KR940703884A - 씨딩된 다공성 공중합체 및 이로부터 제조된 이온 교환 수지(Seeded porous copolymers and ion-exchange resins prepared therefrom) - Google Patents

씨딩된 다공성 공중합체 및 이로부터 제조된 이온 교환 수지(Seeded porous copolymers and ion-exchange resins prepared therefrom)

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KR940703884A
KR940703884A KR1019940702083A KR19940702083A KR940703884A KR 940703884 A KR940703884 A KR 940703884A KR 1019940702083 A KR1019940702083 A KR 1019940702083A KR 19940702083 A KR19940702083 A KR 19940702083A KR 940703884 A KR940703884 A KR 940703884A
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monomer
monovinylidene
seed particles
crosslinking
phase separation
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KR1019940702083A
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English (en)
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아이. 해리스 윌리암
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리챠드 지. 워터맨
더 다우 케미칼 캄파니
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

본 발명은 겔 공중합체 씨드 입자를 사용하는 씨딩 중합법으로 다공성 공중합체 비이드를 제조하는 방법에 관한 것이다. 이 방법은 먼저 하나 이상의 제1모노비닐리덴 단량체와 제1가교결합 단량체를 중합시킴으로써 제조된 다수의 겔형 공중합체 씨드 입자를 제공함을 포함한다. 이후에, 하나 이상의 제2모노비닐리덴 단량체, 제2가교결합 단량체 및 상 분리 희석제를 함유하는 제2단량체 혼합물에 씨드 입자를 흡수시키고 내부에서 중합시킨다. 이 방법은 상 분리 희석제와 제2모노비닐리덴 단량체가 다공성 공중합체를 형성하기에 충분한 양의 씨드 입자를 흡수할 수 있도록 제1모노비닐리덴 단량체를 선택함을 특징으로 한다. 생성된 다공성 공중합체 비이드는 안정한 중합체성 구조를 지니며 이온 교환 수지 및 중합체성 흡수제를 제조하는데 유용하도록 하는 양호한 물리적 특성을 지닌다.

Description

씨딩된 다공성 공중합체 및 이로부터 제조된 이온 교환 수지(Seeded porous copolymers and ion-exchange resins prepared therefrom)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제1도는 실시예2에서 제조된 다공성 공중합체 비이드의 현미경 사진, 제2도는 통상적인 거대다공성 공중합체 비이드의 현미경 사진, 제3도는 실시예3에서 제조한 약염기 음이온 교환수지에 있어서 가공 직경(Å)에 대한 기공 크기의 분포(%)를 도시한 그래프이다. 통상적인 약염기 음이온 수지에 대한 분포도 나타내었다.

Claims (16)

  1. (a) 하나 이상의 제1모노비닐리덴 단량체와 제1가교결합 단량체를 포함하는 제1단량체 혼합물을 중합시켜 제조한, 임의로 에틸렌계 불포화 단량체의 중합을 개시시킬 수 있는 유리 라디칼 공급원을 내부에 포함하는 다수의 겔형 공중합체 씨드 입자를 제공하고, (b) 씨드 입자를 상 분리 희석제, 하나 이상의 제2모노비닐리덴 단량체, 제2가교결합 단량체 및 유리 라디칼 개시제를 포함하는 제2단량체 혼합물[여기서, 유리 라디칼 개시제는, 씨드 입자가 유리 라디칼 공급원을 포함하는 경우에는 임의의 성분이고, 상 분리 희석제와 제2모노비닐리덴 단량체는 제2단량체 혼합물의 70중량% 이상이 씨드 입자에 의해 흡수되도록 하나 이상의 제1모노비닐리덴 단량체의 상응하는 용해도 파라메터 및 쌍극자 모멘트와 조화되는 용해도 파라메터와 쌍극자 모멘트를 갖는다]에 흡수시키며, (c) 흡수된 씨드 입자를, 제2단량체 혼합물을 목적하는 전환도로 중합시켜 다공성 공중합체 비이드를 수득하기에 충분한 시간 동안 현탁중합 조건하에서 유지시킴을 포함하는 다공성 공중합체 비이드의 제조 방법.
  2. 제1항에 있어서, 씨드 입자가 하나 이상의 제1모노비닐리덴 단량체와 제1가교결합 단량체를 함유하는 제1단량체 혼합물을 연속 현탁 매질내에서 동일계 현탁중합시킴으로써 제조되는 방법.
  3. 제2항에 있어서, 하나 이상의 제1모노비닐리덴 단량체와 제1가교결합 단량체의 전환율이 제1단량체 혼합물중의 단량체의 총 중량을 기준으로 하여 50 내지 90%인 방법.
  4. 제1항에 있어서, 단계(a)가 씨드 입자를 연속 현탁 매질내에서 현탁시킴을 포함하는 방법.
  5. 제1항 내지 제4항 중의 어느 한 항에 있어서, 제1모노비닐리덴 단량체가 t-부틸스티렌, 비닐톨루엔, 에틸비닐벤젠, 라우릴메타크릴레이트 또는 이소보르닐메타크릴레이트로부터 선택되는 방법.
  6. 제1항 내지 제5항 중의 어느 한 항에 있어서, 하나 이상의 제1가교결합 단량체가 디비닐벤젠, 트리비닐벤젠, 에틸렌 글리콜 디메타크릴레이트 또는 이들의 혼합물인 방법.
  7. 제1항 내지 제6항 중의 어느 한 항에 있어서, 씨드 입자가, 단량체의 총 중량을 기준으로 하여, 하나 이상의 제1모노비닐리덴 단량체 95 내지 99.99중량%와 제1가교결합 단량체 0.01 내지 5중량%를 포함하는 방법.
  8. 제1항 내지 제7항 중의 어느 한 항에 있어서, 하나 이상의 제2모노비닐리덴 단량체가 스티렌, 알킬 치환된 스티렌 또는 비닐벤질클로라이드부터 선택되고, 가교결합 단량체가 디비닐벤젠인 방법.
  9. 제1항 내지 제8항 중의 어느 한 항에 있어서, 제2단량체 혼합물이, 제2단량체 혼합물 중의 단량체의 총 중량을 기준으로 하여, 하나 이상의 제2모노비닐리덴 단량체 75 내지 97중량%와 제2가교결합 단량체 3내지 25중량%를 포함하는 방법.
  10. 제5항에 있어서, 상 분리 희석제가 헥산, 헵탄 또는 이소-옥탄으로부터 선택되는 방법.
  11. 제1항에 있어서, 상 분리 희석제와 하나 이상의 제2모노비닐리덴 단량체의 용해도 파라메터가 하나 이상의 제1모노비닐리덴 단량체의 용해도 파라메터의 ±10% 이내인 방법.
  12. 제1항에 있어서, 상 분리 희석제와 하나 이상의 제2모노비닐리덴 단량체의 쌍극자 모멘트가 하나 이상의 제1모노비닐리덴 단량체의 쌍극자 모멘트의 ±0.25 디바이(debye) 이내인 방법.
  13. 제10항에 있어서, 상 분리 희석제가, 제2단량체 혼합물의 총 중량을 기준으로 하여, 20 내지 50중량%의 양으로 존재하는 방법.
  14. 제1항 내지 제13항 중의 어느 한 항에 있어서, (d) 다공성 공중합체 비이드를 이온 교환 작용 그룹으로 작용화시켜 이온 교환 수지를 수득함을 추가로 포함하는 방법.
  15. 제1항 내지 제13항 중의 어느 한 항에 따르는 방법으로 제조한 다공성 공중합체 비이드.
  16. 제14항의 방법으로 제조한 이온 교환 수지.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019940702083A 1991-12-19 1992-11-25 씨딩된 다공성 공중합체 및 이로부터 제조된 이온 교환 수지(Seeded porous copolymers and ion-exchange resins prepared therefrom) KR940703884A (ko)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/810,948 US5231115A (en) 1991-12-19 1991-12-19 Seeded porous copolymers and ion-exchange resins prepared therefrom
US07/810,948 1991-12-19
PCT/US1992/010226 WO1993012167A1 (en) 1991-12-19 1992-11-25 Seeded porous copolymers and ion-exchange resins prepared therefrom

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KR940703884A true KR940703884A (ko) 1994-12-12

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Country Link
US (1) US5231115A (ko)
EP (1) EP0617714B1 (ko)
JP (1) JP3261533B2 (ko)
KR (1) KR940703884A (ko)
CN (1) CN1073458A (ko)
CA (1) CA2122028A1 (ko)
DE (1) DE69212162T2 (ko)
HU (1) HUT67857A (ko)
TW (1) TW241282B (ko)
WO (1) WO1993012167A1 (ko)

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WO1993012167A1 (en) 1993-06-24
EP0617714B1 (en) 1996-07-10
CN1073458A (zh) 1993-06-23
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US5231115A (en) 1993-07-27

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