JPH0117412B2 - - Google Patents
Info
- Publication number
- JPH0117412B2 JPH0117412B2 JP59085132A JP8513284A JPH0117412B2 JP H0117412 B2 JPH0117412 B2 JP H0117412B2 JP 59085132 A JP59085132 A JP 59085132A JP 8513284 A JP8513284 A JP 8513284A JP H0117412 B2 JPH0117412 B2 JP H0117412B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- crosslinked polymer
- crosslinked
- complex
- polymerization
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- 229920006037 cross link polymer Polymers 0.000 claims description 56
- 229920000642 polymer Polymers 0.000 claims description 23
- -1 polyoxyethylene chain Polymers 0.000 claims description 23
- 239000003463 adsorbent Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 20
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 125000006353 oxyethylene group Chemical group 0.000 description 11
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 9
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 9
- 229940098773 bovine serum albumin Drugs 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920006158 high molecular weight polymer Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 235000018102 proteins Nutrition 0.000 description 6
- 102000004169 proteins and genes Human genes 0.000 description 6
- 108090000623 proteins and genes Proteins 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 229940088598 enzyme Drugs 0.000 description 4
- 108010088751 Albumins Proteins 0.000 description 3
- 102000009027 Albumins Human genes 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 108010038061 Chymotrypsinogen Proteins 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 102000004407 Lactalbumin Human genes 0.000 description 2
- 108090000942 Lactalbumin Proteins 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000003743 erythrocyte Anatomy 0.000 description 2
- 210000003714 granulocyte Anatomy 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 210000004698 lymphocyte Anatomy 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 108060003951 Immunoglobulin Proteins 0.000 description 1
- 102000006992 Interferon-alpha Human genes 0.000 description 1
- 108010047761 Interferon-alpha Proteins 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 102000008192 Lactoglobulins Human genes 0.000 description 1
- 108010060630 Lactoglobulins Proteins 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 229960003121 arginine Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 1
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 108010063176 gamma-chymotrypsin Proteins 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 229960002885 histidine Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000951 immunodiffusion Effects 0.000 description 1
- 102000018358 immunoglobulin Human genes 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229960003646 lysine Drugs 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000004899 motility Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 235000021241 α-lactalbumin Nutrition 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Peptides Or Proteins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
(イ) 技術分野
本発明は新規な吸着剤、特に構成成分としてす
ぐれた高分子間錯体形成性能を有する成分を高分
子中に含有する架橋高分子重合体からなる吸着剤
に関する。
(ロ) 従来技術
高分子重合体が吸着剤として用いられ、特にイ
オン交換樹脂は特定のイオン性物質を吸、脱着す
ることにより、物質の分離、精製に利用されるこ
とはよく知られており、又、水素結合により形成
される高分子間錯体がPHにより可逆的に高分子間
錯体形成−解離を行い、これに伴つて大きく物性
が変化することもよく知られているが、この物性
変化を利用して、物質を分離することは未だ為さ
れていないのが現状である。
本発明者は、このたび高分子間錯体のこの物性
変化を物質分離に利用し得ることを見出し、又、
容易に被分離物質を吸脱着する担体を得るには、
高分子間錯体構造を架橋高分子重合体中へ導入す
ることが不可欠であるとの知見を得、そのような
高分子間錯体形成成分を含有する架橋高分子重合
体からなる吸着剤を得たものである。
これまで架橋高分子重合体中に高分子間錯体形
成成分を導入した重合体に関しては、ポリオキシ
エチレンをトリイソシアネートで架橋した後、ア
クリル酸と架橋剤を加えて重合するいわゆる相互
侵入網目構造(IPN)のものがある〔小高、
Polymer Journal、14、P985(′82)〕。
(ハ) 発明が解決しようとする問題点
しかしながらこのIPN構造ではポリオキシエチ
レン(POE)鎖両末端が固定されているため
POE鎖の運動性のダイナミツクな変化は少なく、
ここで生ずる高分子間錯体形成−解離現象は、分
離担体(吸着剤)の物理、化学的特性差として利
用できるほど十分なものではなかつた。
(ニ) 問題点を解決するための手段
本発明者は分離担体(吸着剤)としての利用を
目的として架橋高分子重合体中に高分子間錯体形
成成分の導入を鋭意研究の結果、(A)ポリオキシエ
チレン(POE)連鎖及び重合可能な二重結合を
分子内に同時に有する化合物、(B)重合可能な二重
結合を有するカルボン酸(誘導体)及び(C)架橋剤
とを重合することにより架橋高分子重合体中に高
分子間錯体形成成分を導入することが可能となる
こと、また得られた架橋高分子重合体はPOE鎖
がグラフトした型の新規な化学構造を有し、従来
にないすぐれた吸着剤であることを見出し、本発
明に到達したものである。
すなわち本発明は(1)一般式()、
(式中、Rは各々同一でも異なつてもよく、Hま
たは有機基を表わし、l、m、pは1以上の整数
である。)
で表わされる高分子間錯体形成成分を含有する架
橋高分子重合体からなる吸着剤、及び(2)A.ポリ
オキシエチレン連鎖及び重合可能な二重結合を分
子内に同時に有する化合物、B.重合可能な二重
結合を有するカルボン酸もしくはその誘導体、C.
架橋剤とを反応させることを特徴とする、一般式
()、
(式中、Rは各々同一でも異なつてもよく、Hま
たは有機基を表わし、l、m、pは1以上の整数
である。)
で表わされる高分子間錯体形成成分を含有する架
橋高分子重合体からなる吸着剤の製造法に関する
ものである。
(ホ) 発明の作用
本発明における重合反応は、A.ポリオキシエ
チレン連鎖及び重合可能な二重結合を分子内に同
時に有する化合物と、B.重合可能な二重結合を
有するカルボン酸(誘導体)とが重合しながら、
POE鎖と高分子間錯体を形成するマトリツクス
重合で進行し、POE鎖に対応する、二重結合を
含有するカルボン酸(誘導体)由来のブロツクを
生成し、これらが架橋剤にて架橋されるものであ
り、例えば次のような構造を含む架橋高分子重合
体が得られるのである。
(l、m、n、pは1以上の整数である。)
このように本発明で得られる架橋高分子重合体
においては、POE鎖の一方の末端のみが固定さ
れ、他方の末端はフリーとなつたグラフト型であ
り、このグラフト型のPOE鎖と(B)の二重結合含
有カルボン酸(誘導体)に基因するカルボキシル
基とが高分子間錯体形成成分を構成すると共に、
上記グラフト型のPOE鎖は両末端を固定されて
いるものと比べ、PH変化による高分子間錯体の形
成解離に伴うPOE鎖の運動性が顕著であり、こ
れが物質の吸着、分離に有効なものとなるのであ
る。
(ヘ) 発明の構成要素の具体的開示
本発明において高分子間錯体形成構造を架橋高
分子重合体中へ導入するのに用いる化合物に関し
ては、ポリオキシエチレン連鎖及び重合可能な二
重結合を分子内に有する化合物(A)とそのポリオキ
シエチレン単位と重合後に高分子間錯体を作る化
合物(B)であり、そのような化合物であれば理論的
にはいずれの化合物も用いることが可能である
が、(A)としては
メトキシポリオキシエチレン(メタ)アクリレ
ート
メトキシポリオキシエチレンビニルエーテル
CH3O(−CH2CH2O)−oCH=CH2
n=1〜45
ポリオキシエチレン(メタ)アクリレート
(日油;ブレンマーPE90、PE200、PE350)等
が挙げられ、(B)としてはアクリル酸、メタクリル
酸等のカルボン酸の他、ポリイタコン酸モノメチ
ルエステル、無水マレイン酸、イタコン酸モノメ
チルエステルのようなカルボン酸誘導体が挙げら
れる。
特に、オキシエチレン単位(p)が100以下で
あるメトキシポリオキシエチレンメタクリレート
(アクリレート)及びポリオキシエチレン単位と
重合後高分子間錯体を形成するメタクリル酸ある
いはアクリル酸が好ましく用いられる。
(A)と(B)の添加割合は、オキシエチレン単位とメ
タクリル酸あるいはアクリル酸等の該オキシエチ
レン単位と重合後に高分子間錯体形成性能を有す
る重合可能な二重結合を有するカルボン酸(誘導
体)のモル比で0.1〜10、好ましくは1である。
上記(A)、(B)の種類により、本発明吸着剤が含有
する下記一般式の高分子間錯体形成成分
におけるR、R′はH、メチル、エチル等のアル
キル基やアリール基等の有機基を表わし、R′は
この他、
(a) Technical Field The present invention relates to a novel adsorbent, and particularly to an adsorbent comprising a crosslinked polymer containing a component having excellent interpolymer complex-forming performance as a constituent component. (b) Prior art It is well known that high molecular weight polymers are used as adsorbents, and in particular, ion exchange resins are used to separate and purify substances by adsorbing and desorbing specific ionic substances. It is also well known that inter-polymer complexes formed by hydrogen bonds undergo reversible inter-polymer complex formation and dissociation due to PH, and as a result, physical properties change significantly. At present, it has not yet been possible to separate substances using the method. The present inventors have recently discovered that this change in physical properties of interpolymer complexes can be utilized for substance separation, and
To obtain a carrier that easily adsorbs and desorbs the substance to be separated,
We found that it is essential to introduce an inter-polymer complex structure into a cross-linked polymer, and obtained an adsorbent made of a cross-linked polymer containing such an inter-polymer complex-forming component. It is something. Up until now, polymers in which interpolymer complex-forming components have been introduced into crosslinked polymers have so-called interpenetrating network structures in which polyoxyethylene is crosslinked with triisocyanate and then polymerized by adding acrylic acid and a crosslinking agent. IPN) [Odaka,
Polymer Journal, 14 , P985 (′82)]. (c) Problems to be solved by the invention However, in this IPN structure, both ends of the polyoxyethylene (POE) chain are fixed.
There are few dynamic changes in POE chain motility;
The inter-polymer complex formation-dissociation phenomenon that occurs here is not sufficient to be utilized as a difference in the physical and chemical properties of separation carriers (adsorbents). (d) Means for Solving the Problems As a result of intensive research into the introduction of inter-polymer complex-forming components into crosslinked polymers for the purpose of use as separation carriers (adsorbents), the present inventors found (A ) Polymerizing a compound that simultaneously has a polyoxyethylene (POE) chain and a polymerizable double bond in the molecule, (B) a carboxylic acid (derivative) having a polymerizable double bond, and (C) a crosslinking agent. It is possible to introduce an inter-polymer complex-forming component into a cross-linked polymer, and the resulting cross-linked polymer has a new chemical structure in which POE chains are grafted. The inventors have discovered that this is an excellent adsorbent, and have arrived at the present invention. That is, the present invention provides (1) general formula (), (In the formula, each R may be the same or different and represents H or an organic group, and l, m, and p are integers of 1 or more.) A crosslinked polymer containing an interpolymer complex-forming component represented by Adsorbents made of polymers, and (2) A. Compounds that simultaneously have a polyoxyethylene chain and a polymerizable double bond in the molecule, B. Carboxylic acids or derivatives thereof that have polymerizable double bonds, C.
General formula (), characterized by reacting with a crosslinking agent, (In the formula, each R may be the same or different and represents H or an organic group, and l, m, and p are integers of 1 or more.) A crosslinked polymer containing an interpolymer complex-forming component represented by This invention relates to a method for producing an adsorbent made of a polymer. (e) Effect of the invention The polymerization reaction in the present invention involves the use of A. a compound having a polyoxyethylene chain and a polymerizable double bond in the molecule at the same time, and B. a carboxylic acid (derivative) having a polymerizable double bond. While polymerizing,
Proceeds through matrix polymerization that forms an intermolecular complex with the POE chain, producing blocks derived from carboxylic acid (derivatives) containing double bonds that correspond to the POE chain, and these are crosslinked with a crosslinking agent. For example, a crosslinked polymer having the following structure can be obtained. (l, m, n, and p are integers of 1 or more.) In this way, in the crosslinked polymer obtained by the present invention, only one end of the POE chain is fixed, and the other end is free. The POE chain of this graft type and the carboxyl group based on the double bond-containing carboxylic acid (derivative) of (B) constitute an inter-polymer complex-forming component,
Compared to the graft type POE chain mentioned above, which has both ends fixed, the POE chain has remarkable mobility due to the formation and dissociation of an inter-polymer complex due to pH change, and this is effective for adsorption and separation of substances. It becomes. (f) Specific disclosure of constituent elements of the invention Regarding the compound used in the present invention to introduce an inter-polymer complex-forming structure into a crosslinked polymer, polyoxyethylene chains and polymerizable double bonds are It is a compound (B) that forms an inter-polymer complex after polymerization with the compound (A) contained within and its polyoxyethylene unit, and theoretically any such compound can be used. However, (A) is methoxypolyoxyethylene (meth)acrylate Methoxypolyoxyethylene vinyl ether CH 3 O (-CH 2 CH 2 O) - o CH=CH 2 n=1-45 Polyoxyethylene (meth)acrylate (NOF; Blenmar PE90, PE200, PE350), etc. (B) includes carboxylic acids such as acrylic acid and methacrylic acid, as well as carboxylic acids such as polyitaconic acid monomethyl ester, maleic anhydride, and itaconic acid monomethyl ester. Examples include acid derivatives. In particular, methoxypolyoxyethylene methacrylate (acrylate) having an oxyethylene unit (p) of 100 or less, and methacrylic acid or acrylic acid that forms an interpolymer complex with the polyoxyethylene unit after polymerization are preferably used. The ratio of addition of (A) and (B) is determined by the addition ratio of oxyethylene units and carboxylic acids (derivatives) having polymerizable double bonds that have the ability to form inter-polymer complexes after polymerization with the oxyethylene units such as methacrylic acid or acrylic acid. ) is 0.1 to 10, preferably 1. Depending on the types of (A) and (B) above, the interpolymer complex-forming component of the following general formula contained in the adsorbent of the present invention R and R' in the formula represent H, an alkyl group such as methyl or ethyl, or an organic group such as an aryl group;
【式】あるいは他方の[expression] or the other
【式】と結合して酸無水物残基を表わすこ
ともある。
架橋剤(C)に関しては分子内にラジカル重合可能
な二重結合を2個以上有する次のような化合物を
使用することができる。すなわちエチレングリコ
ールジメタクリレート、ポリエチレングリコール
ジメタクリレート、ジビニルベンゼン、トリアリ
ルイソシアネート等であり、添加量は対モノマー
比で0.1〜50%、好ましくは0.5〜30%である。
ラジカル重合開始剤としては、アゾイソブチロ
ニトリル、t−ブチルヒドロペルオキシド、クメ
ンヒドロペルオキシド、過酸化ベンゾイル、過酸
化アセチル、過酸化−ジ−tブチル、アゾジシク
ロヘキシルカルボニトリル、アゾジイソ酪酸ジメ
チル、コハク酸過酸化物、ジクメン過酸化物等
の、この種重合反応に通常使用されるものを用い
ることができ、これらの添加量は0.1〜10重量%
である。
本発明の架橋高分子重合体は溶液重合、塊状重
合、懸濁重合等のいずれの重合方法によつても製
造でき、重合反応は好ましくは窒素等の不活性気
体の雰囲気下にて40〜100℃、好ましくは60〜80
℃に加熱し、重合時間3〜20時間で行なう。
懸濁重合反応における希釈剤は特に限定されな
いが、例えば次のようなものを単独または混合物
として使用することができる。すなわちベンゼ
ン、トルエン、キシレン等の芳香族炭化水素、n
−オクタン等の脂肪族炭化水素、シクロヘキサノ
ール、ラウリルアルコール等のアルコール類等で
あり、添加量はモノマー混合物に対して10〜100
%である。又、モノマー混合物、重合開始剤、希
釈剤混合物を適当な保護コロイド、塩を含有する
分散媒で通常の懸濁重合を行なうことができる。
すなわち高分子間錯体構造を架橋高分子重合体中
へ導入可能なモノマー混合物、架橋剤及びラジカ
ル重合開始剤に適当な希釈剤、例えば水等を加
え、モノマー類、希釈剤と混和しないシクロヘキ
サノール、流動パラフイン等を分散媒として適当
な保護コロイドあるいは界面活性剤の存在下重合
を行うこともできる。
以上述べたような方法にて得られた架橋高分子
重合体はロ過することにより反応液から分離さ
れ、純水、メタノール、アセトン等の溶媒にて洗
浄の後アルカリ、酸水溶液、純水にて繰り返し洗
浄し40〜80℃で減圧乾燥する。
本発明の架橋高分子重合体を用いての物質の吸
着、分離は通常行なわれているバツチ法、カラム
法等を適用でき、必要に応じてそれらを適宜選択
して有利に行なうことができる。
(ト) 発明の効果
本発明の高分子間錯体形成成分を含有する架橋
高分子重合体は金属イオン類、塩基性アミノ酸、
抗生物質、タンパク質、酵素等、広範囲にわたる
物質の吸着、分離ができ、特にタンパク質、酵素
に対してすぐれた吸着能を有し、PHを調整するこ
とにより容易に吸、脱着が可能なので、操作が簡
単であり、又設備も縮減でき、工業的にも有用な
吸着剤である。
(チ) 発明の利用分野
本発明で得られる架橋高分子重合体は具体的に
はポリオキシエチレンとポリメタクリル酸、ポリ
アクリル酸等よりなる高分子間錯体形成成分を含
有する架橋高分子重合体であり、POE鎖がグラ
フトした型で、POE鎖の一端が遊離であるため
高分子間錯体形成−解離に伴うPOE鎖の運動性
が顕著で物質の吸着、分離に有効であり、吸着担
体として、また固定化酵素担体等への応用可能な
実用性の高い化合物である。
更に応用範囲を説明すると本架橋高分子重合体
は本来的に弱酸性陽イオン交換樹脂であり、一般
の弱酸性陽イオン交換樹脂が関係する被分離物質
たとえばカルシウムイオン(Ca++)、マグネシウ
ムイオン(Mg++)等の金属イオン類、またアル
ギニン、ヒスチヂン、リジン、オルニチン等の塩
基性アミノ酸、またストレプトマイシン、ペニシ
リン、クロラムフエニコール、クロロテトラサイ
クリン等の抗生物質、メチレンブルー等の塩基性
色素等の吸着、分離に関していずれも適用するこ
とが可能である。また本架橋高分子重合体は生体
成分と温和な相互作用のみを示す合成高分子であ
るポリオキシエチレン鎖を含有し、この運動性の
PHによる変化を介して吸脱着特性を発現するもの
であり、γ−グロブリン、血清アルブミン、α−
ラクトアルブミン、β−ラクトグロブリン、キモ
トリプシノーゲン、γ−キモトリプシン、ヒト白
血球インターフエロン等のタンパク質、酵素、ま
た赤血球、顆粒球、リンパ球等の生体関連物質を
分離あるいは吸着するのに用いて好適である。
(リ) 発明の具体的実施例
以下の実施例にてこの発明を具体的に説明する
が、勿論本発明はこれら実施例のみに限定される
ものではない。
実施例 1
撹拌装置、冷却管の付いた100ml三ツ口フラス
コに、下記原料におけるアクリル酸とオキシエチ
レン単位がモル比1になるように仕込む。すなわ
ちアクリル酸10.44g、エチレングリコールジメ
タクリレート3.02g、メトキシポリオキシエチレ
ンメタクリレート(オキシエチレン単位は90)
6.54g、アゾイソブチロニトリル0.30g、トルエ
ン30gを入れ、窒素雰囲気下、重合温度60℃で3
時間重合を行つた。
得られた白色塊状架橋重合体はロ別し、純水、
メタノール、アセトンで洗浄後、アルカリ、酸水
溶液、純水にて洗浄し、減圧80℃で乾燥後、乳鉢
で粉砕し白色粉末17.88gを得た。
この架橋高分子重合体の赤外線吸収スペクトル
は1100cm-1、1710cm-1、3450cm-1付近に吸収帯を
有し、アクリル酸由来のカルボキシル基及びメト
キシポリオキシエチレンメタクリレート由来のエ
ーテル結合の存在が確認された。
元素分析によるこの架橋高分子重合体の百分率
組成は次のようであつた。
C;52.77 H;6.85
また、架橋度はエチレングリコールジメタクリ
レート9.42モル%であつた。
重合反応はアクリル酸が重合しながらポリオキ
シエチレン鎖と高分子間錯体を形成するマトリツ
クス重合で進行する為、ポリオキシエチレン鎖に
対応するアクリル酸ブロツクが生成し、これらが
架橋剤であるエチレングリコールジメタクリレー
トにより架橋されたものであり、以上の分析結果
からこの架橋高分子重合体は次に示す構造を含有
し、
各ブロツクの比率l:m:n=14500:161:
1520である。
なお、この架橋高分子重合体は通常の有機溶媒
に不溶であつた。
実施例 2
撹拌装置、冷却管の付いた500mlの分解フラス
コに下記原料におけるメタクリル酸とオキシエチ
レン単位がモル比1になるように仕込む。すなわ
ちメタクリル酸21.25g、エチレングリコールジ
メタクリレート5.15g、メトキシポリオキシエチ
レンメタクリレート(オキシエチレン単位は9)
13.60g、アゾイソブチロニトリル0.60g、トル
エン5.00gを混合溶解したもの及び1%ポリビニ
ルアルコールを含む1.3g/ml塩化カルシウム水
溶液200mlを入れ、窒素雰囲気下、重合温度70℃、
撹拌速度300rpmで8時間、懸濁重合を行つた。
得られた多孔質白色架橋重合体はロ別し、純
水、メタノール、アセトンで洗浄後、アルカリ、
酸水溶液、純水にて洗浄し減圧80℃で乾燥した。
直径約100μの白色球状粉末36.24gを得た。
この架橋高分子重合体の赤外線吸収スペクトル
は1100cm-1、1720cm-1、3450cm-1付近に吸収帯を
有し、メタクリル酸由来のカルボキシル基及びメ
トキシポリオキシエチレンメタクリレート由来の
エーテル結合の存在が確認され、元素分析による
この架橋高分子重合体の百分率組成は次のようで
あつた。
C;55.67 H;7.48
また次のように 13CNMRスペクトルを測定し
た。所定PH条件で重水を磁場ロツク試剤として所
定量加え、この架橋高分子重合体を浸漬させ室温
で 13CNMRスペクトルを測定した。3000〜
30000回積算することにより架橋高分子重合体中
のオキシエチレン連鎖に由来するエーテル炭素の
シグナルがテトラメチルシランを基準として
70ppm付近に観測された(このことは架橋高分子
重合体中へメトキシポリオキシエチレンメタクリ
レート由来のエーテル炭素が導入されていること
を証明するものである)。
このエーテル炭素のシグナルの半値巾とPHとの
関係を第1表に示した。It may also be combined with [Formula] to represent an acid anhydride residue. As for the crosslinking agent (C), the following compounds having two or more radically polymerizable double bonds in the molecule can be used. Namely, they are ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, divinylbenzene, triallyl isocyanate, etc., and the amount added is 0.1 to 50%, preferably 0.5 to 30%, based on the monomer ratio. Examples of radical polymerization initiators include azoisobutyronitrile, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, azodicyclohexylcarbonitrile, dimethyl azodiisobutyrate, and succinic acid. Peroxides, dicumene peroxides, etc. commonly used in this type of polymerization reaction can be used, and the amount added is 0.1 to 10% by weight.
It is. The crosslinked polymer of the present invention can be produced by any polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, etc., and the polymerization reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen. ℃, preferably 60-80
The polymerization time is 3 to 20 hours. The diluent used in the suspension polymerization reaction is not particularly limited, but for example, the following can be used alone or as a mixture. i.e. aromatic hydrocarbons such as benzene, toluene, xylene, etc.
- Aliphatic hydrocarbons such as octane, alcohols such as cyclohexanol, lauryl alcohol, etc., and the amount added is 10 to 100% based on the monomer mixture.
%. Ordinary suspension polymerization of the monomer mixture, polymerization initiator, and diluent mixture can be carried out in a dispersion medium containing an appropriate protective colloid and salt.
That is, a suitable diluent such as water is added to a monomer mixture capable of introducing an inter-polymer complex structure into a crosslinked polymer, a crosslinking agent and a radical polymerization initiator, and cyclohexanol, which is immiscible with the monomers and diluent, is prepared. Polymerization can also be carried out in the presence of a suitable protective colloid or surfactant using liquid paraffin or the like as a dispersion medium. The crosslinked polymer obtained by the method described above is separated from the reaction solution by filtration, washed with a solvent such as pure water, methanol, or acetone, and then washed with an alkali, acid aqueous solution, or pure water. Wash repeatedly and dry under reduced pressure at 40-80°C. Adsorption and separation of substances using the crosslinked high molecular weight polymer of the present invention can be carried out by commonly used batch methods, column methods, etc., and they can be suitably selected as necessary to carry out the adsorption and separation. (g) Effects of the invention The crosslinked polymer containing the inter-polymer complex-forming component of the present invention can contain metal ions, basic amino acids,
It can adsorb and separate a wide range of substances such as antibiotics, proteins, enzymes, etc. It has particularly excellent adsorption ability for proteins and enzymes, and can be easily adsorbed and desorbed by adjusting the pH, making it easy to operate. It is simple, requires less equipment, and is an industrially useful adsorbent. (H) Field of Application of the Invention The crosslinked polymer obtained by the present invention is specifically a crosslinked polymer containing an interpolymer complex-forming component consisting of polyoxyethylene, polymethacrylic acid, polyacrylic acid, etc. It is a grafted type of POE chain, and since one end of the POE chain is free, the mobility of the POE chain due to the formation of a complex between polymers and dissociation is remarkable, making it effective for adsorption and separation of substances, making it useful as an adsorption carrier. It is also a highly practical compound that can be applied to immobilized enzyme carriers, etc. To further explain the range of application, this crosslinked polymer is inherently a weakly acidic cation exchange resin, and can be used to separate substances that are related to general weakly acidic cation exchange resins, such as calcium ions (Ca ++ ), magnesium ions, etc. (Mg ++ ), basic amino acids such as arginine, histidine, lysine, ornithine, antibiotics such as streptomycin, penicillin, chloramphenicol, and chlorotetracycline, and basic dyes such as methylene blue. It is possible to apply both adsorption and separation. In addition, this cross-linked polymer contains polyoxyethylene chains, which are synthetic polymers that only have mild interactions with biological components, and this
It exhibits adsorption and desorption properties through changes due to pH, and it exhibits adsorption and desorption properties through changes due to pH.
Suitable for use in separating or adsorbing proteins such as lactalbumin, β-lactoglobulin, chymotrypsinogen, γ-chymotrypsin, and human leukocyte interferon, enzymes, and biological substances such as red blood cells, granulocytes, and lymphocytes. . (li) Specific Examples of the Invention The present invention will be specifically explained in the following Examples, but the present invention is of course not limited to these Examples. Example 1 A 100 ml three-necked flask equipped with a stirring device and a cooling tube was charged with the following raw materials so that the molar ratio of acrylic acid and oxyethylene units was 1. That is, 10.44 g of acrylic acid, 3.02 g of ethylene glycol dimethacrylate, and methoxypolyoxyethylene methacrylate (oxyethylene units are 90).
Add 6.54g, azoisobutyronitrile 0.30g, and toluene 30g, and polymerize at 60℃ under nitrogen atmosphere.
Time polymerization was carried out. The obtained white bulk cross-linked polymer was filtered, purified water,
After washing with methanol and acetone, washing with alkali, acid aqueous solution and pure water, drying under reduced pressure at 80°C, and grinding in a mortar to obtain 17.88 g of white powder. The infrared absorption spectrum of this crosslinked polymer has absorption bands around 1100 cm -1 , 1710 cm -1 , and 3450 cm -1 , confirming the presence of carboxyl groups derived from acrylic acid and ether bonds derived from methoxypolyoxyethylene methacrylate. It was done. The percentage composition of this crosslinked high molecular weight polymer according to elemental analysis was as follows. C: 52.77 H: 6.85 The degree of crosslinking was 9.42 mol% of ethylene glycol dimethacrylate. The polymerization reaction proceeds as a matrix polymerization in which acrylic acid forms an intermolecular complex with polyoxyethylene chains while polymerizing, so acrylic acid blocks corresponding to polyoxyethylene chains are generated, and these blocks form ethylene glycol, which is a crosslinking agent. It is crosslinked with dimethacrylate, and from the above analysis results, this crosslinked polymer contains the following structure, Ratio of each block l:m:n=14500:161:
It is 1520. Note that this crosslinked high molecular weight polymer was insoluble in ordinary organic solvents. Example 2 A 500 ml decomposition flask equipped with a stirring device and a cooling tube was charged with the following raw materials so that the molar ratio of methacrylic acid and oxyethylene units was 1. Namely 21.25g of methacrylic acid, 5.15g of ethylene glycol dimethacrylate, methoxypolyoxyethylene methacrylate (oxyethylene unit is 9)
13.60 g of azoisobutyronitrile, 0.60 g of azoisobutyronitrile, 5.00 g of toluene mixed and dissolved, and 200 ml of a 1.3 g/ml aqueous calcium chloride solution containing 1% polyvinyl alcohol were added, under a nitrogen atmosphere, at a polymerization temperature of 70°C.
Suspension polymerization was carried out for 8 hours at a stirring speed of 300 rpm. The obtained porous white crosslinked polymer was filtered, washed with pure water, methanol, and acetone, and then treated with alkali,
It was washed with an acid aqueous solution and pure water, and dried under reduced pressure at 80°C.
36.24 g of white spherical powder with a diameter of about 100 μm was obtained. The infrared absorption spectrum of this crosslinked polymer has absorption bands around 1100 cm -1 , 1720 cm -1 , and 3450 cm -1 , confirming the presence of carboxyl groups derived from methacrylic acid and ether bonds derived from methoxypolyoxyethylene methacrylate. The percentage composition of this crosslinked polymer was determined by elemental analysis to be as follows. C; 55.67 H; 7.48 13 CNMR spectrum was also measured as follows. A predetermined amount of heavy water was added as a magnetic field locking agent under predetermined PH conditions, and the crosslinked polymer was immersed in it to measure the 13 CNMR spectrum at room temperature. 3000~
By integrating 30,000 times, the signal of the ether carbon derived from the oxyethylene chain in the crosslinked polymer is determined based on tetramethylsilane.
It was observed at around 70 ppm (this proves that ether carbon derived from methoxypolyoxyethylene methacrylate was introduced into the crosslinked polymer). Table 1 shows the relationship between the half-width of the ether carbon signal and the pH.
【表】
そして架橋度はエチレングリコールジメタクリ
レート8.65モル%であつた。この架橋高分子重合
体も実施例1で述べたと同じ理由で、ポリオキシ
エチレン鎖に対応するメタクリル酸ブロツクが生
成し、これらが架橋剤であるエチレングリコール
ジメタクリレートにより架橋されたものであり、
以上述べた分析結果を総合すると、この架橋高分
子重合体は次に示す構造を含有し、
各ブロツクの比率l:m:n=2470:274:260
である。
なお、この架橋高分子重合体は通常の有機溶媒
に不溶であつた。
また第1表に示したようにPHを変えることによ
り架橋高分子重合体の特性すなわち本架橋高分子
重合体ではポリオキシエチレン鎖の運動性が大き
く変化することが判る。
次にこの架橋高分子重合体を用いて牛血清アル
ブミン(BSA)の吸着能を測定した。すなわち
1gの架橋高分子重合体と所定PHの50mg/dl
BSA溶液20mlを室温下平衝吸着量に達した後、
上澄のBSA量をミクロビユレツト法により求め
た。この結果を第2表に示す。[Table] The degree of crosslinking was 8.65 mol% of ethylene glycol dimethacrylate. This crosslinked polymer also produced methacrylic acid blocks corresponding to polyoxyethylene chains for the same reason as described in Example 1, and these were crosslinked with ethylene glycol dimethacrylate as a crosslinking agent.
Combining the above analysis results, this crosslinked polymer contains the following structure, Ratio of each block l:m:n=2470:274:260
It is. Note that this crosslinked high molecular weight polymer was insoluble in ordinary organic solvents. Furthermore, as shown in Table 1, it can be seen that by changing the pH, the characteristics of the crosslinked polymer, that is, the mobility of the polyoxyethylene chains in the present crosslinked polymer, change greatly. Next, the adsorption capacity of bovine serum albumin (BSA) was measured using this crosslinked polymer. That is, 1g of crosslinked polymer and 50mg/dl of the specified pH
After reaching the equilibrium adsorption amount of 20ml of BSA solution at room temperature,
The amount of BSA in the supernatant was determined by the microbiuret method. The results are shown in Table 2.
【表】
第2表に示したようにPHを変えることにより架
橋高分子重合体の吸着特性が大きく変化すること
が判る。
PH4.9でこの架橋高分子重合体が重大の吸着能
を示した理由としては、架橋高分子重合体中でカ
ルボキシル基が解離せず、しかもポリオキシエチ
レン鎖と安定な高分子間錯体を形成し、しかも
BSA分子の等電点付近である為、BSA分子は電
荷を有しておらずコンパクトな分子形状をしてい
る為、主として疎水性相互作用により安定に架橋
高分子重合体が吸着した為であると考えられる。
いずれにせよ第2表より明らかなとおり、本発明
の架橋高分子重合体はPHを変えることにより
BSAを容易に吸、脱着することができ、吸着剤
としてすぐれたものである。
したがつて本架橋高分子重合体を用いることに
より、PHの調節のみで容易に目的物質を吸着分離
でき、工業的にも非常に有用な高分子吸着剤であ
ることが判る。
実施例 3
撹拌装置、冷却管の付いた500mlの分解フラス
コに下記原料におけるメタクリル酸とオキシエチ
レン単位がモル比1になるように仕込む。すなわ
ちメタクリル酸22.65g、エチレングリコールジ
メタクリレート5.49g、メトキシポリオキシエチ
レンメタクリレート(オキシエチレン単位は90)
11.87g、75%過酸化ベンゾイル1.20g、トルエ
ン4.00gを混合溶解したもの及び1%ポリビニル
アルコールを含む1.3g/ml塩化カルシウム水溶
液200mlを入れ、窒素雰囲気下、重合温度70℃、
撹拌速度300rpmで8時間、懸濁重合を行つた。
得られた多孔質白色架橋重合体はロ別し、純
水、メタノール、アセトンで洗浄後、アルカリ、
酸水溶液、純水にて洗浄し減圧80℃で乾燥した。
直径約100μの白色球状粉末34.08gを得た。
この架橋高分子重合体の赤外線吸収スペクトル
は1100cm-1、1710cm-1、3450cm-1付近に吸収帯を
有し、メタクリル酸由来のカルボキシル基及びメ
トキシポリオキシエチレンメタクリレート由来の
エーテル結合の存在が確認された。元素分析によ
るこの架橋高分子重合体の百分率組成は次のよう
であつた。
C;55.79 H;7.52
また実施例2と同様に 13CNMRスペクトルを
測定した。この架橋高分子重合体もオキシエチレ
ン連鎖に由来するエーテル炭素のシグナルがテト
ラメチルシランを基準として70ppmあたりに観測
された。これにより、架橋高分子重合体中へメト
キシポリオキシエチレンメタクリレート由来のエ
ーテル炭素が導入されていることが判る。
次に、このエーテル炭素のシグナルの半値巾と
PHとの関係を第3表に示す。[Table] As shown in Table 2, it can be seen that the adsorption characteristics of crosslinked polymers change greatly by changing the pH. The reason why this cross-linked polymer showed significant adsorption ability at pH 4.9 is that the carboxyl group does not dissociate in the cross-linked polymer, and moreover, it forms a stable inter-polymer complex with the polyoxyethylene chain. And moreover
This is because the cross-linked polymer was stably adsorbed mainly due to hydrophobic interaction because the BSA molecule has no charge and has a compact molecular shape because it is near the isoelectric point of the BSA molecule. it is conceivable that.
In any case, as is clear from Table 2, the crosslinked polymer of the present invention can be
It can easily adsorb and desorb BSA, making it an excellent adsorbent. Therefore, by using this crosslinked polymer, the target substance can be easily adsorbed and separated by simply adjusting the pH, and it is found that it is a very useful polymer adsorbent from an industrial perspective. Example 3 A 500 ml decomposition flask equipped with a stirring device and a cooling tube was charged with the following raw materials so that the molar ratio of methacrylic acid and oxyethylene units was 1. Namely 22.65g of methacrylic acid, 5.49g of ethylene glycol dimethacrylate, methoxypolyoxyethylene methacrylate (oxyethylene unit is 90)
Add 200 ml of a 1.3 g/ml calcium chloride aqueous solution containing 11.87 g, 75% benzoyl peroxide, 1.20 g, and toluene 4.00 g, and 1% polyvinyl alcohol, under a nitrogen atmosphere, at a polymerization temperature of 70°C.
Suspension polymerization was carried out for 8 hours at a stirring speed of 300 rpm. The obtained porous white crosslinked polymer was filtered, washed with pure water, methanol, and acetone, and then treated with an alkali,
It was washed with an acid aqueous solution and pure water, and dried under reduced pressure at 80°C.
34.08 g of white spherical powder with a diameter of about 100 μm was obtained. The infrared absorption spectrum of this crosslinked polymer has absorption bands around 1100 cm -1 , 1710 cm -1 , and 3450 cm -1 , confirming the presence of carboxyl groups derived from methacrylic acid and ether bonds derived from methoxypolyoxyethylene methacrylate. It was done. The percentage composition of this crosslinked high molecular weight polymer according to elemental analysis was as follows. C: 55.79 H: 7.52 In addition, the 13 CNMR spectrum was measured in the same manner as in Example 2. In this crosslinked polymer, a signal of ether carbon derived from oxyethylene chains was observed at around 70 ppm based on tetramethylsilane. This shows that ether carbon derived from methoxypolyoxyethylene methacrylate has been introduced into the crosslinked polymer. Next, the half-width of this ether carbon signal and
The relationship with PH is shown in Table 3.
【表】
また架橋度はエチレングリコールジメタクリレ
ート9.43モル%であつた。この架橋高分子重合体
も実施例1で述べたと同じ理由で、ポリオキシエ
チレン鎖に対応するメタクリル酸ブロツクが生成
し、これらが架橋剤であるエチレングリコールジ
メタクリレートにより架橋されたものであり、以
上述べた分析結果を総合すると、この架橋高分子
重合体は次に示す構造を含有し、
各ブロツクの比率l:m:n=26300:292:
2770である。
なお、この架橋高分子重合体は通常の有機溶媒
に不溶であつた。
また第3表に示したようにPHを変えることによ
り架橋高分子重合体の特性すなわち本架橋高分子
重合体ではポリオキシエチレン鎖の運動性が大き
く変化することが判る。またこの変化の割合は実
施例2に示した変化より大きい。このことはPH変
化により、より大きな吸着特性差を発現させるこ
とができることを示すものであり、物質の分離吸
着に効果があることを示している。
次にこの架橋高分子重合体を用いて実施例2と
同様にBSAの吸着能を測定した。この結果を第
4表に示す。[Table] The degree of crosslinking was 9.43 mol% of ethylene glycol dimethacrylate. This crosslinked polymer also produces methacrylic acid blocks corresponding to polyoxyethylene chains for the same reason as described in Example 1, and these are crosslinked with the crosslinking agent ethylene glycol dimethacrylate. Combining the above analysis results, this crosslinked polymer contains the following structure, Ratio of each block l:m:n=26300:292:
It is 2770. Note that this crosslinked high molecular weight polymer was insoluble in ordinary organic solvents. Furthermore, as shown in Table 3, it can be seen that by changing the pH, the properties of the crosslinked polymer, that is, the mobility of the polyoxyethylene chains in this crosslinked polymer, change greatly. Moreover, this rate of change is larger than the change shown in Example 2. This shows that a larger difference in adsorption characteristics can be expressed by changing the pH, and shows that it is effective in separating and adsorbing substances. Next, the BSA adsorption capacity was measured in the same manner as in Example 2 using this crosslinked polymer. The results are shown in Table 4.
【表】
第4表に示したようにPHを変えることにより架
橋高分子重合体の吸着特性が大きく変化すること
が判る。また吸着挙動は実施例2で述べた理由と
同様に理解される。
第4表より明らかなとおり、本発明の架橋高分
子重合体はPHを変えることにより被分離物質を容
易に吸、脱着することができ、したがつて、本架
橋高分子重合体を用いることにより、PHの調節の
みで容易に目的物質を吸着分離でき、有用な高分
子吸着剤であることが判る。
BSAのほかに、α−ラクトアルブミン、キモ
トリプシノーゲン等のタンパク質、酵素、又、赤
血球、顆粒球、リンパ球等においても本架橋高分
子重合体により同様の分離吸着を行なうことがで
きた。
実施例 4
実施例1と同じ架橋高分子重合体50mgを生理食
塩水であらかじめ浸漬し十分に膨潤させた後、過
剰の生理食塩水を除去した。これにヒト血漿2ml
を加え、37℃で2時間ふりまぜ吸着させた後の上
澄みを取り出し、残留タンパク量を定量すること
により吸着率を求めた。
アルブミン、IgG(ノムノグロブリンG)、IgM
(イムノグロブリンM)はRID法(免疫拡散法)
により定量を行ない、免疫複合体はPEG(ポリエ
チレングリコール)沈殿法−RID法によつて定量
した。結果を第5表に示す。[Table] As shown in Table 4, it can be seen that the adsorption characteristics of crosslinked polymers change greatly by changing the pH. Further, the adsorption behavior can be understood for the same reason as described in Example 2. As is clear from Table 4, the crosslinked polymer of the present invention can easily adsorb and desorb the substance to be separated by changing the pH. It can be seen that the target substance can be easily adsorbed and separated simply by adjusting the pH, making it a useful polymeric adsorbent. In addition to BSA, similar separation and adsorption of proteins such as α-lactalbumin and chymotrypsinogen, enzymes, red blood cells, granulocytes, lymphocytes, etc., could be carried out using this crosslinked polymer. Example 4 50 mg of the same crosslinked polymer as in Example 1 was soaked in physiological saline in advance to sufficiently swell it, and then excess physiological saline was removed. Add this to 2ml of human plasma.
was added and stirred at 37°C for 2 hours to allow adsorption, then the supernatant was taken out and the adsorption rate was determined by quantifying the amount of residual protein. Albumin, IgG (nomnoglobulin G), IgM
(Immunoglobulin M) is RID method (immunodiffusion method)
The immune complex was quantified by the PEG (polyethylene glycol) precipitation method-RID method. The results are shown in Table 5.
【表】
アルブミンの外、IgG、IgM及びI.C.等の蛋白
質が本発明の吸着剤により有効に吸着されること
が分る。なお、本実施例ではPH約7.0であつた。
アルブミンの吸着量が少ないのは、このPHの影響
と考えられる。[Table] It can be seen that in addition to albumin, proteins such as IgG, IgM, and IC are effectively adsorbed by the adsorbent of the present invention. In this example, the pH was approximately 7.0.
The reason why the amount of albumin adsorbed is small is thought to be due to the influence of this pH.
Claims (1)
たは有機基を表わし、l、m、pは1以上の整数
である。) で表わされる高分子間錯体形成成分を含有する架
橋高分子重合体からなる吸着剤。 2 A ポリオキシエチレン連鎖及び重合可能な
二重結合を分子内に同時に有する化合物、 B 重合可能な二重結合を有するカルボン酸もし
くはその誘導体、 C 架橋剤 とを反応させることを特徴とする、 一般式()、 (式中、Rは各々同一でも異なつてもよく、Hま
たは有機基を表わし、l、m、pは1以上の整数
である。) で表わされる高分子間錯体形成成分を含有する架
橋高分子重合体からなる吸着剤の製造法。[Claims] 1 General formula (), (In the formula, each R may be the same or different and represents H or an organic group, and l, m, and p are integers of 1 or more.) A crosslinked polymer containing an interpolymer complex-forming component represented by Adsorbent made of polymer. 2 A: A compound having a polyoxyethylene chain and a polymerizable double bond at the same time in the molecule; B: A carboxylic acid or its derivative having a polymerizable double bond; C: A general compound characterized by reacting with a crosslinking agent. formula(), (In the formula, each R may be the same or different and represents H or an organic group, and l, m, and p are integers of 1 or more.) A crosslinked polymer containing an interpolymer complex-forming component represented by A method for producing an adsorbent made of a polymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59085132A JPS60232243A (en) | 1984-04-28 | 1984-04-28 | Adsorbent comprising crosslinked high-molecular polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59085132A JPS60232243A (en) | 1984-04-28 | 1984-04-28 | Adsorbent comprising crosslinked high-molecular polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60232243A JPS60232243A (en) | 1985-11-18 |
JPH0117412B2 true JPH0117412B2 (en) | 1989-03-30 |
Family
ID=13850121
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59085132A Granted JPS60232243A (en) | 1984-04-28 | 1984-04-28 | Adsorbent comprising crosslinked high-molecular polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60232243A (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6147713A (en) * | 1984-08-14 | 1986-03-08 | Hidetoshi Tsuchida | Polymeric compound and ionic conductive material |
DE3500180A1 (en) * | 1985-01-04 | 1986-07-10 | Ernst Prof. Dr. 7400 Tübingen Bayer | Graft copolymers from crosslinked polymers and polyoxyethylene, process for their preparation and their use |
DE68923444D1 (en) * | 1988-09-22 | 1995-08-17 | Univ Utah | SUPER SURFACE-ACTIVE POLYMER AGENT FOR GIVING RESISTANCE TO PROTEINS AND ELIMINATING PROTEINS. |
JPH03238704A (en) * | 1990-02-16 | 1991-10-24 | Toyo Ink Mfg Co Ltd | High polymer solid electrolyte |
JP4612272B2 (en) * | 2002-12-27 | 2011-01-12 | 日本曹達株式会社 | Composition for polymer solid electrolyte |
JP5372397B2 (en) * | 2008-03-31 | 2013-12-18 | エムアールシーポリサッカライド株式会社 | Method for producing hyaluronic acid and salts thereof |
JP5565377B2 (en) * | 2011-05-31 | 2014-08-06 | コニカミノルタ株式会社 | Water treatment agent |
CN104028245B (en) * | 2014-05-12 | 2015-12-09 | 张家俊 | A kind of have modified nano-titanium dioxide of better adsorption effect and preparation method thereof |
JP2020529484A (en) * | 2017-07-31 | 2020-10-08 | ダウ グローバル テクノロジーズ エルエルシー | Detergent additive |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS585193A (en) * | 1981-06-28 | 1983-01-12 | Yoshihito Osada | Preparation of immobilized enzyme entrapping with complex between high polymers |
JPS5874552A (en) * | 1981-10-30 | 1983-05-06 | 株式会社日本触媒 | Cement dispersant |
JPS60147419A (en) * | 1984-01-09 | 1985-08-03 | Yoshiaki Motozato | Amphipathic gel |
-
1984
- 1984-04-28 JP JP59085132A patent/JPS60232243A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS585193A (en) * | 1981-06-28 | 1983-01-12 | Yoshihito Osada | Preparation of immobilized enzyme entrapping with complex between high polymers |
JPS5874552A (en) * | 1981-10-30 | 1983-05-06 | 株式会社日本触媒 | Cement dispersant |
JPS60147419A (en) * | 1984-01-09 | 1985-08-03 | Yoshiaki Motozato | Amphipathic gel |
Also Published As
Publication number | Publication date |
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JPS60232243A (en) | 1985-11-18 |
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