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KR950703583A - Water-absorbent polymer having improved properties - Google Patents

Water-absorbent polymer having improved properties Download PDF

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KR950703583A
KR950703583A KR1019950701447A KR19950701447A KR950703583A KR 950703583 A KR950703583 A KR 950703583A KR 1019950701447 A KR1019950701447 A KR 1019950701447A KR 19950701447 A KR19950701447 A KR 19950701447A KR 950703583 A KR950703583 A KR 950703583A
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water
crosslinked polymer
crosslinker
absorbent
coated
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KR1019950701447A
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Korean (ko)
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티. 그레이함 앤드류
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스티븐 에스. 그레이스
더 다우 케미칼 캄파니
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Priority claimed from US07/960,675 external-priority patent/US5447727A/en
Priority claimed from US07/975,171 external-priority patent/US5385983A/en
Application filed by 스티븐 에스. 그레이스, 더 다우 케미칼 캄파니 filed Critical 스티븐 에스. 그레이스
Publication of KR950703583A publication Critical patent/KR950703583A/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04Macromolecular 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
    • C08F265/06Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/60Liquid-swellable gel-forming materials, e.g. super-absorbents

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

본 발명은 하나의 양태로 개선된 특성을 갖는 표면-가교 결합된 수-흡수성 중합체 및 이의 제조방법을 제공한다. 바람직한 1차 가교결합제를 표면 가교결합제와 함께 사용함으로써, 바람직한 흡수 특성이 얻어진다. 적합한 가교결합제에는 메틸렌비스아크릴 아미드, 비스(아크릴아미도)아세트산 및 이의염, 알릴 아크릴레이트, 알릴 메타크릴레이트 및 비닐 작용기와 알릴 작용기를 둘다 갖는 에스테르 또는 아미드가 포함된다. 또 다른 양태로, 본 발명은 표면 가교결합제를 계면활성제의 부재하에 하이드로겔에 가하여 수-흡수성 중합체를 제조하는 방법을 제공한다.The present invention provides, in one embodiment, surface-crosslinked water-absorbent polymers having improved properties and methods for their preparation. By using a preferred primary crosslinker together with the surface crosslinker, desirable absorption properties are obtained. Suitable crosslinkers include methylenebisacryl amide, bis (acrylamido) acetic acid and salts thereof, allyl acrylate, allyl methacrylate and esters or amides having both vinyl and allyl functional groups. In another aspect, the present invention provides a method of preparing a water-absorbent polymer by adding a surface crosslinker to a hydrogel in the absence of a surfactant.

Description

개선된 특성을 갖는 수-흡수성 중합체(Water-absorbent polymer having im-proved properties)Water-absorbent polymer having im-proved properties

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

Claims (26)

메틸렌비스아크릴아미드, 비스(아크릴아미도)아세트산 및 이의 염, 알릴 아크릴레이트, 알릴 메타크릴레이트 및 비닐 작용기와 알릴 작용기를 둘 다 갖는 에스테르 또는 아미드 또는 고도의 에톡시화된 트리메탈올프로판 트리아크릴레이트로 이루어진 그룹으로부터 선택된 1차 가교결합제로 가교결합되고, 표면 가교결합제로 추가로 가교결합된(이때. 중합체의 표면 근처에 존재하는 분자쇄가 가교결합된다), 부분적으로 중화된 α, β-에틸렌계 분포화 단량체의 가교결합된 중합체를 포함하는 수-흡수성 중합체 물질.Methylenebisacrylamide, bis (acrylamido) acetic acid and salts thereof, allyl acrylate, allyl methacrylate and esters or amides having both vinyl and allyl functional groups or highly ethoxylated trimetalolpropane triacrylates Cross-linked with a primary crosslinker selected from the group consisting of, and further crosslinked with a surface crosslinker, wherein the molecular chains present near the surface of the polymer are crosslinked, partially neutralized α, β-ethylene A water-absorbent polymer material comprising a crosslinked polymer of system distribution monomers. 제1항에 있어서, 표면 가교결합제가 폴리하이드록시 화합물인 수-흡수성 중합체 물질.The water-absorbent polymer material of claim 1, wherein the surface crosslinker is a polyhydroxy compound. 제2항에 있어서, 폴리하이드록시 화합물이 디에틸렌글리콘, 트리에틸렌 글리콜, 글리세롤, 프로필렌 글리콜, 트리메틸올프로판, 펜타에리트리톨, 소르비톨 및 폴리에틸렌 글리콜로 이루어진 그룹으로부터 선택된 수-흡수성 중합체물질.3. The water-absorbent polymer material of claim 2, wherein the polyhydroxy compound is selected from the group consisting of diethylene glycol, triethylene glycol, glycerol, propylene glycol, trimethylolpropane, pentaerythritol, sorbitol and polyethylene glycol. 제2항에 있어서, 폴리히이드록시 화합물이 글리세롤인 수-흡수성 중합체 물질The water-absorbent polymer material of claim 2, wherein the polyhydroxy compound is glycerol. 제1항에 있어서, 1차 가교결합제가 알릴메타크릴레이트인 수-흡수성 중합체 물질.The water-absorbent polymer material of claim 1, wherein the primary crosslinker is allyl methacrylate. 제1항에 있어서, 표면 가교결합제가 가교결합된 중합체의 중량을 기준으로 하여 0.00025 내지 2중량 %의 양으로 제공되는 수-흡수성 중합체 물질.The water-absorbent polymer material of claim 1, wherein the surface crosslinker is provided in an amount of 0.00025 to 2% by weight, based on the weight of the crosslinked polymer. (a) 메틸렌비스아크릴아미드, 비스(아크릴아미도)아세트산 및 이의 염, 알릴 아크릴레이트, 알릴 메타크릴레이트 및 비닐 작용기와 알릴 작용기를 둘 다 갖는 에스테르 또는 아미드로 이루어진 그룹으로부터 선택된 1차 가교결합제로 가교결합된, 부분적으로 중화된 α, β-에틸렌계 불포화 단량체의 가교결합된 중합체를 제조하는 단계, (b) 표면 가교결합제가 가교결합된 중합체의 내부로 실질적으로 침투되지 않으면서 가교결합된 중합체를 피복시키는 조건하에서, 가교결합된 중합체를 표면 가교결합제와 접촉시켜 피복된 가교결합된 중합체를 형성시키는 단계 및 (c) 표면 가교결합제가 가교결합된 중합체와 반응하여 피복된 가교결합된 중합체의 표면을 가교결합시키는 조건하에서, 피복된 가교결합된 중합체를 가열하는 단계를 포함하여, 수성 유체 흡수성 물질을 제조하는 방법.(a) with a primary crosslinker selected from the group consisting of methylenebisacrylamide, bis (acrylamido) acetic acid and salts thereof, allyl acrylate, allyl methacrylate and esters or amides having both vinyl and allyl functional groups Preparing a crosslinked polymer of crosslinked, partially neutralized α, β-ethylenically unsaturated monomers, (b) the crosslinked polymer without the surface crosslinker substantially penetrating into the crosslinked polymer Contacting the crosslinked polymer with a surface crosslinker to form a coated crosslinked polymer under conditions that coat the surface and (c) the surface crosslinker reacts with the crosslinked polymer to surface the coated crosslinked polymer. Heating the coated crosslinked polymer under conditions that crosslink the Process for producing a water absorbent material. 제7항에 있어서, 가교결합된 중합체가 (b)의 접족단계에서 가교결합된 중합체 20 내지 95%와 물 5 내지 80%를 포함하는 하이드로겔로서 존재하는 방법.8. The process of claim 7, wherein the crosslinked polymer is present as a hydrogel comprising from 20 to 95% of the crosslinked polymer and from 5 to 80% of water in the step of (b). 제7항에 있어서 (b)의 접촉단계 후에, 그러나, (c)의 가열단계 전에, 하이드로겔에 보유된 물이 적어도 부분적으로 제거되지만, 표면 가교결합제가 피복된 가교결합된 중합체와 반응하지 않도록 하는 조건하에서, 피복된 가교결합된 중합체를 건조시키는 단계(d)를 추가로 포함하는 방법.8. The method of claim 7, wherein after the contacting step of (b), but before the heating step of (c), the water retained in the hydrogel is at least partially removed, but the surface crosslinker does not react with the coated crosslinked polymer. Under conditions that further comprise drying (d) the coated crosslinked polymer. 제7항에 있어서, (b)의 접촉단계 전에, 가교결합된 중합체를 약 15% 미만의 함수율로 건조시킴(d)을 추가로 포함하는 방법.8. The method of claim 7, further comprising drying (d) the crosslinked polymer at a moisture content of less than about 15% prior to the contacting step of (b). 제9항 또는 제10항에 있어서, (d)의 건조단계 후에, 그러나 (c)의 가열단계 전에, 피복된 가교결합된 중합체의 입자 크기를 기계적 수단에 의해 감소시키는 단계(e)를 추가로 포함하는 방법.The process according to claim 9 or 10, further comprising the step (e) of reducing the particle size of the coated crosslinked polymer by mechanical means after the drying step of (d) but before the heating step of (c). How to include. 제7항에 있어서, 가교결합된 중합체가 (b)의 접촉 단계시에 함수율이 약 5중량% 미만인 분말로서 존재하는 방법.8. The method of claim 7, wherein the crosslinked polymer is present as a powder having a moisture content of less than about 5 weight percent at the contacting step of (b). (a) 카복실 잔기 함유 수-흡수성 수지 20 내지 95%와 물 5 내지 80%를 포함하는 하이드로겔을, 표면 가교결합제가 하이드로겔의 흡수성 수지 입자의 내부로 실질적으로 침투되지 않으면서 하이드로겔을 피복시키는 조건하에서, 계면 활성제의 부재하에서 표면 가교결합제를 포함하고 임의로 추가의 물 및/또는 수헌화성 극성 용매를 추가로 포함하는 조성물과 접촉시켜 피복된 하이드로겔을 형성시키는 단계, (b) 물과 임의의 추가의 물 및 임의의 용매(존재할 경우)가 실질적으로 제거되고 표면 가교결합제가 카복실 잔기와 실질적으로 반응하지 않는 조건하에서, 피벅된 하이드로겔을 건조시켜 건조된 피목된 수지를 형성시키는 단계, (c) 건조된 피복된 수지의 입자 크기를 기계적 수단에 의해 감소시켜 건조된 피복된 자를 형성시키는 단계 및 (d) 표면 가교결합제가 카복실 잔기와 반응하는 조건하에서, 건조된 피복된 임자를 가열하여 건조된 피복된 입자의 표면을 가교결합시키는 단계를 포함하여, 수성 유체 흡수성 물질을 제조하는 방법.(a) coating a hydrogel comprising 20 to 95% of a carboxyl residue-containing water-absorbent resin and 5 to 80% of water, with the surface crosslinking agent substantially infiltrating the interior of the hydrogel's absorbent resin particles; Under conditions to form a coated hydrogel, in the absence of a surfactant, in contact with a composition comprising a surface crosslinker and optionally further comprising additional water and / or a water-degradable polar solvent, (b) optionally Drying the picked hydrogel to form a dried, topical resin, under conditions in which additional water and any solvent (if present) of substantially is removed and the surface crosslinker does not substantially react with the carboxyl moiety, ( c) reducing the particle size of the dried coated resin by mechanical means to form dried coated pores and (d) surface crosslinking A method of making an aqueous fluid absorbent material, comprising crosslinking a surface of a dried coated particle under conditions in which the binder reacts with a carboxyl moiety. 제13항에 있어서, (b)의 건조단계에 의해 함수율이 약 10% 미만인 건조된 피복된 수지가 생성되는 방법.The process of claim 13 wherein the drying step of (b) produces a dried coated resin having a moisture content of less than about 10%. 제7항 또는 제13항에 있어서, 표면 가교결합제가, 표면 가교결합제를 포함하고 임의로 물, 유기용매 및 계면 활성제로 이루어진 그룹으로부터 선택된 하나 이상의 성분을 함유하는 조성물의 형태로 제공되는 방법.The method of claim 7 or 13, wherein the surface crosslinker is provided in the form of a composition comprising the surface crosslinker and optionally containing one or more components selected from the group consisting of water, organic solvents and surfactants. 제7항 또는 제13항에 있어서, 조성물이 폴리하이드록시 화합물 50 내지 100%와 물 0 내지 50% 를 포함하고, 조성물이 유기 용매를 함유하지 않는 방법.The method of claim 7 or 13, wherein the composition comprises 50-100% of the polyhydroxy compound and 0-50% of water and the composition does not contain an organic solvent. 제7항 또는 제13항에 있어서, 표면 가교결합제가 폴리하이드록시 화합물인 방법.The method of claim 7 or 13, wherein the surface crosslinker is a polyhydroxy compound. 제7항 또는 제13항에 있어서, 폴리하이드록시 화합물이 디에틸렌 글리콜, 트리에틸렌 글리콜, 글리세롤, 프로필렌 글리콜, 트리메틸올프로판, 펜타에리트리톨, 소르비톨 및 폴리에틸렌 글리콜로 이루어진 그룹으로부터 선택된 방법.The method according to claim 7 or 13, wherein the polyhydroxy compound is selected from the group consisting of diethylene glycol, triethylene glycol, glycerol, propylene glycol, trimethylolpropane, pentaerythritol, sorbitol and polyethylene glycol. 제7항 또는 제13항에 있어서, 폴리하이드록시 화합물이 글리세롤인 방법.The method of claim 7 or 13, wherein the polyhydroxy compound is glycerol. 제7항 또는 제13항에 있어서, 표면 가교결합제가 수-흡수성 수지의 중량을 기준으로 하여 약 200ppm 이상의 양으로 제공되는 방법.The method of claim 7 or 13, wherein the surface crosslinker is provided in an amount of at least about 200 ppm based on the weight of the water-absorbent resin. 제7항 또는 제13항에 있어서, 표면 가교결합제가 수-흡수성 수지의 중량을 기준으로 하여 약 500ppm 이상의 양으로 제공되는 방법.The method of claim 7 or 13, wherein the surface crosslinker is provided in an amount of at least about 500 ppm based on the weight of the water-absorbent resin. 제7항 또는 제13항에 있어서, 표면 가교결합제가 수-흡수성 수지의 중량을 기준으로 하여 약 1000ppm 이상의 양으로 제공되는 방법.The method of claim 7 or 13, wherein the surface crosslinker is provided in an amount of at least about 1000 ppm based on the weight of the water-absorbent resin. 제7항 또는 제13항에 있어서, 표면 가교결합제가 수-흡수성 수지의 중량을 기준으로 하여 약 3000ppm 이상의 양으로 제공되는 방법.The method of claim 7 or 13, wherein the surface crosslinker is provided in an amount of at least about 3000 ppm based on the weight of the water-absorbent resin. 제8항에 있어서, 가열단계가 175 내지 230℃의 온도에서 5 내지 75분 동안 수행되는 방법.The method of claim 8, wherein the heating step is performed at a temperature of 175 to 230 ° C. for 5 to 75 minutes. 제7항 또는 제13항의 방법에 따라 제조된 수성 유체 흡수성 물질.An aqueous fluid absorbent material prepared according to the method of claim 7 or 13. 흡수성 물질을 개인 보호용품에 혼입시킴을 포함하여, 제1항 또는 제22항의 수성 유체 흡수성 물질을 사용하는 방법.The method of using the aqueous fluid absorbent material of claim 1, including incorporating the absorbent material into a personal care product. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019950701447A 1992-10-14 1993-10-14 Water-absorbent polymer having improved properties KR950703583A (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US96067492A 1992-10-14 1992-10-14
US07/960675 1992-10-14
US07/960674 1992-10-14
US07/960,675 US5447727A (en) 1992-10-14 1992-10-14 Water-absorbent polymer having improved properties
US07/975171 1992-11-12
US07/975,171 US5385983A (en) 1992-11-12 1992-11-12 Process for preparing a water-absorbent polymer
PCT/US1993/009848 WO1994009043A1 (en) 1992-10-14 1993-10-14 Water-absorbent polymer having improved properties

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BR9307292A (en) 1999-06-01

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