WO1980001164A1 - Solvent polymerization of carboxyl containing monomers - Google Patents

Solvent polymerization of carboxyl containing monomers Download PDF

Info

Publication number
WO1980001164A1
WO1980001164A1 PCT/US1979/001013 US7901013W WO8001164A1 WO 1980001164 A1 WO1980001164 A1 WO 1980001164A1 US 7901013 W US7901013 W US 7901013W WO 8001164 A1 WO8001164 A1 WO 8001164A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight percent
monomer
acid
ester
carbon atoms
Prior art date
Application number
PCT/US1979/001013
Other languages
English (en)
French (fr)
Inventor
L Cohen
Original Assignee
Goodrich Co B F
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Goodrich Co B F filed Critical Goodrich Co B F
Priority to BR7908940A priority Critical patent/BR7908940A/pt
Publication of WO1980001164A1 publication Critical patent/WO1980001164A1/en
Priority to DK338980A priority patent/DK338980A/da

Links

Classifications

    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • 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
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/923—Ethylenic monomers containing at least one salt group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/93—Water swellable or hydrophilic

Definitions

  • Representative acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, methyl ethacrylate, ethyl methacrylate, octyl acrylate, heptyl acrylate, octyl methacrylate, isopropyl methacrylate, 2-ethylhexyl acrylate, nonyl acrylate, hexyl acrylate, n-hexyl methacrylate, and the like. Mixtures of these two classes of acrylates provide useful copolymers.
  • Typical agents are allyl pentaerythritol, allyl sucrose, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, tetramethylene dimethacrylate, tetramethylene diacrylate, ethylene diacrylate, ethylene dimethacrylate, triethylene glycol dimethacrylate, and the like. Allyl pentaerythritol andallyl sucrose provide excellent polymers in'amounts lessthan 5, as 3.0 weight percent. Cross-linking of the polymers provides improved ability for the copolymers to swell under a confining pressure.
  • the acrylic amides include monoolefinically unsaturated amides which may be incorporated in the interpolymers of this invention having at least one hydrogen on the amide nitrogen and the olefinicr unsaturation is alpha-beta to the carbonyl group.
  • Representative amides include acrylamide, methacrylamide, N-methyl acrylamide, N-t-butyl acrylamide, N-cyclohexyl acrylamide, N-ethyl acrylamide and others.
  • acrylic amides include N-alkylol amides of alpha, beta-olefinic ally unsaturated carboxylic acids including those having from 4 to 10 carbon atoms such as N-methylol acrylamide, N-ethanol acrylamide, N-propanol acrylamide, N-methylol methacrylamide, N-ethanol methacrylamide, N-methylol maleimide, N-methylol maleamide, N-methylol maleamic acid, N-methylol maleamic acid esters, the N-alkylol amides of the vinyl aromatic acids such as N-methylol-p-vinyl benzamide, and the like and others.
  • copolymers may include as little as 8 weight percent of the total polymer of a carboxyl containing monomer, up to 100%, i.e. hqmopolymer.
  • a useful range of materials include those containing about 8 to 70 weight percent carboxyl containing monomer, with 92 to 30 weight percent of other vinylidene comonomers as described.
  • Copolymers wherein the carboxyl containing monomer is a minor constituent, and the other vinylidene monomers are present on major components are readily prepared in accordance with the process of this invention.
  • Polymerization of the monomer in the solvent medium is usually carried out in the presence of a free radical catalyst in a closed vessel in an inert atmosphere and under autogenous pressure or artificially-induced pressure, or in an open vessel under reflux at atmospheric pressure. Temperature of the polymerization may be varied from about 0° to 100°C or lower or higher, depending to a degree on the molecular weight desired in the polymer.
  • Polymerization at 50° to 90°C under autogenous pressure using a free radical catalyst is generally effective in producing a polymer yield of 75% to 100%.
  • the carboxyl groups and monomer are neutralised or formed into a salt of the above listed materials. More preferably, greater than 3 weight percent, up to about 50 weight percent of the carboxyl groups are neutralized or converted to the equivalent salt prior to polymerization. A particularly useful range is from greater than 5 to about 25 weight percent of the carboxyl groups in the carboxyl monomers to be neutralized. It is understood, that if desired, the carboxyl groups may be restored by removal of the alkali ion after polymerization is complete. Normally, polar and medium to strongly hydrogen bonded solvents are not suitable as solvents for carboxyl containing polymers free of the salts because they swell the free acid containing polymers to difficult to process gels.
  • Solvents with solubility parameters outside the preferred range include for example, mineral spirits, pentene, hexane, heptane, octane and the like, methyl cyclohexane and diethyl ether.
  • moderately bonded solvents including their solubility parameters are methyl acetate 9.6, ethyl acetate 9.1, methyl ethyl ketone 9.3, dioxane 9.9, methyl propyl ketone 8.7, methyl cellosolve 10.8, butyl propionate 8.8, cyclohexanone 9.9, carbitol 9.6, and the like.
  • Strongly hydrogen bonded materials include for example, methanol 14.5, ethanol 12.7, isopropanol 11.5, n-propanol 11.9, sec.
  • Suitable solvents having both defined solubility parameters and hydrogen bonding parameters are listed in the articles referred to hereinabove which are incorporated herein and made a part hereof. Particularly useful are moderately hydrogen bonded ketone, ester and alcohol solvents having solubility parameters of about 9 to 11;
  • the polymerization may be conducted beginning with none of the carboxyl groups converted to a salt so long as a mole percent of the carboxyl group in amount up to greater than 1%, more preferably greater than 3%, is continuously or intermittently neutralized and/or converted to the salt form at a rate substantially equivalent to the polymerization rate.
  • additional neutralization continuously or intermittently may take place during the course of the polymerization, but more probably and for ease of operation, the polymerization reaction is begun when more than 1 and preferably more than about 3 weight percent of the carboxyl groups of the acid monomers are converted into a salt form in order to obtain the optimum advantages of the invention.
  • EXAMPLE II A series of polymerizations were conducted in small sealed reactors. The total amount of ethyl acetate and acrylic acid used was about 15 grams. In the table following hereinafter the parts per 100 of acrylic acid will be recited for the allylpentaerythritol and the catalyst. In these examples the acrylic acid was neutralized with 50% NaOH sol. to 7% neutralization and this mixture was charged to the reactors. This resulted in 4.35 phm H 2 O contained during poly merization. The polymerizations were conducted at the temperature and the times indicated in the Table, along with the resulting recovered yield of polymer. The Brookfield Viscometer values at 20 rpm for water mucilages at pH 7 were also set forth. The catalysts will be indicated as "L” for lauroyl peroxide and "S" for secondary sec. butyl peroxydicarbonate. PHM is weight parts per hundred of monomer.
  • EXAMPLE III In these examples, rather than introducing water into the small polymerization reactors by neutralizing as above, a sample of acrylic acid was completely neutralized with sodium hydroxide solution, isolated and dried as a crystalline solid, then mixed with additional acrylic acid in amounts so that the mixture was equivalent to 7% neutralization of the acrylic acid carboxyl groups of the mixture and this mixture was charged to the reactors. The data is recorded in Table 2 in the manner set forth in Example 1 above.
  • EXAMPLE IV Another example was run following the procedure of Examples II and III wherein allyl sucrose (not APE) in amount of 0.5 PHM was used with 0.15 PHM of lauroyl peroxide with sodium acrylate mixed with acrylic acid, at a polymerization temperature, of 82°C, in a monomer concentration in ethyl acrylate of 20%, for 208 minutes. The recovered yield of polymer was 72.3%. The Brookfield viscosity of a 1% solution was 23,750 cps and the 0.5% solution viscosity was 16,200 cps.
  • EXAMPLE V To a one (1) quart reactor there was added 11.6 grams of anhydrous potassium carbonate and 83.0 grams of acrylic acid to convert 14.6 % of the carboxyl groups to the potassium salt form. 7.0 grams of lauryl methacrylate and 10.0 grams of methyl methacrylate in 300 grams of ethyl acetate were then added to the reactor. 25 ml. of a 1% solution of lauroyl peroxide in ethyl acetate was added, and the solution deaerated with nitrogen for seven minutes and sealed. The reaction vessel- was rotated at 22 r.p.m. in a constant temperature bath at 65°C for 18 hours.
  • the water of neutralization was removed by running the reflex condensate through a molecular sieve before returning to the reactor.
  • EXAMPLE VII In this example allyl sucrose was used as the cross-linking agent for acrylic acid, and the polymers were prepared as in Example VI above. The acrylic acid was neutralized so that 4% of the carboxyl groups were in the potassium salt form. 1.1 phm of allyl sucrose was used and 0.4 phm of lauroyl peroxide. The polymerization temperature was 62°C and the weight % solids was 13. The 0.5 weight percent viscosity in water (cps.) was 36,500 and the 1.0 weight percent viscosity (cps.) was 82,000.
  • EXAMPLE VIII A series of solvents are used in this example to demonstrate the practice of the invention.
  • a master batch was prepared with 93 weight parts acrylic acid, 7 weight parts sodium acrylate, 1.0 weight parts allyl pentaerythritol, 0.15 weight parts lauroyl peroxide and 0.78 weight parts of water.
  • three weight parts of the master batch plus 12 weight parts of the solvents set forth in the table hereinbelow were added to polymerization vessel, flushed with nitrogen for 3 minutes, sealed and heated to 80°C for a period of time to obtain greater than about 80 weight percent conversion of monomers to polymer.
  • the resulting fine slurry of polymers were readily filtered and washed with 150 ml of ethyl acetate.
  • the neutralizing agent is preferably a monovalent alkali such as sodium, potasium, lithium, ammonium hydroxide, the carbonates and bicarbonates thereof, and the like or mixtures of the same, and also amine bases having not more than one primary or secondary amino group.
  • amines include, for example, triethanolamine, ethanolamine, isopropanolamine, triethylamine, trimethyl amine, and the like. At least 30% of the acid, carboxyl, groups are generally neutralized to an ionic state, that is, --CO 2 -M+.
  • the acid groups are neutralized to --CO 2 M for thickening purposes.
  • the counter ion M + is the alkali cation, the ammonia ion NH 4 + or quaternary cationic compounds resulting from the neutralization with an organic amine. Excellent results have been obtained with K+ and NH 4 + .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
PCT/US1979/001013 1978-12-07 1979-11-13 Solvent polymerization of carboxyl containing monomers WO1980001164A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
BR7908940A BR7908940A (pt) 1978-12-07 1979-11-13 Processo para a preparacao de polimeros de monomeros de acido carboxilico polimerizaveis insaturados e polimerizavel olefinicamente insaturado
DK338980A DK338980A (da) 1978-12-07 1980-08-06 Fremgangsmaade til polymerisation i oploesningsmiddel af carxoxylholdige monomere

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/967,447 US4267103A (en) 1978-12-07 1978-12-07 Solvent polymerization of carboxyl containing monomers
US967447 1978-12-07

Publications (1)

Publication Number Publication Date
WO1980001164A1 true WO1980001164A1 (en) 1980-06-12

Family

ID=25512810

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1979/001013 WO1980001164A1 (en) 1978-12-07 1979-11-13 Solvent polymerization of carboxyl containing monomers

Country Status (14)

Country Link
US (1) US4267103A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0020680A4 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPH0262561B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU5300179A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE880235A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA1147898A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ES (1) ES486697A0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GR (1) GR69729B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IL (1) IL58751A0 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IT (1) IT1127279B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NO (1) NO793966L (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
PT (1) PT70554A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1980001164A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ZA (1) ZA796373B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2120259A (en) * 1979-08-10 1983-11-30 Coopervision Preparation of non-cross-linked polymers and moulding process therefor
US4835231A (en) * 1986-08-26 1989-05-30 Nippon Paint Co., Ltd. Disintegration type, crosslinked acrylic resin particles
US8084561B2 (en) 2006-03-31 2011-12-27 Basf Se Process for preparing acrylate copolymers

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4500693A (en) * 1981-07-07 1985-02-19 Nippon Shokubai Kagaku Kogyo Co., Ltd. Water soluble copolymer method for manufacture therefore and use thereof
US4470814A (en) * 1981-12-21 1984-09-11 Block Drug Company, Inc. Method of adhering dentures
US4420586A (en) * 1982-11-29 1983-12-13 Nalco Chemical Company Non-aqueous dispersion polymerization of vinyl monomers
US4542168A (en) * 1983-09-02 1985-09-17 Block Drug Co., Inc. Denture fixative composition with partially neutralized and crosslinked polyacrylic acid
DE3631070A1 (de) * 1986-09-12 1988-03-24 Basf Ag Verfahren zur herstellung von terpolymeren
US4758641A (en) * 1987-02-24 1988-07-19 The B F Goodrich Company Polycarboxylic acids with small amount of residual monomer
DE3875788D1 (de) * 1987-04-11 1992-12-17 Basf Ag Wasserloesliche copolymerisate, verfahren zu ihrer herstellung und ihre verwendung.
DE3882166D1 (de) * 1987-04-11 1993-08-12 Basf Ag Wasserloesliche copolymerisate, verfahren zu ihrer herstellung und ihre verwendung.
US5073612A (en) * 1987-12-28 1991-12-17 Nippon Shokubai Kagaku Kogyo, Co., Ltd. Hydrophilic polymer and method for production thereof
US4996274A (en) * 1988-02-19 1991-02-26 The B. F. Goodrich Company Polycarboxylic acids with higher thickening capacity and better clarity
US4923940A (en) * 1988-02-19 1990-05-08 The B.F. Goodrich Company Polycarboxylic acids with higher thickening capacity and better clarity
DE3818426A1 (de) * 1988-05-31 1989-12-07 Basf Ag Verfahren zur herstellung von wasserloeslichen polymerisaten und ihre verwendung
US5059664A (en) * 1988-06-22 1991-10-22 Mitsubishi Petrochemical Company Limited Process for the preparation of water absorptive resin
US5021526A (en) * 1988-07-05 1991-06-04 The Standard Oil Company Anionic polymeric stabilizers for oil-in-water emulsions
CA2003808C (en) * 1988-11-28 1999-11-09 Eugene Joseph Sehm Crosslinked polyacrylic acid
US5173551A (en) * 1990-03-09 1992-12-22 Board Of Control Of Michigan Technological University Free-radical retrograde precipitation-polymerization process
US5270415A (en) * 1990-12-21 1993-12-14 Allergan Inc. Balanced charge polymer and hydrophilic contact lens manufactured therefrom
US5612429A (en) * 1992-04-21 1997-03-18 National Starch And Chemical Investment Holding Corporation Process for the polymerization of polymers in non-aqueous liquid media
US5336423A (en) * 1992-05-05 1994-08-09 The Lubrizol Corporation Polymeric salts as dispersed particles in electrorheological fluids
US5364581A (en) * 1993-05-06 1994-11-15 Kenneth Wilkinson Process of making polyacrylonitrile fibers
US5523366A (en) * 1993-05-06 1996-06-04 Wilkinson; Kenneth Process for the preparation of an acrylonitrile copolymer and product prepared therefrom
US5616292A (en) * 1993-05-06 1997-04-01 Wilkinson; Kenneth Process of making PAN fibers
US5399639A (en) * 1993-07-12 1995-03-21 National Starch And Chemical Investment Holding Corporation Method for manufacturing of polymers
US5342911A (en) * 1993-08-25 1994-08-30 3V Inc. Crosslinked polyacrylic acids having low solvent residue, a process for the preparation thereof and the use thereof as thickening agents
IT1264989B1 (it) * 1993-12-14 1996-10-17 Sigma Prod Chim Copolimeri di alchile e/o alchilfenile poli(ossialchilene)sorbati e loro uso come addensanti
US5663253A (en) * 1996-06-20 1997-09-02 3V Inc. Policarboxylic acids
US6492488B1 (en) 1998-08-02 2002-12-10 Pmd Holdings Corp. Controlled release polyacrylic acid granules and a process for preparing the same
GB9903140D0 (en) 1999-02-12 1999-04-07 Basf Ag Interpolymers
US6297337B1 (en) 1999-05-19 2001-10-02 Pmd Holdings Corp. Bioadhesive polymer compositions
US6623756B1 (en) * 2000-04-27 2003-09-23 Noveon Ip Holdings Corp. Directly compressed solid dosage articles
AU2000268638B2 (en) 2000-06-29 2004-09-23 Kopran Research Laboratories Limited A synthetic bulk laxative
US6433061B1 (en) 2000-10-24 2002-08-13 Noveon Ip Holdings Corp. Rheology modifying copolymer composition
US6623754B2 (en) * 2001-05-21 2003-09-23 Noveon Ip Holdings Corp. Dosage form of N-acetyl cysteine
JP3940009B2 (ja) * 2002-03-18 2007-07-04 住友精化株式会社 カルボキシル基含有水溶性重合体の製造方法
CA2595692A1 (en) * 2005-01-28 2006-08-03 Basf Aktiengesellschaft Use of a water-in-water emulsion polymers in the form of a thickener for cosmetic preparations
EP2027162A1 (de) * 2006-01-23 2009-02-25 Basf Se Verfahren zur herstellung von polymeren in wässrigen lösungsmitteln
US20090257960A1 (en) * 2006-05-04 2009-10-15 Basf Aktiengesellschaft Neutralized acid group-containing polymers and the use thereof
KR100844181B1 (ko) * 2007-02-15 2008-07-04 애경정밀화학 주식회사 카르복시기 함유 중합체 제조용 조성물 및 이를 이용하여제조된 중합체
EP2403884B1 (en) * 2008-11-21 2014-09-10 Hercules Incorporated Non-hydrocarbyl hydrophobically modified polycarboxylic polymers
JP5709888B2 (ja) 2009-11-26 2015-04-30 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 化粧料及び皮膚用製剤における超分岐ポリカーボネートの使用
CN102639597B (zh) 2009-11-26 2014-05-21 巴斯夫欧洲公司 超支化聚酯在化妆品和皮肤病配制剂中的用途
US20110123473A1 (en) * 2009-11-26 2011-05-26 Basf Se Use of highly-branched polycarbonates in cosmetic and dermatological formulations
CA2789068A1 (en) 2010-03-02 2011-09-06 Basf Se Block copolymers and their use
US20110218295A1 (en) * 2010-03-02 2011-09-08 Basf Se Anionic associative rheology modifiers
US8673275B2 (en) 2010-03-02 2014-03-18 Basf Se Block copolymers and their use
JP2017519854A (ja) 2014-05-05 2017-07-20 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 均質フィルム組成物
TWI707909B (zh) 2014-07-09 2020-10-21 美商盧伯利索先進材料有限公司 水凝膠摻合組成物及其製造方法
WO2017079248A1 (en) 2015-11-05 2017-05-11 Lubrizol Advanced Materials, Inc. Thermoformable dual network hydrogel compositions
US20200375890A1 (en) 2017-03-23 2020-12-03 Particle Sciences, Inc. Implantable and removable drug delivery device
JP7214647B2 (ja) 2017-03-23 2023-01-30 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 改良された義歯接着剤
WO2018204317A1 (en) 2017-05-02 2018-11-08 Lubrizol Advanced Materials, Inc. Improved extended release highly loaded drug compositions
FR3111899A1 (fr) * 2020-06-25 2021-12-31 Snf Sa Copolymère réticulé, procédé de préparation et pâte d’impression comprenant ledit copolymère
WO2022187604A1 (en) 2021-03-05 2022-09-09 Lubrizol Advanced Materials, Inc. Method for wetting and dispersion of acrylic acid polymers

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3025219A (en) * 1956-12-28 1962-03-13 Ciba Ltd Aerosol hair dressing composition
US3379702A (en) * 1965-06-14 1968-04-23 Dow Chemical Co Method for preparing terpolymers of ethylene, acrylic acids and salts of acrylic acids
US4028290A (en) * 1975-10-23 1977-06-07 Hercules Incorporated Highly absorbent modified polysaccharides
US4062817A (en) * 1977-04-04 1977-12-13 The B.F. Goodrich Company Water absorbent polymers comprising unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, and another acrylic ester containing alkyl group 2-8 carbon atoms
US4066583A (en) * 1977-05-16 1978-01-03 The B. F. Goodrich Company Flexible water absorbent polymer compositions comprising (a) unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, additional monomer plus (b) aliphatic diol
US4138539A (en) * 1975-06-19 1979-02-06 American Cyanamid Company Process for water-soluble synthetic polymer in powder form
US4167464A (en) * 1978-10-16 1979-09-11 The B. F. Goodrich Company Photopolymerized hydrophilic interpolymers of unsaturated carboxylic acid and esters

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2244703A (en) * 1938-04-16 1941-06-10 Du Pont Water soluble salts of interpolymers containing methacrylic acid
US2878237A (en) * 1955-06-15 1959-03-17 American Cyanamid Co Mercapto dibasic acids as regulators for the polymerization of acrylic acids, amidesand salts
US3336269A (en) * 1964-04-07 1967-08-15 Hercules Inc Preparation of acrylamide-type water-soluble polymers
JPS453979Y1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1966-04-08 1970-02-24
US3479284A (en) * 1967-03-30 1969-11-18 Hercules Inc Separation of finely divided solids from liquid suspensions thereof
US3509113A (en) * 1967-08-14 1970-04-28 Hercules Inc Preparation of acrylamide-type water-soluble polymers
FR2190846B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1972-03-16 1976-09-10 Mitsubishi Rayon Co
US3872063A (en) * 1972-08-29 1975-03-18 American Cyanamid Co Polymerization process
US3919140A (en) * 1972-08-31 1975-11-11 Sumitomo Chemical Co Process for producing acrylamide polymers in an acetone-water solvent system
US3970633A (en) * 1973-05-16 1976-07-20 Rohm And Haas Company Thermosetting powder coatings composition
JPS5539170B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1975-01-16 1980-10-08
JPS6024122B2 (ja) * 1977-01-05 1985-06-11 三菱化学株式会社 ビ−ズ状重合体の製造方法
US4237253A (en) * 1977-04-21 1980-12-02 L'oreal Copolymers, their process of preparation, and cosmetic compounds containing them
JPS5548212A (en) * 1978-10-02 1980-04-05 Nippon Junyaku Kk Preparation of novel water-soluble crosslinked copolymer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3025219A (en) * 1956-12-28 1962-03-13 Ciba Ltd Aerosol hair dressing composition
US3379702A (en) * 1965-06-14 1968-04-23 Dow Chemical Co Method for preparing terpolymers of ethylene, acrylic acids and salts of acrylic acids
US4138539A (en) * 1975-06-19 1979-02-06 American Cyanamid Company Process for water-soluble synthetic polymer in powder form
US4028290A (en) * 1975-10-23 1977-06-07 Hercules Incorporated Highly absorbent modified polysaccharides
US4062817A (en) * 1977-04-04 1977-12-13 The B.F. Goodrich Company Water absorbent polymers comprising unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, and another acrylic ester containing alkyl group 2-8 carbon atoms
US4066583A (en) * 1977-05-16 1978-01-03 The B. F. Goodrich Company Flexible water absorbent polymer compositions comprising (a) unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, additional monomer plus (b) aliphatic diol
US4167464A (en) * 1978-10-16 1979-09-11 The B. F. Goodrich Company Photopolymerized hydrophilic interpolymers of unsaturated carboxylic acid and esters

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DERWENT ABSTRACT NUMBER 4410B/24 DECEMBER 22, 1977 D52757329 "LOW MOL. WT. POLYMER PREPARED BY MONOMER POLYMER UNDER HEAT AND PRESSURE IN ISOPROPANOL MIXED WITH WATER. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2120259A (en) * 1979-08-10 1983-11-30 Coopervision Preparation of non-cross-linked polymers and moulding process therefor
US4835231A (en) * 1986-08-26 1989-05-30 Nippon Paint Co., Ltd. Disintegration type, crosslinked acrylic resin particles
US8084561B2 (en) 2006-03-31 2011-12-27 Basf Se Process for preparing acrylate copolymers

Also Published As

Publication number Publication date
IT1127279B (it) 1986-05-21
JPS55500941A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1980-11-13
CA1147898A (en) 1983-06-07
ZA796373B (en) 1980-11-26
PT70554A (en) 1980-01-01
IL58751A0 (en) 1980-02-29
JPH0262561B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1990-12-26
EP0020680A1 (en) 1981-01-07
ES8101629A1 (es) 1980-12-16
IT7927843A0 (it) 1979-12-04
GR69729B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1982-07-09
AU5300179A (en) 1980-06-12
EP0020680A4 (en) 1981-01-28
NO793966L (no) 1980-06-10
ES486697A0 (es) 1980-12-16
US4267103A (en) 1981-05-12
BE880235A (fr) 1980-03-17

Similar Documents

Publication Publication Date Title
US4267103A (en) Solvent polymerization of carboxyl containing monomers
CA1283246C (en) Polycarboxylic acids with small amount of residual monomer
US4800220A (en) Crosslinked carboxylic copolymers usable as thickeners in aqueous media and preparation thereof
US4062817A (en) Water absorbent polymers comprising unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, and another acrylic ester containing alkyl group 2-8 carbon atoms
US3723375A (en) Novel anhydride interpolymers
KR970007242B1 (ko) 점도 부여 능력이 더 높고 투명성이 보다 더 우수한 폴리카르복실산
US3915921A (en) Unsaturated carboxylic acid-long chain alkyl ester copolymers and tri-polymers water thickening agents and emulsifiers
US4190562A (en) Improved water absorbent copolymers of copolymerizable carboxylic acids and acrylic or methacrylic esters
US2798053A (en) Carboxylic polymers
US5288814A (en) Easy to disperse polycarboxylic acid thickeners
US4526937A (en) Polycarbonates having plasticizers with fugitive activity
JPS61112062A (ja) ラジカル重合可能なｕｖ‐吸収化合物及びその製造法
US5297740A (en) Process for the production of polyacrylic acids
US4692502A (en) Polymerization process for carboxyl containing polymers utilizing oil soluble ionic surface active agents
US3880793A (en) Emulsifiers for emulsion polymerization of vinyl monomers
US3032538A (en) Cross-linked carboxylic polymers
US3426004A (en) Crosslinked acrylic acid interpolymers
US3288883A (en) Copolymers of alkyl alpha-hydroxymethyl acrylates and other unsaturated monomers
US4345949A (en) Cleaning reactors contaminated with carboxyl containing polymers
Bikales Preparation of acrylamide polymers
JPH06184211A (ja) アクリルモノマーの逆懸濁重合による粉末超吸収剤の製造に於ける改良
JPS588704A (ja) 水膨潤性組成物
EP0005363A1 (en) Process for the preparation of carboxyl-containing polymers in an anionic form in the dry state; interpolymers thus obtained
US2941969A (en) Copolymer of a quaternary ammonium compound and acrylonitrile, solution thereof, and fiber formed therefrom
CA2043384A1 (en) Bioadhesive carboxylic polymer composition and method relating thereto

Legal Events

Date Code Title Description
AK Designated states

Designated state(s): BR DK JP SU

AL Designated countries for regional patents

Designated state(s): AT CH DE FR GB LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1980900030

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1980900030

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1980900030

Country of ref document: EP