KR20180104298A - 적어도 바이모달 분자량 분포를 갖는 양이온성 중합체를 수득하기 위한 방법 - Google Patents

적어도 바이모달 분자량 분포를 갖는 양이온성 중합체를 수득하기 위한 방법 Download PDF

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KR20180104298A
KR20180104298A KR1020187021430A KR20187021430A KR20180104298A KR 20180104298 A KR20180104298 A KR 20180104298A KR 1020187021430 A KR1020187021430 A KR 1020187021430A KR 20187021430 A KR20187021430 A KR 20187021430A KR 20180104298 A KR20180104298 A KR 20180104298A
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monomer
polymerization
sved
cationic polymer
polymer
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Korean (ko)
Inventor
라인홀트 제이 라일러
글레디슨 폰세카
아론 플로레스-피게로아
보로디미르 보이코
로버트 리차드 딕스트라
마크 로버트 시빅
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바스프 에스이
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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
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08F2/22—Emulsion polymerisation
    • 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
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (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
    • C08F222/00—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
    • C08F222/10—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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/08—N-Vinyl-pyrrolidine
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10—N-Vinyl-pyrrolidone
    • 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
    • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/12—N-Vinylcarbazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/05—Bimodal or multimodal molecular weight distribution
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently

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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)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
KR1020187021430A 2016-01-25 2017-01-16 적어도 바이모달 분자량 분포를 갖는 양이온성 중합체를 수득하기 위한 방법 Withdrawn KR20180104298A (ko)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP16152590 2016-01-25
EP16152590.2 2016-01-25
PCT/EP2017/050829 WO2017129434A1 (en) 2016-01-25 2017-01-16 A process for obtaining a cationic polymer with an at least bimodal molecular weight distribution

Publications (1)

Publication Number Publication Date
KR20180104298A true KR20180104298A (ko) 2018-09-20

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KR1020187021430A Withdrawn KR20180104298A (ko) 2016-01-25 2017-01-16 적어도 바이모달 분자량 분포를 갖는 양이온성 중합체를 수득하기 위한 방법

Country Status (12)

Country Link
US (1) US10920001B2 (https=)
EP (1) EP3408301B1 (https=)
JP (1) JP7068190B2 (https=)
KR (1) KR20180104298A (https=)
CN (1) CN108602902B (https=)
BR (1) BR112018014989B1 (https=)
CA (1) CA3009585A1 (https=)
ES (1) ES2794828T3 (https=)
MX (1) MX2018009117A (https=)
PL (1) PL3408301T3 (https=)
RU (1) RU2734916C9 (https=)
WO (1) WO2017129434A1 (https=)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108495868B (zh) 2016-01-25 2021-03-19 巴斯夫欧洲公司 具有至少双峰分子量分布的阳离子聚合物
FR3079833B1 (fr) 2018-04-10 2020-10-09 Rhodia Operations Composition aqueuse gelifiee pour l'extraction petroliere
FR3096985B1 (fr) * 2019-06-05 2021-05-14 S N F Sa Procede de preparation de polymeres structures sous forme de poudre par voie gel

Family Cites Families (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5578682A (en) * 1995-05-25 1996-11-26 Exxon Chemical Patents Inc. Bimodalization of polymer molecular weight distribution
ID22894A (id) * 1996-10-03 1999-12-16 Cytec Tech Corp Dispersi berair
US6258504B1 (en) * 1999-10-13 2001-07-10 Nashua Corporation Toner containing resin prepared by a combination of emulsion followed by suspension polymerization
DE10059824A1 (de) * 2000-12-01 2002-06-13 Clariant Gmbh Elektrolythaltige kosmetische, pharmazeutische und dermatologische Mittel
US6864223B2 (en) 2000-12-27 2005-03-08 Colgate-Palmolive Company Thickened fabric conditioners
US7452854B2 (en) 2002-06-04 2008-11-18 Ciba Specialty Chemicals Corporation Aqueous fabric softener formulations comprising copolymers of cationic acrylates and N-alkyl acrylamides
MXPA05001801A (es) * 2002-08-15 2005-04-19 Ciba Spec Chem Water Treat Ltd Polimeros cationicos de alto peso molecular obtenidos por reaccion de reticulacion posterior a la polimerizacion.
JP4673064B2 (ja) * 2002-11-29 2011-04-20 チバ ホールディング インコーポレーテッド ホモポリマー及び／又はコポリマーを含む水性組成物
FR2879607B1 (fr) 2004-12-16 2007-03-30 Seppic Sa Nouveaux latex inverse concentre, procede pour sa preparation, et utilisation dans l'industrie
ES2573538T3 (es) * 2004-12-28 2016-06-08 Kemira Oyj Dispersión de polímero y proceso de preparación de una dispersión de polímero
KR101322387B1 (ko) * 2005-01-27 2013-10-30 시바 홀딩 인코포레이티드 헤어 케어 제제에서 고분자량의 교차결합된 수용성양이온성 중합체의 용도
US7639737B2 (en) 2006-04-27 2009-12-29 Rambus Inc. Adaptive equalization using correlation of edge samples with data patterns
EP2373773B2 (en) 2009-01-06 2016-09-14 S.P.C.M. Sa Cationic polymer thickeners
US20110269663A1 (en) 2009-01-06 2011-11-03 Elizabeth Ann Clowes Fabric conditioners
WO2010118841A1 (en) * 2009-04-17 2010-10-21 Ashland Licensing And Intellectual Property Llc. Bimolecular inverse emulsion polymer
JP2012254430A (ja) * 2011-06-10 2012-12-27 Hymo Corp 凝集処理剤およびそれを用いた汚泥脱水方法
PH12014500893A1 (en) * 2011-11-11 2014-02-06 Basf Se Thickener containing at least one cationic polymer which can be obtained by inverse emulsion poylmerisation.
PH12014500895A1 (en) * 2011-11-11 2014-02-06 Basf Se Thickener containing at least one cationic polymer
RU2630309C2 (ru) * 2012-05-21 2017-09-07 Басф Се Обратная дисперсия, содержащая катионный полимер и стабилизирующий агент
JP2014233647A (ja) * 2013-05-31 2014-12-15 ハイモ株式会社 凝集処理剤及び汚泥の脱水方法
CN106133120B (zh) 2014-01-29 2019-12-13 巴斯夫欧洲公司 用于燃料和润滑油的腐蚀抑制剂
WO2015143644A1 (en) 2014-03-26 2015-10-01 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
WO2016127387A1 (en) 2015-02-13 2016-08-18 The Procter & Gamble Company Cleaning compositions containing alkyl sulfate surfactants and cationic polymer for holistic improvement of sudsing profile
WO2016074142A1 (en) 2014-11-11 2016-05-19 The Procter & Gamble Company Detergent or cleaning compositions with improved sudsing profile
WO2015143645A1 (en) 2014-03-26 2015-10-01 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
WO2015143997A1 (en) 2014-03-26 2015-10-01 The Procter & Gamble Company Cleaning compositions containing cationic polymers, and methods of making and using same
CN106536579A (zh) 2014-07-23 2017-03-22 巴斯夫欧洲公司 包含阳离子聚合物、稳定剂和三官能和/或更多官能交联剂的反相分散体
CA2952987A1 (en) 2014-07-23 2016-01-28 The Procter & Gamble Company Treatment compositions
WO2016014732A1 (en) 2014-07-23 2016-01-28 The Procter & Gamble Company Fabric and home care treatment compositions
CA2952982C (en) 2014-07-23 2020-04-28 The Procter & Gamble Company Fabric and home care treatment compositions
MX2017000978A (es) 2014-07-23 2017-04-27 Procter & Gamble Composiciones de tratamiento para el cuidado de las telas y el hogar.
WO2016014798A1 (en) 2014-07-23 2016-01-28 The Procter & Gamble Company Fabric and/or home care compositions
EP3172307A1 (en) 2014-07-23 2017-05-31 The Procter and Gamble Company Treatment compositions
US20160024432A1 (en) 2014-07-23 2016-01-28 The Procter & Gamble Company Treatment compositions
US9809782B2 (en) 2014-08-27 2017-11-07 The Procter & Gamble Company Detergent composition comprising a cationic polymer and anionic/nonionic surfactant mixture
JP6728132B2 (ja) 2014-08-27 2020-07-22 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ カチオン性ポリマーを含む洗剤組成物
WO2016032996A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of preparing a detergent composition
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
RU2560177C1 (ru) * 2014-10-16 2015-08-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Волгоградский государственный технический университет" (ВолгГТУ) Способ получения водорастворимых полимеров на основе четвертичных солей диметиламиноэтилметакрилата
WO2016079003A1 (en) 2014-11-18 2016-05-26 Basf Se Rheology modifier
US10689600B2 (en) 2016-01-25 2020-06-23 The Procter & Gamble Company Treatment compositions
CN108495868B (zh) 2016-01-25 2021-03-19 巴斯夫欧洲公司 具有至少双峰分子量分布的阳离子聚合物

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BR112018014989B1 (pt) 2022-06-28
RU2734916C9 (ru) 2021-04-26
EP3408301A1 (en) 2018-12-05
PL3408301T3 (pl) 2020-08-24
CA3009585A1 (en) 2017-08-03
JP2019505657A (ja) 2019-02-28
RU2018130687A (ru) 2020-02-27
US20190062478A1 (en) 2019-02-28
JP7068190B2 (ja) 2022-05-16
ES2794828T3 (es) 2020-11-19
CN108602902A (zh) 2018-09-28
US10920001B2 (en) 2021-02-16
RU2734916C2 (ru) 2020-10-26
CN108602902B (zh) 2021-06-04
WO2017129434A1 (en) 2017-08-03
EP3408301B1 (en) 2020-03-11
MX2018009117A (es) 2018-11-09
BR112018014989A2 (en) 2018-12-11
RU2018130687A3 (https=) 2020-03-25

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Patent event date: 20180724

Patent event code: PA01051R01D

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WITN Application deemed withdrawn, e.g. because no request for examination was filed or no examination fee was paid