized to reduce engineering processing tolerances. Polishing pads are used to polish computer wafer substrates. Materials that specifically make polishing pads, such as particulate crosslinked polymers, typically also conform to a set of narrowly controlled physical properties such as particle size, particle size distribution, particle shape, and crosslink density. Polyurethane-urea particles are known to be prepared by an interfacial polymerization method. In the interfacial polymerization process, the isocyanate functional material is dispersed in water, followed by the addition of the polyamine to the dispersion, resulting in the formation of polyurethane-urea particles. If the polyurethane-urea particles are separated after interfacial polymerization, for example by filtration, the aqueous phase typically contains polyamines, requiring additional processing steps prior to disposal. It is hoped that a granular crosslinked polymer such as a particulate crosslinked polyamine group will be developed.

-4 1298074 A7 I---~--- B7_ V. INSTRUCTIONS (2) Formic acid vinegar-stepping and polyepoxide production. It is also desirable to develop a process for the production of particulate crosslinked polymers which minimize the formation of waste streams such as polyamine-containing water streams. U.S. Patent No. 5,041,467, the disclosure of which is incorporated herein by reference in its entirety, the entire disclosure of the entire disclosure of the entire disclosure of the entire disclosure of the entire disclosure of the disclosure of the entire disclosure of The compound of the active agent is emulsified and allowed to harden in a dispersion medium which does not dissolve the isocyanate compound. The method of the '467 patent is described as being carried out in the presence of an unprotected colloid. U.S. Patent No. 5,292,829 describes the preparation of a crosslinked polyaminomethyl Sjl Sa polyurea spherical particulate polymer which involves the reaction of a polyisocyanate compound containing an isocyanurate ring with a polyhydroxy compound to form an organic phase, organic The phase is dispersed in water and the polyamine is added to the dispersion. The '829 patent describes interfacial polymerization between a dispersed organic phase and a polyamine, and a polyurethane formation reaction between particles. According to the present invention there is provided a process for the preparation of a particulate crosslinked polymer comprising: (a) preparing an organic phase comprising, (1) a first component comprising a polyisocyanate having at least two isocyanato groups and having at least two At least one of a polyepoxide of an epoxy group, and optionally a capped polyisocyanate having at least two capped isocyanato groups; and (ii) a second component comprising A basic paper scale with at least two active hydrogen standards®® (CNS) A4 specification (21GX297>i^^ " ---

Order 请 (Please read the notes on the back and fill out this page) 5 1298074

An active hydrogen functional reactant reactive with an isocyanate group and an epoxy group of the first component. The active hydrogen functional reactant comprises a polyamine having at least two selected from the group consisting of a first amine, a functional group of a second-stage amine and a combination thereof; (b) forming a suspension of the organic phase droplets in a liquid suspension medium, the organic phase being substantially insoluble in the liquid organic medium; and (c) polymerizing the organic phase The suspension is suspended in a liquid suspension medium, thereby forming a particulate crosslinked polymer. Except in the case of operation examples or other instructions, the full number or representation of the specification and the scope of application, for example, the number of weights, molar equivalents, weight ratios, molar equivalent ratios, etc., must be understood in each case. "about" modification. DETAILED DESCRIPTION OF THE INVENTION As used herein and in the scope of the claims, the term "particulate crosslinked polymer" means a particulate polymer having a three degree space intersection network and having no melting point or sintering point. Thus, the particulate crosslinked polymer of the present invention does not sinter together when heated. The shape of the particulate crosslinked polymer prepared according to the process of the present invention may be regular and/or irregular, and may be selected from the group consisting of spheres, disks, sheets, and combinations thereof and/or mixed shapes. Typically, the particulate crosslinked polymer is substantially spherical in shape. The particulate crosslinked polymer of the present invention has a broad particle size range such as from colloid to bead size. Typically, the particulate crosslinked polymer has a particle size of at least 20 microns, preferably at least 50 microns and more preferably at least 1 inch. The particulate crosslinked polymer typically has an average particle size of less than 2 mm, more typically less than 1298074 A7 -----_________B7 5. Description of the invention (4) - a " --- 5 〇 0 micron, preferably less than _ (four) And more preferably less than 300 microns. The average particle size of the granular cross-linking κ can be combined with any of these high and low values (including quoted values). The average particle size of the particulate crosslinked polymer can be determined by methods well known to those skilled in the art, for example, using an analytical instrument such as a Coulter LS particle size analyzer. The particulate crosslinked polymer can be porous or substantially solid. "Substantially solid" means that the particulate polymer is not hollow, for example, not in the form of a hollow microcapsule. The particulate crosslinked polymer which can be prepared according to the method of the present invention is a granular parent urethane urethanamide urea polymerization 16, a particulate crosslinked polyepoxide and a particulate crosslinked polyaminocarbamate urea _ ring Oxide polymer. The particulate crosslinked polyurethane-urea polymer prepared by the method of the present invention has a bond selected from the group consisting of urethane linkage (-NC(O)-O-) and urea linkage (-NH_c(〇)- NHj / or -NH-C(0)-N(R)- wherein R is hydrogen, aliphatic, cycloaliphatic or aromatic (and backbone linkages thereof). Granules prepared according to the process of the invention The crosslinked polyepoxide has a backbone linkage selected from the group consisting of ether linkages, amine linkages, and combinations thereof. In a particular embodiment of the invention, the first component of the organic phase comprises a mixture of polyisocyanate and polyepoxide 'Results The obtained granular cross-linked polymer is a particulate cross-linked polyurethane-urea-epoxide polymer. It is used herein for "granular cross-linked polyurethane-urea-ring" The oxide polymer has a backbone linkage selected from the group consisting of a urethane linkage, a urea linkage, an ether linkage, and an amine linkage. In the method of the present invention, the preliminary preparation comprises the first and second groups. Part of the organic phase. Since the first and second components typically start to react when they are combined, in other words, form a covalent bond, the organic phase typically has a limited shelf life, if This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

Order - (Please read the notes on the back and fill out this page) V. INSTRUCTIONS (5) Step (b) Before the suspension is formed, it will gel for a long time. Although the gel formation can be delayed by cooling the organic phase, e.g., to a temperature below 25 °C, the organic phase is typically prepared with ambient room temperature, e.g., 25 t, and the suspension formation step (b) is carried out quickly or immediately. The organic phase can be prepared by a batch process, such as by mixing the first and second components via the use of a propeller. Alternatively, it may be continuously prepared, for example, by continuously combining the separate feed streams of the first and second components by the mixing head and continuously discharging the organic phase from the mixing head. The polyisocyanate of the first reactant of the organic phase has at least two isocyanato groups (-NCO groups) such as 2 to 1 异 isocyanate groups. Typical polyisocyanates contain from 2 to 4 isocyanato groups. The polyisocyanate may be selected from the group consisting of aliphatic polyisocyanate monomers, aromatic polyisocyanate monomers, polyamine-based prepolymers containing at least two isonitro acid groups, and mixtures thereof. It is used here and in the middle of the patent 1巳月曰 aliphatic isocyanate monomer” to mean saturated polyisocyanate monomer, ethylenically unsaturated polyisocyanate g monomer, cycloaliphatic polyisocyanate A monomer and a mixture of two or more of them. The aliphatic polyisomeric acid monomers useful in the process of the invention typically contain at least 4 carbon atoms, for example 4 carbon atoms. As used herein and in the scope of patent application, "aromatic polyisocyanate monomer" means that the aromatic polyisocyanate monomer of the towel is not directly attached to the ring, such as xylene Cyanic acid; an aromatic polyisocyanate in which an isocyanate group is directly bonded to an aromatic ring, such as a stupid diisocyanate; and a mixture thereof. The polyisocyanate of the process of the invention may have at least 8 carbon atoms, such as 8 to 2 carbon atoms, from the monomer. α: The aliphatic saturated polyisocyanate monomer of the method of the present invention includes, for example, but not limited to, ethyl diisocyanate, trimethylene diisocyanate 1298074 A7 ____B7 5. Inventive Note (6) Read the notes on the back page and fill out this page} Ester, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 9-methylene diisocyanate, 2,2, dimethyl ketone Diisocyanate ' 2,2,4-trimethylhexanyl diisocyanate, decamethyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, sesquioxalic isocyanate, U, 6 - hexamethylene triisocyanate, diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-diisocyanato-5-(isocyanato Methyl)octane, anthracene (isocyanatoethyl) carbonate, anthracene (isocyanatoethyl) ether, 2-isocyanatopropyl-2,6-diisocyanatohexanoic acid Ester, dicyanic acid diisocyanate methyl ester and triisocyanatomethyl methacrylate. The first component polyisocyanate may be selected from the group consisting of ethylenically unsaturated polyisocyanate monomers. Not limited to Ding Alkene diisocyanate and 13 · butyl hydrazine • 1,4-diisocyanate. The isocyanate functional reactant can be selected from aliphatic polyisocyanates such as, but not limited to, isophorone diisocyanate, cyclohexene diisocyanate 'methylcyclohexane Burned diisocyanate, hydrazine (isocyanatomethyl) cyclohexane, hydrazine (isocyanatocyclohexyl)methane, hydrazine (isocyanatocyclohexyl)-2,2-propane, hydrazine (isocyanato Cyclohexyl h,2-ethane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2·2·1]-g Burning '2-isoxylmethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl·bicyclo[2·2·1]-heptane, 2-isocyanate Methyl-2-(3-isocyanatopropyl)-indole isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-iso Cyanate propyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6- (2-isocyanatoethyl)-bicyclo[2·2·1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropylisocyanatoethyl) ·Double ring Ρ·2.1]-heptane, and 2-isocyanate Base methyl paper size applicable to China National Standard (CNS) Α 4 specifications (210X297 mm) 7 1298074 V. Description of the invention ^ Isocyanide "propyl" _6_(2_isocyanatoethyl) bicyclo [221] Geng Zhizhi A wide variety of aromatic polyisotopic samples in which the isofluoric acid group is connected to the aromatic ring, such as (4) s-ethyl acetonide, α, α, α, α-isocyanate, 1,3-贰 ( 1_ 昱 觫 一 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲Base) 22nd base shouting, with isocyanatoethyl) benzodicarboxylic acid from the purpose, stretching trimethylphenyl triisolactic acid vinegar and 2,5_: (isocyanatomethyl sulfonate. The isocyanate-functional reactant may be selected from the group consisting of hetero-groups directly bonded to the aromatic ring of the polyisocyanate, including but not limited to phenyl diisocyanate, ethyl phenyl diisocyanate Purpose, isopropyl phenyl diisocyanate, dimethyl phenyl diiso citrate 'diethyl phenyl diisophthalate, diisopropyl phenyl diiso-succinic acid S 曰 ' two Methyl stupid two test g purpose 'stupid three different test, naphthalene triisocyanate, methyl naphthalene diisocyanate 'biphenyl diisocyanate, o-amylamine diisocyanate, 4,4'-two Stupid base smoldering diisocyanate, a family of (3.methyl-4-isoxylphenyl)methane, anthracene (isocyanatophenyl)ethylene, 3,3,_dimethoxy- Biphenyl _4, 4, _ a different chaotic bismuth, two base ketone diiso-gas vinegar, polymer _4 4, _diphenylmethane diisocyanate, naphthalene triisocyanate, diphenyl methyl ketone-2, 4,4,_three isogastric acid vinegar '4-methyldiphenylmethane-3,5,2',4',6,-penta-isocyanate, diphenyl scale-iso-n-acid from the purpose of 'qi (different Gasoline phenyl scale) ethyl ethane, gas (isolactic lactyl ether) - 1,3-stretch Propyl diol, benzophenone diisocyanate, Kaba 嗤一 "Disorder acid 6 means 'Ethyl Kaba Jun' - isotonic acid cool, and two gas kaba squat diisocyanate. This paper scale applies to the Chinese National Standard (CNS) Α 4 specification (210X297 mm) 10 to 1298074

In one embodiment of the invention, the polycyanate vinegar of the first component of the organic phase is a polyisocyanate monomer containing two isocyanato groups. Preferred polyisocyanate monomers having two isocyanato groups include, for example, (iv), xylene diisocyanate, α,α,α',α,_tetramethyl dimethyl diisocyanate, isophorone isocyanate, (not shown) cyclohexyl)methane, toluene diisocyanate (tetra), hydrazine, diphenylcarbazone diisocyanate and mixtures thereof. The polyisocyanate of the first component of the organic phase may also be selected from the group consisting of polyurethane prepolymers having at least two ionic acid groups. The isocyanate functional polyurethane prepolymer can be prepared according to methods well known to those skilled in the art. Typically at least one polyol such as a diol and/or a triol is reacted with at least one isocyanate functional monomer such as a diisocyanate monomer to form a prepolymer having at least two isocyanate groups. Isocyanate functional monomers useful in the preparation of isocyanate functional polyurethane prepolymers include the polyisocyanate classes and examples as previously cited. The molecular weight of the isocyanate-functional polyurethane prepolymer can vary widely, for example, using a polystyrene standard by gel permeation chromatography (GPC) with a number average molecular weight (Μη) of 5〇〇 to 15〇〇. 〇 or 5〇〇 to 5000. The class of polyols that can be used to prepare the isocyanate functional polyurethane prepolymer of the first component of the organic phase include, but are not limited to, linear or branched chain burn polyols such as 1,2-ethanediol, i. 3. Propylene glycol, l, 2-propanediol, iota, 4-butanediol '1,3-butanediol, glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, di-trishydroxyl Methylpropane, erythritol, pentaerythritol and pentaerythritol; polyalkylene glycols such as di-, tri- and tetra-ethyl diols and di-, tri- and tetra-propyl diols; Polyols such as cyclopentanediol are applicable to the Chinese National Standard (CNS) Α4 specifications (210X297 public) 11 (Please read the notes on the back and fill out this page)

1298074 A7 Γ------Β7_ V. Description of invention (9) Cyclohexanediol, cyclohexanetriol, cyclohexanedimethanol, hydroxypropylcyclohexanol, and % hexanol-ethanol, Fangxiang Polyols such as diphenylbenzene, benzenetriol, mercapto and dihydroxytoluene; bisphenols such as 4,4,-isopropylidenediol; 4,4,-oxybisphenol, 4,4,-dihydroxyl Benzophenone, 4,4'-thiobisphenol, phenolphthalein, hydrazine (4-hydroxyphenyl)methane, 4,4'-(1,2-ethylenediyl)bisphenol and 4,4,-sulfonate Bisphenols; halogenated bisphenols such as 4,4'-isopropylidene (2,6·dibromophenol), 4 4,_isopropylidene (2,6-dichloro)' and 4 , 4'-isopropylidene hydrazine (2,3,5,6-tetrachlorophenol); alkoxylated bisphenols, for example, containing from 1 to 70 alkoxy groups such as ethoxy, propoxy, ... butoxy And 4,4'-isopropylidenediphenol of F butoxy; and anthracyclines such as 4,4'-isopropylidene dicyclohexanol, 4, 4 which can be prepared by hydrogenating the corresponding bisphenol ,-oxocyclohexanol, 4,4'-thioxancyclohexanol and martial acid (4-cyclohexanol). The antimony alcohol type which can be used for the preparation of the isogas acid g functional polycarbamic acid g prepolymer includes, for example, a south carbon polyalkylene glycol such as polyethylene having a number average molecular weight (Μη) of 200 to 2000. Glycols; and those having a trans-functionalized polyacetate such as from 200 to 2000, such as via the reaction of a diol such as butanediol with a diacid or a diester such as adipic acid or diethyl adipate. In a specific embodiment of the invention, the isocyanate functional polyurethane prepolymer is prepared from a diisocyanate such as toluene diisocyanate and a polyalkylene glycol such as poly(tetrahydrofuran). The isocyanate functional polyurethane prepolymer can be prepared as needed in the presence of a catalyst. Suitable catalysts include, but are not limited to, tertiary amines such as triethylamine' and organometallic compounds such as dibutyltin dilaurate. Additional examples of catalysts useful in the preparation of isocyanate-functional polyurethane prepolymers are listed below. If the catalyst is used to prepare isocyanate-functional polyurethanes, the paper scale applies to the Chinese National Standard ((10)) Α 4 specifications (2 〇χ 297 ()) "' " (Please read the notes on the back and fill out this page)

12 1298074 V. Description of the invention (10) The vinegar prepolymer 'typically exists in a quantity that accounts for the total weight of the polyol and the isoindole functional single rhyme> rhyme weight ratio is preferably less than 3% by weight and more preferably less than (iv) Quantity ratio. The epoxide group of the first component of the organic phase is two: for example: 2 to 1 fluorene. Typical polyepoxides have 4 to difficult rings: Group η, the polyepoxide can be selected from aliphatic polyepoxide monooxide epoxide monomers, polycyclic emulsions containing at least two epoxy groups And their mixtures. As used herein and in the application of a proprietary aliphatic polyepoxide monomer, it also means a cycloaliphatic polyepoxide monomer. The aliphatic polyepoxide useful in the present invention typically contains at least 4 carbon atoms 2 = 1 carbon I atom. The material group polyepoxide monomer A 3 of the present invention has 10 carbon atoms, for example, 10 to 20 carbon atoms. I. The epoxy functional monomer used in the present invention can be prepared via a polyol oxime, a private gas reaction. Can be used to prepare more epoxide functional monomers = package for the preparation of isocyanate 6 functional polyfilament (tetra) prepolymer one = multiple read. The aliphatic polyepoxide monomer includes, for example, butyl baking and 1,2,7,8 bis epoxide. Cyclic waxy polyepoxy monomers such as: two S'5, cyclohexene 'like 6 · diepoxy ring octyl burning, 7 oxa oxime [.1.0] Gengyuan-3-carboxylic acid and 7_oxygen Miscellaneous. Bicyclo[4 1〇]hept-3_base =, U-epoxy-4_epoxyethylidene·cyclohexene and 2,3_(epoxypropyl)cyclohexane. Aromatic polyepoxide monomers include those based on the reaction of aromatic diols (such as catechol, resorcinol and bisphenols) with surface alcohols, such as 4,4,_isopropylidene two Glycidyl ether. Commercially available polyepoxide precursors useful in the present invention include Ep〇N epoxy resins available from Shell, such as this paper scale for China; (CNS)-Μ specifications (210X297 mm) 1298074 A7 ____ B7_ V. Invention Description (Π) Yibian 828 epoxy resin and Yibian 880 epoxy resin. (Please read the precautions on the back and fill out this page.) The polyepoxide prepolymer constituting the first component of the organic phase can be prepared by reacting a polymer polyol with a surface alcohol. Polymer polyols useful in the preparation of epoxy functional prepolymers include, but are not limited to, polyalkylene glycols such as polyethylene glycol and polytetrahydropyrene; polyester polyols; polyaminocarboxylic acids Ester polyols; poly((meth)acrylate) polyols; and mixtures thereof. The class of polymer polyols cited can be prepared according to methods well known to those skilled in the art. In a specific embodiment of the invention, the epoxy functional prepolymer is an epoxy functional poly (manufactured by a (meth) acrylate monomer and an epoxy functional group polymerizable monomer such as glycidyl (meth) acrylate ( (Meth)acrylate) polymer. As used herein, "(meth) acrylate" means a acrylate monomer, a methacrylate monomer, and a mixture of an acrylate and a methacrylate monomer. The polyepoxide prepolymers useful in the present invention can have a broad molecular weight range, for example, using a polystyrene standard by gel permeation chromatography (GPC) to determine a broad average number of molecular weights of 500 to 15,000 or 500 to 5,000. range. The first component of the organic phase used to prepare the particulate crosslinked polymer may optionally further comprise a polyisocyanate having at least two capped isocyanato groups. "Polyisocyanate as used herein and in the scope of the patent application r" means that the isocyanate group having a terminal end and/or a side cover can be converted into a detachable cover under controlled conditions, in other words, free Isocyanate groups and separate or free capping monomers or prepolymers. The capped polyisocyanate cap base may be fugitive or non-escape. "Non-escape cover base" means that the cover base is substantially retained in the three-dimensional space network or parent material of the granular polymer when the isocyanate is removed or removed. China National Standard (CNS) A4 specification (210X297 mm) "' -14 - 1298074 A7 -----___B7_ V. Invention description (12) 邛. "Removal cover base" means a cover that is removed from the isocyanate group (please read this before reading the back of the page) or remove the particulate polymer when it is removed. The space is outside the network road or parent material. The capped polyisocyanate is typically characterized by a de-covering temperature. As used herein and in the scope of the patent application "de-covering temperature" means that the single-coated isocyanate group of the polyiso-acidic vinegar that has been capped is converted into a detachable cover, in other words, free isocyanate and separated or The lowest temperature of the free cover base. The capping temperature of various capped polyisocyanates is typically from 12 rC (250 °F) to 191 °C (375 °F). The capped polyisocyanate polyfunctional isocyanate may be selected from the polyisocyanate classes and examples cited above. The non-escape capping base of the capped polyisocyanate includes, for example but not limited to: 1H·salt, such as 1H-imida, 1仏吼 sal' 3,5-dimethyl-1H-port 嗤, 1H- 1,2,3-trimethyl, 1H-1,2,3-benzotrisene, 1H-1,2,4-triazole, 1H-5-methyl-1,2,4-triazole and 1Η ·3·Amino-1,2,4-triazole; indoleamines such as e-caprolactam and 2-indanone; and others including morphine, 3-aminopropyl morphine and N - benzodiazepine. The escape capping base of the polyisocyanate capping includes, for example but not limited to, alcohols such as propanol, isopropanol, butanol, isobutanol, tert-butanol and hexanol; alkyl diol monoalkyl ether For example, ethylene glycol-sintering scaly such as ethylene glycol monobutyl sulphate and ethylene glycol monohexyl ether, and propylene glycol monoalkyl ether such as propylene glycol monomethyl ether and ketone prevention such as methyl ethyl ketone brick. Shaped articles such as light-removing mats may be elevated by mixing the particulate cross-linked polymer of the present invention with a hardenable organic polymer binder such as a two-component polyurethane adhesive and a hardening mixture, typically in a mold The temperature and the paper scale apply to the Chinese National Standard (CNS) A4 specification (210X297 public) 1298074

It is prepared by hardening under elevated pressure as needed. The covered polyisocyanate may be included in the first component of the organic phase. The particulate cross-linking polymerization of the present invention is improved by the granular cross-linking polymerization of the present invention (please read the back of the back sheet) and the hardenable organic polymer. The shaped article prepared from the adhesive mixture, such as the shape stability of the polishing pad. While not wishing to be bound by any theory, it is believed that the capped polyisocyanate is included in the first component of the organic phase used to prepare the particulate parent polymer to allow for the formation of covalent bonds later during formation of the shaped article. (a) forming a covalent bond between at least a portion of the particulate crosslinked polymer particles and/or (b) forming a covalent bond between the particulate parent polymer and the crosslinked organic polymer binder. The capped polyisocyanate, if used, is typically present in an organic phase. The first set of knives contains a masked isocyanate group based on polyisocyanate-based isocyanato groups, polyepoxide-based epoxy groups, and hoods. The total isomer equivalent of the capped polyisocyanate, the cleavable isocyanate group is less than 5 〇 mol%, for example based on polyisocyanate-based isocyanato groups, polyepoxide-based epoxy groups and The total isomer equivalent of the isocyanate of the capped polyisocyanate is from 5 mole percent to 40 mole percent. In a particular embodiment of the invention, the polyisocyanate, polyepoxide, and capped polyisocyanate of the first reactant are each preferably substantially free of ionic groups such as % ionic and anionic groups. As used herein and in the scope of the patent, polyisocyanates, polyepoxides, and capped polyisocyanates are preferably not included in the "ion group" and are also indicated in aqueous suspension media, for example, by adjusting the pH of the aqueous suspension' mussel. Ionic based ionic precursor. As used herein and in the scope of the patent application, "substantially free of ionic groups" means that the polyisocyanate, polyepoxide and the capped polyisocyanate do not contain sufficient ionic groups to result in the formation of a stable dispersion. Preferred polyisocyanate, polyepoxide and

1298074 A7 B7 V. INSTRUCTIONS OF THE INVENTION (14) The polyisolactic acid S which has been subjected to the liberation does not contain an ionic group. (Please read the note on the back and then fill out this page.) Polyisocyanates, polyepoxides, and capped polyisocyanates are preferably substantially free of cationic groups including, but not limited to, cationic amine groups such as by the first or The cationic amine group formed by the reaction of the secondary amine group with an inorganic or organic acid and a test group such as feldspar f, a scale and a fourth-order ammonium group. The polyisocyanate, polyepoxide and capped polyisocyanate preferably each substantially free of anionic groups including, for example, carboxylates, for example, carboxylates formed by reaction of a carboxylic acid group with an amine or an alkali metal hydroxide. . The active hydrogen functional reactant of the second component of the organic phase has at least two active hydrogen groups selected from at least a first amine and a second amine, and optionally a hydroxyl group and combinations thereof. . The active hydrogen functional reactant of the second reactant comprises a polyamine having at least two functional groups selected from the group consisting of a first stage amine, a second stage amine, and combinations thereof. The polyamine may be selected from the group consisting of aliphatic polyamine monomers (including cycloaliphatic polyamines), aromatic polyamine monomers, polyamine prepolymers, and mixtures thereof. The aliphatic polyamine monomer which can be used as the polyamine of the second component includes an ethylamine such as ethylenediamine (EDA), diethyltriamine (DETA), and triethylamine (TETA). ), tetraethylidene pentaamine (TEPA), pentaethylidene hexamine (PEHA), piperene, ie diethylidene diamine (DEDA) & 2-aminoethylpiped. Aromatic polyamine monomers include, for example but are not limited to, one or more CrG-alkyl-based methylidene diamine isomers such as 3,5-dimethyl-2,4-tolyldiamine, 3,5-one Methyl-2,6-exotolyldiamine, 3,5-diethyl-2,4-tolyldiamine, 3,5-diethyl-2,6-exotolyldiamine, 3 , Hongdi-isopropyl-2, '-tolyldiamine, 3,5-diisopropyl-2,6-tolyldiamine and mixtures thereof. Other examples of aromatic polyamine monomers include, but are not limited to, methylene diphenyl 17 1298074 A7 V. Description of the invention (15) Amine and trimethylene glycol di(p-amino benzidine vinegar). Further, the monomer which can be used in the method of the present invention is a monomer having a polyglycol-free polyamine which is only 4,4,-methylene, dialkylaniline, and can be exemplified as follows:

Wherein R4R4 is each a Cl.C3 alkyl group and a ruler 5 is selected from the group consisting of gas and drawing atoms such as chlorine. Aromatic polyamine monomers based on 4,4, methylene. (dialkylaniline) include, for example, but are not limited to, 4,4,_methylene-贰(2,xin dimethylaniline), 4, 4,-methylene-Wu (2,6-diethylaniline), 4 broad methylene _ wu (2_ethyl-6-methylaniline), 4,4,·methylene-martial arts Isopropylaniline), 4,4'-methylene-anthracene (2-isopropyl-6-mercaptoaniline), and 4,4,_methylene-anthracene (2,6-diethyl- 3-air aniline). In a particular embodiment of the invention, the first component comprises a polyisocyanate and optionally a polyisocyanate that is capped, and the polyamine of the second component is preferably selected from the group consisting of aromatic polyamine monomers, and more preferably It is selected from aromatic polyamine monomers based on 4,4-methylene-Wu (secondary aniline). Polyamine prepolymers useful in the present invention include polyamine precursors having at least two amine groups selected from the group consisting of first stage amines, second stage amines, and combinations thereof. Polyamine precursors having at least two amine groups are typically prepared by reacting a polyamine such as a diamine such as diethylenediamine with a polyacid such as a difunctional carboxylic acid. Commercially available polyamide precursors for the second reactant polyamines include VERSAMID polyamide precursors from C〇gnis. This paper scale applies to Chinese national standards ( CNS) A4 size (210X297 mm) (Please read the notes on the back and fill out this page)

18 - 1298074 A7 !--_:- B7 —__ V. INSTRUCTIONS (16) ~ — COMPANY'' Coating and Ink Branch. In a specific embodiment of the invention, the first component comprises a polyepoxide, and the polyamine of the second component is preferably selected from the group consisting of polyamines (IV), and more preferably selected from the group consisting of two amine groups containing less than i. The polyamine prepolymer. In a particular embodiment of the invention, the second component of the organic phase further comprises a polyol having at least two hydroxyl groups and having at least one hydroxyl group and up to one selected from the group consisting of a first amine, a second amine, and combinations thereof. At least one of an amine based hydroxylamine reactant. The polyol constituting the second reactant may optionally include an aliphatic polyol, an aromatic polyol, a polyol prepolymer, and a mixture thereof. Useful polyol classes and examples include those exemplified above. Hydroxy-amine reactants include, for example but are not limited to, ethanolamine, diethanolamine, 2-(diisopropylamino)ethanol, 2-amino-1-hexanol, 6-amino-1-hexanol, and 2-( Tri-butylamino)ethanol. The first and second components are typically present in the relative amounts of the organic phase to obtain a particulate crosslinked polymer in the present method. The sum of the isocyanate groups of the first component (a) (i), the epoxy group and the molar equivalent of the capped isocyanate group to the active hydrogen group of the second component (a) (ii) The molar equivalent ratio of the sum of the ear equivalents is typically 0·5: 1.0 to ι·5: ΐ·〇, for example, 〇7: im 3 : ! 〇 or 〇8 ·· j 〇 to j 2 : 1.0. When the first component contains a polyisocyanate and/or a capped polyisocyanate, the organic phase may further contain a urethane/urea generating catalyst as needed. The urethane/urea-forming catalysts include, for example but are not limited to, tertiary amines such as triethylamine, triisopropylamine and N,N-dimethyldecylamine, and organometallic compounds such as dilauric acid Butyltin, dibutyltin diacetate and octanoic acid This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm)

(Please read the notes on the back and fill out this page.) 1298074 A7 B7 V. INSTRUCTIONS (17 (Please read the note on the back and fill out this page). Stannous. Other examples of tertiary amines are listed in US Patent 5,693. No. 1 to pp. 6 to 38, the disclosure of which is hereby incorporated by reference, and other examples of organometallic compounds useful as catalysts are listed in U.S. Patent No. 5,631,339, No. 4, No. 26-46. The disclosure is incorporated herein by reference. When a catalyst is used, the catalyst is typically mixed with the second component of the organic phase prior to combining the first and second components of the organic phase. Amino formate/urea formation The content of the catalyst is typically less than 5% by weight, preferably less than 3% by weight and more preferably less than 1% by weight based on the total weight of the first and second component combinations. § In the case of an epoxide, the organic phase further comprises a non-bad oxide ring-opening catalyst as needed. Useful epoxide ring-opening catalysts include those known to those skilled in the art such as tertiary amines such as tri-t-butylamine and PTFE, epoxide ring opening The agent, if used, is typically added to the second component prior to mixing the first and second components. The epoxide ring opening catalyst is typically present if present based on the total weight of the first and second components. 5% by weight, such as less than 3% or by weight. In a particular embodiment of the invention, at least one of the organic phase and the liquid suspending medium comprises an anionic surfactant, a cationic surfactant, An organic surfactant for an amphoteric surfactant, a nonionic surfactant, and a mixture thereof. The reason for the desirable organic surfactant is that it stabilizes the suspension of the organic phase in a liquid suspension medium, and correspondingly improves the resulting particles. Control of the particle size of the crosslinked polymer. The organic surfactant is typically present in an amount based on the total weight of the organic phase, the total weight of the liquid suspension medium, or based on the total weight of the organic phase in the liquid suspension medium of at least 0.01% by weight. , preferably at least 0 02% by weight and better to the paper scale applicable to China National Standard (CNS) A4 specification (210X297 mm) 20 1298074 A7 B7 18 V. Description of invention ( Please read the precautions on the back and fill out this page. Less 0.05% by weight. The organic surfactant is typically present when used, based on the total weight of the organic phase, the total weight of the liquid suspension medium, or the total weight of the organic phase and liquid suspension medium. Also less than 3% by weight, preferably less than 2% by weight and more preferably less than 1.5% by weight. The amount of organic surfactant used in the process of the invention is between any combination of such high and low values ( Containing a reference value). Anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants useful in the methods of the present invention include those known to those skilled in the art. Anionic interface activity The agent includes a block copolymer of alkylene oxide (for example, a block copolymer of any one of ethylene oxide, propylene oxide and butylene oxide) and has a terminal group selected from a carboxylic acid group, a sulfate group, and a sulfonate. Acid groups, phosphate groups, and combinations thereof. The terminal carboxylic acid, sulfuric acid, sulfonic acid and phosphoric acid group can be converted into an anionic group in the presence of a base, and the base includes, for example, an alkali metal hydroxide such as sodium hydroxide, an organic amine such as triethylamine, and an alcoholic amine such as a-, Di- or triethanolamine. Further details of the anionic surfactants which can be used in the process of the present invention are described in U.S. Patent No. 6, 〇59,944, vol. 6, line 57 to line 7, line 27, the disclosure of which is incorporated herein by reference. Cationic surfactants which can be used in the process of the present invention include those known to those skilled in the art, typically containing a first and/or second amine group, or a f group such as ammonium, sulfo or squara. Cationic surfactants useful in the present invention include, but are not limited to, dialkanolamine salts, trialkanolamine salts, polyoxyalkylalkylamine ether salts, trialkanolamine fatty acid ester salts, Polyoxoalkyl succinyl alcohol diether salts, polyoxyalkylene trisodium alcohol diether salts, di(polyoxyalkylene)alkyl mercaptoalkyl ammonium salts, alkylaminomethyl sulfonyl groups Methyl bis(polyoxyalkyl)ammonium salt, polyoxyalkylene alkyl ammonium salt and polyoxyalkylene dialkyl ammonium paper size applicable to China National Standard (CNS) A4 specification (210X297 mm) 21 1298074

The amphoteric surfactants useful in the methods of the present invention contain acidic and basic hydrophilic moieties in the structure. Commercially available amphoteric surfactant classes are imidazoline derivatives. Amphoteric surfactants include, for example, cocoa amphoteric propionate, cocoa amphoteric carboxypropionate, cocoa amphoteric glycinate, cocoa aglycone, cocoamphopropyl sulfonate, and cocoa propyl acid. Further classes of amphoteric surfactants include alkaloids and derivatives thereof such as sulphonic acid. Further details of the amphoteric surfactants are described in U.S. Patent No. 6,059,944, the disclosure of which is incorporated herein by reference. The nonionic surfactant used in the method of the present invention comprises an epoxy-fired block copolymer having a terminal group selected from a hydroxyl group, an alkyl group (such as an ATM alkyl group), an aromatic group (such as a phenyl group and a fluorenyl group), and a halogen anion group. (such as chlorine and bromine) and combinations thereof. A preferred class of nonionic surfactants are alkylene oxide block copolymers having terminal hydroxyl groups (e.g., di- and tri-block copolymers of ethylene oxide and propylene oxide). Commercially available nonionic surfactants are useful in the present inventors including, for example, PLUR0NIC surfactants available from BASF Corporation. Further details of the nonionic surfactants which can be used in the process of the present invention are described in U.S. Patent No. 6,059,944, the entire disclosure of which is incorporated herein by reference. In a particular embodiment of the invention, the organic surfactant is a nonionic surfactant (e.g., a triblock copolymer of ethylene oxide and propylene oxide with terminal hydroxyl groups) that is added only to the organic phase. Further examples of anionic, cationic, amphoteric and nonionic surfactants useful in the process of the invention (and commercial sources thereof) are described and listed in the publication 22 1298074 A7 ____ B7_ V. Description of the invention (20)

McCutcheon's Emulsifiers & Cleansers, 1st Edition, Manufacturers Publishing Company, McCutcheon Branch, Greenleaf, New Jersey, ISBN 944254-63-2 In particular embodiments of the invention, the organic phase further comprises abrasive particles material. The milled particulate material can be uniformly or non-uniformly dispersed throughout the particulate crosslinked polymer. Typically, the abrasive particulate material is substantially uniformly dispersed throughout the particulate crosslinked polymer. Although the milled particulate material may combine the first or second component, it is typically mixed with the second component prior to the preparation of the organic phase (俾 reduces the isocyanate and/or epoxy generation of the mono-reactant) The possibility of adverse reactions). The abrasive particulate material, if used, is typically present in an organic phase in an amount of less than 70% by weight based on the total weight of the organic phase, e.g., from 8% by weight to 65% by weight based on the total weight of the organic phase. The abrasive particulate material is in the form of individual particles, aggregates of particles, or a combination of individual particles and aggregates. The shape of the abrasive particulate material may be selected from, for example, a sphere, a rod, a triangle, a pyramid, a cone, a regular cube, an irregular cube, and mixtures thereof, and/or combinations thereof. The abrasive particulate material typically has an average particle size of at least 1 micron, typically at least 0. 01 microns, and more typically at least "micron". The average particle size of the abrasive particulate material is typically less than 50 microns, typically less than 1 micron, and more typically less than 1 micron. The average particle size of the abrasive particulate material can be any combination of high and low values (including quoted values). The average particle size of the abrasive particulate material is typically measured along the longest dimension of the particle. Abrasive particulate materials that can be used in the present invention include, for example, but are not limited to, alumina such as gamma alumina, fused alumina, heat treated alumina, and white paper scales applicable to the Chinese National Standard (CNS) Α4 specification (21〇><297 public Chu) (Please read the notes on the back and fill out this page)

23 5 21 1298074, invention description (Fusion Oxidation and sol-gel derived oxidation Ming: carbon cut such as green carbon carbide fossil and black carbon cut; second job titanium; carbon (four); nitrogen cut; (four); Nitriding butterfly such as cubic boron nitride and hexahedral boron nitride; Shiquanshi · Fusion Oxidation Oxidation error; Oxidation oxide such as fusion oxygen cutting; Iron oxide 'Field chromium oxide; Oxygen oxidation fault; Titanium oxide; Oxidation Tin; oxidized clock; and its mixed slag. Preferably, the abrasive particulate material includes, for example, alumina, cerium oxide, cerium carbide, cerium oxide, and mixtures thereof. The abrasive particulate material used in the present invention may optionally contain a surface modifier. Typically, the surface modifier is selected from the group consisting of surfactants, couplers, and combinations thereof. The surfactant can be used to improve the dispersibility of the abrasive particles in the organic phase used to prepare the particulate crosslinked polymer. The abrasive particles are more preferably bonded to the particulate crosslinked polymeric parent material. The surface modifying agent is typically present in an amount that is less than 25% by weight of the abrasive particulate material at the total weight of the surface modifier. More code Type, the surface modifier is present in an amount of from 〇5 to 丨〇% by weight of the abrasive particulate material to the total weight of the surface modifier. The surfactant class that can be used as a surface modifier for the abrasive particulate material includes Those skilled in the art are aware of surfactants such as anionic, cationic, amphoteric and nonionic surfactants as cited above. More preferred examples of surfactants that may be used include, but are not limited to, metal alkoxides. Alkylene oxides, long chain carboxylates, known in the industry to modify the coupling agent of the abrasive particulate material, including, for example, decanes such as organic broths, titanates, and stearic acid Salts. Useful coupling agents include, for example, the Hilster paper grade available from Witco on the market. The Chinese National Standard (CNS) A4 specification (210X297)

• Order | (Please read the note on the back and fill in this page) 24 - 1298074 A7 B7 V. INSTRUCTIONS (22) (SILQUEST) Austenite A-174 and A-1230. The organic phase may further comprise customary additives as needed. Such conventional additives include thermal stabilizers, antioxidants, static dyes, pigments, and tackifying additives such as alkylated phenol benzoates and poly(alkylene glycol) dibenzoates. The additive, if used, is present in the organic phase in a total amount of less than 10% by weight, preferably less than 5% by weight and more preferably less than 3% by weight based on the total weight of the organic phase. Although conventional additives may be added to the first or second component of the organic phase, it is typical that the second component is mixed with the second component to reduce the possibility of adverse reactions with the individual oleic acid groups or epoxy groups of the first component. . In still another embodiment of the invention, the organic phase further comprises an organic solvent as needed. The organic solvent is typically used to reduce the viscosity of the organic phase, allowing it to be introduced into the liquid suspension medium in a controlled manner in the suspension forming step of the present invention. The volume is preferably inert, in other words, does not react with the oleic acid group, the epoxy group, the blocked isocyanate group and the active hydrogen group. Alternatively, the solvent may contain one or more active hydrogen groups such as hydroxyl groups and be reacted with a polyisocyanate or polyepoxide, in which case the solvent is a reactive diluent. The organic solvent types that can be added to the organic phase include, but are not limited to, esters such as acetic acid vinegar; mysteries such as methyl ethyl ether; ketones such as methyl isobutyl ketone; hospitals such as calcined and heptane and alkylene One of the diols is an alkyl ether such as propylene glycol. The organic solvent is typically present in the organic phase in small amounts when used, more typically in an amount of less than 30% by weight, such as from 5 to 25% by weight, based on the total weight of the organic phase. In the method of the present invention, the organic phase is suspended in a liquid suspension medium in droplets. The organic phase is substantially insoluble in the liquid suspension medium selected from the group consisting of organic

(Please read the precautions on the back and fill the nest page), ^τ—5, invention description (23) Suspended medium such as organic (four) and water (four) floating medium f such as deionized water. The organic solvent which can be used as an organic suspending medium includes an organic solvent which is inert to an isocyanate group and an epoxy group, such as money, lysine, _, an aromatic hydrocarbon compound, an ether, and a mixture thereof. Preferred liquid suspending media are aqueous suspension media. Although aqueous suspension media contain organic materials such as alcohols, ethers, and organic surfactants, they typically contain large amounts of water. Aqueous suspension media typically have a water content of at least 51% by weight, such as from 51% to 99% by weight, based on the total amount of aqueous suspension medium. In a particular embodiment of the invention, the liquid suspending medium is substantially free of polyamines, e.g., containing less than 1% by weight of polyamine based on the total weight of the liquid suspending medium. In order to ensure that the liquid suspending medium is substantially free of polyamines, it can be achieved by: (a) selecting an organic phase (including the polyamine of the second component) which is substantially insoluble in the liquid suspending medium; and (b) not adding Any polyamine to liquid suspension medium. The organic phase can be suspended in a liquid suspension medium in small droplets by means well known to those skilled in the art. Typically, the organic phase is slowly poured into a liquid suspending medium while agitating the liquid suspending medium, e.g., using a high speed propeller. After the organic phase is added to the liquid suspension medium, the suspension is still stirred under high agitation for a period of time sufficient to obtain the predetermined particle size (typically determined by trial and error), followed by continuous stirring with less agitation to maintain the suspension of the organic droplets. Settling by liquid suspension medium. The suspension of the polymeric organic phase in a liquid suspension medium is typically carried out by heating the suspension above room temperature but below the liquid suspension medium.

This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1298074 A7 B7 24 V. INSTRUCTIONS Heating under atmospheric pressure, but typically under atmospheric conditions (eg 76 Torr). Typically, the suspension is heated at atmospheric pressure with continuous perturbation to a temperature of 30 ° C to 95 ° or 50 ° C to 85 ° C. The suspension is typically continuously stirred at elevated temperature for a period of time sufficient to allow the suspended organic droplets to fully polymerize, for example, from 10 minutes to 8 hours, and to form a particulate crosslinked polymer. In a particular embodiment of the invention, the first component of the organic phase comprises a capped polyisocyanate, and the suspension of the organic phase droplets in a liquid suspension medium is polymerized in step (c) below the capped The polyisocyanate is removed from the cover temperature. For example, if the capping temperature of the polyisocyanate is 121 ° C (250 ° F), the polymerization step is preferably carried out at a temperature lower than 12 r C, for example 3 (rc to 95 C. The droplet suspension is lower than The capped polyisocyanate is capped to a temperature polymerisation to allow formation of a particulate crosslinked polymer comprising a capped isocyanate group. The capped isocyanate groups inside the particulate crosslinked polymer can then be The cover and reaction are removed by heating the particulate polymer above the decap temperature, as previously described. When the polymerization step is completed, the particulate crosslinked polymer suspension is typically cooled to room temperature, such as 25 ° C. And can be stored in a suitable container for later use. Although the particulate crosslinked polymer can be stored in a liquid suspension medium, it is typically separated by a liquid suspension medium. The separation of the particulate crosslinked polymer can be achieved by methods well known in the art. The particulate crosslinked polymer allows sedimentation from the liquid suspending medium to 'pour the liquid suspension medium out of the settled particulate crosslinked polymer. More typically, the particulate crosslinked polymer can be separated by filtration, followed by drying Separated granular polymer. The present invention will be specifically illustrated by the following examples, which are for example only, the standard of the paper (2) 〇χ 297 mm" (please read the note on the back and fill out this page) _ order 27 22.5 8.8 0.1 1298074 V. INSTRUCTIONS (25) The skilled person will make numerous modifications and variations, unless otherwise stated, all parts and percentages are by weight.

Examples A and B

Preparation of Granular Crosslinked Polymers Example A Granular crosslinked polyurethane guanidines were prepared according to the method of the present invention from the constituents listed in Table A.

1 diamine hardener (a) diamine hardener (b) surfactant (c) isocyanate functional prepolymer (d) mp_RSALINK) p·650 from air products and chemicals company poly (tetramethylene Glycol) (C) PLURONIC F108 surfactant was obtained from Basf. ARITHANE PHP_75I^ prepolymer is obtained from Air Products and Chemicals Co., Ltd. and is described as a reaction of toluene-isohetero acid δ with poly(tetramethylene-monohydric alcohol) product. Feed 1 was added to the open vessel and placed in a hot plate set at a temperature of 9 ° C until the contents of the trough were melted. The feed was then added to the container while the container was still on the hot plate. The contents were thoroughly mixed to uniform with a motor driven pusher. The contents of the container were slowly introduced into 400 g of deionized water at 80 ° C while vigorously disturbing the ionized water. When the grain in the grain is added, the deionized water is vigorously mixed for 10 minutes, and then the granular cross-linked polyaminocarboxylic acid formed by filtration separation is applied to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the notes on the back and fill out this page)

28 1298074 A7B7 V. INSTRUCTIONS (26) Ester. The separated granular crosslinked polyurethane was dried in 13 (TC oven for 2 hours. (Please read the back note first and then fill out this page)

The dried particulate crosslinked polyurethane is sieved using a stack of sieves having a top to bottom mesh size of 40 mesh (420 micron mesh) and 50 mesh (297 micron mesh). ), 70 mesh (210 micron mesh), 140 mesh (105 micron mesh) and 325 mesh (44 micron mesh). The particulate material is collected from each screen and weighed. The weight of the particulate material collected from each screen is used to calculate the particle size distribution of the particulate crosslinked polyurethane, and is summarized in the table. For example, the granular material collected by the No. 70 sieve is based on sieves 50 and 70. The mesh size was measured to have a particle size ranging from about 210 to 297 microns. The particulate cross-linked polyurethane after drying is free flowing, and the individual particles are observed to be substantially spherical. Example B Granular crosslinked polyepoxides were prepared according to the process of the present invention from the constituents listed in Table B. Table B Ingredients Feed 1 Weight (g) Polyamine Hardener (e) 40.9 Surfactant (C) 1.0 Isopropanol Solvent 15.8 Solvent (1) Feed 2 11.9 Epoxy Resin (g) 58.1 (e) Wosha Fan 253 polyamine "polyamine hardener, obtained from Knitz. 1 DOWANOL PM propylene glycol monomethyl ether available from The Dow Chemical Company. (g) Yibian 880 epoxy resin, available from Shell. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 29 1298074 A7 B7 V. INSTRUCTIONS (27) Feed 1 is added to the open container and driven by motor drive at ambient room temperature (about 25 °C) The device was stirred until all the ingredients were observed to dissolve substantially and form a homogeneous mixture. Feed 2 was then added to the vessel and the contents were further mixed until homogeneous. The contents of the container were then slowly poured into 300 g of 8 ° C deionized water while vigorously stirring the deionized water. When the addition of the contents of the container was completed, the deionized water was continuously stirred vigorously, and then the formed particulate crosslinked polyepoxide was separated by filtration. The separated particulate crosslinked polyepoxide was dried in a WOt: oven. The dried particulate crosslinked polyepoxide was sieved using a stack of sieves as described in Example A. Granular crosslinked polyepoxides were separately collected from each of the screens. The weight of the particulate material collected from each of the sieves was used to calculate the particle size distribution of the particulate crosslinked polyepoxide, which is summarized in Table 1. The dried particulate crosslinked polyepoxide was free-flowing and visually observed to be spherical. Table 1 _Particle cross-linked polymer granules _ Screen sieve target indication (i) Estimated particle size range ω Examples obtained from each screen are obtained from each sieve Α weight percentage (3⁄4_% mutual percentage (k 40 is greater than 420 microns 3.1 1.5 50 297-420 microns 3.9 5.2 70 210-297 microns 10.5 31.9 140 105-210 microns 36.6 57.8 325 44-105 microns 45.9 3.6 disks (1) less than 44 microns 0 0 (h) Example A and The crosslinked particulate polymer of B was sieved using a stack of sieves as described in Example A. The particulate crosslinked polymer was collected from each sieve and weighed. ^ 1 sieve target is provided by the manufacturer. Screen No. 40 has a mesh size of 420 microns. 1 The estimated particle size range of the particulate crosslinked polymer removed from a screen is determined based on the mesh opening of the screen in which the material is collected and the mesh directly above it. For example, a particulate crosslinked polymer collected from a No. 40 sieve is estimated to have a particle size greater than 420 microns; and a particulate crosslinked polymer collected from a No. 50 sieve is estimated to have a particle size ranging from 297 to 420 microns, more particularly greater than 297 microns. 420 μm range. (8) Granules collected from each screen The weight of the cross-linked polymer and the total weight of the particulate cross-linked polymer collected from all the screens were calculated by using _ to calculate the weight percentage of the particulate cross-linked polymer collected from each of the screens. (1) The label "Plate" is indicated on the No. 325 sieve. In the lower tray, the accumulation of any particulate crosslinked polymer was not observed on the disk during the sieving period P曰1 of the particulate crosslinked polymers of Examples A and B. This paper scale applies to the Chinese National Standard (CNS) A4 specification. (210X297 mm) (Please read the notes on the back and fill out this page)

30 1298074 A7 ___ B7___ V. INSTRUCTIONS (28) (Please read the note on the back and then fill out this page) The invention has been described with reference to the specific details of the specific embodiments. However, the scope of the invention is not intended to be limited by the scope of the invention, which is defined by the scope of the appended claims. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 31

Claims (1)

Mine year, month G, repair (pain) original 32 1298074 s夂S曰 early body, π having at least two isocyanate groups of polyurethane urethane prepolymer and mixtures thereof, the poly-epoxide of the first reactant is selected from: aliphatic polycyclic An oxide monomer, an aromatic polyepoxide monomer, a polyepoxide prepolymer having at least two epoxy groups, and mixtures thereof; and the optionally coated polyisocyanate is selected from the group consisting of : Covered aliphatic multimonomer 'capped aromatic polyisocyanate monomer, with At least two covered isocyanate-coated covered polyurethane prepolymers and mixtures thereof. 5 The method of claim 4, wherein the polyisocyanate is selected from the group consisting of polyisocyanate (tetra) polymer to μ isocyanate; the multi-component; aromatic polyepoxide monomer; The need for r:: different: (d) is selected from the group consisting of: covered aliphatic polyisocyanate: -, a masked aromatic polyisocyanate monomer and mixtures thereof. Method wherein the first component is different The multiple bad oxides, as well as the capped polyisocyanate, are each substantially free of ionic groups. 7. The method of claim 1, wherein the first component (4) (1) comprises: the isocyanate content of the cap is small (four) mol%, polyisoxamic acid = isocyanate, polycyclic The epoxy group of the oxide and the masked polyisotrope are based on the total molar equivalent of the anaerobic acid group of the cap. (4) The method of claim 1, wherein the polyisocyanate is capped with the first component (a) (i), and the organic phase droplets are suspended in the liquid suspension in step (4) below the The eve of the cover is performed at the temperature of the cover temperature. 33 1298074 9. The method of claim 2, wherein the polyamine is selected from the group consisting of: an aliphatic polyamine monomer, an aromatic polyamine monomer, a polyamine prepolymer, and a mixture thereof. The method of claim 2, wherein the second component (a) (ii) active hydrogen functional reactant further comprises at least one of the following: a polyol having two hydroxyl groups up to and including at least one hydroxyl group and at least A trans-amine reactant of an amine group selected from the group consisting of a first stage 15, a second stage amine, and combinations thereof. 11. The method of claim 1 , wherein the organic phase and the liquid are at least one selected from the group consisting of: anionic interface active I*, cationic surfactant, and amphoteric interface. An organic surfactant for active agents, nonionic surfactants, and mixtures thereof. [alpha] The method of claim </RTI> wherein the organic phase comprises a nonionic surfactant. 13·If the scope of patent application is 1 The method of the present invention, wherein the particulate crosslinked polymer has a particle diameter of from 20 μm to 2 μm. 14·If the scope of patent application is the first one, the organic phase further comprises a milled (four) granular material selected from the group consisting of: oxidized, carbonized stone, titanium oxide, boron carbide, nitrogen cut, carbonized Tungsten, titanium carbide, iron, nitrogen, rotten, garnet, oxidized oxidized oxidized, oxidized stone, iron oxide, gasified chromium, cerium oxide, cerium oxide, wrong titanium, oxygen, oxidized mixture. 15. The method of claim 1, wherein the first component (a) (i) of the isonic acid group, the epoxy group, and the capped isocyanate group molar equivalent weight Violet 34 1298074 The molar equivalent weight ratio of the active hydrogen group of the second component (4) (9) is 0.5: ΐ·〇 to 15: 1.〇. A. The method of claim 4, wherein the method further comprises separating the particulate crosslinked polymer from the liquid suspending medium. 17_ A method for preparing a particulate crosslinked polymer, comprising: (3) preparing an organic phase comprising, (i) a first component comprising, a polyisocyanate having at least two isocyanato groups and having two At least one of the polyepoxides of the % oxy group, and - optionally, - (iv) a polyisocyanate having at least two capped isocyanate groups; and (a) a second group a reactive hydrogen functional reactant having at least two reactive mercapto groups reactive with an isocyanate group and an epoxy group of the first component, the active hydrogen functional reactant comprising at least a two functional polyamine selected from the group consisting of: a first amine, a second amine, and a combination thereof; (b) a droplet of the organic phase in an aqueous suspension medium to form a suspension/night The organic phase is substantially insoluble in the aqueous suspension medium; and (c) polymerizing the organic phase droplet suspension in the aqueous suspension medium to form a particulate crosslinked polymer; comprising the organic phase and the aqueous phase thereof At least one of the suspension media : Anionic surfactant, cationic surfactant cut amphoteric surfactant, an organic nonionic surfactant and surfactant mixtures. 35 1298074 The method of claim 17, wherein the aqueous suspension medium is substantially free of polyamines, the organic phase comprises a nonionic surfactant; and the polyisocyanate, polyepoxy of the component (4)(1) The polyisocyanate, which is capped and optionally capped, is substantially free of ionic groups. The method of claim 18, wherein the polyisocyanate is selected from the group consisting of f-to-J/two isocyanate-based polyurethane prepolymers and the same The multi-alkaline oxide is selected from the group consisting of aromatic polyepoxide monomers; and the polyisocyanate which is required to be masked is selected from the group consisting of a covered aliphatic polyisocyanate 6 monomer, covered by a cover (4) Aromatic polyisocyanate monomer and mixtures thereof. The method of claim 19, wherein the polyamine is selected from the group consisting of aliphatic aliphatic amine monomers, aromatic polyamine monomers, polyamine prepolymers, and mixtures thereof. The method of claim 18, wherein the first component comprises a polyamino citrate prepolymer having at least two isocyanate groups and the polyamine is selected from the group consisting of Polyamine, Wherein R3 and R4 are each a Ci-C3 alkyl group, and R5 is selected from the group consisting of hydrogen and a halogen atom. 22. The method of claim 18, wherein the first component comprises an aromatic polyepoxide monomer, and the polyamine is selected from the group consisting of at least two 36 1298074 Amino-polyamine. The method of claim 18, wherein the second component (4) (9) tongue 14 hydrogen S-reactant further comprises at least one of: a polyol having at least two (four) groups and At least one radical and at least one selected from the group consisting of a first amine amine reactant. The hydroxyl group of the amine of the second-stage amine and the combination thereof is as described in the patent application range of 1,000,000//2: wherein the particulate crosslinked polymer has a particle size of 20 μm to 2 mm. 25. The method of claim 18, wherein the smectite method further comprises separating the particulate crosslinked polymer from the aqueous suspension medium. 37