WO2001010920A1 - Fabrication de polymere d'acide (meth)acrylique - Google Patents

Fabrication de polymere d'acide (meth)acrylique Download PDF

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Publication number
WO2001010920A1
WO2001010920A1 PCT/JP1999/004277 JP9904277W WO0110920A1 WO 2001010920 A1 WO2001010920 A1 WO 2001010920A1 JP 9904277 W JP9904277 W JP 9904277W WO 0110920 A1 WO0110920 A1 WO 0110920A1
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Prior art keywords
meth
acrylic acid
acid
weight
parts
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PCT/JP1999/004277
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English (en)
Japanese (ja)
Inventor
Kengo Shibata
Haruya Minou
Haruyuki Sato
Toshinao Ukena
Yoshinao Kono
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Kao Corporation
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Priority to PCT/JP1999/004277 priority Critical patent/WO2001010920A1/fr
Publication of WO2001010920A1 publication Critical patent/WO2001010920A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants

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.
  • Polycarboxylic acid polymers are useful as dispersants for cement, and various techniques have been proposed.
  • Japanese Patent Publication No. 59-183338 discloses polyalkylene glycol mono (meth) acrylate monomer and (meth) acrylic monomer, Further, a polymer containing a copolymer produced by reacting these monomers with a copolymerizable monomer at a specific ratio is disclosed, and Japanese Patent Application Laid-Open No. Hei 5-238795 discloses.
  • Japanese Patent Application Laid-Open Publication No. H11-163,086 discloses a polymer containing a copolymer of a polyalkylene glycol ester monomer having an unsaturated bond and a specific monomer.
  • these prior arts do not describe specific polymerization conditions.
  • the polymer of the present invention is known. It can be manufactured by the method described in Disclosure of the invention
  • This invention can obtain the (meth) acrylic-acid type polymer suitable as a dispersing agent for cement with a stable quality by setting polymerization conditions concretely. It is intended to provide a method.
  • the inventors of the present invention deactivated the acid catalyst by adding an alcohol catalyst to the esterification reaction product containing the acid catalyst and the polymerization inhibitor, and further caused the polymerization reaction in a specific range of pH.
  • the inventors have found that the object can be achieved, and have completed the present invention.
  • (meth) acrylic acid and polyalkylene glycol monoalkyl ether are added in a molar ratio of 3 ::! To 50: 1, and an esterification reaction is performed in the presence of an acid catalyst and a polymerization inhibitor.
  • a step (2) of copolymerizing (meth) acrylic acid ester with (meth) acrylic acid A monomer copolymerizable with these monomers may be included.
  • the monomer of step 2 may include the reactants of step 1, residues, and newly added monomers.
  • the monomer (meth) acrylate of Step 2 includes the reactant of Step 1. Further, it may contain a newly added monomer.
  • the (meth) acrylic acid may include the residue of step 1 and further newly added monomers.
  • the reaction product of step 1 may be polymerized as it is, or (meth) acrylic acid may be removed by distillation. Polymerization may be carried out by adding a monomer. These may be combined and polymerized. It polymerizes in the range of pH 3.5 to 3.5. Polymerization may be performed without adding an acid.
  • step 1 Either all or part of the unreacted (meth) acrylic acid is distilled off in step 1, and Z or (meth) acrylic acid ester and (meth) acrylic acid can be copolymerized with (meth) acrylic acid in step 2.
  • a copolymer having a desired monomer ratio can be obtained. That is, the polymer monomer includes the reactant in step 1 and the monomer added in step 2.
  • an acid may be added to the esterification reaction product to adjust the pH to a range of from 5 to 3.5.
  • the monomer copolymerizable with the (meth) acrylic ester added in step 2 may be (meth) acrylic acid, methyl (meth) acrylate or methoxypolyethylene glycol mono (meth) acrylate. preferable.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid.
  • step 1 first, (meth) acrylic acid and polyalkylene glycol monoalkyl ether are subjected to an esterification reaction in the presence of an acid catalyst and a polymerization inhibitor.
  • the (meth) acrylic acid used in the esterification reaction is not particularly limited, and a commercially available one containing a polymerization inhibitor in advance can be used.
  • polyalkylene glycol monoalkyl ether used in the esterification reaction examples include those in which the polyalkylene moiety consists of an alkylene oxide adduct such as an adduct of ethylene oxide alone or a mixed adduct of ethylene oxide and propylene oxide.
  • the total number of moles of the alkylene oxide is from 1 to 300.
  • the alkyl group constituting the monoalkyl ether moiety is preferably an alkyl group having 1 to 3 carbon atoms.
  • the mixing ratio of the (meth) acrylic acid and the polyalkylene glycol monoalkyl ether in the reaction system is in a molar ratio of 3: 1 to 50: 1, preferably 10: 5, in order to further increase the esterification reaction rate.
  • Examples of the acid catalyst used in the esterification reaction include sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and benzenesulfonic acid, and mineral acids such as sulfuric acid and phosphoric acid.
  • the acid catalyst is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polyalkylene glycol monoalkyl ether.
  • the amount is 0.1 part by weight or more, the reaction speed can be maintained at an appropriate level, and when the amount is 10 parts by weight or less, it is economical, without cleaving the alkylene oxide chain of the polyalkylene glycol monoalkyl ether. This is preferable because the reaction can smoothly proceed.
  • Examples of the polymerization inhibitor used in the esterification reaction include a combination of one or more selected from hydroquinone, benzoquinone, methoquinone, BHT, and the like in an arbitrary ratio. Further, by passing a gas containing oxygen through the reaction system, the polymerization inhibiting effect can be further enhanced.
  • the polymerization inhibitor is preferably used in an amount of 0.001-1 part by weight based on 100 parts by weight of the polyalkylene glycol monoalkyl ether.
  • the reaction temperature in the esterification reaction is preferably from 80 to 130 ° C. If the temperature is 80 ° C or higher, an appropriate reaction rate can be maintained. If the temperature is 130 ° C or lower, deterioration of the quality of the polyalkylene glycol monoalkyl ether can be prevented, and the viscosity of the reaction system is maintained at an appropriate level. It is preferable because it can be performed.
  • the pressure of the reaction system in the esterification reaction is not particularly limited, but is preferably a reduced pressure from the viewpoint of distilling water generated by the reaction out of the system.
  • step 1 after the esterification reaction, an alkali agent is added to deactivate the acid catalyst.
  • the alkaline agent include alkaline metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide.
  • the amount of the alkali agent to be used is preferably 0.9 to 1.5 equivalent times, more preferably 1.0 to 1.3 equivalent times, based on the acid catalyst used.
  • step 1 after deactivating the acid catalyst, unreacted (meth) acrylic acid is distilled off, and mainly contains (meth) acrylic acid ester represented by the following general formula (I). Further, an esterification reaction product containing a (meth) acrylic acid residue represented by the following general formula (II) is obtained.
  • R represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 1 to 3 carbon atoms
  • AO represents an oxyalkylene group having 2 to 3 carbon atoms
  • n represents 1 to 30.
  • R 3 represents a hydrogen atom or a methyl group
  • M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or the like].
  • step 1 a large excess amount of (meth) acrylic acid is used to make the reaction proceed smoothly. Therefore, if an excess amount of (meth) acrylic acid is present in excess of the desired amount of (meth) acrylic acid in step 2, unreacted (meth) acrylic acid is distilled off in step 1. is there.
  • the degree of distillation of the unreacted (meth) acrylic acid is appropriately set according to the molar ratio of copolymerization of (meth) acrylate and (meth) acrylic acid in the next step 2.
  • Methods for removing unreacted (meth) acrylic acid include vacuum distillation and steam evaporation. A distillation method or a method of distilling together with the carrier gas at normal pressure can be applied.
  • step 2 the (meth) acrylic ester and the (meth) acrylic acid residue contained in the esterification reaction product obtained in step 1 are combined with each other in a pH range of 5 to 3.5.
  • the copolymerization reaction is performed.
  • a monomer copolymerizable with (meth) acrylic acid ester and Z or (meth) acrylic acid represented by the general formula (I) can be further added.
  • this monomer include acrylic acid, methacrylic acid, crotonic acid, and (meth) acrylic monomers such as alkali metal salts, alkaline earth metal salts, ammonium salts and amine salts thereof; maleic anhydride, Unsaturated dicarboxylic acid monomers such as maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, fumaric acid and their alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts; (Meth) alkyl acrylate, (meth) hydroxy phenol acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene polypropylene glycol (meth) acrylate, styrene
  • the monomer copolymerizable with the (meth) acrylic ester must be (meth) acrylic acid, methyl (meth) acrylate or methoxypolyethylene glycol mono (meth) acrylate. Is preferred.
  • the amount of such a monomer copolymerizable with the (meth) acrylic ester is 0.3 to 100 parts by weight of the (meth) acrylic ester represented by the general formula (I). It is preferably 170 parts by weight, particularly preferably 0.3 to 100 parts by weight.
  • the pH of the reaction system is in the range of 1.5 to 3.5, preferably pH 2.0 to 3.0. It is possible to suppress the occurrence of a hydrolysis reaction of the (meth) acrylate during the polymerization reaction in which 13 ⁇ 4 is 1.5 or more. When the pH is 3.5 or less, the copolymerization rate can be kept high, and the structure of each monomer in the copolymer can be appropriately controlled. As a result, stable quality can be obtained.
  • a (meth) acrylic acid polymer useful as a dispersant for cement can be obtained.
  • the pH in step 2 is the pH of a 5% by weight aqueous solution of the polymerization reaction mixture.
  • the pH of the esterification reaction product is outside or within the range of 1.5 to 3.5, it is preferable to add an acid or a base for preparing the pH, if desired.
  • Examples of the acid used for adjusting the pH include phosphoric acid, sulfuric acid, nitric acid, alkylphosphoric acid, alkylsulfuric acid, alkylsulfonic acid, alkylbenzenesulfonic acid, and benzenesulfonic acid.
  • 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.
  • Examples of the base include sodium hydroxide and a hydroxylating rhine.
  • the reaction can be performed in the presence of a solvent to reduce the viscosity of the polymerization reaction system.
  • a solvent include water, lower alcohols such as methanol, ethanol, isopropanol and butanol; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane; and fats such as n-hexane.
  • 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 The molar ratio is preferably 1 to 50 times the total of the general formula (1), the general formula (II) and other monomers.
  • a chain transfer agent can be added.
  • the chain transfer agent include lower alkali mercaptan, lower mercapto fatty acid, thioglycerin, thiolingoic 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 subjected to a deodorizing treatment, if necessary.
  • a deodorizing treatment if necessary.
  • a thiol such as mercaptoethanol
  • an unpleasant odor remains in the polymer.
  • a method of converting thiol to disulfide with an oxidizing agent can be exemplified.
  • 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 added is preferably from 100 to 2000 ppm, particularly preferably from 100 to 1000 ppm, based on the polymer.
  • the deodorizing temperature is preferably from 70 to 100 ° C, particularly preferably from 80 to 90 ° C. When the temperature is 70 ° C or more, the deodorizing effect is enhanced, and when the temperature is 100 ° C or less, 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 is an acid Can also be used as a dispersant for cement, but from the viewpoint of suppressing the hydrolysis of the ester by an acid, it is preferable to form a salt by neutralization with an alkali.
  • the alkali include a hydroxide of an alkali metal or an alkaline earth metal, ammonium, alkylammonium, alkanolamine, N-alkyl-substituted polyamine, ethylenediamine, polyethylenepolyamine and the like.
  • the pH is preferably adjusted to 5 to 7 by neutralization.
  • the (meth) acrylic acid-based polymer obtained by the production method of the present invention may be used as a dispersant for hydraulic cement other than cement, such as portland cement, alumina cement, various mixed cements, and gypsum. it can. Industrial applicability
  • Ethylene oxide melted at 80 ° C
  • 3 parts by weight of hydroquinone and 32 parts by weight of p-toluenesulfonic acid were added.
  • air was introduced into the reaction solution at a flow rate of 6 ml / min per 1 kg of the total weight of polyethylene glycol monomethyl ether and methacrylic acid, and nitrogen was further introduced into the gas phase of the reaction vessel at a flow rate of 12 ml min.
  • This (A) -1 has a methacrylate concentration of 91.2%, an unreacted polyethylene glycol monomethyl ether concentration of 2.8%, a polymerization inhibitor concentration of 0.3%, and a catalyst salt (sodium p-toluenesulfonate) concentration. The concentration was 3.4% and the methacrylic acid concentration was 2.3%.
  • step 1 In the same glass reaction vessel as in step 1 in which the cooling condenser was replaced with a reflux condenser, 485 parts by weight of water was charged, and while stirring, the gas phase of the reaction vessel was replaced with nitrogen. The temperature was raised to 80 ° C.
  • esterification reaction product (A) -1 600 parts by weight of esterification reaction product (A) -1; 21 parts by weight of methacrylic acid; Dequest (phosphonic acid chelating agent; manufactured by Nippon Monsanto Co.) 0.7 parts by weight, 85% A solution prepared by mixing and dissolving 5 parts by weight of phosphoric acid and 400 parts by weight of water and 3 parts by weight of 3 parts by weight of 2-mercaptoethanol and 39 parts by weight of a 15% aqueous solution of ammonium persulfate were simultaneously added dropwise. The dropping was completed over 0 minutes. Next, 15 parts by weight of a 15% aqueous solution of ammonium persulfate was added dropwise over 30 minutes, and the mixture was aged at 80 ° C. for about 1 hour.
  • the pH at the time of dropping and aging was 2.5. Further, after neutralizing by adding 30 parts by weight of a 48% aqueous sodium hydroxide solution, 0.7 parts by weight of 35% hydrogen peroxide was added dropwise, and the mixture was aged at 90 ° C for 1 hour. A (meth) ataryl acid polymer was obtained.
  • the viscosity of the (meth) acrylic acid polymer was measured (B-type viscometer manufactured by Tokyo Keiki Seisakusho, rotor No. 2, 30 rpm) and found to be 420 mPa's.
  • 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 used instead of 5 parts by weight of phosphoric acid.
  • the pH during the polymerization reaction in Step 2 was 2.2 to 2.8.
  • the viscosity of the obtained (meth) atalylic acid 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.
  • 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 was added, 76 parts by weight of metadallylic acid, methoxypolyethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., average number of moles of ethylene oxide 9 1) 3 parts by weight of a mixture of 18 parts by weight, 2 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 water 485 weight was added to the same glass reaction vessel as in step 1.
  • 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 mixed solution, 3 parts by weight of 2-mercaptoethanol, and 46 parts by weight of a 15% aqueous solution of ammonium persulfate were simultaneously dropped at a time, and the dropping was completed over 90 minutes.
  • step 1 of Example 1 the same procedures as in Example 1 were carried out except that 1,000 parts by weight of polyethylene glycol monomethyl ether (average number of moles of added ethylene 200, weight average molecular weight 8864) and 291 parts by weight of methacrylic acid were used.
  • an esterification reaction product (A) -2 was obtained.
  • This (A) -2 is the concentration of methacrylic acid ester 90.5%, unreacted polyethylene glycol monomethyl ether 2.7%, polymerization inhibitor concentration 0.3%, catalyst salt (sodium p-toluenesulfonate) concentration 3.0% and methacrylic acid concentration was 3.5%.
  • (Meth) acrylic acid polymer was obtained in the same manner as in Example 1 except that 21 parts by weight of methacrylic acid was not used in Step 2 of Example 1 using the esterification reaction product (A) -2. Was.
  • the pH during the polymerization reaction in step 2 was 3.1. Profit
  • the viscosity of the obtained (meth) acrylic acid polymer was 455 mPa's.
  • the paste flow value of this (meth) acrylic acid polymer was determined in the same manner as in Example 1. Table 1 shows the results.
  • Step 1 of Example 1 polyethylene glycol monomethyl ether (average number of moles added of ethylene: 9, weight average molecular weight: 429) 1000 parts by weight, methacrylic acid 1200 parts by weight and p-toluenesulfonic acid 40 parts by weight were used.
  • esterification reaction product (A) -3 was obtained.
  • This (A) -3 has a methacrylate concentration of 91.5%, an unreacted polyethylene glycol monomethyl ether concentration of 2.4%, a polymerization inhibitor concentration of 0.2%, and a catalyst salt (sodium p-toluenesulfonate). The concentration was 3.4% and the methacrylic acid concentration was 2.5%.
  • step 2 of Example 1 except that 16 parts by weight of 48% sodium hydroxide was used instead of 5 parts by weight of 85% phosphoric acid, a (meth) acrylic acid-based polymer was prepared in the same manner as in Example 1. A coalescence was obtained. The pH during the polymerization reaction in step 2 was 4.4. The viscosity of the obtained (meth) acrylic acid polymer was 480 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 2 of Example 5 a (meth) acrylic acid-based polymer was obtained in the same manner as in Example 5, except that 5 parts by weight of phosphoric acid was not used.
  • the pH during the polymerization reaction in step 2 was 4.1.
  • the viscosity of the obtained (meth) acrylic acid-based polymer was 500 mPa's.
  • the paste flow value of this (meth) acrylic acid polymer was determined in the same manner as in Example 1. Table 1 shows the results.
  • the (meth) acrylic acid-based polymers obtained by the production methods of Comparative Examples 1 and 2 had a lower pace because the pH of the polymerization reaction system in Step 2 was outside the range specified in the present invention.
  • the flow rate value was significantly inferior. Therefore, it was confirmed that when the production method of the present invention was not applied, a (meth) acrylic acid-based polymer having a low paste flow value was obtained, and a high-quality cement dispersant could not be provided.

Abstract

Cette invention concerne un procédé permettant de fabriquer un polymère d'acide (meth)acrylique convenant comme dispersant pour ciment de qualité stable. Ce procédé consiste à: (1) soumettre un acide (meth)acrylique et un polyalkylène glycol monoalkyl éther à une estérification avec un rapport molaire compris entre 5/1 et 50/1 en présence d'un catalyseur acide et d'un inhibiteur de polymérisation, l'acide (meth)acrylique étant ultérieurement désactivé au moyen d'un alcali et l'acide (meth)acrylique non réagi étant ensuite distillé en vue de l'obtention d'un produit d'estérification contenant un ester (meth)acrylique et l'acide (meth)acrylique non réagi résiduel; et (2) copolymériser l'ester (meth)acrylique et l'acide (meth)acrylique non réagi résiduel du produit d'estérification dans la plage de pH de 1,5 à 3,5.
PCT/JP1999/004277 1999-08-06 1999-08-06 Fabrication de polymere d'acide (meth)acrylique WO2001010920A1 (fr)

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Cited By (11)

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US6454850B2 (en) 2000-04-28 2002-09-24 Nippon Shokubai Co., Ltd. Cement admixture and cement composition comprising this
WO2004087635A2 (fr) 2003-04-03 2004-10-14 Basf Aktiengesellschaft Melanges de composes ayant au moins deux liaisons doubles et leur utilisation
WO2007029837A1 (fr) * 2005-09-05 2007-03-15 Kao Corporation Procédé de production d’un polymère phosphaté
US7199211B2 (en) 2002-06-11 2007-04-03 Basf Aktiengesellschaft (Meth)acrylic esters of polyalkoxylated trimethylolpropane
JP2007186635A (ja) * 2006-01-16 2007-07-26 Kao Corp リン酸エステル系重合体の製造方法
US7250481B2 (en) 2002-06-11 2007-07-31 Basf Aktiengesellschaft Method for the production of esters of polyalcohols
US7259212B2 (en) 2002-06-11 2007-08-21 Basf Aktiengesellschaft (Meth)acrylic esters of polyalkoxylated trimethylolpropane
US7405321B2 (en) 2003-06-06 2008-07-29 Basf Aktiengesellschaft (Meth)acrylic ester of alkenylene glycols and the use thereof
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
JP2008543997A (ja) * 2005-06-15 2008-12-04 花王株式会社 コンクリートおよびモルタル混和剤
CN109485806A (zh) * 2018-10-29 2019-03-19 广东科之杰新材料有限公司 一种酯类超缓释型聚羧酸保坍剂及其制备方法

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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
US6454850B2 (en) 2000-04-28 2002-09-24 Nippon Shokubai Co., Ltd. Cement admixture and cement composition comprising this
EP2345431A2 (fr) 2002-06-11 2011-07-20 Basf Se Procédé de fabrication d'esters de polyalcools
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