WO2000012577A1 - Procede de production d'un polymere d'acide (meth)acrylique - Google Patents

Procede de production d'un polymere d'acide (meth)acrylique Download PDF

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Publication number
WO2000012577A1
WO2000012577A1 PCT/JP1999/004527 JP9904527W WO0012577A1 WO 2000012577 A1 WO2000012577 A1 WO 2000012577A1 JP 9904527 W JP9904527 W JP 9904527W WO 0012577 A1 WO0012577 A1 WO 0012577A1
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Prior art keywords
meth
acrylate
weight
acid
parts
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PCT/JP1999/004527
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English (en)
Japanese (ja)
Inventor
Kengo Shibata
Haruya Minou
Haruyuki Sato
Toshinao Ukena
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Kao Corporation
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Publication of WO2000012577A1 publication Critical patent/WO2000012577A1/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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers

Definitions

  • the present invention relates to a method for producing a (meth) acrylic acid-based polymer useful as a dispersant for cement for improving the dispersibility of cement particles in a hydraulic composition such as cement paste, mortar, and concrete.
  • a hydraulic composition such as cement paste, mortar, and concrete.
  • Polycarboxylic acid polymers are useful as dispersants for cement, and various techniques have been proposed.
  • JP-B-59-18338 and JP-A-8-123396 disclose a polyalkylene glycol ester monomer having an unsaturated bond.
  • One containing a copolymer with the following monomer is disclosed.
  • these prior arts do not describe specific polymerization conditions. Disclosure of the invention
  • the present invention can provide a (meth) acrylic acid-based polymer suitable as a dispersant for cement with a stable quality by setting polymerization conditions specifically. It aims to provide a manufacturing method.
  • the present inventors have found that the above object can be achieved by subjecting the esterification reaction product to a polymerization reaction at a specific pH range.
  • the present invention provides a process for producing a (meth) acrylic acid-based polymer comprising the following steps 1 and 2 Is the law.
  • Step 1 Alkyl (meth) acrylate and polyalkylene glycol monoalkyl ether are subjected to transesterification at a molar ratio of 3: 1 to 50: 1 to obtain a polyalkylene glycol monoalkyl ether (meth) acrylate ( (Hereinafter referred to as PGMA (meta) acrylate), followed by distilling off by-produced alcohol to obtain an esterification reaction product containing PGMA (meth) atalylate.
  • PGMA polyalkylene glycol monoalkyl ether
  • Step 2 a step of copolymerizing PGMA (meth) acrylate and a monomer copolymerizable with PGMA (meth) acrylate in the range of pH 1.5 to 3.5.
  • the reaction product of step 1 may be polymerized as it is, or the reaction product may be distilled off and polymerized. Polymerization may be carried out by adding a monomer. These may be combined for polymerization. It polymerizes in the range of pH 1.5 to 3.5. Polymerization may be performed without adding an acid. The pH may be adjusted with an acid and polymerized.
  • step 2 After step 1, but before step 2, unreacted alkyl (meth) acrylate is removed by distillation and a monomer copolymerizable with PGMA (meth) acrylate in step 2 is added. It is preferable to have a monomer ratio of
  • step 2 the monomer copolymerizable with the PGMA (meth) acrylate which is copolymerized is (meth) acrylic acid, methyl (meth) acrylate or methoxypolyethylene glycol mono (meth) acrylate.
  • alkyl (meth) acrylate refers to both alkyl acrylate and alkyl methacrylate
  • PGMA (meth) acrylate refers to both acrylate and methacrylate.
  • step 1 first, alkyl (meth) acrylate and polyalkylene
  • the ester exchange reaction of the recohol monoalkyl ether hereinafter referred to as “glycol ether”.
  • the alkyl (meth) acrylate used in the transesterification is not particularly limited, and a commercially available one containing a polymerization inhibitor in advance is used.
  • This alkyl group preferably has 1 to 4 carbon atoms.
  • glycol ether used in the transesterification reaction examples include those in which the polyalkylene moiety is composed of an alkylene oxide adduct such as an adduct of ethylene oxide alone or a mixed adduct of ethylene oxide and propylene oxide. Is preferably 1 to 30 °.
  • the alkyl group constituting the monoalkyl ether moiety preferably has 1 to 3 carbon atoms.
  • One or more polyalkylenes having one or more moles of added alkylene oxide and / or different carbon atoms in the alkyl group are used. Mixtures of glycol monoalkyl ethers can be used. .
  • the mixing ratio in the reaction system of alkyl (meth) atalylate and dalicol ether is in the range of 3: 1 to 50: 1 in terms of molar ratio, and preferably 10:50, in order to further increase the transesterification reaction rate. 1 to 40: 1
  • an acid catalyst or a basic catalyst examples include sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid, and mineral acids such as sulfuric acid and phosphoric acid.
  • the basic catalyst include those described in JP-A-9-328463, page 7, column 11, lines 15 to 26. Among them, alkali metals such as sodium hydroxide are exemplified. Alkali metal alkoxides such as hydroxides and sodium methoxide are preferred.
  • the amount of the acid catalyst or the basic catalyst used is preferably from 0.1 to 10 parts by weight based on 100 parts by weight of dalicol ether. If the amount is 0.1 parts by weight or more, the reaction speed It is economical if the amount is less than 10 parts by weight.
  • a polymerization inhibitor in the transesterification reaction, and examples thereof include hydroquinone, benzoquinone, methoquinone, BHT, phenothiazine, and catechol. Further, by passing a gas containing oxygen into the reaction system, the polymerization inhibiting effect can be further enhanced.
  • the polymerization inhibitor was used in an amount of 0.001 part per 100 parts by weight of dalicol ether.
  • the reaction temperature in the transesterification is preferably 60 to 130 ° C. If the temperature is 60 ° C or higher, an appropriate reaction rate can be maintained. If the temperature is 130 ° C or lower, deterioration of the glycol ether quality can be prevented, and the viscosity of the reaction system can be maintained at an appropriate level. preferable.
  • the pressure of the reaction system in the transesterification reaction is not particularly limited, and is preferably a reduced pressure from the viewpoint of distilling off the alcohol generated by the reaction to the outside of the system.
  • an alkali agent is added to deactivate the acid catalyst.
  • the alkali agent include alkali metal hydroxides such as sodium hydroxide and hydro-oxidizing rim, and alkaline earth metal hydroxides such as calcium hydroxide.
  • the amount of the alkali agent used is preferably 0.9 to 1.5 equivalent times, particularly preferably 1.0 to 1.3 equivalent times, relative to the acid catalyst used.
  • unreacted (meth) acrylate may remain after the reaction.
  • Unreacted (meth) acrylate can be distilled off, or it can be used in the polymerization reaction as it is without distilling it off, but if it is distilled off, use a basic catalyst in step 1. Then, after the reaction, unreacted alkyl (meth) acrylate is distilled off, and when an acid catalyst is used in step 1, it is deactivated. After that, unreacted alkyl (meth) acrylate is distilled off.
  • the PGMA (meth) acrylate represented by the following general formula (I) is mainly contained, and the alkyl (meth) acrylate residue represented by the following general formula (II) is combined with the residue of the general formula (III) An esterification reaction product containing a by-product represented by) is obtained.
  • R 2 is an alkyl group having 1 to 3 carbon atoms
  • AO is an oxyalkylene group having 2 to 3 carbon atoms
  • n is a number of 1 to 300
  • R 3 is hydrogen
  • R 5 represents a hydrogen atom or a methyl group
  • M represents a hydrogen atom, an alkali metal or an alkaline earth metal.
  • the content of the alkyl (meth) acrylate residue is preferably at most 5% by weight, particularly preferably at most 0.5% by weight.
  • a (meth) acrylic acid-based polymer having stable quality and useful as a dispersant for cement can be obtained.
  • the above-mentioned by-products can be used as they remain because they copolymerize with the (meth) acrylate.
  • a method for distilling unreacted alkyl (meth) acrylate a vacuum distillation method, a steam distillation method, a method of distilling together with a carrier gas at normal pressure, or the like can be applied.
  • step 2 the PGMA (meth) atalylate obtained in step 1 and a monomer copolymerizable with PGMA (meth) atalylate are copolymerized at pH 1.5 to 3.5.
  • Examples of monomers copolymerizable with PGMA (meth) acrylate include acrylic acid, methacrylic acid, crotonic acid, and (meth) acrylic acid such as alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts thereof.
  • Acid monomers such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, fumaric acid and their alkali metal salts, alkaline earth metal salts, ammonium salts or ammonium salts, etc.
  • Unsaturated dicarboxylic acid monomer alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene polypropylene glycol (meth) acrylate, etc.
  • Methoxy polyalkylene dalicol (meta) Rate-based monomers styrene, (meth) ataliamide, acrylonitrile, styrenesulfonic acid and its salts, sulfoalkyl (meth) acrylate and its salts, 2-acrylamide 2-methylpropanesulfonic acid and its salts, etc. (Where (meta) is as defined above). Two or more monomers may be added.
  • (meth) acrylic acid, methyl (meth) acrylate or methoxypolyethylene glycol mono (meth) acrylate is preferred, and methacrylic acid is particularly preferred.
  • the amount of the monomer copolymerizable with the PGMA (meth) acrylate is 0.3 to 170 parts by weight based on 100 parts by weight of the PGMA (meth) acrylate represented by the general formula (I). Is preferred, and 0.3 to 100 parts by weight is particularly preferred.
  • the pH of the polymerization reaction system is in the range of 1.5 to 3.5, preferably pH 2.0 to 3.0. If 11 is 15 or more, PGMA (meta) The occurrence of a rate hydrolysis reaction can be suppressed. When the pH is 3.5 or less, the copolymerization rate can be kept high, and the composition of each monomer in the copolymer can be appropriately controlled.As a result, it is useful as a stable-quality cement dispersant. A (meth) acrylic acid-based polymer is obtained.
  • the pH in step 2 was 5 weight of the polymerization reaction mixture. /. PH of aqueous solution.
  • Examples of the acid used for adjusting the pH include phosphoric acid, sulfuric acid, nitric acid, alkylphosphoric acid, alkylsulfuric acid, alkylsulfonic acid, alkylbenzenesulfonic acid, benzenesulfonic acid and the like.
  • phosphoric acid is preferred because it has a pH buffering action, easily adjusts pH to a predetermined range, and can suppress foaming of the polymerization reaction system.
  • the reaction can be performed in the presence of a solvent to reduce the viscosity of the polymerization reaction system.
  • the solvent examples include water, lower alcohols such as methanol, ethanol, isopropanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane; aliphatics such as n-hexane. Hydrocarbon; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. Of these, water and lower alcohols are preferred because they are easy to handle and easy to evaporate.
  • lower alcohols such as methanol, ethanol, isopropanol and butanol
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • alicyclic hydrocarbons such as cyclohexane
  • aliphatics such as n-hexane.
  • Hydrocarbon esters such as ethyl acetate
  • ketones such as acetone and methyl ethyl
  • a polymerization initiator can be added.
  • the polymerization initiator include organic peroxides, inorganic peroxides, nitrile compounds, azo compounds, diazo compounds, and sulfinic acid compounds.
  • the amount of the polymerization initiator to be added is preferably from 1 to 5 mol times the total of the general formula (1), the general formula (III) and other monomers.
  • a chain transfer agent can be added.
  • the chain transfer agent include lower alkyl mercaptan, lower mercapto fatty acid, thioglycerin, thiomalic acid, 2-mercaptoethanol, and the like. Particularly when water is used as the solvent, the molecular weight can be adjusted more stably by adding these chain transfer agents.
  • the reaction temperature of the copolymerization reaction in step 2 is preferably from 0 to 120 ° C.
  • the (meth) acrylic acid-based polymer obtained through the above-mentioned processes 1 and 2 can be further deodorized if necessary.
  • a thiol such as mercaptoethanol
  • a method of deodorizing when thiol is used as a chain transfer agent a method of converting thiol to disulfide with an oxidizing agent can be mentioned.
  • the oxidizing agent used in this method include hydrogen peroxide, air, oxygen, and the like, but hydrogen peroxide is preferred because of its high deodorizing effect by oxidation.
  • the amount of hydrogen peroxide to be added is preferably from 100 to 2000 ppm, more preferably from 100 to 100 ppm, based on the polymer.
  • the deodorizing temperature is preferably from 70 to 100 ° C, particularly preferably from 80 to 90 ° C. If the temperature is at least 70 ° C, the deodorizing effect will be enhanced. If the temperature is at most 100 ° C, generation of by-products due to thermal decomposition of the polymer can be prevented.
  • the (meth) acrylic acid-based polymer obtained by the production method of the present invention can be applied as a dispersant for cement even when it is in the form of an acid.
  • the salt is neutralized with an alkali.
  • the alkali include hydroxides of alkali metals or alkaline earth metals, ammonium, alkylammonium, alkanolamine, N-alkyl-substituted polyamine, ethylenediamine, polyethylenepolyamine and the like.
  • a (meth) acrylic acid-based polymer is used as a dispersant for cement, it is preferable to adjust the pH to 5 to 7 by neutralization.
  • the (meth) acrylic acid-based polymer obtained by the production method of the present invention is used as a dispersing agent for hydraulic materials other than cement such as Portland cement, alumina cement, various mixed cements, and gypsum.
  • hydraulic materials other than cement such as Portland cement, alumina cement, various mixed cements, and gypsum.
  • a glass reactor was charged with 1,000 parts by weight of polyethylene glycol monomethyl ether (weight average molecular weight: 5344) having ethylene oxide addition mole number of 120 melted in C. Next, 3 parts by weight of hydroquinone and 32 parts by weight of p-toluenesulfonic acid were added. While introducing air and nitrogen, methyl methacrylate 56 5 parts by weight (30 mole times of polyethylene dalicol monomethyl ether) ), And heating and depressurization in the reaction vessel were started. The pressure was controlled at 40 to 90 kPa, and the reaction was performed while maintaining the temperature of the reaction solution at 110 ° C. Nine hours after the start of the reaction, the pressure was returned to normal pressure, neutralized by adding 1.05 equivalents of a 48% aqueous sodium hydroxide solution to p-toluenesulfonic acid, and terminating the reaction.
  • Step 1 After the completion of Step 1, the temperature of the reaction solution was kept at 130 ° C. or lower, and unreacted methyl (meth) acrylate was recovered by a vacuum distillation method to obtain an esterification reaction product (A) -1.
  • the PGMA methacrylate concentration of this (A) -1 was 93.4%.
  • Step 2 of Example 1 a (meth) acrylic acid-based polymer was obtained in the same manner as in Example 1, except that 5 parts by weight of sulfuric acid was used instead of 5 parts by weight of phosphoric acid.
  • the pH during the polymerization reaction in step 2 was 2,6.
  • the viscosity of the obtained (meth) acrylic acid-based polymer was 450 mPa's.
  • the paste flow value of this (meth) acrylic acid-based polymer was determined in the same manner as in Example 1. Table 1 shows the results.
  • Example 3 shows the results.
  • step 2 of Example 1 485 parts by weight of water was charged into the same glass reaction vessel as in step 1, and the gas phase of the reaction vessel was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C under a nitrogen atmosphere. The temperature rose.
  • 269 parts by weight of the esterification reaction product (A) _1, 84 parts by weight of methacrylic acid, and methoxypolyethylene glycol monomethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., average number of moles of ethylene oxide 9
  • 3 parts by weight of a solution obtained by mixing and dissolving 121 parts by weight, 85 parts by weight of 85% phosphoric acid and 200 parts by weight of water, 3 parts by weight of 2-mercaptoethanol and 19 parts by weight of a 15% aqueous solution of ammonium persulfate was simultaneously dropped, and the dropping of all three solutions was completed in 90 minutes.
  • step 2 of Example 1 485 parts by weight of water was charged into the same glass reaction vessel as in step 1, and the gas phase of the reaction vessel was replaced with nitrogen while stirring, and the temperature was raised to 80 ° C under a nitrogen atmosphere. The temperature rose.
  • 600 parts by weight of the esterification reaction product (A) -1, 18 parts by weight of methacrylic acid, 63 parts by weight of methyl acrylate, 2.5 parts by weight of 85% phosphoric acid, and 400 parts by weight of water 3 parts of 2-mercaptoethanol and 15 parts of a 15% aqueous solution of ammonium persulfate (48 parts by weight) were simultaneously added dropwise to the three liquids, and the addition of all three liquids was completed in 90 minutes.
  • step 1 of Example 1 a catalyst was used at a reaction temperature of 290 ° C, using 15 parts by weight of 48% sodium hydroxide as a catalyst, 1.5 parts by weight of hydroquinone and 1.5 parts by weight of phenothiazine as a polymerization inhibitor.
  • An esterification reaction product (A) -2 was obtained in the same manner as in Example 1 except that neutralization was not performed after the completion of the reaction.
  • This (A) — 2 P GMA methacrylate The concentration was 93.7%.
  • a (meth) acrylic acid-based polymer was obtained in the same manner as in Example 1 except that the esterification reaction product (A) -2 was used, except that 5 parts by weight of phosphoric acid was changed to 26 parts by weight.
  • the pH during the polymerization reaction in step 2 was 3.1.
  • the viscosity of the obtained (meth) acrylic acid-based polymer was 44'9 mPa's.
  • the paste flow value of this (meth) acrylic acid-based polymer was determined in the same manner as in Example 1. Table 1 shows the results.
  • step 1 of Example 1 1000 parts by weight of polyethylene glycol monomethyl ether (mol number of added ethylene oxide 9, weight average molecular weight 429), 1,200 parts by weight of methyl methacrylate, and 40 parts by weight of p-toluenesulfonic acid were used.
  • the esterification reaction product (A) -3 was obtained in the same manner as in Example 1.
  • the PGMA meta-tallylate concentration of this (A) -3 was 93.4%.
  • a (meth) acrylic acid-based polymer was obtained in the same manner as in Example 1, except that in Step 2 of Example 1, 16 parts by weight of 48% sodium hydroxide was used instead of 85% phosphoric acid. .
  • the pH during the polymerization reaction in Step 2 was 4.5.
  • the viscosity of the obtained (meth) acrylic acid polymer was 490 mPa's.
  • the paste flow value of this (meth) atalylic acid polymer was determined in the same manner as in Example 1. Table 1 shows the results.
  • step 2 of Example 1 a (meth) acrylic acid-based polymer was obtained in the same manner as in Example 1 except that 5 parts by weight of phosphoric acid was not added.
  • the pH during the polymerization reaction in step 2 was 4.0.
  • the viscosity of the obtained (meth) acrylic acid-based polymer was 460 mPa's.
  • the paste flow value of this (meth) acrylic acid-based polymer was determined in the same manner as in Example 1. Table 1 shows the results.

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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)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de production d'un polymère d'acide (méth)acrylique propre à être utilisé comme dispersant de ciment d'une qualité stable. Le procédé consiste (1) à soumettre un alkyl(méth)acrylate et un monoalkyléther de polyalkylène glycol à une transestérification dans un rapport molaire de 3/1 à 50/1, puis à séparer par distillation le produit secondaire alcool pour obtenir un produit d'estérification comprenant le PGMA (méth)acrylate; et (2) à copolymériser le PGMA (méth)acrylate avec un monomère copolymérisable dans une gamme de pH allant de 1,5 à 3,5.
PCT/JP1999/004527 1998-08-27 1999-08-23 Procede de production d'un polymere d'acide (meth)acrylique WO2000012577A1 (fr)

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JP24125698 1998-08-27
JP10/241256 1998-08-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4137445B2 (ja) * 1999-08-23 2008-08-20 花王株式会社 （メタ）アクリル酸系重合体の製造方法
US7435857B2 (en) 2004-12-10 2008-10-14 Clariant Produkte (Deutschland) Gmbh Method for producing pure α-alkoxy-Ω-hydroxy-polyalkylene glycols

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100487011C (zh) * 2005-05-09 2009-05-13 中国科学院过程工程研究所 聚乙二醇改性的甲基丙烯酸缩水甘油酯树脂及制备方法和应用
DE602006018484D1 (de) * 2005-09-05 2011-01-05 Kao Corp Verfahren zur herstellung von phosphatpolymer

Citations (5)

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JPS3620385B1 (fr) * 1960-08-01 1961-10-25
JPS4842473B1 (fr) * 1970-11-19 1973-12-12
JPS5092985A (fr) * 1973-12-24 1975-07-24
JPS53126093A (en) * 1977-04-12 1978-11-02 Japan Exlan Co Ltd Preparation of aqueous polymer emulsion having modified stability
JPH09267034A (ja) * 1996-04-01 1997-10-14 Toyo Ink Mfg Co Ltd 消泡性ノニオン系高分子界面活性剤及びその用途

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS3620385B1 (fr) * 1960-08-01 1961-10-25
JPS4842473B1 (fr) * 1970-11-19 1973-12-12
JPS5092985A (fr) * 1973-12-24 1975-07-24
JPS53126093A (en) * 1977-04-12 1978-11-02 Japan Exlan Co Ltd Preparation of aqueous polymer emulsion having modified stability
JPH09267034A (ja) * 1996-04-01 1997-10-14 Toyo Ink Mfg Co Ltd 消泡性ノニオン系高分子界面活性剤及びその用途

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4137445B2 (ja) * 1999-08-23 2008-08-20 花王株式会社 （メタ）アクリル酸系重合体の製造方法
US7435857B2 (en) 2004-12-10 2008-10-14 Clariant Produkte (Deutschland) Gmbh Method for producing pure α-alkoxy-Ω-hydroxy-polyalkylene glycols

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