WO2011132869A2 - Procédé de polymérisation en suspension d'une résine méthacrylique utilisant une émulsion de polymère soluble dans les alcalins en tant que stabilisateur de dispersion - Google Patents

Procédé de polymérisation en suspension d'une résine méthacrylique utilisant une émulsion de polymère soluble dans les alcalins en tant que stabilisateur de dispersion Download PDF

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WO2011132869A2
WO2011132869A2 PCT/KR2011/002411 KR2011002411W WO2011132869A2 WO 2011132869 A2 WO2011132869 A2 WO 2011132869A2 KR 2011002411 W KR2011002411 W KR 2011002411W WO 2011132869 A2 WO2011132869 A2 WO 2011132869A2
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Prior art keywords
suspension polymerization
polymerization method
weight
soluble polymer
acrylate
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PCT/KR2011/002411
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English (en)
Korean (ko)
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WO2011132869A3 (fr
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문상진
하종욱
소원욱
박동순
이수복
박인준
김광제
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한국화학연구원
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Priority to CN201180004251.1A priority Critical patent/CN102574935B/zh
Publication of WO2011132869A2 publication Critical patent/WO2011132869A2/fr
Publication of WO2011132869A3 publication Critical patent/WO2011132869A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation

Definitions

  • the present invention relates to an economical suspension polymerization method of methacrylic resin, which is excellent in polymerization stability, easy to reuse of solvent, and recoverable of dispersion stabilizer using alkali water-soluble emulsion polymer as dispersion stabilizer.
  • the composite acrylic resin coating composition based on methyl methacrylate is a special coating product for various purposes such as waterproofing and flooring for special use, and concrete and steel coating and thin film pavement of road asphalt. It is utilized.
  • the composite acrylic resin coating composition may realize various physical properties for use by changing various types of acrylic polymerization compositions, and has great use in the so-called elastic coating field, which is characterized by elasticity according to temperature change.
  • Methacrylic resin a composite acrylic resin coating composition
  • Methacrylic resin is a polymer of methyl methacrylate, which is a core monomer, and one or more reactive monomers, and then dissolved in a (meth) acrylic monomer. In this case, it is a solvent-free coating that starts curing at a high speed so that both the polymer and the monomer form one polymer.
  • methyl methacrylate and one or more reactive monomers are polymerized by a bulk polymerization method to prepare a composite acrylic resin coating composition, and unreacted monomers are removed therefrom and purified, followed by (meth)
  • a method of preparing a coating composition by mixing with an acrylic monomer and additives is disclosed.
  • due to the characteristics of the bulk polymerization it is not easy to control the heat of the polymerization reaction. Accordingly, even a minute change in the reaction conditions may cause a large difference in the physical properties of the polymer, particularly the molecular weight.
  • the bulk polymerization method as the degree of polymerization increases, the viscosity of the polymer increases, so that difficulty in agitation increases and recovery of the final product and separation and purification of unreacted monomers are not easy.
  • an environmentally friendly aqueous phase may be used as the solvent for polymerization.
  • Representative examples include emulsion polymerization and suspension polymerization. According to the emulsion polymerization method, the control of polymerization heat is excellent, a high molecular weight polymer is produced, and the conversion rate of the monomer is very high. However, since fine particles of less than 1 micrometer are formed, it is not easy to separate them by filtration.
  • Korean Patent Laid-Open Publication No. 2007-0044603 discloses a powdery acrylic copolymer having an average particle diameter of at least 0.3 ⁇ m, first prepared by emulsion polymerization, and then spray-dried to obtain a powdery acrylic copolymer having an average particle size of 100 ⁇ m or less.
  • Known methods are known, but considering the energy costs for spray drying, it is not economical, and there is a disadvantage in that it is not easy to remove additives such as surfactants.
  • suspension polymerization is commonly used to industrially polymerize vinyl-based polymers, especially methacrylate and acrylate polymers, styrene-based polymers, and polyvinyl chloride resins.
  • vinyl-based polymers especially methacrylate and acrylate polymers, styrene-based polymers, and polyvinyl chloride resins.
  • a vinyl monomer such as (meth) acrylate is dispersed in an aqueous medium and then polymerized in the presence of an oil-soluble initiator.
  • the conversion rate of the monomer, the ratio of the monomer and water, the polymerization temperature, the type and amount of the initiator, the stirring speed and the form and amount of the dispersion stabilizer may be considered. .
  • the form of the dispersion stabilizer has the most important influence on the quality of the polymer.
  • Preferred dispersion stabilizer conditions include: (1) a small amount of sufficient protective colloidal capacity and dispersibility, (2) less foaming during polymerization, and (3) formation of fine particles that are difficult to separate by filtration. (4) It must be possible to completely remove it from the aqueous medium after the end of the polymerization so that the polymerization medium can be reused. It is more preferable if the reaction can be separated and recovered from the medium after completion of the reaction.
  • cellulose derivatives such as methyl cellulose and carboxymethyl cellulose and partially hydrolyzed polyvinyl alcohol (PVA) have been used alone or in combination.
  • PVA polyvinyl alcohol
  • U.S. Patent No. 4868238 discloses that hydrophobically modified nonionic cellulose ethers and copolymers thereof and ethylene oxide can be used to reduce the formation of latex particles during suspension polymerization.
  • WO 91/15518 discloses a dispersant for suspension polymerization of vinyl-based compounds having an amino group, an ammonium group, a carboxyl group or a sulfonic acid group at the terminal and containing PVA having a degree of polymerization of 100 or more and a degree of hydrolysis of 50 to 90 mol%. Is described.
  • U.S. Patent No.5629378 discloses a method of using PVA having a degree of hydrolysis of at least 60 mol% and having a mecaptan group at its end as a dispersion stabilizer for suspension polymerization. It is known to use PVA-based resins containing 1.9 mol% or more of glycol bonds as dispersion stabilizers.
  • dispersion stabilizer for suspension polymerization of a vinyl compound a method of using a homopolymer of acrylic acid or methacrylic acid or a copolymer of these acids and methyl methacrylate as a dispersion stabilizer is also known (Korea Patent No. 10-0215515). .
  • a method of using a slurry of poorly soluble inorganic compounds such as calcium phosphate, talc, silica and the like as a dispersion stabilizer is known from US Pat. No. 5,89285.
  • Korean Patent No. 10-0926347 discloses a method for preparing amorphous toner particles using an alkali-soluble polymer having an ethylene or styrene monomer and a carboxylic acid group.
  • an alkali-soluble polymer having an ethylene or styrene monomer and a carboxylic acid group is used as the hydrophobic monomer.
  • improvement is necessary because it is difficult to provide sufficient dispersion stability in suspension polymerization of the methacrylic resin.
  • An object of the present invention is to provide a suspension polymerization method of a methacrylic resin using an alkali water-soluble polymer emulsion as a dispersion stabilizer.
  • the present invention is a suspension of methacryl-based resin comprising the step of suspending polymerization of methyl methacrylate and at least one reactive monomer using an alkali water-soluble polymer emulsion represented by the formula (1) as a dispersion stabilizer Provide polymerization method:
  • R 1 is hydrogen or methyl
  • R 2 is straight or branched alkyl having 1 to 4 carbon atoms
  • R3 is hydrogen or straight or branched alkyl having 1-18 carbon atoms
  • a is a weight fraction of maleic acid or its ester compound
  • b is a weight fraction of acrylic acid or methacrylic acid
  • c is the weight fraction of alkyl methacrylate or alkyl acrylate
  • d is the weight fraction of the styrene monomer
  • a + b is 10-40 weight percent
  • c + d is from 60 to 90% by weight
  • the present invention further comprises the step of separating the polymer by filtration after the reaction is completed, and additionally adjusting the pH of the filtered aqueous medium to have a value of 3-5 to recover the alkaline water-soluble polymer from the aqueous medium. It provides a suspension polymerization method characterized in that.
  • the present invention provides an alkali water-soluble polymer emulsion represented by the formula (1) as a dispersion stabilizer used in the suspension polymerization method of methacryl resin.
  • the alkali water-soluble emulsion polymer is used as a dispersion stabilizer, which is excellent in polymerization stability, generates little scale in the reactor, and can suppress generation of fine particles that are difficult to filter.
  • the alkali water-soluble emulsion polymer used as a dispersion stabilizer is recovered from the aqueous medium together with the polymerized copolymer, thereby providing an economical and convenient suspension polymerization method for easy reuse of the solvent used.
  • the present invention provides a suspension polymerization method of a methacrylic resin comprising a step of suspending polymerizing methyl methacrylate and at least one reactive monomer using an alkali water-soluble polymer emulsion represented by the following formula (1) as a dispersion stabilizer.
  • R 1 is hydrogen or methyl
  • R 2 is straight or branched alkyl having 1 to 4 carbon atoms
  • R3 is hydrogen or straight or branched alkyl having 1-18 carbon atoms
  • a is a weight fraction of maleic acid or its ester compound
  • b is a weight fraction of acrylic acid or methacrylic acid
  • c is the weight fraction of alkyl methacrylate or alkyl acrylate
  • d is the weight fraction of the styrene monomer
  • a + b is 10-40 weight percent
  • the alkali water-soluble polymer emulsion generally contains a large amount of acrylic acid, methacrylic acid or maleic acid in the molecular structure, and alkyl methacrylates such as methyl methacrylate and alkyl acrylate as comonomers. Or styrene-based monomers.
  • the molecule contains in the range of 10-40% by weight of at least one monomer of acrylic acid, methacrylic acid, maleic acid or maleic acid ester compound, and at least one of alkyl methacrylate, alkyl acrylate or styrene monomer
  • the copolymer alkali water-soluble polymer emulsion which comprises in the range of weight% is used.
  • alkyl methacrylate in the structure of the alkali-soluble polymer emulsion, and preferably 50-80 wt%.
  • Alkali-soluble polymer emulsions are dispersed in the form of latex particles in an aqueous medium having an acidic or neutral pH, but are characterized by dissolving when the pH of the aqueous medium is alkaline to form a uniform phase.
  • various acid groups included in the molecular structure may be neutralized by the cation to serve as a polymer anionic surfactant.
  • the alkaline water-soluble polymer emulsion may reduce the solubility in the medium to be recovered as solid particles by reducing the pH of the aqueous medium back to acidic.
  • the alkali water-soluble polymer emulsion may be prepared by an emulsion polymerization method using a surfactant or no surfactant.
  • a surfactant or no surfactant.
  • Ciba Specialty Chemicals Inc. The DISPEX G40 or DISPEX GA40, Rohm and Haas's ACRYSOL TM ASE, RHOPLEX TM I-2426D, or RHOPLEX TM 1531, Sartomer Company's SMAResin, Rohm and Haas's Morez101 or Morez300.
  • the alkali water-soluble polymer emulsion having a weight average molecular weight in the range of 3,000-30,000.
  • a large amount of chain transfer agent must be included, which is not preferable to obtain an alkali water-soluble emulsion polymer itself because it significantly lowers the conversion of monomers.
  • it exceeds 30,000 even if the same amount is used, there is a problem that the viscosity of the polymerization medium is excessively increased and the filtration rate is lowered when the polymer is recovered from the polymerization medium.
  • the amount of the alkali water-soluble polymer emulsion is preferably used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of methyl methacrylate and at least one reactive monomer.
  • the alkali water-soluble polymer emulsion added in the form of latex particles is dissolved in an aqueous medium at the same time as adding an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, or ammonia water to form a homogeneous phase and serve as an ionic dispersion stabilizer.
  • one or more of the reactive monomers may be used all the reactive monomers which are usually suspended, such as acrylic acid, esters of methacrylic acid or vinylaromatic monomers.
  • acrylic acid esters of methacrylic acid or vinylaromatic monomers.
  • the suspension polymerization method according to the present invention uses an aqueous medium containing an aqueous alkali solution, the pH of the aqueous medium is preferably 6.5 ⁇ 12. If the pH of the aqueous medium is lower than the suggested range due to the insufficient amount of the aqueous alkali solution, the solubility of the alkaline water-soluble polymer emulsion is low so that it cannot fully serve as a dispersion stabilizer, and the addition of an excessively large amount does not help the dispersion stability, but the reaction process It is not preferable because a large amount of raw material must be added additionally.
  • a free radical initiator catalyst in addition to the suspension polymerization reaction, a free radical initiator catalyst, a chain transfer agent or both may be used.
  • a free radical initiator catalyst a 10-hour half-life, peroxides and azo compounds having a temperature of 120 ° C. or less can be used as a polymerization initiator, and preferably a 10-hour half-life and a peroxide-type polymerization initiator having a temperature of 90 ° C. or less can be used.
  • Such polymerization initiators include 1,1-bis (t-butylperoxycyclohexane), isobutyl peroxide, lauroyl peroxide, succinic acid peroxide, 3,5,5-trimethylhexanoyl peroxide, di-2 Ethoxyethyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, di-methoxybutyl peroxy dicarbonate, t-butyl peroxy isobutyrate, t-butyl per Oxy neodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy pivalate, a, a-bis neodecanoyl peroxy diisopropyl benzene, cumyl peroxy neodecanoate, t -Hexyl peroxy neodecanoate, t-he
  • the chain transfer agent may use any one selected from n-octyl mecaptan, alkyl mecaptan such as n-dodecyl mecaptan, ester compound of thioglycolic acid or thioglycolic acid, dimer of alpha-methyl styrene, and the like.
  • the suspension polymerization method of the present invention can be carried out in a classical manner.
  • an aqueous medium comprising a dispersion stabilizer and an aqueous alkali solution is prepared and introduced into an appropriate reactor.
  • An organic phase is prepared which contains dissolved additives in methyl methacrylate and at least one monomer, such as polymerization initiators, chain transfer agents and the like, in dissolved form, which are then added to the aqueous medium with stirring.
  • Suspension is carried out according to known techniques. In order to obtain a polymer powder of methacrylic resin having a particle size of 20 ⁇ m or more, an impeller or anchor type stirring device is generally used. The reaction medium is then heated to initiate the polymerization.
  • the ratio of organic phase / aqueous medium is usually between 1/10 and 1/1, preferably between 1/5 and 1/1. It is customary for the polymerization temperature to be determined between approximately 40 ° C. and 90 ° C., depending on the polymerization initiator used.
  • the polymerization takes place in an adiabatic manner or by removing at least a portion of the heat of polymerization by cooling, depending on the ratio of organic phase / aqueous medium used. Suspension polymerization generally lasts from 1 hour to 3 hours. Thereafter, the temperature of the reactant is increased to sufficiently decompose the polymerization initiator, so that the polymerization initiator is substantially free from residual polymer particles. The polymerization initiator decomposition temperature at this time is terminated within 2 hours by adopting a temperature at which the half-life of the initiator is approximately 10 minutes.
  • the polymer is separated by filtration, and an aqueous solution of an inorganic acid such as hydrochloric acid or sulfuric acid is slowly added to the filtrate to adjust the pH of the aqueous medium to a weak acid, preferably pH 3-5.
  • an inorganic acid such as hydrochloric acid or sulfuric acid
  • Alkali-soluble polymers dissolved in an aqueous medium are precipitated in the form of particles due to a decrease in solubility with decreasing pH.
  • the polymerized methacrylic resin and the alkali water-soluble polymer precipitate are separated by filtration or centrifugation.
  • Various salts and the like can be removed by washing with water directly on a filter paper or in a centrifuge. And recovered by drying in a suitable drying apparatus, for example in a drying furnace or in a dryer having a fluidized bed.
  • the average diameter of the methacrylic resin powder obtained by the above method depends on the amount of the dispersion stabilizer used, preferably having a pearl-like bead having an average diameter of 100 ⁇ m or more.
  • the monomers and various additives used in the polymerization in particular the alkali water-soluble polymer emulsions used as dispersion stabilizers, remain and only inorganic salts generated during the neutralization process of the alkaline aqueous medium, for example, the aqueous alkaline solution used.
  • sodium chloride, potassium chloride, ammonium chloride, sodium sulfide, potassium sulfide, or ammonium sulfide may remain in a small amount, which may be removed using a general wastewater treatment process such as ion exchange or water purification.
  • the present invention provides an alkali water-soluble polymer emulsion represented by the following formula 1 as a dispersion stabilizer used in the suspension polymerization method of the methacrylic resin:
  • R 1 is hydrogen or methyl
  • R 2 is straight or branched alkyl having 1 to 4 carbon atoms
  • R3 is hydrogen or straight or branched alkyl having 1-18 carbon atoms
  • a is a weight fraction of maleic acid or its ester compound
  • b is a weight fraction of acrylic acid or methacrylic acid
  • c is the weight fraction of alkyl methacrylate or alkyl acrylate
  • d is the weight fraction of the styrene monomer
  • a + b is 10-40 weight percent
  • c + d is from 60 to 90% by weight
  • Example 1-1 Suspension Polymerization of Methacrylic Resin Using Alkali Water Soluble Polymer Emulsion Dispersant
  • MMA methyl methacrylate
  • BMA butyl methacrylate
  • a-MSD alpha-methyl styrene dimer
  • BPO benzoyl peroxide
  • Examples 1-2 to 1-10 Suspension polymerization of methacrylic resins using alkali water-soluble polymer emulsion dispersion stabilizer 1
  • Copolymer suspension of methyl methacrylate (MMA) and butyl methacrylate (BMA) was carried out in the same manner as in Example 1-1, wherein the used methyl methacrylate (MMA) and butyl methacrylate (MMA).
  • the amount of BMA) and the amount of the aqueous alkali solution, the type and amount of the chain transfer agent, the type and amount of the initiator, the amount of aqueous hydrochloric acid solution and the like are summarized in Table 1.
  • Example 2-1 Suspension Polymerization of Methacrylic Resin Using Alkali Water Soluble Polymer Emulsion Dispersant
  • MMA methyl methacrylate
  • BMA butyl methacrylate
  • a-MSD alpha-methyl styrene dimer
  • BPO benzoyl peroxide
  • Examples 2-2 to 2-3 suspension polymerization 2 of methacrylic resins using alkali water-soluble polymer emulsion dispersion stabilizer
  • Copolymer suspension of methyl methacrylate (MMA) and butyl methacrylate (BMA) was carried out in the same manner as in Example 2-1, wherein the used methyl methacrylate (MMA) and butyl methacrylate (MMA).
  • the amount of BMA) and the amount of the aqueous alkali solution, the type and amount of the chain transfer agent, the type and amount of the initiator, the amount of aqueous hydrochloric acid solution and the like are summarized in Table 1.
  • the polymerization stability was excellent for the comparative example, but after the filtration of the polymer particles, a large amount of fine particles were present in the filtrate, and the amount of the remaining stabilizer was determined by using liquid chromatography and gel permeation chromatography with water as the mobile phase. It was hard to do. Therefore, reuse of the aqueous medium is not easy.
  • Table 2 summarizes the weight average molecular weight of the polymerized methacrylic resin, the aqueous medium state after filtration, and the recovery rate for each Example.
  • the present invention relates to an economical suspension polymerization method of methacrylic resin, which is excellent in polymerization stability by using alkali water-soluble emulsion polymer as dispersion stabilizer, easy reuse of solvent and recovery of dispersion stabilizer. It is possible to suppress the generation of fine particles in the inside, the generation of fine particles difficult to filter as much as possible, and the reuse of the solvent used is easy to provide an economical and simple suspension polymerization method has industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Polymerisation Methods In General (AREA)

Abstract

La présente invention a pour objet un procédé de polymérisation en suspension d'une résine méthacrylique utilisant une émulsion de polymère soluble dans les alcalins en tant que stabilisateur de dispersion. Le procédé est excellent pour la stabilité de la polymérisation, réduit la quantité de tartre produit dans un réacteur et supprime la production de particules fines autant que possible, ce qui permet un rendement et une productivité. En outre, la présente invention concerne un procédé de polymérisation en suspension qui est économique et commode étant donné que tous les polymères de l'émulsion soluble dans les alcalins utilisés en tant que stabilisateur de dispersion sont recueillis à partir d'un milieu aqueux, ce qui facilite la réutilisation du solvant usagé.
PCT/KR2011/002411 2010-04-19 2011-04-06 Procédé de polymérisation en suspension d'une résine méthacrylique utilisant une émulsion de polymère soluble dans les alcalins en tant que stabilisateur de dispersion WO2011132869A2 (fr)

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CN201180004251.1A CN102574935B (zh) 2010-04-19 2011-04-06 将碱性水溶性高分子乳液用作分散稳定剂的甲基丙烯酸类树脂的悬浮聚合法

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KR1020100036021A KR101217027B1 (ko) 2010-04-19 2010-04-19 알칼리 수용성 고분자 에멀젼을 분산안정제로 사용하는 메타아크릴계 수지의 현탁중합법
KR10-2010-0036021 2010-04-19

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CN116715989A (zh) * 2023-06-08 2023-09-08 嘉兴泰格高新材料股份有限公司 一种无溶剂体系彩砂悬浮剂及其制备方法、彩砂涂料

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CN110591006A (zh) * 2019-09-29 2019-12-20 武汉迪赛环保新材料股份有限公司 一种纸品印刷用耐高温成膜苯丙乳液的制备方法
KR20210065371A (ko) 2019-11-27 2021-06-04 한화솔루션 주식회사 3성분 산을 포함하는 알칼리 수용성 수지 제조방법 및 그에 따른 알칼리 수용성 수지

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4415703A (en) * 1981-01-13 1983-11-15 Daicel Chemical Industries, Ltd. Aqueous dispersion of a cellulose derivative
US4435524A (en) * 1981-09-08 1984-03-06 The B. F. Goodrich Company Process for preparing spherical and porous vinyl resin particles
US4659793A (en) * 1986-03-03 1987-04-21 Alco Chemical Corporation Preparation of aqueous solutions of copolymers of dicarboxylic acids having a low dicarboxylic acid monomer content
JPH10152508A (ja) * 1996-09-30 1998-06-09 Nippon Synthetic Chem Ind Co Ltd:The ビニル系化合物の懸濁重合用分散助剤
KR0159124B1 (ko) * 1993-11-18 1999-01-15 에스. 박 흥 수상 비닐 할라이드 중합에 사용되는 카르복실기를 갖는 유화제
KR19990044335A (ko) * 1995-08-31 1999-06-25 박흥순 염화비닐 중합용 중합체 유화제
KR100674373B1 (ko) * 2005-11-30 2007-01-29 엘지엠엠에이 주식회사 비닐계 수지의 현탁중합용 분산제 및 이를 이용한현탁중합방법
KR20090062454A (ko) * 2007-12-13 2009-06-17 엘지엠엠에이 주식회사 내충격성이 우수한 투명 아크릴계 수지 및 이의 제조 방법
KR20100039509A (ko) * 2008-10-08 2010-04-16 엘지엠엠에이 주식회사 내충격성이 우수한 투명 아크릴계수지의 제조방법

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4415703A (en) * 1981-01-13 1983-11-15 Daicel Chemical Industries, Ltd. Aqueous dispersion of a cellulose derivative
US4435524A (en) * 1981-09-08 1984-03-06 The B. F. Goodrich Company Process for preparing spherical and porous vinyl resin particles
US4659793A (en) * 1986-03-03 1987-04-21 Alco Chemical Corporation Preparation of aqueous solutions of copolymers of dicarboxylic acids having a low dicarboxylic acid monomer content
KR0159124B1 (ko) * 1993-11-18 1999-01-15 에스. 박 흥 수상 비닐 할라이드 중합에 사용되는 카르복실기를 갖는 유화제
KR19990044335A (ko) * 1995-08-31 1999-06-25 박흥순 염화비닐 중합용 중합체 유화제
JPH10152508A (ja) * 1996-09-30 1998-06-09 Nippon Synthetic Chem Ind Co Ltd:The ビニル系化合物の懸濁重合用分散助剤
KR100674373B1 (ko) * 2005-11-30 2007-01-29 엘지엠엠에이 주식회사 비닐계 수지의 현탁중합용 분산제 및 이를 이용한현탁중합방법
KR20090062454A (ko) * 2007-12-13 2009-06-17 엘지엠엠에이 주식회사 내충격성이 우수한 투명 아크릴계 수지 및 이의 제조 방법
KR20100039509A (ko) * 2008-10-08 2010-04-16 엘지엠엠에이 주식회사 내충격성이 우수한 투명 아크릴계수지의 제조방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116715989A (zh) * 2023-06-08 2023-09-08 嘉兴泰格高新材料股份有限公司 一种无溶剂体系彩砂悬浮剂及其制备方法、彩砂涂料
CN116715989B (zh) * 2023-06-08 2024-06-11 嘉兴泰格高新材料股份有限公司 一种无溶剂体系彩砂悬浮剂及其制备方法、彩砂涂料

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