JPS6317905A - Production of crosslinked porous polyvinyl alcohol particle - Google Patents
Production of crosslinked porous polyvinyl alcohol particleInfo
- Publication number
- JPS6317905A JPS6317905A JP61161727A JP16172786A JPS6317905A JP S6317905 A JPS6317905 A JP S6317905A JP 61161727 A JP61161727 A JP 61161727A JP 16172786 A JP16172786 A JP 16172786A JP S6317905 A JPS6317905 A JP S6317905A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- water
- crosslinking
- crosslinking agent
- particles
- 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.)
- Pending
Links
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 46
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 43
- 239000002245 particle Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 16
- -1 dialdehyde compound Chemical class 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims 1
- 150000008282 halocarbons Chemical group 0.000 claims 1
- 229920002307 Dextran Polymers 0.000 abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 9
- 239000000945 filler Substances 0.000 abstract description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005227 gel permeation chromatography Methods 0.000 abstract description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229940015043 glyoxal Drugs 0.000 abstract description 2
- 238000013019 agitation Methods 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical class N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000001641 gel filtration chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 102000007562 Serum Albumin Human genes 0.000 description 1
- 108010071390 Serum Albumin Proteins 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NJIWVMGUAFXONX-UHFFFAOYSA-J [C+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [C+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NJIWVMGUAFXONX-UHFFFAOYSA-J 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、架橋剤とポリビニルアルコールとを反応させ
て多孔質架橋ポリビニルアルコール粒子を製造する方法
に関するものであシ、詳しくは、クロマトグラフィー、
特に水系ゲルパーミエイション（水系ＧＰｏ）クロマト
グラフィー用の充填剤として好適な多孔質架橋ポリビニ
ルアルコール粒子の製造方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing porous crosslinked polyvinyl alcohol particles by reacting a crosslinking agent and polyvinyl alcohol.
In particular, the present invention relates to a method for producing porous crosslinked polyvinyl alcohol particles suitable as a filler for aqueous gel permeation (aqueous GPo) chromatography.
ポリビニルアルコールと架橋剤とを反応させて水不溶性
の架橋ポリビニルアルコールヲ裂造することは知られて
いる。しかし、このようＫして得られる架橋ポリビニル
アルコールはゲル状である。多孔質な架橋ポリビニルア
ルコールの製造方法としては、酢酸ビニルとジエチレン
グリコールジメタクリレートの如く架橋剤とを生
共重合させ、≠放物をケン化したのち再びエピクロルヒ
ドリンで架橋する方法（特開昭ｊ２−ｉ、ｙｇｏり７号
公報）、酢酸ビニルとトリアジン環構造を有する架橋剤
よシなる共重合体をケン化する方法（％開昭３３−３１
２０３号公報〕等が知られている。しかし、いずれの方
法も酢酸ビニルを出発原料として用い、重合後ケン化反
応を行なわなければならないので、製造方法は複雑であ
シ、再現性よく一定の品質をもつ多孔質架橋ポリビニル
アルコールゲルな得ることは困難であった。It is known to react polyvinyl alcohol with a crosslinking agent to produce water-insoluble crosslinked polyvinyl alcohol. However, the crosslinked polyvinyl alcohol obtained by K in this manner is in the form of a gel. Porous crosslinked polyvinyl alcohol can be produced by biocopolymerizing vinyl acetate and a crosslinking agent such as diethylene glycol dimethacrylate, saponifying the parabolite, and then crosslinking it again with epichlorohydrin (Japanese Unexamined Patent Application Publication No. 2002-120011). , ygori No. 7), a method for saponifying a copolymer of vinyl acetate and a crosslinking agent having a triazine ring structure (%
No. 203] and the like are known. However, since both methods use vinyl acetate as a starting material and require a saponification reaction after polymerization, the production method is complicated, and it is difficult to obtain a porous cross-linked polyvinyl alcohol gel with good reproducibility and constant quality. That was difficult.
本発明の目的は、特に水系ゲルパーミエイション（水系
ＧＰＯ）クロマトグラフィー用の充填剤として好適な機
械的強度の優れた多孔質架橋ポリビニルアルコール粒子
の工業的に有利な製造方法を提供することにある。An object of the present invention is to provide an industrially advantageous method for producing porous crosslinked polyvinyl alcohol particles with excellent mechanical strength, which are particularly suitable as fillers for aqueous gel permeation (aqueous GPO) chromatography. be.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
本発明は、水溶性高分子化合物からなる多孔質化剤、架
橋剤及びポリビニルアルコールの混合水溶液を有機溶剤
中にて分散造球させたのち、昇温して架橋反応を行うこ
とを特徴とする多孔質架橋ポリビニルアルコール粒子の
製造方法に関する。The present invention is characterized in that a mixed aqueous solution of a porosity-forming agent made of a water-soluble polymer compound, a crosslinking agent, and polyvinyl alcohol is dispersed to form balls in an organic solvent, and then the temperature is raised to perform a crosslinking reaction. The present invention relates to a method for producing porous crosslinked polyvinyl alcohol particles.
ポリビニルアルコールとしては、重合度数十〜数千、好
ましくはコ００〜．２ｏｏｏで、ケン化度３０モルチ以
上、好ましくは７０モル係以上のものが用いられる。ポ
リビニルアルコールは２〜３０係、好ましくは５〜ｉｓ
％となるように水に溶解して架橋剤と反応させる。The polyvinyl alcohol has a degree of polymerization of several tens to several thousand, preferably 0.00 to .000. 200, and the degree of saponification is 30 molar or more, preferably 70 molar or higher. Polyvinyl alcohol has a molecular weight of 2 to 30, preferably 5 to 30
% in water and reacted with a crosslinking agent.
架橋剤としては、グリオキザール、グルタルアルデヒド
、テレフタルアルデヒド等のジアルデヒド化合物；１．
−ｚ＋３ｔダージエボキシプタン等のジェポキシ化合物
；エチレングリコールジグリシジルエーテル、／、Ｑ−
ブタンジオールジグリシジルエーテル等のグリシジルエ
ーテル化合物；エピクロルヒドリン、エビブロモヒドリ
ン等のエピハロヒドリン化合物などポリビニルアルコー
ル間に、２個以上の炭素原子を有する架橋部分を形成し
得るものが用いられる。好適にはアセタール化架橋が形
成するジアルデヒド化合物が用いられる。架橋剤は、ポ
リとニルアルコニルの全水酸基に対し通常弘モル係以上
用いる。As the crosslinking agent, dialdehyde compounds such as glyoxal, glutaraldehyde, terephthalaldehyde; 1.
-z+3t Jepoxy compounds such as di-epoxyptane; ethylene glycol diglycidyl ether, /, Q-
Glycidyl ether compounds such as butanediol diglycidyl ether; epihalohydrin compounds such as epichlorohydrin and shrimp bromohydrin, which can form a crosslinking moiety having two or more carbon atoms between polyvinyl alcohols, are used. Dialdehyde compounds that form acetalization crosslinks are preferably used. The crosslinking agent is usually used in an amount of 10 molar or more based on the total hydroxyl groups of poly and nylalconyl.
本発明においては、ポリビニルアルコールと架橋剤との
反応は、水溶性高分子化合物が共存溶解している水中で
行なわれる。水溶性高分子化合物としては通常、ポリビ
ニルアルコールと相溶性の良好なデキストラン、澱粉、
ポリエチレングリコール、ポリビニルピロリドン、カル
ボキシメチルセルロース、ヒドロキシエチルセルロース
、メチルセルロース、ホ＋）＜Ｊ３１）７クリル酸ソー
ダ、ポリスチレンスルホン酸ソーダ、アルキル・フェノ
ール・ポリオキシエチレン・エーテル等の乳化剤、血清
アルブミン等の水溶性蛋白質等が用いられるが、好適に
はデキストラン、ポリエチレングリコールか用いられる
。In the present invention, the reaction between polyvinyl alcohol and the crosslinking agent is carried out in water in which a water-soluble polymer compound is co-dissolved. Water-soluble polymer compounds usually include dextran, starch, and
Polyethylene glycol, polyvinylpyrrolidone, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, Ho+)<J31) Sodium 7acrylate, sodium polystyrene sulfonate, emulsifiers such as alkyl phenol polyoxyethylene ether, water-soluble proteins such as serum albumin etc., but dextran and polyethylene glycol are preferably used.
その使用濃度〔ポリビニルアルコール水溶液中の重量チ
〕は水溶性高分子化合物の種類、分子量により異なる。The concentration used (weight in polyvinyl alcohol aqueous solution) varies depending on the type and molecular weight of the water-soluble polymer compound.
水溶性高分子化合物の分子量が小さいほど使用濃度を高
くできるが、通常は／チ以上が好ましく、ポリビニルア
ルコールカー 番 −
析出しない範囲内の濃度で添加される。The lower the molecular weight of the water-soluble polymer compound, the higher the concentration can be used, but usually it is preferably 100% or more, and it is added at a concentration within the range that does not precipitate polyvinyl alcohol.
デキストランの添加量に関しては、ポバールの重合度、
ケン化度及び濃度によシ異なるが、たとえば、分子量１
０００θ位のデキストランを用いる場合は、ｌ〜１０係
（好ましくはλ〜７チ）、分子量７００００位のものを
用いる場合は、／−ｊ％（好ましくはコ〜ダ％）の量で
添加される。Regarding the amount of dextran added, the degree of polymerization of Poval,
Although it varies depending on the saponification degree and concentration, for example, molecular weight 1
When using dextran with a molecular weight of 000θ, it is added in an amount of l to 10 (preferably λ to 7), and when using a dextran with a molecular weight of 70,000, it is added in an amount of /-j% (preferably coda%). .
ポリエチレングリコールの添加量に関しても前述のデキ
ストランの場合と同様一義的に決めるのは難しいが、た
とえば、分子量２００００位のポリエチレングリコール
な用いる場合は、コ〜ｉｓチ（好ましくは５〜１０憾）
、分子量４００位のものを用いる場合は、１０，１７０
％（好ましくは７５〜３０チ）の量で添加される。Although it is difficult to determine the amount of polyethylene glycol to be added, as in the case of dextran, for example, when using polyethylene glycol with a molecular weight of about 20,000, it is necessary to
, when using one with a molecular weight of 400, 10,170
% (preferably 75 to 30 inches).
これらの水溶性高分子化合物は、単独で用いても、又、
ポリビニルアルコールが析出しない範囲であれば一種以
上混合して用いても差支えない。These water-soluble polymer compounds can be used alone or
As long as polyvinyl alcohol does not precipitate, one or more types may be used in combination.
水溶性高分子化合物が多孔質化剤になる理由は明らかで
はないが、おそらくポリビニルアルコールが架橋反応に
伴い、分子量が増加したときに、これらの水溶性高分子
化合物がポリビニルアルコールの不均一層を生じさせ、
多孔質化するものと考えられる。The reason why water-soluble polymer compounds become porosity-forming agents is not clear, but perhaps when polyvinyl alcohol increases in molecular weight due to cross-linking reaction, these water-soluble polymer compounds form a non-uniform layer of polyvinyl alcohol. cause
It is thought that it becomes porous.
ここで言う多孔質とは、架橋剤によシ形成される網目構
造にもとすくものでなく、上記したようなポリビニルア
ルコールの不均一構造にもとすくものである。添加する
水溶性高分子化合物の種類、量を選択調節することによ
シ、容易ニ所望の多孔化度の架橋ポリビニルアルコール
粒子を得ることができる。架橋反応は、ポリビニルアル
コール水溶液に水溶性高分子化合物を溶解し、更にこれ
に架橋剤を添加したものを、有機溶剤中忙て分散造球さ
せた後行なう。分散造球は、０〜３０℃の温度でｌｊ分
〜６０分間攪拌して行なうのが好ましいが、温度を高く
しすぎると良好な球状粒子が得られる前に架橋反応が進
行するので好ましくない。The term "porous" as used herein refers not only to the network structure formed by the crosslinking agent, but also to the heterogeneous structure of polyvinyl alcohol as described above. By selectively controlling the type and amount of the water-soluble polymer compound to be added, crosslinked polyvinyl alcohol particles having a desired degree of porosity can be easily obtained. The crosslinking reaction is carried out after a water-soluble polymer compound is dissolved in an aqueous polyvinyl alcohol solution, a crosslinking agent is added thereto, and the mixture is dispersed to form balls in an organic solvent. Dispersion spherule formation is preferably carried out by stirring at a temperature of 0 to 30° C. for 1j to 60 minutes, but if the temperature is too high, the crosslinking reaction will proceed before good spherical particles are obtained, which is not preferable.
有機溶剤としては、通常、トルエン、ベンゼン、クロル
ベンゼン、ジクロルベンゼン等の芳香族炭化水素および
そのハロゲン誘導体、ｎ−へブタン、ｎ−ヘキサン、流
動パラフィン、シクロヘキサン、ジクロルメタン、ジク
ロルエタン等の脂肪族炭化水素、脂環式炭化水素および
そのハロゲン誘導体などが用いられる。これらの有機溶
剤は通常は単独で用いられるが、２樵以上を混合して用
いても差支えない。Organic solvents are usually aromatic hydrocarbons such as toluene, benzene, chlorobenzene, and dichlorobenzene, and their halogen derivatives, and aliphatic carbons such as n-hebutane, n-hexane, liquid paraffin, cyclohexane, dichloromethane, and dichloroethane. Hydrogen, alicyclic hydrocarbons and their halogen derivatives are used. These organic solvents are usually used alone, but two or more organic solvents may be used in combination.
分散造球の面からは、ポリビニルアルコール水溶液層よ
勺も比重の重いものが好ましく、又架橋反応時加温する
替金か参−ので沸点はＳＯ℃以上のものが好ましい。こ
のような観点からジクロルエタンが特に好適に用いられ
る。From the viewpoint of dispersion and ball formation, it is preferable that the polyvinyl alcohol aqueous solution layer and the layer have a high specific gravity, and since they are used as a substitute for heating during the crosslinking reaction, it is preferable that the boiling point is at least SO DEG C. From this point of view, dichloroethane is particularly preferably used.
有機溶剤の使用量はポリビニルアルコール水溶液の２（
容量）倍以上、好ましくは３〜６（容量）倍である。ま
た有機溶媒中には分散安定剤トシて、エチルセルロース
、セルロースアセテートブチレート、エチルヒドロキシ
エチルセルロース等の油溶性セルロース、アラビアゴム
、ソルビタンセスキオレエート、ソルビタンモノオレエ
ート、ソルビタンモノステアレート等の油溶性分散安定
剤を添加するのが好ましい。その量は有機溶剤に対して
通常Ｏ，Ｏｊ〜７０％、好ましくは０．／−ｊ％である
。The amount of organic solvent used is 2 (2) of the polyvinyl alcohol aqueous solution.
(capacity) times or more, preferably 3 to 6 (capacity) times. In addition, dispersion stabilizers are used in the organic solvent to disperse oil-soluble celluloses such as ethyl cellulose, cellulose acetate butyrate, and ethyl hydroxyethyl cellulose, as well as oil-soluble dispersions of gum arabic, sorbitan sesquioleate, sorbitan monooleate, and sorbitan monostearate. Preference is given to adding stabilizers. The amount is usually O.Oj to 70%, preferably 0.0% to the organic solvent. /-j%.
架橋反応は、分散造球操作温して、０℃ないしｉｏｏ℃
、好ましくは３０℃ないしざ０℃で１時間ないし２０時
間、好ましくは２時間ないし３時間行なう。架橋反応の
際、架橋剤に応じて触媒として塩酸、硫酸等の酸、又は
、水酸化ナトリウム、水酸化カリウム等のアルカリを用
いる。架橋剤として、ジアルデヒド化合物を用いる場合
は、触媒として酸を用いる。酸の使用量は、ポリビニル
アルコール水溶液層中の濃度が０．ｊＮ以上になる様に
添加するのが好ましい。The crosslinking reaction is carried out at a dispersion ball making operation temperature of 0°C to ioo°C.
, preferably at 30° C. to 0° C. for 1 hour to 20 hours, preferably 2 hours to 3 hours. During the crosslinking reaction, an acid such as hydrochloric acid or sulfuric acid, or an alkali such as sodium hydroxide or potassium hydroxide is used as a catalyst depending on the crosslinking agent. When using a dialdehyde compound as a crosslinking agent, an acid is used as a catalyst. The amount of acid used is such that the concentration in the polyvinyl alcohol aqueous solution layer is 0. It is preferable to add it in such a way that it is equal to or higher than jN.
又、添加時期は、分・散造球操作の前でも後でも差支え
ないが、凝集球の少ない球状の粒子を得るには、分散造
球操作の前後２回に分けて添加するのが好ましい。架橋
剤として、エピハロヒドリン化合物を用いる場合は、触
媒としてアルカリを用いる。アルカリの使用量はポリビ
ニルアルコール水溶液層中の濃度が−Ｎ以上になる様に
添加するのが好ましい。Further, the addition time may be before or after the dispersion/dispersion ball-forming operation, but in order to obtain spherical particles with fewer agglomerated spheres, it is preferable to add it twice, before and after the dispersion/ball-forming operation. When an epihalohydrin compound is used as a crosslinking agent, an alkali is used as a catalyst. The amount of alkali to be used is preferably such that the concentration in the polyvinyl alcohol aqueous solution layer is -N or higher.
このようにして得られた架橋ポリビニルアルコール粒子
は、濾過して有機溶剤と分離する。The crosslinked polyvinyl alcohol particles thus obtained are separated from the organic solvent by filtration.
次いでアセトン、メタノール等の水混合性の有機溶剤で
洗浄したのち充分水洗することによシ包含されている水
溶性高分子化合物を抽出するか、あるいは有機溶剤と分
離した架橋ポリビニルアルコール粒子を水中で加熱し、
共沸によシ粒子内に残存している有機溶剤を留去し、そ
の後充分水洗することによシ、包含されている水溶性高
分子化合物を抽出することによシ多孔質架橋ポリビニル
アルコール粒子が得られる。Next, the contained water-soluble polymer compounds are extracted by washing with a water-miscible organic solvent such as acetone or methanol and then sufficient water, or the cross-linked polyvinyl alcohol particles separated from the organic solvent are submerged in water. Heat,
The organic solvent remaining in the particles is distilled off by azeotropic distillation, and then the water-soluble polymer compound contained therein is extracted by washing thoroughly with water to form porous crosslinked polyvinyl alcohol particles. is obtained.
本発明方法によシ得られる多孔質架橋ポリビニルアルコ
ール粒子はクロマトグラフィー、特ニ水系ゲルパーミエ
イションクロマトグラフイー用の充填剤として有用であ
る。The porous crosslinked polyvinyl alcohol particles obtained by the method of the invention are useful as fillers for chromatography, especially aqueous gel permeation chromatography.
また、ポリビニルアルコールの水酸基に糧々の官能基又
はリガンドを付加することによシイオン交換クロマトグ
ラフィー、疎水性クロマトグラフィー、アフィニティー
クロマトグラフィー等積々のクロマトグラフィー用の担
体とすることもできる。Furthermore, by adding various functional groups or ligands to the hydroxyl groups of polyvinyl alcohol, it can be used as a carrier for a variety of chromatography such as ion exchange chromatography, hydrophobic chromatography, and affinity chromatography.
以下に実施例により本発明を更に具体的忙説明するが、
本発明はその要旨を超えない限り、以下の実施例に限定
されるものではない。なお以下の実施例において多孔度
の指標である含水炭及び膨潤度は下記の方法によシ測定
した。The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, in the following examples, hydrous carbon and swelling degree, which are indicators of porosity, were measured by the following methods.
く含水炭及び膨潤度の測定〉
樹脂を十分に水洗したのち１０ｍのメスシリンダーに入
れ、底部を軽くたたきながら正確に１０ゴ秤取する。こ
の樹脂を遠心分離機で８０Ｇで３分間脱水したのち、そ
の重量（ａｌ ？ ）を精秤する。次いで、この樹脂を
６０℃、／ ０ ＋ｎＨｇの真空乾燥器中で２ｑ時間乾
燥したのち、再び重量（ａ！？ンを精秤する。Measurement of water-containing charcoal and degree of swelling> After thoroughly washing the resin with water, place it in a 10 m measuring cylinder and accurately weigh out 10 cylinders while tapping the bottom. This resin was dehydrated using a centrifuge at 80G for 3 minutes, and then its weight (al?) was accurately weighed. Next, this resin was dried in a vacuum dryer at 60° C. and /0+nHg for 2 q hours, and then the weight (a!?) was accurately weighed again.
含水炭−−Ｘ ／ ００ （％）
膨潤度＝ −（ｍｌ／ ｆ ）
実施例１
攪拌機と還流冷却管を取シつけたθ、ｊ ／の三ツロフ
ラスコに１ジクロルエタンａｓｏｘｔｌを入れ、セル四
−スアセテートフチレー）（１−ストマンコダック社裂
、商標０ＡＢＪざ／−２０）ｏ、ｓｙを溶解した。Water-containing carbon - Acetate futile) (1-Stoman Kodak Co., Ltd., trademark 0ABJza/-20) o, sy was dissolved.
別に、攪拌機を取りつけた５ｏｙ−の三ツロフラスコに
、１０チボリビニルアルコール水溶液（ポリビニルアル
コールは日本合成■製、商標ゴーセノールＮＬ０．３使
用）ｉｏｏｘｔをとシ、攪拌しながらこれにコＳチグル
タルアルデヒド水溶液コゴな加え、更忙デキストラン（
ファルマシア社製Ｄｅｘｔｒａｎ Ｔ ／ ０分子量１
万）ｊｙを加えて善孝→禎５溶解したのち、ｌ規定塩酸
／ｙｎｌを加え、すばやく攪拌したのち、室温で上記の
有機溶媒中に分散した。Separately, add 10 tivolivinyl alcohol aqueous solution (polyvinyl alcohol manufactured by Nippon Gosei ■, trademark Gohsenol NL 0.3) to a 5-oy Mitsuro flask equipped with a stirrer, and add iooxt to this while stirring. In addition to Kogo, Kojo Dextran (
Dextran T/0 molecular weight 1 manufactured by Pharmacia
After adding 5) jy and dissolving Yoshitaka → Tei5, 1 normal hydrochloric acid/ynl was added, and after stirring quickly, it was dispersed in the above organic solvent at room temperature.
室温で１時間攪拌を行なったのち、６３℃で一時間半加
熱した。次いで３Ｎ塩酸を１０ｒｎｌ添加し、更に６３
℃でａ時間半加熱して、架橋反応を行なった。After stirring at room temperature for 1 hour, the mixture was heated at 63° C. for 1.5 hours. Next, 10 rnl of 3N hydrochloric acid was added, and an additional 63
The crosslinking reaction was carried out by heating at ℃ for a hour and a half.
室温まで冷却したのち、ｆ過し、アセトン、メタノ−ル
で洗浄後水洗し、再び攪拌機付きの／ｊの三ツロフラス
コに移し、水７００ゴを添加し、？５℃で７時間加熱し
、架橋ポリビニルアルコール粒子中に残存しているジク
ロルエタンを留去した。この後、該粒子をフラスコより
とりだし十分水洗した。得られた架橋ポリビニルアルコ
ール粒子は白色不透明の球状粒子であシ、その含水炭、
膨潤度は表−１に示した通シであった。After cooling to room temperature, it was filtered, washed with acetone and methanol, and then washed with water, transferred again to a Mitsuro flask equipped with a stirrer, and 700 g of water was added. The mixture was heated at 5° C. for 7 hours to distill off dichloroethane remaining in the crosslinked polyvinyl alcohol particles. After this, the particles were taken out from the flask and thoroughly washed with water. The obtained cross-linked polyvinyl alcohol particles are white opaque spherical particles, their hydrous carbon,
The degree of swelling was as shown in Table 1.
実施例コ〜Ｓ
コ３チグルタルアルデヒド水溶液の添加量及び添加する
水溶性高分子の種類及び量を表−７の如く変えた以外は
実施例−７と全く同様の操作を行った。各々得られた粒
子の含水炭、膨潤度を表−７に示した。Examples C to S C3 The same operation as in Example 7 was performed except that the amount of the aqueous tiglutaraldehyde solution and the type and amount of the water-soluble polymer added were changed as shown in Table 7. Table 7 shows the hydrous carbon and swelling degree of each of the particles obtained.
比較例７〜３
水溶性高分子非共存下で、表−７の条件で実施例−７と
全く同様の操作を行った。各々得られた粒子の含水炭、
膨潤度を表−７に示した。Comparative Examples 7 to 3 The same operations as in Example 7 were carried out under the conditions shown in Table 7 in the absence of water-soluble polymers. Hydrous carbon of each obtained particle,
The degree of swelling is shown in Table 7.
応用例
実施例−３、−６及び比較例−一で得られた架橋ポリビ
ニルアルコール粒子を／ Ｏｗｒ ５６ Ｘ３０θＷＨ
のガラスカラムに詰め十分水洗した後、較正曲線を作成
するために以下の操作を行ない、ゲル濾過クロマトグラ
フィー用担体としての性能評価を行った。Application Examples The crosslinked polyvinyl alcohol particles obtained in Examples 3 and 6 and Comparative Example 1 were
After filling a glass column and washing thoroughly with water, the following operations were performed to create a calibration curve, and the performance as a carrier for gel filtration chromatography was evaluated.
分子量既知のポリエチレングリコール水溶液（濃度コＷ
／Ｖ ％ ）を３００μノ上述のカラムにチャージし、
次いで流速ｏ、 ａ ｒｔｔｔ ７ ＝で蒸留水を流し
、ポリエチレングリコールを溶出した。流出液中のポリ
エチレングリコールを示差屈折計を用いて検出し、その
溶出位置（ピークのトップ位置）を求めた。図−７にそ
の結果を示した。Polyethylene glycol aqueous solution with known molecular weight (concentration W)
/V%) was charged to the above column at 300μ,
Distilled water was then flowed at a flow rate o, a rttt 7 =, to elute the polyethylene glycol. Polyethylene glycol in the effluent was detected using a differential refractometer, and its elution position (peak top position) was determined. Figure 7 shows the results.
本発明によシ得られる多孔質架橋ポリビニルアルコール
粒子は、含水率が大きい割シには、機械的強度に優れて
いることから特に水系ゲルパーミエイションクロマトグ
ラフイー用充填剤として有用である。The porous crosslinked polyvinyl alcohol particles obtained according to the present invention are particularly useful as a filler for aqueous gel permeation chromatography because they have excellent mechanical strength and have a high water content.
図−７は実施例５．６及び比較例コで製造した架橋ポリ
ビニルアルコール粒子を用いてゲル濾過クロマトグラフ
ィーにより求めた較正曲線である。横軸には保持容量、
縦軸にはポリエチレングリコールの分子量を示しである
。
出 願 人 三菱化成工業株式会社
代 理 人 弁理士 長谷用 −
ほか１名FIG. 7 is a calibration curve obtained by gel filtration chromatography using the crosslinked polyvinyl alcohol particles produced in Example 5.6 and Comparative Example 2. The horizontal axis is the holding capacity,
The vertical axis shows the molecular weight of polyethylene glycol. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent attorney Yo Hase - 1 other person
Claims (4)
及びポリビニルアルコールの混合水溶液を有機溶剤中に
て分散造球させたのち、昇温して架橋反応を行うことを
特徴とする多孔質架橋ポリビニルアルコール粒子の製造
方法。(1) A porous structure characterized by forming balls by dispersing a mixed aqueous solution of a porosity-forming agent made of a water-soluble polymer compound, a crosslinking agent, and polyvinyl alcohol in an organic solvent, and then raising the temperature to carry out a crosslinking reaction. A method for producing quality crosslinked polyvinyl alcohol particles.
する特許請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the crosslinking agent is a dialdehyde compound.
徴とする特許請求の範囲第１項または第２項記載の製造
方法。(3) The manufacturing method according to claim 1 or 2, wherein the crosslinking reaction is carried out in the presence of an acid catalyst.
とする特許請求の範囲第１項記載の製造方法。(4) The manufacturing method according to claim 1, wherein the organic solvent is a halogenated hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61161727A JPS6317905A (en) | 1986-07-09 | 1986-07-09 | Production of crosslinked porous polyvinyl alcohol particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61161727A JPS6317905A (en) | 1986-07-09 | 1986-07-09 | Production of crosslinked porous polyvinyl alcohol particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6317905A true JPS6317905A (en) | 1988-01-25 |
Family
ID=15740737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61161727A Pending JPS6317905A (en) | 1986-07-09 | 1986-07-09 | Production of crosslinked porous polyvinyl alcohol particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6317905A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254248A (en) * | 1988-04-01 | 1989-10-11 | Mitsubishi Kasei Corp | Complex separation agent and manufacture thereof |
-
1986
- 1986-07-09 JP JP61161727A patent/JPS6317905A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01254248A (en) * | 1988-04-01 | 1989-10-11 | Mitsubishi Kasei Corp | Complex separation agent and manufacture thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6317904A (en) | Production of crosslinked porous polyvinyl alcohol particle | |
| US5114577A (en) | Composite separating agent | |
| US4052343A (en) | Crosslinked, macroreticular poly(dimethylaminoethyl methacrylate) ion-exchange resins and method of preparation by aqueous suspension polymerization using trialkylamine phase extender | |
| CA2137360A1 (en) | An adiabatic process for the preparation of ion exchange and adsorbent copolymers | |
| JPS5858026B2 (en) | Packing material for chromatography and its manufacturing method | |
| JP2896571B2 (en) | Composite separating agent and method for producing the same | |
| JPS5830327B2 (en) | Method for producing insoluble macroreticular polymer of vinylbenzyl chloride | |
| US4339500A (en) | Hydrophilic packing material for chromatography | |
| US4327191A (en) | Preparation of anion exchange resins by bromination of vinyl aromatic polymers | |
| JP2002543224A (en) | Sulfonated polymer resin and its preparation | |
| JPS6317905A (en) | Production of crosslinked porous polyvinyl alcohol particle | |
| JPH0160296B2 (en) | ||
| JPH09150066A (en) | Manufacture of anionic exchange resin | |
| JPH0125761B2 (en) | ||
| CN109575161B (en) | Sulfonamide allyl polystyrene crosslinked microspheres and preparation method thereof | |
| US3008927A (en) | Process for the chloromethylation of aromatic vinyl polymers | |
| US20240207817A1 (en) | Agarose-cellulose nanocomposite porous gel microsphere, preparation method, and application | |
| CN111790444B (en) | Ionic resin-based catalyst and method for catalytically synthesizing aminomethylbenzoic acid by using same | |
| JP2767251B2 (en) | Composite separating agent and method for producing the same | |
| CN112642484B (en) | Universal temperature-resistant acid-reinforced resin catalyst and preparation method thereof | |
| JPS6150016B2 (en) | ||
| EP0436630B1 (en) | Polymer-supported 4-(n-benzyl-n-methylamino)pyridine catalyst and process for same | |
| Al-Sabti et al. | Preparation of macroporous styrene—divinylbenzene copolymers | |
| KR0134558B1 (en) | Method for preparing ion exchange resin with high density and pores | |
| JP3530527B2 (en) | Method for producing dispersion and method for producing polymer particles |