JPS6210245B2 - - Google Patents
Info
- Publication number
- JPS6210245B2 JPS6210245B2 JP54031595A JP3159579A JPS6210245B2 JP S6210245 B2 JPS6210245 B2 JP S6210245B2 JP 54031595 A JP54031595 A JP 54031595A JP 3159579 A JP3159579 A JP 3159579A JP S6210245 B2 JPS6210245 B2 JP S6210245B2
- Authority
- JP
- Japan
- Prior art keywords
- starch
- graft
- water
- modified
- glycol
- 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
- 229920002472 Starch Polymers 0.000 claims description 32
- 235000019698 starch Nutrition 0.000 claims description 31
- 239000008107 starch Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 20
- 229920000881 Modified starch Polymers 0.000 claims description 19
- 239000004368 Modified starch Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 235000019426 modified starch Nutrition 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 229920000578 graft copolymer Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- -1 allyl propylene glycol Chemical compound 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 6
- 238000010559 graft polymerization reaction Methods 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- JFZUABNDWZQLIJ-UHFFFAOYSA-N methyl 2-[(2-chloroacetyl)amino]benzoate Chemical compound COC(=O)C1=CC=CC=C1NC(=O)CCl JFZUABNDWZQLIJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 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
- 239000004615 ingredient Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical group C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
【発明の詳細な説明】
本発明は新規なグラフト変性澱粉およびその製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel graft-modified starch and a method for producing the same.
更に詳しくは澱粉を幹ポリマーとし、アリル基
を有する単量体をグラフト側鎖とする皮膜強度お
よび接着力の改善されたグラフト変性澱粉および
その製造法に関する。 More specifically, the present invention relates to a graft-modified starch with improved film strength and adhesive strength, in which starch is used as a backbone polymer and a monomer having an allyl group is used as a grafted side chain, and a method for producing the same.
従来より澱粉―ポリビニルアルコールグラフト
共重合体は接着剤、繊維や紙のサイジング剤、コ
ーテイング剤、各種水溶性フイルムなどの成分と
して種々の分野においてその有用性が認められ、
実用化が検討されているが、その製造に種々の難
点が存在し未だ満足するものは見当たらない。 Starch-polyvinyl alcohol graft copolymers have long been recognized for their usefulness in a variety of fields as ingredients for adhesives, fiber and paper sizing agents, coating agents, and various water-soluble films.
Although their practical use is being considered, there are various difficulties in their manufacture, and no satisfactory product has yet been found.
このような難点はビニルアルコールモノマーが
存在しないため澱粉にポリビニルアルコールをグ
ラフト化させるのにまずビニルエステル類をグラ
フト化させ、その後でケン化を行い澱粉―ポリビ
ニルアルコールグラフト共重合体を製造しようと
することより生ずる。すなわちグラフト化とケン
化との２つの工程が必要であり、又グラフト化は
水中で、ケン化はアルコール中で行なわれる。こ
うした工程の煩雑さ、およびアルコールを用いる
ことによる火災の危険性、作業還境、アルコール
の回収設備等、多くの問題点を残している。 The problem is that there is no vinyl alcohol monomer, so in order to graft polyvinyl alcohol onto starch, it is first necessary to graft vinyl esters and then saponify it to produce a starch-polyvinyl alcohol graft copolymer. It arises from this. That is, two steps are required: grafting and saponification, and the grafting is performed in water and the saponification is performed in alcohol. Many problems remain, including the complexity of this process, the risk of fire due to the use of alcohol, the need to return work to the surrounding area, and equipment for recovering alcohol.
かかる事情にかんがみ、本発明者らは澱粉―ポ
リビニルアルコールグラフト共重合体以上の性能
を持ち、かつ製造工程の煩雑さ、種々の問題点を
解消すべく鋭意研究を重ねた結果、一般式(1)なる
単量体を必須として適当な条件下で澱粉類にグラ
フト共重合することにより一般式(11)なるグラフト
変性澱粉が得られることを見出し本発明を完成す
るに至つた。 In view of these circumstances, the present inventors have conducted extensive research in order to have performance superior to that of starch-polyvinyl alcohol graft copolymers, as well as to eliminate the complexity of the manufacturing process and various other problems. The present inventors have discovered that a graft-modified starch of the general formula (11) can be obtained by graft copolymerizing the monomer () with starch under appropriate conditions, thereby completing the present invention.
一般式
〔式中R1，R2はＨまたはCH3，R3はＨまた
は、炭素数１〜５のアルキル基またはそのハロゲ
ン化物、ｎは０または１〜20の整数、ただしｎ＝
０のときは、R3はＨ以外の基、ｍは１以上の整
数を意味する。〕
なる新規なグラフト変性澱粉。general formula [In the formula, R 1 and R 2 are H or CH 3 and R 3 are H or an alkyl group having 1 to 5 carbon atoms or a halide thereof, n is 0 or an integer of 1 to 20, where n =
When it is 0, R 3 means a group other than H, and m means an integer of 1 or more. ] A novel graft-modified starch.
一般的にアリルアルコール等の一般式(1)で表わ
される単量体は単独ではほとんど重合しない。ア
クリル酸やそのエステル、あるいは酢酸ビニル、
スチレン等と共重合することが知られているが、
澱粉にアリルアルコール等の一般式(1)なる単量体
をグラフト化させた例はない。 In general, monomers represented by general formula (1) such as allyl alcohol hardly polymerize alone. Acrylic acid and its esters, or vinyl acetate,
It is known to copolymerize with styrene, etc.
There is no example of grafting a monomer represented by general formula (1) such as allyl alcohol to starch.
本発明は澱粉類を幹ポリマーとして一般式(1)な
る単量体をグラフト共重合した新規グラフト変性
澱粉、およびその製造法である。 The present invention is a novel graft-modified starch obtained by graft-copolymerizing a monomer represented by general formula (1) using starch as a backbone polymer, and a method for producing the same.
本発明において必須とする単量体は
一般式
〔式中R1，R2はＨまたはCH3，R3はＨまた
は、炭素数１〜５のアルキル基またはそのハロゲ
ン化物、ｎは０または１〜20の整数、ただしｎ＝
０のときはR3はＨ以外の基を意味する。〕
上記なる一般式を持つ単量体としてはアリルエ
チレングライコール、アリルプロピレングライコ
ール、アリルポリエチレングライコール、アリル
ポリプロピレングライコールおよびこれらの末端
エーテル置換単量体が挙げられる。 The essential monomers in the present invention have the general formula [In the formula, R 1 and R 2 are H or CH 3 and R 3 are H or an alkyl group having 1 to 5 carbon atoms or a halide thereof, n is 0 or an integer of 1 to 20, where n=
When it is 0, R 3 means a group other than H. ] Examples of monomers having the above general formula include allyl ethylene glycol, allyl propylene glycol, allyl polyethylene glycol, allyl polypropylene glycol, and ether-terminated monomers thereof.
本発明において原料物質として用いる澱粉は、
馬鈴薯澱粉、甘藷澱粉、トウモロコシ澱粉、モチ
トウモロコシ澱粉、高アミローストウモロコシ澱
粉、小麦澱粉、米澱粉、タピオカ澱粉、サゴ澱粉
などの天然澱粉やこれらの分解物、アミロースや
アミロペクチン分画物、架橋澱粉、エーテル化澱
粉、酸化澱粉、エステル化澱粉、酸処理澱粉、グ
ラフト変性澱粉、酵素処理澱粉、デキストリンな
どの化工澱粉、小麦粉、トウモロコシ粉、切干甘
藷、切干タピオカなどの澱粉含有物が挙げられ
る。しかし、天然澱粉へのグラフト化はその効率
が余り良くない。これを改善するには、予じめ重
合性官能基を澱粉に導入した変性澱粉、たとえ
ば、アリルエーテル化澱粉、マレイン酸片エステ
ル澱粉、アクリル酸エステル化澱粉、メタクリル
酸エステル澱粉、或は、グリシジルアクリレート
等を側鎖に導入した澱粉などを原料澱粉として使
用すれば、グラフト化効率は著しく高くなる。こ
の場合、置換度は低くてもよく、１×10-3以上の
値があればよい。 The starch used as a raw material in the present invention is
Natural starches such as potato starch, sweet potato starch, corn starch, waxy corn starch, high amylose corn starch, wheat starch, rice starch, tapioca starch, sago starch and their decomposition products, amylose and amylopectin fractions, cross-linked starches, ethers Examples include modified starch, oxidized starch, esterified starch, acid-treated starch, graft-modified starch, enzyme-treated starch, modified starch such as dextrin, and starch-containing substances such as wheat flour, corn flour, dried sweet potato, and dried tapioca. However, the efficiency of grafting to natural starch is not very good. To improve this, modified starch in which a polymerizable functional group has been introduced into the starch in advance, such as allyl etherified starch, maleic acid fragment starch, acrylic ester starch, methacrylic ester starch, or glycidyl ester starch, is recommended. If starch with acrylate or the like introduced into the side chain is used as the raw material starch, the grafting efficiency will be significantly increased. In this case, the degree of substitution may be low, as long as it has a value of 1×10 −3 or more.
これらの原料澱粉とモノマーのグラフト重合反
応はメタノール、アセトンなどの有機溶媒、また
は水あるいはこれらの混合溶液を溶媒として、第
二セリウム塩、過硫酸塩、過硫酸塩―亜硫酸塩、
過酸化水素―モール塩などの通常のグラフト重合
開始剤を用い10〜95℃、好ましくは20〜60℃で常
法に従つて行うことができる。グラフト率は0.01
〜200％、好ましくは0.05〜100％とし、かかるグ
ラフト率にすることにより水溶性又は親水性のグ
ラフト変性澱粉が製造できる。グラフト率が0.01
％以下の場合、澱粉の十分なる改質が行えず、
200％を越えると不溶性となり好ましくない。こ
こに言うグラフト率とはグラフト重合による重量
増加の用いた原料澱粉重量に対する百分率を意味
する。 Graft polymerization reactions between these raw material starches and monomers are carried out using organic solvents such as methanol, acetone, water, or a mixed solution of these to form ceric salts, persulfates, persulfate-sulfites,
The graft polymerization can be carried out using a conventional graft polymerization initiator such as hydrogen peroxide-Mohr's salt at a temperature of 10 to 95°C, preferably 20 to 60°C, according to a conventional method. Grafting rate is 0.01
By setting the grafting ratio to 200%, preferably 0.05 to 100%, a water-soluble or hydrophilic graft-modified starch can be produced. Grafting rate is 0.01
% or less, starch cannot be sufficiently modified,
If it exceeds 200%, it becomes insoluble, which is not preferable. The graft ratio referred to herein means the percentage of weight increase due to graft polymerization relative to the weight of the raw material starch used.
本発明で用いるグラフト変性澱粉はグラフト側
鎖に常法に従つてグラフト重合の前または後、あ
るいはグラフト重合と同時に他の共重合可能なモ
ノマー、例えば酢酸ビニル、アクリルアミド、ア
クリロニトリル、アクリル酸、アクリル酸エステ
ル、メタクリル酸、メタクリル酸エステル、スチ
レン、無水マレイン酸、イタコン酸等の不飽和結
合性モノマーなどと共重合してもよい。かかるモ
ノマーを共重合させる場合、一般式(1)なる単量体
に対する割合は適宜選択できるが、一般式(1)なる
単量体の重量と同じかまたはそれ以下が好まし
い。 The graft-modified starch used in the present invention may be added to the graft side chain by adding other copolymerizable monomers, such as vinyl acetate, acrylamide, acrylonitrile, acrylic acid, acrylic acid, before or after graft polymerization, or simultaneously with graft polymerization. It may be copolymerized with unsaturated bonding monomers such as esters, methacrylic acid, methacrylic esters, styrene, maleic anhydride, and itaconic acid. When such monomers are copolymerized, the proportion to the monomer of general formula (1) can be selected as appropriate, but it is preferably the same as or less than the weight of the monomer of general formula (1).
また該グラフト変性澱粉は水溶性又は親水性で
あるが、本発明において必須とする単量体以外
に、水溶性単量体をさらに共重合することによ
り、より高い水溶性等の特性を出すことも可能で
ある。 Furthermore, although the graft-modified starch is water-soluble or hydrophilic, properties such as higher water solubility can be obtained by further copolymerizing water-soluble monomers in addition to the monomers essential in the present invention. is also possible.
かくして得られるグラフト変性澱粉は非常に保
水性に富みかつすぐれた造膜性および接着性を示
し、被膜強度にすぐれているので各種の加工およ
び成型素材に用いることができる。例えば、繊維
や紙のサイジング剤、コーテイング剤、内添剤、
各種水溶性フイルム成型用素材、ガラス繊維の集
束剤、あるいは各種化粧品、水溶性塗料、絵具な
どにおける賦型剤、エマルジヨン安定剤などとし
て使用できる。 The graft-modified starch thus obtained has extremely high water retention properties and exhibits excellent film-forming and adhesive properties, and has excellent film strength, so it can be used in various processing and molding materials. For example, sizing agents for fibers and paper, coating agents, internal additives,
It can be used as a material for molding various water-soluble films, a sizing agent for glass fibers, an excipient for various cosmetics, water-soluble paints, paints, etc., and an emulsion stabilizer.
次に実施例を挙げて本発明をさらに詳しく説明
する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
コーンスターチ1.4Kgを水1.8中に分散させ40
〜45℃にてアリルプロピレングライコール200
ml、硝酸第二セリウムアンモニウム11ｇ、硝酸10
mlを加えて攪拌下45℃、２時間反応させた。反応
後中和、水洗を行いグラフト率3.2％の澱粉―ポ
リアリルプロピレングライコールグラフト共重合
体を得た。Example 1 1.4 kg of corn starch was dispersed in 1.8 kg of water and 40
Allylpropylene glycol 200 at ~45℃
ml, ceric ammonium nitrate 11g, nitric acid 10
ml was added and reacted for 2 hours at 45°C with stirring. After the reaction, neutralization and water washing were performed to obtain a starch-polyallylpropylene glycol graft copolymer with a graft ratio of 3.2%.
実施例 ２
酸化澱粉1.5Kgを水２中に分散させ40℃にて
アリルエチルエーテル180ml、アクリル酸エチル
30ml、硝酸第二セリウムアンモニウム15ｇ、硝酸
12mlを加え攪拌下45℃、３時間反応させた。反応
後中和、水洗を行いアリルエチルエーテルのグラ
フト率2.1％、アクリル酸エチルのグラフト率1.4
％の酸化澱粉―ポリアリルエチルエーテル―ポリ
アクリル酸エチルグラフト共重合体を得た。Example 2 Disperse 1.5 kg of oxidized starch in 2 water and add 180 ml of allyl ethyl ether and ethyl acrylate at 40°C.
30ml, ceric ammonium nitrate 15g, nitric acid
12 ml was added and reacted at 45°C for 3 hours with stirring. After the reaction, neutralization and water washing were performed to obtain a grafting rate of allyl ethyl ether of 2.1% and a grafting rate of ethyl acrylate of 1.4.
% of oxidized starch-polyallylethyl ether-polyethyl acrylate graft copolymer was obtained.
実施例 ３
アリル化澱粉（置換度0.01）３Kgを水５中に
分散させ、40℃にてアリルブチレングライコール
250ml、酢酸ビニル100ml、モール塩３ｇ、過酸化
水素水20mlを加え、25℃２時間反応させた。反応
後水洗し、アリルブチレングライコールのグラフ
ト率3.8％、酢酸ビニルのグラフト率1.3％のアリ
ル化澱粉―ポリアリルブチレングライコール―ポ
リ酢酸ビニルグラフト共重合体を得た。更にこの
グラフト共重合体をメタノール３中に分散さ
せ、50％の水酸化ナトリウム水溶液50mlを加え50
℃にて１時間反応を行い側鎖のケン化を行つた。
反応後中和、水洗を行いアリル化澱粉―ポリアリ
ルブチレングライコール―ポリビニルアルコール
グラフト共重合体を得た。Example 3 3 kg of allylated starch (substitution degree 0.01) was dispersed in water 5, and allyl butylene glycol was added at 40°C.
250 ml, vinyl acetate 100 ml, Mohr's salt 3 g, and hydrogen peroxide solution 20 ml were added, and the mixture was reacted at 25°C for 2 hours. After the reaction, the mixture was washed with water to obtain an allylated starch-polyallylbutylene glycol-polyvinyl acetate graft copolymer having a grafting rate of 3.8% of allylbutylene glycol and a grafting rate of vinyl acetate of 1.3%. Furthermore, this graft copolymer was dispersed in methanol 3, and 50 ml of 50% sodium hydroxide aqueous solution was added thereto.
The reaction was carried out at ℃ for 1 hour to saponify the side chains.
After the reaction, neutralization and water washing were performed to obtain an allylated starch-polyallylbutylene glycol-polyvinyl alcohol graft copolymer.
実施例 ４
酸処理澱粉２Kgを水３中に分散させ40℃にて
アリルジエチレングライコール250ml、アクリル
酸メチル50ml、硝酸第二セリウムアンモニウム20
ｇ、硝酸15mlを加え攪拌下45℃４時間反応を行つ
た。反応終了後、水酸化ナトリウム40ｇを加え50
℃で８時間側鎖のアクリル酸メチル部分の部分ケ
ン化を行い、塩酸で中和し、水洗を行い、アリル
ジエチレングライコールのグラフト率1.8％、ア
クリル酸メチルのグラフト率0.5％、アクリル酸
ナトリウムのグラフト率0.5％の酸処理澱粉―ポ
リアリルジエチレングライコール―ポリアクリル
酸メチル―ポリアクリル酸ナトリウムグラフト共
重合体を得た。Example 4 2 kg of acid-treated starch was dispersed in 3 parts of water and heated at 40°C with 250 ml of allyldiethylene glycol, 50 ml of methyl acrylate, and 20 ml of ceric ammonium nitrate.
g and 15 ml of nitric acid were added thereto, and the reaction was carried out at 45° C. for 4 hours with stirring. After the reaction is complete, add 40g of sodium hydroxide and add 50g of sodium hydroxide.
Partial saponification of the methyl acrylate moiety in the side chain was carried out at °C for 8 hours, neutralized with hydrochloric acid, and washed with water.The grafting rate of allyl diethylene glycol was 1.8%, the grafting rate of methyl acrylate was 0.5%, and sodium acrylate. An acid-treated starch-polyallyldiethylene glycol-methyl polyacrylate-sodium polyacrylate graft copolymer with a graft ratio of 0.5% was obtained.
実施例 ５
アリル化澱粉（置換度0.05）３Kgを水５に分
散させ、アリルモノエチレングライコール1.5
Kg、モール塩３ｇ、過酸化水素30mlを加えて攪拌
下30℃、２時間反応を行い、水洗、乾燥後、グラ
フト率39％のアリル化澱粉―ポリアリルモノエチ
レングライコールグラフト共重合体を得た。Example 5 3 kg of allylated starch (degree of substitution 0.05) was dispersed in 5 parts of water, and 1.5 kg of allyl monoethylene glycol was dispersed in 5 parts of water.
Kg, 3 g of Mohr's salt, and 30 ml of hydrogen peroxide were added, and the reaction was carried out at 30°C for 2 hours with stirring. After washing with water and drying, an allylated starch-polyallyl monoethylene glycol graft copolymer with a grafting ratio of 39% was obtained. Ta.
Claims (1)
選ばれる澱粉類に下記なる単量体を必須単量体と
してグラフト開始剤の存在下で製造されるグラフ
ト澱粉の製造法。 〔式中R1，R2はＨまたはCH3，R3はＨまたは
炭素数１〜５のアルキル基またはそのハロゲン化
物、ｎは０または１〜20の整数、ただしｎ＝０の
ときはR3はＨ以外の基を意味する。〕 ２ 澱粉に二重結合を有する置換基を導入した変
性澱粉を幹ポリマーとした特許請求の範囲第１項
のグラフト変性澱粉の製造法。 ３ 式（）の単量体のグラフト率が0.01〜200
％である特許請求の範囲第１項のグラフト変性澱
粉の製造法。[Scope of Claims] 1. A method for producing grafted starch by adding the following monomers as essential monomers to starch selected from naturally produced starches and/or various modified starches in the presence of a graft initiator. [In the formula, R 1 and R 2 are H or CH 3 , R 3 is H or an alkyl group having 1 to 5 carbon atoms, or a halide thereof, n is 0 or an integer of 1 to 20, provided that when n = 0, R 3 means a group other than H. 2. The method for producing graft-modified starch according to claim 1, in which a modified starch obtained by introducing a substituent having a double bond into starch is used as a backbone polymer. 3 The grafting rate of the monomer of formula () is 0.01 to 200
% of the graft-modified starch according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3159579A JPS55123610A (en) | 1979-03-17 | 1979-03-17 | Modified starch and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3159579A JPS55123610A (en) | 1979-03-17 | 1979-03-17 | Modified starch and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55123610A JPS55123610A (en) | 1980-09-24 |
| JPS6210245B2 true JPS6210245B2 (en) | 1987-03-05 |
Family
ID=12335540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3159579A Granted JPS55123610A (en) | 1979-03-17 | 1979-03-17 | Modified starch and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55123610A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090884A (en) * | 1998-05-07 | 2000-07-18 | S. C. Johnson Commercial Markets, Inc. | Starch degradation/graft polymerization composition, process, and uses thereof |
| AU2002353736B2 (en) * | 2001-11-26 | 2008-05-08 | Ge Healthcare Bio-Sciences Ab | Post-modification of a porous support |
| US7060187B2 (en) * | 2001-11-26 | 2006-06-13 | Ge Healthcare Bio-Sciences Ab | Post-modification of a porous support |
| JP5460651B2 (en) * | 2010-07-28 | 2014-04-02 | ローム アンド ハース カンパニー | Grafting method for improving chromatographic media performance |
| JP5631271B2 (en) * | 2010-07-28 | 2014-11-26 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | Method for making and using improved chromatographic media |
| JP5474881B2 (en) * | 2010-07-28 | 2014-04-16 | ローム アンド ハース カンパニー | Method for making and using improved chromatographic media |
-
1979
- 1979-03-17 JP JP3159579A patent/JPS55123610A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55123610A (en) | 1980-09-24 |
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