JP2006045363A - Copolymer of diallyl dialkyl ammonium alkyl sulfate with sulfur dioxide and method for producing the same - Google Patents
Copolymer of diallyl dialkyl ammonium alkyl sulfate with sulfur dioxide and method for producing the same Download PDFInfo
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- JP2006045363A JP2006045363A JP2004228807A JP2004228807A JP2006045363A JP 2006045363 A JP2006045363 A JP 2006045363A JP 2004228807 A JP2004228807 A JP 2004228807A JP 2004228807 A JP2004228807 A JP 2004228807A JP 2006045363 A JP2006045363 A JP 2006045363A
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229920001577 copolymer Polymers 0.000 title claims abstract description 85
- -1 diallyl dialkyl ammonium alkyl sulfate Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 150000008051 alkyl sulfates Chemical group 0.000 claims description 32
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 5
- 229920005603 alternating copolymer Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 6
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 21
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 13
- 238000007747 plating Methods 0.000 description 13
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910000365 copper sulfate Inorganic materials 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000012847 fine chemical Substances 0.000 description 5
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 3
- 229940008406 diethyl sulfate Drugs 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 3
- 125000005527 methyl sulfate group Chemical group 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BGDTWOQNFJNCKH-UHFFFAOYSA-N n-ethyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(CC)CC=C BGDTWOQNFJNCKH-UHFFFAOYSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SPQMVUPFYWDFCB-UHFFFAOYSA-N 2-hydroperoxybutane Chemical compound CCC(C)OO SPQMVUPFYWDFCB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QTJISTOHDJAKOQ-UHFFFAOYSA-N 2-hydroxyethylazanium;methyl sulfate Chemical group [NH3+]CCO.COS([O-])(=O)=O QTJISTOHDJAKOQ-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JEUWWKROIYYVII-UHFFFAOYSA-N C(O)CN.C(C)OS(O)(=O)=O Chemical compound C(O)CN.C(C)OS(O)(=O)=O JEUWWKROIYYVII-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000006200 ethylation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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Abstract
Description
本発明は、ジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体およびその製造方法に関する。
さらに詳しくは本発明は、ファインケミカル分野に使用可能で、かつ水に可溶で、有機溶媒への溶解性の高い、ジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体およびその製造方法に関する。
The present invention relates to a copolymer of diallyldialkylammonium alkyl sulfate and sulfur dioxide and a method for producing the same.
More particularly, the present invention relates to a copolymer of diallyldialkylammonium alkyl sulfate and sulfur dioxide, which can be used in the fine chemical field, is soluble in water, and has high solubility in an organic solvent, and a method for producing the same.
ジアリルジアルキルアンモニウムクロリドと二酸化イオウとの共重合体は、ジアリルジアルキルアンモニウムクロリドと二酸化イオウとを共重合させることにより簡単に製造できる点から工業的に製造され、水溶性塗料や染色物の染色堅牢度向上剤等のファインケミカル分野で使用することが提案されている（例えば、特許文献１参照）。 Copolymers of diallyldialkylammonium chloride and sulfur dioxide are industrially produced because they can be easily produced by copolymerizing diallyldialkylammonium chloride and sulfur dioxide, and dyeing fastness of water-soluble paints and dyeings It has been proposed to be used in the field of fine chemicals such as improvers (see, for example, Patent Document 1).
しかしながら、地球環境の保全の高まりとともにファインケミカル分野で使用される各種薬剤も、塩素を含まないものが求められてきており、ジアリルジアルキルアンモニウムクロリドと二酸化イオウとの共重合体の代りに、ジアリルジアルキルアンモニウムのクロリド以外の塩と二酸化イオウとの共重合体が求められるようになってきている。 However, various chemicals used in the field of fine chemicals have been demanded along with the enhancement of global environment conservation, and chlorine-free chemicals have been demanded. Instead of a copolymer of diallyldialkylammonium chloride and sulfur dioxide, diallyldialkylammonium is used. Copolymers of salts other than chlorides with sulfur dioxide have been demanded.
ところが、特許文献１に記載のように、ジアリルジアルキルアンモニウムのクロリド以外の塩と二酸化イオウとの共重合体を、対応するジアリルジアルキルアンモニウムの塩と二酸化イオウとの反応により実用的に製造することは困難である。
However, as described in
例えば、ジアリルジアルキルアンモニウムのヨウ化物塩と二酸化イオウとを共重合して得られる共重合体は、重合中にヨウ素が一部遊離するために着色することがある。また、ジアリルジアルキルアンモニウムの有機酸塩と二酸化イオウとを共重合しても、得られる有機酸塩の共重合体の収率は低い。さらに、ジアリルジアルキルアンモニウムの硫酸塩または亜硫酸塩と二酸化イオウとを共重合しようとしても、得られる共重合体の硫酸塩または亜硫酸塩を、製造単離することが困難である。 For example, a copolymer obtained by copolymerizing an iodide salt of diallyldialkylammonium and sulfur dioxide may be colored due to partial liberation of iodine during the polymerization. Moreover, even if the organic acid salt of diallyldialkylammonium and sulfur dioxide are copolymerized, the yield of the resulting organic acid salt copolymer is low. Further, even if diallyldialkylammonium sulfate or sulfite is to be copolymerized with sulfur dioxide, it is difficult to produce and isolate the resulting copolymer sulfate or sulfite.
本発明は、このような事情のもとで、ジアリルジアルキルアンモニウムのクロリド以外の塩と二酸化イオウとの新規な共重合体を提供することを第一の目的とし、また該新規共重合体を簡単な操作により高収率で製造する方法を提供することを第二の目的とする。 Under such circumstances, a primary object of the present invention is to provide a novel copolymer of sulfur dioxide other than diallyldialkylammonium chloride and the novel copolymer. A second object is to provide a method for producing a high yield by simple operation.
本発明者らは、上記の問題を解決するため、ジアリルジアルキルアンモニウムのクロリド以外の塩と二酸化イオウとの共重合体の製造を種々検討したところ、意外にも原料として、ジアリルジアルキルアンモニウムクロリドの代わりに有機酸塩の一種であるジアリルジアルキルアンモニウムアルキルサルフェイトを用いて、これを二酸化イオウと共重合させると、ジアリジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの新規な共重合体が収率良く得られることを見出した。また、本発明者らはこの新規共重合体は、水溶性であり、かつ、対応するジアリルジアルキルアンモニウムクロリドと二酸化イオウとの共重合体に比べると、有機溶媒への溶解性に優れ、ファインケミカル分野の用途に極めて有効なことを見出した。 In order to solve the above problems, the present inventors have made various studies on the production of a copolymer of a salt other than diallyldialkylammonium chloride and sulfur dioxide. Surprisingly, as a raw material, instead of diallyldialkylammonium chloride, When a diallyldialkylammonium alkylsulfate, a kind of organic acid salt, is copolymerized with sulfur dioxide, a new copolymer of diarydialkylammonium alkylsulfate and sulfur dioxide is obtained in high yield. I found out that Further, the present inventors have found that this novel copolymer is water-soluble and has excellent solubility in organic solvents as compared with the corresponding copolymer of diallyldialkylammonium chloride and sulfur dioxide. It was found to be extremely effective for the use of.
さらに、本発明者らは、二酸化イオウとの共重合に用いられるジアリルジアルキルアンモニウムアルキルサルフェイトのうち、ジアリルエチルメチルアンモニウムエチルサルフェイトが文献未載の新規化合物であることを見出した。
本発明は上記の知見に基いてなされたものであり、
（１） 一般式（Ｉ）
Furthermore, the present inventors have found that among the diallyldialkylammonium alkyl sulfates used for copolymerization with sulfur dioxide, diallylethylmethylammonium ethyl sulfate is a novel compound not described in any literature.
The present invention has been made based on the above findings,
(1) General formula (I)
（式中、Ｒ１、Ｒ２は、独立にメチル基、エチル基またはヒドロキシエチル基であるが、Ｒ１、Ｒ２が共にヒドロキシエチル基ではなく、Ｒ３は、メチル基またはエチル基である）
で表されるジアリルジアルキルアンモニウムアルキルサルフェイト単位と、
式（II）
(In the formula, R 1 and R 2 are each independently a methyl group, an ethyl group or a hydroxyethyl group, but R 1 and R 2 are not both a hydroxyethyl group, and R 3 is a methyl group or an ethyl group. )
A diallyldialkylammonium alkyl sulfate unit represented by:
Formula (II)
で表される二酸化イオウ単位とを含むことを特徴とするジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体、
（２） 一般式（Ｉ）において、Ｒ１がエチル基、Ｒ２がメチル基、Ｒ３がエチ
ル基である、上記（１）に記載のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体、
（３） ジアリルジアルキルアンモニウムアルキルサルフェイト単位／
二酸化イオウ単位のモル比が１／１である交互共重合体である、上記（１）または（２）に記載のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体、
（４） 一般式（III）
A copolymer of diallyldialkylammonium alkylsulfate and sulfur dioxide, characterized by comprising a sulfur dioxide unit represented by:
(2) Co-weight of diallyldialkylammonium alkyl sulfate and sulfur dioxide according to (1), wherein in general formula (I), R 1 is an ethyl group, R 2 is a methyl group, and R 3 is an ethyl group Coalescence,
(3) Diallyldialkylammonium alkyl sulfate units /
A copolymer of diallyldialkylammonium alkyl sulfate and sulfur dioxide according to (1) or (2) above, which is an alternating copolymer having a molar ratio of sulfur dioxide units of 1/1,
(4) General formula (III)
（式中、Ｒ１、Ｒ２は、独立にメチル基、エチル基またはヒドロキシエチル基であるが、Ｒ１、Ｒ２が共にヒドロキシエチル基ではなく、Ｒ３は、メチル基またはエチル基である）
で表されるジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとを、極性溶媒中で共重合させることを特徴とする請求項１に記載のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体の製造方法、および
（５） 式（IV）
(In the formula, R 1 and R 2 are each independently a methyl group, an ethyl group or a hydroxyethyl group, but R 1 and R 2 are not both a hydroxyethyl group, and R 3 is a methyl group or an ethyl group. )
The production of a copolymer of diallyldialkylammonium alkylsulfate and sulfur dioxide according to
で表されることを特徴とするジアリルエチルメチルアンモニウムエチルサルフェイト
を提供するものである。
The present invention provides diallylethylmethylammonium ethyl sulfate characterized by the following:
本発明によれば、水溶性であり、かつ有機溶媒への溶解性に優れ、ファインケミカル分野の用途に極めて有用な、新規ジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体を、簡単な操作により収率良く工業的に有利に得ることができる。
また本発明によれば、新規なジアリルエチルメチルアンモニウムエチルサルフェイトを得ることができる。
According to the present invention, a novel diallyldialkylammonium alkyl sulfate and sulfur dioxide copolymer which is water-soluble and excellent in solubility in an organic solvent and is extremely useful for applications in the fine chemical field can be easily manipulated. Thus, it can be obtained industrially advantageously with good yield.
In addition, according to the present invention, novel diallylethylmethylammonium ethyl sulfate can be obtained.
まず、本発明のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体（以下、単に本発明の共重合体と記載することもある）について説明する。
本発明の共重合体は、
一般式（Ｉ）
First, a copolymer of diallyldialkylammonium alkyl sulfate and sulfur dioxide of the present invention (hereinafter sometimes simply referred to as the copolymer of the present invention) will be described.
The copolymer of the present invention is
Formula (I)
（式中、Ｒ１、Ｒ２は、独立にメチル基、エチル基またはヒドロキシエチル基であるが、Ｒ１、Ｒ２が共にヒドロキシエチル基ではなく、Ｒ３は、メチル基またはエチル基である）
で表されるジアリルジアルキルアンモニウムアルキルサルフェイト単位と式（ＩＩ）
(In the formula, R 1 and R 2 are each independently a methyl group, an ethyl group or a hydroxyethyl group, but R 1 and R 2 are not both a hydroxyethyl group, and R 3 is a methyl group or an ethyl group. )
A diallyldialkylammonium alkyl sulfate unit represented by the formula (II)
本発明の共重合体において、ジアリルジアルキルアンモニウムアルキルサルフェイト単位としては、ジアリルジメチルアンモニウムメチルサルフェイト単位、ジアリルエチルメチルアンモニウムメチルサルフェイト単位、ジアリルジエチルアンモニウムメチルサルフェイト単位、ジアリル（ヒドロキシエチル）メチルアンモニウムメチルサルフェイト単位、ジアリルエチル（ヒドロキシエチル）アンモニウムメチルサルフェイト単位、ジアリルジメチルアンモニウムエチルサルフェイト単位、ジアリルエチルメチルアンモニウムエチルサルフェイト単位、ジアリルジエチルアンモニウムエチルサルフェイト単位、ジアリル（ヒドロキシエチル）メチルアンモニウムエチルサルフェイト単位、ジアリルエチル（ヒドロキシエチル）アンモニウムエチルサルフェイト単位を好ましく例示できるが、一般式（Ｉ）においてＲ１がエチル基、Ｒ２がメチル基、Ｒ３がエチル基であるジアリルエチルメチルアンモニウムエチルサルフェイト単位が特に好ましい。なお、本発明において、ヒドロキシエチルは、好ましくは２−ヒドロキシエチルである。 In the copolymer of the present invention, diallyldialkylammonium alkylsulfate units include diallyldimethylammonium methylsulfate units, diallylethylmethylammonium methylsulfate units, diallyldiethylammonium methylsulfate units, diallyl (hydroxyethyl) methylammonium. Methylsulfate units, diallylethyl (hydroxyethyl) ammonium methylsulfate units, diallyldimethylammonium ethylsulfate units, diallylethylmethylammonium ethylsulfate units, diallyldiethylammoniumethylsulfate units, diallyl (hydroxyethyl) methylammoniumethyl Sulfate units, diallylethyl (hydroxyethyl) ammonium Although chill Sulfate unit can be preferably exemplified, in the general formula (I) R 1 is ethyl, R 2 is a methyl group, R 3 is diallyl methyl ammonium ethyl sulfates units an ethyl group is particularly preferred. In the present invention, hydroxyethyl is preferably 2-hydroxyethyl.
本発明の共重合体は、製造上の観点から、ジアリルジメチルアンモニウムメチルサルフェイトと二酸化イオウとの共重合体、ジアリルエチルメチルアンモニウムメチルサルフェイトと二酸化イオウとの共重合体、ジアリルジエチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体、ジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体が好ましいが、ジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体が特に好ましい。 From the viewpoint of production, the copolymer of the present invention comprises a copolymer of diallyldimethylammonium methylsulfate and sulfur dioxide, a copolymer of diallylethylmethylammonium methylsulfate and sulfur dioxide, diallyldiethylammonium ethylsulfate. A copolymer of fate and sulfur dioxide and a copolymer of diallylethylmethylammonium ethylsulfate and sulfur dioxide are preferred, but a copolymer of diallylethylmethylammonium ethylsulfate and sulfur dioxide is particularly preferred.
本発明の共重合体の製造においては、ジアリルジアルキルアンモニウムアルキルサルフェイト／二酸化イオウのモノマーモル比は、得られる共重合体の安定性の観点から、通常、０．５／０．５以上であり、好ましくは０．５／０．５〜０．９５／０．０５であり、より好ましくは０．５／０．５〜０．８／０．２であり、さらに好ましくは０．５／０．５〜０．６／０．４、特に好ましくは０.５／０.５である。
本モノマーのモル比が０.５／０.５の場合、得られた共重合体は、下記(Ｖ)のような環化交互共重合体で表されると考えられる。
In the production of the copolymer of the present invention, the monomer molar ratio of diallyldialkylammonium alkyl sulfate / sulfur dioxide is usually 0.5 / 0.5 or more from the viewpoint of the stability of the resulting copolymer. Preferably it is 0.5 / 0.5-0.95 / 0.05, More preferably, it is 0.5 / 0.5-0.8 / 0.2, More preferably, it is 0.5 / 0. 5 to 0.6 / 0.4, particularly preferably 0.5 / 0.5.
When the molar ratio of this monomer is 0.5 / 0.5, the obtained copolymer is considered to be represented by a cyclized alternating copolymer such as the following (V).
本発明の共重合体の分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によるポリエチレングリコール換算の重量平均分子量で、通常３００〜５０，０００、好ましくは５００〜２５，０００、より好ましくは８００〜１０，０００の範囲である。 The molecular weight of the copolymer of the present invention is a weight average molecular weight in terms of polyethylene glycol as measured by gel permeation chromatography (GPC), and is usually 300 to 50,000, preferably 500 to 25,000, more preferably 800 to 10. , 000.
次に、本発明の共重合体の製造方法について説明する。
本発明のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体の製造方法は、
一般式（ＩＩＩ）
Next, the manufacturing method of the copolymer of this invention is demonstrated.
The method for producing a copolymer of diallyldialkylammonium alkyl sulfate of the present invention and sulfur dioxide,
Formula (III)
（式中、Ｒ１、Ｒ２は、独立にメチル基、エチル基またはヒドロキシエチル基であるが、Ｒ１、Ｒ２が共にヒドロキシエチル基ではなく、Ｒ３は、メチル基またはエチル基である）
で表されるジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとを極性溶媒中で共重合させることを特徴とする。
(In the formula, R 1 and R 2 are independently a methyl group, an ethyl group or a hydroxyethyl group, but R 1 and R 2 are not both a hydroxyethyl group, and R 3 is a methyl group or an ethyl group. )
It is characterized by copolymerizing a diallyldialkylammonium alkyl sulfate represented by the formula (II) and sulfur dioxide in a polar solvent.
モノマーとして用いるジアリルジアルキルアンモニウムアルキルサルフェイトは、例えばジアリルアルキルアミンとジアルキル硫酸との反応によるアルキル化反応等により製造することができる。 The diallyldialkylammonium alkyl sulfate used as the monomer can be produced, for example, by an alkylation reaction by a reaction of diallylalkylamine and dialkylsulfuric acid.
ジアリルジメチルアンモニウムメチルサルフェイト、ジアリルエチルメチルアンモニウムメチルサルフェイト、ジアリル（ヒドロキシエチル）メチルアンモニウムメチルサルフェイトは、それぞれジアリルメチルアミン、ジアリルエチルアミン、ジアリル（ヒドロキシエチル）アミンにジメチル硫酸を加えて反応させるメチル化反応により製造することができる。 Diallyldimethylammonium methylsulfate, diallylethylmethylammonium methylsulfate, and diallyl (hydroxyethyl) methylammonium methylsulfate are methyl compounds that are reacted by adding dimethylsulfuric acid to diallylmethylamine, diallylethylamine, and diallyl (hydroxyethyl) amine, respectively. It can be produced by a chemical reaction.
また、ジアリルジエチルアンモニウムエチルサルフェイト、ジアリルエチルメチルアンモニウムエチルサルフェイト、ジアリルエチル（ヒドロキシエチル）アンモニウムエチルサルフェイトは、それぞれ、ジアリルエチルアミン、ジアリルメチルアミン、ジアリル（ヒドロキシエチル）アミンに、ジエチル硫酸を加えて反応させるエチル化反応により製造することができる。
上述のジアリルジアルキルアンモニウムアルキルサルフェイトのうち、
式（IV）
In addition, diallyl diethylammonium ethyl sulfate, diallylethylmethylammonium ethyl sulfate, diallylethyl (hydroxyethyl) ammonium ethyl sulfate, respectively, add diethyl sulfate to diallylethylamine, diallylmethylamine, diallyl (hydroxyethyl) amine. Can be produced by an ethylation reaction.
Of the above-mentioned diallyldialkylammonium alkyl sulfates,
Formula (IV)
で表されるジアリルエチルメチルアンモニウムエチルサルフェイトは文献未載の新規化合物である。 Is a novel compound not yet described in literature.
本発明の共重合体の製造方法に用いる極性溶媒としては、ジアリルジアルキルアンモニウムアルキルサルフェイトおよび二酸化イオウを溶解する溶媒であるが、例えば水、メチルアルコール、エチルアルコール、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド等を例示することができる。 The polar solvent used in the method for producing the copolymer of the present invention is a solvent that dissolves diallyldialkylammonium alkyl sulfate and sulfur dioxide, such as water, methyl alcohol, ethyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide. Etc. can be illustrated.
本発明の共重合体の製造方法において、ラジカル共重合反応のために用いられる重合触媒としては、ジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとを重合し得るものであれば特に制限はないが、第三−ブチルヒドロパーオキサイド、クメンヒドロパーオキサイドのような有機過酸化物、２，２’−アゾビスイソブチロニトリルのような脂肪族アゾ化合物、過硫酸アンモニウム、過硫酸カリウムのような無機過酸化物、硝酸アンモニウム、硝酸カリウムのような硝酸塩等が挙げられる。また、空気等の酸素を含む気体、放射線、紫外線、可視光線も挙げられる。 In the method for producing a copolymer of the present invention, the polymerization catalyst used for the radical copolymerization reaction is not particularly limited as long as it can polymerize diallyldialkylammonium alkyl sulfate and sulfur dioxide. Organic peroxides such as 3-butyl hydroperoxide and cumene hydroperoxide, aliphatic azo compounds such as 2,2′-azobisisobutyronitrile, inorganic peroxidations such as ammonium persulfate and potassium persulfate And nitrates such as ammonium nitrate and potassium nitrate. Moreover, the gas containing oxygen, such as air, a radiation, an ultraviolet-ray, and visible light are also mentioned.
本発明の共重合体の製造方法においては、通常、上記ジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウを含む極性溶媒溶液に、上記重合触媒を加え、室温下または加熱条件下、適宜撹拌操作を加えることにより共重合が行われる。重合温度は−１００℃〜８０℃が好ましい。また、重合時間は１〜１００時間が好ましい。 In the method for producing a copolymer of the present invention, usually, the polymerization catalyst is added to the polar solvent solution containing the diallyldialkylammonium alkyl sulfate and sulfur dioxide, and the mixture is appropriately stirred at room temperature or under heating conditions. Copolymerization is carried out. The polymerization temperature is preferably -100 ° C to 80 ° C. The polymerization time is preferably 1 to 100 hours.
反応終了した後、アルコールやアセトン等の共重合体を溶解させない溶媒を加えることにより、本発明の共重合体を再沈させ、ろ取することもできる。 After completion of the reaction, the copolymer of the present invention can be reprecipitated and filtered by adding a solvent that does not dissolve the copolymer such as alcohol or acetone.
先ず、実施例で得られた共重合体の重量平均分子量および重合収率の測定方法を以下に示す。
（ｉ） 共重合体の重量平均分子量
共重合体の重量平均分子量（Ｍｗ）は、日立Ｌ−６０００型高速液体クロマトグラフを使用し、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ法）によって測定した。溶離液流路ポンプは日立Ｌ−６０００、検出器はショーデックスＲＩ−１０１示差屈折率検出器、カラムはショーデックスアサヒパックの水系ゲル濾過タイプのＧＳ−２２０ＨＱ（排除限界分子量３，０００）とＧＳ−６２０ＨＱ(排除限界分子量２００万)とを直列に接続したものを用いた。サンプルは溶離液で０．５ｇ／１００ｍｌの濃度に調製し、２０μｌを用いた。溶離液には、０．４モル／リットルの塩化ナトリウム水溶液を使用した。カラム温度は３０℃で、流速は１．０ｍｌ／分で実施した。標準物質として、分子量１０６、１９４、４４０、６００、１４７０、４１００、７１００、１０３００、１２６００、２３０００などのポリエチレングリコールを用いて較正曲線を求め、その較正曲線を基に共重合体の重量平均分子量（Ｍｗ）を求めた。
First, methods for measuring the weight average molecular weight and the polymerization yield of the copolymers obtained in the examples are shown below.
(I) Weight average molecular weight of copolymer The weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC method) using Hitachi L-6000 type high performance liquid chromatograph. The eluent flow path pump is Hitachi L-6000, the detector is a Shodex RI-101 differential refractive index detector, and the column is a water gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS of Shodex Asahi Pack. -620HQ (exclusion limit molecular weight 2 million) connected in series was used. Samples were prepared with an eluent to a concentration of 0.5 g / 100 ml, and 20 μl was used. As an eluent, a 0.4 mol / liter sodium chloride aqueous solution was used. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve is obtained using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard substance, and the weight average molecular weight of the copolymer ( Mw) was determined.
（ii） 共重合体の重合収率
ＧＰＣ法により得られたピーク面積比により求めた。
実施例１ ジアリルエチルメチルアンモニウムエチルサルフェイトモノマーの製造
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコ中にジアリルメチルアミン１６７．１ｇ（１．５モル）を仕込み、攪拌しながら硫酸ジエチル２３２．５ｇ（１．５モル）を２０〜５０℃に保ちながらゆっくり滴下した。そして５０℃で２４時間反応させて、ジアリルエチルメチルアンモニウムエチルサルフェイトをオイルとして得た。収量は、３９９．８ｇ（収率１００％）であった。
得られたジアリルエチルメチルアンモニウムエチルサルフェイトのＩＲスペクトルを図１に示す。図１より、１２２０ｃｍ−１に硫酸エステルに由来する吸収があり、この構造を支持している。リンタングステン酸を用いる重量法による四級塩の基本分子量の測定値は２６４．２７（計算値２６５．３８）であった。
(Ii) Copolymerization yield The copolymer yield was determined by the peak area ratio obtained by the GPC method.
Example 1 Preparation of diallylethylmethylammonium ethyl sulfate monomer 167.1 g (1.5 mol) of diallylmethylamine was placed in a 1 liter four-necked round bottom separable flask equipped with a stirrer, thermometer and Dimroth reflux condenser. ), And while stirring, 232.5 g (1.5 mol) of diethyl sulfate was slowly added dropwise while maintaining the temperature at 20 to 50 ° C. And it was made to react at 50 degreeC for 24 hours, and the diallyl ethyl methyl ammonium ethyl sulfate was obtained as oil. The yield was 399.8 g (yield 100%).
The IR spectrum of the resulting diallylethylmethylammonium ethyl sulfate is shown in FIG. From FIG. 1, there is absorption derived from sulfate ester at 1220 cm −1 and supports this structure. The measured value of the basic molecular weight of the quaternary salt by a gravimetric method using phosphotungstic acid was 264.27 (calculated value 265.38).
実施例２ ジアリルジメチルアンモニウムメチルサルフェイトと二酸化イオウとの共重合体の製造I
（ジアリルジメチルアンモニウムメチルサルフェイトモノマーの製造）
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコ中にジアリルメチルアミン１６７．１ｇ（１．５モル）を仕込み、攪拌しながら硫酸ジメチル１９１．１ｇ（１．５モル）を２０〜５０℃に保ちながらゆっくり滴下した。そして５０℃で２４時間反応させた。次に６５重量％に調整するための水１８９．５ｇを加え、ジアリルジメチルアンモニウムメチルサルフェイトモノマー水溶液を調製した。
Example 2 Preparation of a copolymer of diallyldimethylammonium methylsulfate and sulfur dioxide I
(Production of diallyldimethylammonium methyl sulfate monomer)
Into a 1 liter four-necked round bottom separable flask equipped with a stirrer, a thermometer, and a Dimroth reflux condenser, 167.1 g (1.5 mol) of diallylmethylamine was charged, and 191.1 g of dimethyl sulfate ( 1.5 mol) was slowly added dropwise while maintaining the temperature at 20 to 50 ° C. And it was made to react at 50 degreeC for 24 hours. Next, 189.5 g of water for adjusting to 65% by weight was added to prepare a diallyldimethylammonium methyl sulfate monomer aqueous solution.
（ジアリルジメチルアンモニウムメチルサルフェイトと二酸化イオウとの共重合体の製造）
得られたジアリルジメチルアンモニウムメチルサルフェイトモノマー水溶液（モノマー含有量１．５モル）に、モノマー濃度を調整するための水を加えた後、氷水で冷却・攪拌しながら、二酸化イオウをモノマーに対し当モル量加えた。次に得られたモノマー−二酸化イオウ混合物を所定の重合温度に維持しながら、２８．５重量％過硫酸アンモニウム（以下ＡＰＳと記載する）水溶液４７．６ｇ（モノマーに対して３．０重量％）を分割して加えて共重合させ、ジアリルジメチルアンモニウムメチルサルフェイトと二酸化イオウとの共重合体を水溶液として得た。
(Production of a copolymer of diallyldimethylammonium methylsulfate and sulfur dioxide)
After adding water for adjusting the monomer concentration to the resulting diallyldimethylammonium methylsulfate monomer aqueous solution (monomer content 1.5 mol), the sulfur dioxide is applied to the monomer while cooling and stirring with ice water. Molar amounts were added. Next, while maintaining the obtained monomer-sulfur dioxide mixture at a predetermined polymerization temperature, 47.6 g of an aqueous solution of 28.5 wt% ammonium persulfate (hereinafter referred to as APS) (3.0 wt% based on the monomer) was added. The copolymer was divided and added to obtain a copolymer of diallyldimethylammonium methylsulfate and sulfur dioxide as an aqueous solution.
得られた溶液の一部をアセトンで再沈殿させ、得られた白色固体をろ別し、５０℃で４８時間真空乾燥した。得られた白色粉末状の共重合体のＩＲスペクトルを図２に示す。図２より１３２０ｃｍ−１と１１３０ｃｍ−１に−ＳＯ２−に起因する吸収および１２２０ｃｍ−１に硫酸エステルに起因する吸収が見られることから、ジアリルジメチルアンモニウムメチルサルフェイトと二酸化イオウとの共重合体であることを支持している。 A portion of the resulting solution was reprecipitated with acetone, and the resulting white solid was filtered off and dried in vacuo at 50 ° C. for 48 hours. FIG. 2 shows an IR spectrum of the obtained white powder copolymer. -SO 2 to 1320 cm -1 and 1130 cm -1 from 2 - since the absorption is observed due to the sulfuric acid ester due to absorption and 1220 cm -1, a copolymer of diallyl dimethyl ammonium methyl sulfates and sulfur dioxide I support that.
またこの固体の元素分析値は、Ｓ＝１９．９〜２０．８％であった。この値はジアリルジメチルアンモニウムメチルサルフェイトと二酸化イオウとのモル比１：１の共重合体の値に近い。 The elemental analysis value of this solid was S = 19.9-20.8%. This value is close to that of a 1: 1 molar ratio of diallyldimethylammonium methylsulfate to sulfur dioxide.
得られた共重合体の製造条件、および重合収率と重量平均分子量の結果を表１に示す。またＧＰＣ測定の結果を、図３に示す。
実施例３ ジアリルジメチルアンモニウムメチルサルフェイトと二酸化イオウとの共重合体の製造II
モノマー濃度を変えた以外は、実施例２と同様に操作し、標記の共重合体を得た。得られた共重合体の製造条件、および重合収率と重量平均分子量の結果を表１に示す。
Table 1 shows the production conditions of the obtained copolymer, and the results of the polymerization yield and the weight average molecular weight. The results of GPC measurement are shown in FIG.
Example 3 Preparation of a copolymer of diallyldimethylammonium methylsulfate and sulfur dioxide II
The title copolymer was obtained in the same manner as in Example 2 except that the monomer concentration was changed. Table 1 shows the production conditions of the obtained copolymer, and the results of the polymerization yield and the weight average molecular weight.
実施例４ ジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体の製造I
（ジアリルエチルメチルアンモニウムエチルサルフェイトモノマーの製造）
実施例１と同様にして、攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコ中にジアリルメチルアミン１６７．１ｇ（１．５モル）を仕込み、攪拌しながら硫酸ジエチル２３２．５ｇ（１．５モル）を２０〜５０℃に保ちながらゆっくり滴下した。そして５０℃で２４時間反応させた。次に６５重量％に調整するための水２１２．９ｇを加え、ジアリルエチルメチルアンモニウムエチルサルフェイトモノマー水溶液を調製し、この水溶液をジアリルエチルメチルアンモニウムエチルサルフェイトを単離することなく、二酸化イオウとの共重合反応に用いた。
Example 4 Preparation of a copolymer of diallylethylmethylammonium ethyl sulfate and sulfur dioxide I
(Production of diallylethylmethylammonium ethyl sulfate monomer)
In the same manner as in Example 1, 167.1 g (1.5 mol) of diallylmethylamine was charged into a 1 liter four-necked round bottom separable flask equipped with a stirrer, a thermometer, and a Dimroth reflux condenser. While being maintained at 20 to 50 ° C., 232.5 g (1.5 mol) of diethyl sulfate was slowly added dropwise. And it was made to react at 50 degreeC for 24 hours. Next, 212.9 g of water for adjusting to 65% by weight was added to prepare an aqueous diallylethylmethylammonium ethylsulfate monomer aqueous solution, and this aqueous solution was mixed with sulfur dioxide without isolating diallylethylmethylammonium ethylsulfate. This was used for the copolymerization reaction.
（ジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体の製造）
得られたジアリルエチルメチルアンモニウムエチルサルフェイトモノマー水溶液（モノマー含有量１．５モル）に、モノマー濃度を調整するための水を加えた後、氷水で冷却・攪拌しながら、二酸化イオウをモノマーに対し当モル量加えた。次に得られたモノマー−二酸化イオウ混合物を所定の重合温度に維持しながら、２８．５重量％過硫酸アンモニウム水溶液５２．０ｇ（モノマーに対して３．０重量％）を分割して加えて共重合させ、ジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体を水溶液として得た。
(Production of a copolymer of diallylethylmethylammonium ethyl sulfate and sulfur dioxide)
After adding water for adjusting the monomer concentration to the resulting diallylethylmethylammonium ethylsulfate monomer aqueous solution (monomer content 1.5 mol), the sulfur dioxide is added to the monomer while cooling and stirring with ice water. An equimolar amount was added. Next, while maintaining the obtained monomer-sulfur dioxide mixture at a predetermined polymerization temperature, 52.0 g of an aqueous 28.5 wt% ammonium persulfate solution (3.0 wt% based on the monomer) was added in portions and copolymerized. Thus, a copolymer of diallylethylmethylammonium ethyl sulfate and sulfur dioxide was obtained as an aqueous solution.
得られた溶液の一部をアセトンで再沈殿させ、得られた白色固体をろ別し、５０℃で４８時間真空乾燥した。得られた白色粉末状の共重合体のＩＲスペクトルを図４に示す。図４より１３２０ｃｍ−１と１１３０ｃｍ−１に−ＳＯ２−に起因する吸収および１２２０ｃｍ−１に硫酸エステルに起因する吸収が見られることから、ジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体であることを支持している。 A portion of the resulting solution was reprecipitated with acetone, and the resulting white solid was filtered off and dried in vacuo at 50 ° C. for 48 hours. FIG. 4 shows an IR spectrum of the obtained white powder copolymer. To 1320 cm -1 and 1130 cm -1 from Fig 4 -SO 2 - since the absorption due to sulfate in the absorption and 1220 cm -1 due to the observed, copolymerizing the diallyl methyl ammonium ethyl sulfates and sulfur dioxide Supports being united.
またこの固体の元素分析値は、Ｓ＝１８．８〜１９．３％であった。この値はジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとのモル比１：１の共重合体の値に近い。 The elemental analysis value of this solid was S = 18.8 to 19.3%. This value is close to that of a 1: 1 molar ratio of diallylethylmethylammonium ethyl sulfate to sulfur dioxide.
得られた共重合体の製造条件、および重合収率と重量平均分子量の結果を表２に示す。またＧＰＣ測定の結果を図５に示す。
実施例５ ジアリルエチルメチルアンモニウムエチルサルフェイトと二酸化イオウとの共重合体の製造II
モノマー濃度を変えた以外は、実施例４と同様に操作し、標記の共重合体を得た。得られた共重合体の製造条件、および重合収率と重量平均分子量の結果を表２に示す。
Table 2 shows the production conditions of the obtained copolymer, and the results of the polymerization yield and the weight average molecular weight. The results of GPC measurement are shown in FIG.
Example 5 Preparation of a copolymer of diallylethylmethylammonium ethyl sulfate and sulfur dioxide II
The title copolymer was obtained in the same manner as in Example 4 except that the monomer concentration was changed. Table 2 shows the production conditions of the obtained copolymer, and the results of the polymerization yield and the weight average molecular weight.
試験例１ 溶解性試験
実施例２および実施例４で得られた共重合体０．１ｇを用い、その水、エチレングリコールおよびジメチルスルホキシド（いずれも５ミリリットル）に対する溶解性（３０℃）を検討した。参考例１として、ジアリルジメチルアンモニウムクロリドと二酸化イオウとの共重合体（日東紡（株）、ＰＡＳ−Ａ−１、重量平均分子量約５０００）に対しても同様に溶解性を検討した。それらの結果を表３に示す。本発明の共重合体は、水に可溶で、またジメチルスルホキシドのような有機溶媒にも優れた溶解性を示した。
Test Example 1 Solubility test Using 0.1 g of the copolymer obtained in Example 2 and Example 4, its solubility (30 ° C) in water, ethylene glycol and dimethyl sulfoxide (all 5 ml) was examined. . As Reference Example 1, the solubility was similarly examined for a copolymer of diallyldimethylammonium chloride and sulfur dioxide (Nittobo Co., Ltd., PAS-A-1, weight average molecular weight of about 5000). The results are shown in Table 3. The copolymer of the present invention was soluble in water and showed excellent solubility in organic solvents such as dimethyl sulfoxide.
試験例２ 圧延銅箔へのめっきにおけるレベリング性評価試験
圧延銅箔が設けられたフレキシブルプリント配線基板（ＦＰＣ基板）を用い、実施例４で得られた共重合体を含む、下記組成の硫酸銅めっき浴で圧延銅箔への酸性銅めっき処理を２５℃、陰極電流密度１．５Ａ／ｄｍ２で５０分間、エアレーション攪拌下にて行った。
Test Example 2 Leveling Evaluation Test in Plating on Rolled Copper Foil Using a flexible printed wiring board (FPC board) provided with a rolled copper foil, the copper sulfate of the following composition containing the copolymer obtained in Example 4 The acidic copper plating process was applied to the rolled copper foil in a plating bath at 25 ° C. and a cathode current density of 1.5 A / dm 2 for 50 minutes under aeration stirring.
〈硫酸銅めっき浴組成〉
硫酸銅 ９０ｇ／Ｌ
硫酸 １８０ｇ／Ｌ
塩素イオン ４０ｍｇ／Ｌ
ポリエチレングリコール １） ５００ｍｇ／Ｌ
ＳＰＳ ２） １ｍｇ／Ｌ
実施例４で得られた共重合体 １０００ｍｇ／Ｌ
［注］１）ＨＯ−（Ｃ２Ｈ４Ｏ）ｎ−Ｈ ｎ＝９０
２）ＮａＯ３Ｓ−Ｃ３Ｈ６−Ｓ−Ｓ−Ｃ３Ｈ６−ＳＯ３Ｎａ
<Composition of copper sulfate plating bath>
Copper sulfate 90g / L
Sulfuric acid 180g / L
Chloride ion 40mg / L
Polyethylene glycol 1) 500mg / L
SPS 2) 1mg / L
1000 mg / L of copolymer obtained in Example 4
[Note] 1) HO- (C 2 H 4 O) n -H n = 90
2) NaO 3 S-C 3 H 6 -S-S-C 3 H 6 -SO 3 Na
このようにしてめっきされたＦＰＣ基板について、めっき被膜外観を顕微鏡にて観察し、レベリング性を評価した。 About the FPC board plated in this way, the appearance of the plating film was observed with a microscope, and the leveling property was evaluated.
また上記硫酸銅めっき浴の代わりに、下記に組成を示した、従来の硫酸銅めっき浴（高性能タイプ）を用いた以外は、上記と同様にして、ＦＰＣ基板の圧延銅箔への酸性銅めっきを行い、めっき被膜外観を顕微鏡にて観察し、めっき面のレベリング性を評価した。 In addition, instead of the copper sulfate plating bath, acidic copper to the rolled copper foil of the FPC board was obtained in the same manner as above except that a conventional copper sulfate plating bath (high performance type) having the following composition was used. Plating was performed, and the appearance of the plating film was observed with a microscope to evaluate the leveling property of the plated surface.
〈硫酸銅めっき浴組成〉
硫酸銅 １００ｇ／Ｌ
硫酸 １８０ｇ／Ｌ
塩素イオン ４０ｍｇ／Ｌ
Ｃｕ−Ｂｒｉｔｅ２１ＭＵ １） ５ｍｌ／Ｌ
ＳＰＳ ２） １ｍｇ／Ｌ
［注］１）荏原ユージライト（株）製、商品名
２）ＮａＯ３Ｓ−Ｃ３Ｈ６−Ｓ−Ｓ−Ｃ３Ｈ６−ＳＯ３Ｎａ
<Composition of copper sulfate plating bath>
Copper sulfate 100g / L
Sulfuric acid 180g / L
Chloride ion 40mg / L
Cu-Brite 21MU 1) 5ml / L
SPS 2) 1mg / L
[Note] 1) Ebara Eugleite Co., Ltd., trade name 2) NaO 3 S—C 3 H 6 —S—S—C 3 H 6 —SO 3 Na
その結果、実施例４で得られた共重合体を含むめっき浴でめっき処理されたＦＰＣ基板は、従来のめっき浴でめっき処理されたＦＰＣ基板よりも、めっき被膜が平滑性を有し、レベリング性に優れることが明らかとなった。一方、実施例４で得られた共重合体の代わりにジアリルジメチルアンモニウムクロリドと二酸化イオウとの共重合体（ＰＡＳ−Ａ−１）を用いても、レべリング性の向上はほとんどみられなかった。 As a result, the FPC board plated with the plating bath containing the copolymer obtained in Example 4 has a smoother plating film than the FPC board plated with the conventional plating bath, and the leveling. It became clear that it was excellent in property. On the other hand, even when diallyldimethylammonium chloride / sulfur dioxide copolymer (PAS-A-1) was used instead of the copolymer obtained in Example 4, the leveling property was hardly improved. It was.
本発明によれば、水溶性であり、かつ有機溶媒に対する溶解性に優れ、ファインケミカル分野の用途に極めて有効なジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体を簡単な操作により収率良く工業的に有利に得ることができる。 According to the present invention, a copolymer of diallyldialkylammonium alkyl sulfate and sulfur dioxide, which is water-soluble and has excellent solubility in organic solvents and is extremely effective for applications in the fine chemical field, can be obtained in a high yield by a simple operation. It can be advantageously obtained industrially.
また、本発明によれば、上記共重合体を得るためのモノマーである、新規なジアリルエチルメチルアンモニウムエチルサルフェイトが提供された。 Moreover, according to this invention, the novel diallyl ethyl methyl ammonium ethyl sulfate which is a monomer for obtaining the said copolymer was provided.
Claims (5)
で表されるジアリルジアルキルアンモニウムアルキルサルフェイト単位と、
式（II）
A diallyldialkylammonium alkyl sulfate unit represented by:
Formula (II)
がエチル基である、請求項１に記載のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体。 In the general formula (I), R 1 is an ethyl group, R 2 is a methyl group, R 3
The copolymer of diallyldialkylammonium alkyl sulfate and sulfur dioxide according to claim 1, wherein is an ethyl group.
二酸化イオウ単位のモル比が１／１である交互共重合体である、請求項１または２に記載のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体。 Diallyldialkylammonium alkylsulfate units /
The copolymer of diallyldialkylammonium alkyl sulfate and sulfur dioxide according to claim 1 or 2, wherein the copolymer is an alternating copolymer having a molar ratio of sulfur dioxide units of 1/1.
で表されるジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとを、極性溶媒中で共重合させることを特徴とする請求項１に記載のジアリルジアルキルアンモニウムアルキルサルフェイトと二酸化イオウとの共重合体の製造方法。 General formula (III)
The production of a copolymer of diallyldialkylammonium alkylsulfate and sulfur dioxide according to claim 1, characterized in that a diallyldialkylammonium alkylsulfate represented by the formula (1) and sulfur dioxide are copolymerized in a polar solvent. Method.
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