JP5147010B2 - Cationic vinyl monomer aqueous solution and method for producing the same - Google Patents
Cationic vinyl monomer aqueous solution and method for producing the same Download PDFInfo
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- JP5147010B2 JP5147010B2 JP2008207654A JP2008207654A JP5147010B2 JP 5147010 B2 JP5147010 B2 JP 5147010B2 JP 2008207654 A JP2008207654 A JP 2008207654A JP 2008207654 A JP2008207654 A JP 2008207654A JP 5147010 B2 JP5147010 B2 JP 5147010B2
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- 239000000178 monomer Substances 0.000 title claims description 35
- 229920002554 vinyl polymer Polymers 0.000 title claims description 34
- 239000007864 aqueous solution Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- -1 p-toluenesulfonyl group Chemical group 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 13
- 238000004040 coloring Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 claims description 8
- 239000003125 aqueous solvent Substances 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 7
- 125000006125 ethylsulfonyl group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 7
- 238000000034 method Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005956 quaternization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 241001550224 Apha Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- KDQQMEAEIKFPLQ-UHFFFAOYSA-N n-(1-cyanocyclohexyl)-2-fluorobenzamide Chemical compound FC1=CC=CC=C1C(=O)NC1(C#N)CCCCC1 KDQQMEAEIKFPLQ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Description
本発明は、製造、運搬、または保管時の着色及び重合による変質を防止し、安定性を飛
躍的に向上させたカチオン性ビニルモノマー水系溶液及びその製造方法に関する。
TECHNICAL FIELD The present invention relates to a cationic vinyl monomer aqueous solution and a method for producing the same, which prevent deterioration due to coloring and polymerization during production, transportation or storage, and dramatically improve stability.
カチオン性ビニルモノマーは、耐加水分解を有し、低刺激性であることが知られており
、様々な分野に応用されている。これらカチオン性ビニルモノマーを合成する方法として
は、不飽和第３級アミン類に四級化剤を加えて四級化反応を行わせる方法が公知である（
例えば、四級化反応を、水とアプロティックな有機溶媒からなる混合溶媒存在下で行う方
法（特許文献１）、等）。しかし、これらの公知の方法により得られるカチオン性ビニル
モノマーは、製造、運搬、または保管時に外温、光により色相が劣化し、また、微量の金
属イオン（特に鉄など）等により、増粘やポプコン重合を起こすことがあり、カチオン性
ビニルモノマーの製造や保存時の安定性の向上が大きな課題となっている。
着色したカチオン性ビニルモノマーを原料として各種の重合物を製造すると、得られる
二次製品も着色したものとなる。化粧品等の原料に使用するものにおいては、着色のある
製品は著しく商品価値を減ずる。
Cationic vinyl monomers are known to have hydrolysis resistance, low irritation, and are applied in various fields. As a method for synthesizing these cationic vinyl monomers, a method of adding a quaternizing agent to unsaturated tertiary amines to carry out a quaternization reaction is known (
For example, a method in which the quaternization reaction is performed in the presence of a mixed solvent composed of water and an aprotic organic solvent (Patent Document 1), etc.). However, the cationic vinyl monomers obtained by these known methods are deteriorated in hue due to external temperature and light at the time of production, transportation or storage, and are increased in viscosity by a trace amount of metal ions (especially iron). Popcon polymerization may occur, and the production of cationic vinyl monomers and improvement in stability during storage have become a major issue.
When various polymers are produced using a colored cationic vinyl monomer as a raw material, the resulting secondary product is also colored. In products used as raw materials for cosmetics and the like, colored products significantly reduce the commercial value.
カチオン性ビニルモノマーの安定化方法については、種々の安定剤の添加が検討されて
きたが、これらは主として重合防止を目的としたものであり、着色防止について顕著な効
果を奏する報告はない。重合防止と着色防止を目的としたものとして、アルキレンホスホ
ン酸系金属封鎖剤と重合防止剤とを用いて保存安定性を向上させる方法が開示されている
（特許文献２）が、金属封鎖剤は、一般に高価であるとともに、重合体製造時の重合性の
低下や重合開始剤が限定される可能性がある。
したがって、製造、運搬、または保管時の着色及び重合による劣化が少なく、品質の良
い、安価に製造できるカチオン性ビニルモノマーが望まれていた。
Accordingly, there has been a demand for a cationic vinyl monomer that is less deteriorated due to coloring and polymerization during production, transportation, or storage, has good quality, and can be produced at low cost.
カチオン性ビニルモノマーは、一般に溶液として取り扱われ、かつ、溶液状態で着色及
び重合が著しい。したがって、本発明は、製造、運搬、または保管時の着色及び重合によ
る劣化が少なく、品質が優れた、安価に製造できるカチオン性ビニルモノマー水系溶液及
びその製造方法を提供することを課題とする。
Cationic vinyl monomers are generally handled as solutions and are highly colored and polymerized in solution. Accordingly, it is an object of the present invention to provide an aqueous cationic vinyl monomer solution that is less likely to be deteriorated due to coloring and polymerization during production, transportation, or storage, has excellent quality, and can be produced at low cost, and a method for producing the same.
本発明者らは、これらの課題を解決するため鋭意検討を行った結果、水系溶液のｐＨを
調整することにより課題を解決できることを見いだし、本発明を完成するに至った。
すなわち本発明は、
（１）一般式（１）（式中、Ｒ１は水素原子又はメチル基を、Ｒ２及びＲ３は各々独立に
炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ｒ４は炭素数１
〜３のアルキル基又はベンジル基を、Ａは炭素数１〜３のアルキレン基を、Ｘ はハロゲ
ン原子、メチルスルホニル基、エチルスルホニル基又はｐ−トルエンスルホニル基を、そ
れぞれ表す。）で表されるカチオン性ビニルモノマーを２０〜９５重量％、重合禁止剤と
してハイドロキノン誘導体を１００〜３０００ｐｐｍ含有した水系溶液であって、ｐＨが
７〜８であることを特徴とする、カチオン性ビニルモノマー水系溶液、
（２）一般式（２）（式中、Ｒ１は水素原子又はメチル基を、Ｒ２及びＲ３は各々独立に
炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ａは炭素数１〜
３のアルキレン基を表す。）で表されるジアルキルアミノアルキル（メタ）アクリルアミ
ドと一般式（３）（式中、Ｒ４は炭素数１〜３のアルキル基又はベンジル基を、Ｘはハロ
ゲン原子、メチルスルホニル基、エチルスルホニル基又はｐ−トルエンスルホニル基を表
す。）で表される４級化剤とを、水系溶媒中、重合禁止剤としてハイドロキノン誘導体１
００〜３０００ｐｐｍ存在下反応し一般式（１）（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ａ及
びＸは前記と同じ。）で表されるカチオン性ビニルモノマーに変換後、ｐＨを７〜８にす
ることを特徴とする、製造、運搬、または保管時の着色による劣化が少ないカチオン性ビ
ニルモノマー水系溶液の製造方法、
（３）一般式（２）（式中、Ｒ１は水素原子又はメチル基を、Ｒ２及びＲ３は各々独立に
炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、Ａは炭素数１〜
３のアルキレン基を表す。）で表されるジアルキルアミノアルキル（メタ）アクリルアミ
ドと一般式（３）（式中、Ｒ４は炭素数１〜３のアルキル基又はベンジル基を、Ｘはハロ
ゲン原子、メチルスルホニル基、エチルスルホニル基又はｐ−トルエンスルホニル基を表
す。）で表される４級化剤とを、水系溶媒中、重合禁止剤としてハイドロキノン誘導体１
００〜３０００ｐｐｍ存在下反応し一般式（１）（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ａ及
びＸは前記と同じ。）で表されるカチオン性ビニルモノマーに変換後、ｐＨを７〜８にす
ることを特徴とする、製造、運搬、または保管時の重合による劣化が少ないカチオン性ビ
ニルモノマー水系溶液の製造方法、を提供するものである。
As a result of intensive studies to solve these problems, the present inventors have found that the problem can be solved by adjusting the pH of the aqueous solution, and the present invention has been completed.
That is, the present invention
(1) General formula (1) (wherein R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same or different from each other). Well, R 4 has 1 carbon
1 to 3 alkyl groups or benzyl groups, A represents an alkylene group having 1 to 3 carbon atoms, and X represents a halogen atom, a methylsulfonyl group, an ethylsulfonyl group, or a p-toluenesulfonyl group. Cationic vinyl, characterized in that it is an aqueous solution containing 20 to 95% by weight of a cationic vinyl monomer represented by formula (II) and 100 to 3000 ppm of a hydroquinone derivative as a polymerization inhibitor and having a pH of 7 to 8. Monomer aqueous solution,
(2) General formula (2) (wherein R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same or different from each other). Well, A is C1-C1
3 alkylene groups are represented. ) And a general formula (3) (wherein R 4 is an alkyl group having 1 to 3 carbon atoms or a benzyl group, X is a halogen atom, a methylsulfonyl group, an ethylsulfonyl group) Or a quaternizing agent represented by p-toluenesulfonyl group) as a polymerization inhibitor in an aqueous solvent.
After reacting in the presence of 00 to 3000 ppm and converting to a cationic vinyl monomer represented by the general formula (1) (wherein R 1 , R 2 , R 3 , R 4 , A and X are the same as above), pH 7-8, a method for producing a cationic vinyl monomer aqueous solution with little deterioration due to coloration during production, transportation, or storage,
(3) General formula (2) (wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same or different from each other). Well, A is C1-C1
3 alkylene groups are represented. ) And a general formula (3) (wherein R 4 is an alkyl group having 1 to 3 carbon atoms or a benzyl group, X is a halogen atom, a methylsulfonyl group, an ethylsulfonyl group) Or a quaternizing agent represented by p-toluenesulfonyl group) as a polymerization inhibitor in an aqueous solvent.
After reacting in the presence of 00 to 3000 ppm and converting to a cationic vinyl monomer represented by the general formula (1) (wherein R 1 , R 2 , R 3 , R 4 , A and X are the same as above), pH 7-8, a method for producing a cationic vinyl monomer aqueous solution with little deterioration due to polymerization during production, transportation, or storage.
本発明は、保存時の着色及び重合について検討中、重合防止剤であるハイドロキノン誘
導体と、原料である一般式（２）で表されるジアルキルアミノアルキル（メタ）アクリル
アミドの経時的酸化により生じる微量酸化物が原因であることを見出し、かかる知見をも
とに、重合禁止剤の量を適切化するとともに、反応終了後にｐＨを７〜８に調整すること
により、反応液中に残存する少量の一般式（２）で表される原料を中和したものである。
カチオン性ビニルモノマーは、特に水溶液とした場合、アニオン性対イオンＸ−が水溶
液中の水素イオンと結合することにより強酸を生じることがあり、経時的にｐＨが低下し
、例えば、金属容器保存中や重合体製造時に金属製重合釜の表面を腐食するというおそれ
があった。そのため、重合体製造時のように、脱気や窒素置換により重合防止効果のある
溶存酸素が取り除かれる過酷な条件となるため、この腐食によって溶出した局所的高濃度
の金属イオンが、例えばカチオン性ビニルモノマー中に存在する微量のゲル化要因物質等
に影響を与え、金属容器や金属製重合釜表面にゲルを発生させ、合成収率の低下や、装置
の使用を不可能にするなどの問題があった。ｐＨを７〜８に調整することによって、この
ような強酸を生じること無く、長期にわたり、安定であり、かつ、重合体製造時にゲルを
発生しない、という優れた作用効果を奏する。
したがって、本発明によれば、製造、運搬、または保管時の外温、光、衝撃等による着
色及び重合による劣化を抑制し、一般式（１）で表されるカチオン性ビニルモノマー水系
溶液を長期にわたり着色及び重合を防止することができる。
The present invention is under investigation of coloring and polymerization during storage, and a trace amount of oxidation caused by time-dependent oxidation of a hydroquinone derivative as a polymerization inhibitor and a dialkylaminoalkyl (meth) acrylamide represented by the general formula (2) as a raw material Based on this finding, the amount of the polymerization inhibitor is optimized, and the pH is adjusted to 7-8 after the completion of the reaction. The raw material represented by Formula (2) is neutralized.
The cationic vinyl monomer, especially when an aqueous solution, anionic counterion X - can cause strong acid that binds hydrogen ions in aqueous solution, over time the pH dropped, for example, a metal container during storage In addition, there was a risk of corroding the surface of the metal polymerization kettle during polymer production. Therefore, as in the case of polymer production, it becomes a harsh condition to remove dissolved oxygen that has an effect of preventing polymerization by degassing or nitrogen substitution, so that locally high concentration metal ions eluted by this corrosion are, for example, cationic Problems such as a small amount of gelling substances present in vinyl monomers, causing gels on the surface of metal containers and metal polymerization kettles, resulting in a decrease in synthesis yield and the inability to use the equipment was there. By adjusting the pH to 7-8, such a strong acid is not produced, it is stable for a long time, and there is an excellent effect of not generating a gel during the production of the polymer.
Therefore, according to the present invention, coloring due to external temperature, light, impact, etc. during production, transportation or storage, and deterioration due to polymerization are suppressed, and the cationic vinyl monomer aqueous solution represented by the general formula (1) is used for a long time. Coloring and polymerization can be prevented.
以下、本発明を詳細に説明する。本発明のカチオン性ビニルモノマー水系溶液は、上記
一般式（１）で表されるカチオン性ビニルモノマーを２０〜９５重量％、ハイドロキノン
誘導体を１００〜３０００ｐｐｍ含有し、ｐＨが７〜８である水系溶液である。
一般式（１）で表される化合物は、式中、Ｒ１は水素原子又はメチル基を、Ｒ２及びＲ
３は各々独立に炭素数１〜３のアルキル基で互いに同一であっても異なっていてもよく、
Ｒ４は炭素数１〜３のアルキル基又はベンジル基を、Ａは炭素数１〜３のアルキレン基を
、Ｘ はハロゲン原子、メチルスルホニル基、エチルスルホニル基又はｐ−トルエンスル
ホニル基を、それぞれ表し、上記一般式（２）で表されるジアルキルアミノアルキル（メ
タ）アクリルアミドに、四級化剤として一般式（３）で表される化合物を公知の方法によ
り、水系溶媒中反応させた反応生成物である。
一般式（２）で表される化合物としては、式中、Ｒ１は水素原子又はメチル基を、Ｒ２
及びＲ３は各々独立に炭素数１〜３のアルキル基で互いに同一であっても異なっていても
よく、Ａは炭素数１〜３のアルキレン基を表し、具体的には、Ｎ，Ｎ−ジエチルアミノプ
ロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミ
ド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジプロピルアミ
ノプロピル（メタ）アクリルアミド等が例示される。また、四級化剤としては、メチルク
ロライド、エチルクロライド、メチルブロマイド、エチルブロマイド等のアルキルハライ
ド、ベンジルクロライド、及びベンジルブロマイド等のアラルキルハライド、ジメチル硫
酸、ジエチル硫酸等のアルキル硫酸、パラトルエンスルホン酸メチル、パラトルエンスル
ホン酸エチル等のアルキルトルエンスルフォネートが挙げられる。
Hereinafter, the present invention will be described in detail. The cationic vinyl monomer aqueous solution of the present invention contains 20 to 95% by weight of the cationic vinyl monomer represented by the general formula (1), 100 to 3000 ppm of a hydroquinone derivative, and has a pH of 7 to 8. It is.
In the compound represented by the general formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 and R
3 are each independently an alkyl group having 1 to 3 carbon atoms, which may be the same as or different from each other;
R 4 represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, A represents an alkylene group having 1 to 3 carbon atoms, X represents a halogen atom, a methylsulfonyl group, an ethylsulfonyl group or a p-toluenesulfonyl group. A reaction product obtained by reacting the compound represented by the general formula (3) as a quaternizing agent with a dialkylaminoalkyl (meth) acrylamide represented by the general formula (2) in an aqueous solvent by a known method. It is.
Examples of the compound represented by the general formula (2), wherein the R 1 is a hydrogen atom or a methyl group, R 2
And R 3 each independently represents an alkyl group having 1 to 3 carbon atoms which may be the same or different, and A represents an alkylene group having 1 to 3 carbon atoms, specifically, N, N— Examples include diethylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dipropylaminopropyl (meth) acrylamide and the like. Further, as quaternizing agents, alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and ethyl bromide, aralkyl halides such as benzyl chloride and benzyl bromide, alkyl sulfates such as dimethyl sulfate and diethyl sulfate, p-toluenesulfonic acid Examples thereof include alkyltoluenesulfonates such as methyl and ethyl paratoluenesulfonate.
カチオン性ビニルモノマーは、溶液状、スラリー状等のいずれの形態でもよいが、扱い
やすさの点から、一般式（１）で表されるカチオン性ビニルモノマーを２０〜９５重量％
含有した溶液であることが望ましい。
The cationic vinyl monomer may be in any form such as a solution or slurry, but from the viewpoint of ease of handling, the cationic vinyl monomer represented by the general formula (1) is 20 to 95% by weight.
It is desirable that the solution is contained.
ハイドロキノン誘導体は水系溶液に１００〜３０００ｐｐｍ、好ましくは５００〜１５
００ｐｐｍ、添加される。これ未満の添加量ではカチオン性ビニルモノマーの重合防止効
果が不十分であり、これを超えて添加すると、保存時に着色による障害を生ずる。
用いられるハイドロキノン誘導体としては、カチオン性ビニルモノマーの重合禁止剤と
して用いられるハイドロキノン系の化合物であれば特に制限はないが、中でも、ハイドロ
キノンモノメチルエーテルが特に好ましい。
The hydroquinone derivative is 100-3000 ppm, preferably 500-15 in the aqueous solution.
00 ppm is added. If the addition amount is less than this, the effect of preventing the polymerization of the cationic vinyl monomer is insufficient.
The hydroquinone derivative to be used is not particularly limited as long as it is a hydroquinone compound used as a polymerization inhibitor for a cationic vinyl monomer. Among them, hydroquinone monomethyl ether is particularly preferable.
上記一般式（２）で表されるジアルキルアミノアルキル（メタ）アクリルアミドと上記
一般式（３）で表される４級化剤とは、水系溶媒中、反応される。
水系溶媒としては、水、及び水と任意の割合で混合するアセトン、アルコール等と水の
混合溶媒が例示され、反応条件は公知の条件が適用される。
The dialkylaminoalkyl (meth) acrylamide represented by the general formula (2) and the quaternizing agent represented by the general formula (3) are reacted in an aqueous solvent.
Examples of the aqueous solvent include water and a mixed solvent of water, acetone, alcohol and the like mixed with water at an arbitrary ratio, and known conditions are applied as reaction conditions.
本発明において、反応終了後、水系溶液のｐＨを７〜８に調整することにより、本発明
のカチオン性ビニルモノマーを含有した水系溶液とすることができる。
ｐＨの調整方法としては、特に限定はないが、酸を用いる方法が簡便であり好ましい。
酸としては、有機酸あるいは無機酸が用いられ、具体的には、有機酸としては、酢酸、プ
ロピオン酸等のモノカルボン酸、マロン酸、コハク酸、グルタル酸、アジピン酸、マレイ
ン酸、フマル酸、フタル酸等のジカルボン酸、グリコール酸、乳酸、ヒドロキシアクリル
酸、オキシ酪酸、グリセリン酸、リンゴ酸、酒石酸、クエン酸等のヒドロキシカルボン酸
等が挙げられ、また、無機酸としては、リン酸、塩酸、硝酸、硫酸等を挙げることができ
る。酸の添加方法としては、反応溶液にそのまま、あるいは水溶液として添加する方法が
挙げられる。
In this invention, after completion | finish of reaction, it can be set as the aqueous solution containing the cationic vinyl monomer of this invention by adjusting pH of an aqueous solution to 7-8.
The method for adjusting the pH is not particularly limited, but a method using an acid is simple and preferable.
As the acid, an organic acid or an inorganic acid is used. Specifically, examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, and fumaric acid. , Dicarboxylic acids such as phthalic acid, glycolic acid, lactic acid, hydroxyacrylic acid, oxybutyric acid, glyceric acid, malic acid, tartaric acid, citric acid and other hydroxycarboxylic acids, and inorganic acids include phosphoric acid, Examples include hydrochloric acid, nitric acid, sulfuric acid and the like. Examples of the method for adding an acid include a method of adding it to a reaction solution as it is or as an aqueous solution.
色相は、ＡＰＨＡ２００を超えると目視でもわかる程度の着色となるため、それ以下とす
ることが必要である。そのため、本発明の製造、運搬または保管時の着色が少ないとは、
保存後の使用時に、色相測定においてＡＰＨＡ２００以下であることを言う。
If the hue exceeds APHA200, the coloration is of a level that can be seen with the naked eye. Therefore, there is little coloring during production, transportation or storage of the present invention.
When used after storage, it means APHA 200 or less in hue measurement.
以下、実施例によって本発明をさらに説明するが、本発明はこれに限定されるものでは
ない。
なお、本発明における色相及びゲル生成の有無は、以下の方法で測定した。
（色相測定）重合禁止剤を含有したＮ，Ｎ−ジメチルアミノプロピルアクリルアミド４
級塩の７５％水溶液を、反応直後、及び５０ｍＬガラス製密封褐色瓶に容量の７０％にな
るように注入し、４０℃の恒温槽で３ヶ月保管した後の色相をそれぞれ測定（ＡＰＨＡ）
した。
（ゲル生成有無測定）重合禁止剤を含有したＮ，Ｎ−ジメチルアミノプロピルアクリル
アミド４級塩の７５％水溶液を、反応直後、及び５０ｍＬガラス製密封褐色瓶に容量の７
０％になるように注入し、４０℃の恒温槽で３ヶ月保管した後のものをそれぞれ２０質量
部ステンレス製金属容器に入れ、蒸留水２５質量部に溶解した。次いで、室温で窒素ガス
を吹き込み、系内を窒素置換し、ステンレス金属容器壁面への付着ゲル生成の有無を調べ
た。
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.
In addition, the presence or absence of the hue and gel formation in the present invention was measured by the following method.
(Hue measurement) N, N-dimethylaminopropylacrylamide 4 containing a polymerization inhibitor
A 75% aqueous solution of a grade salt was injected immediately after the reaction and into a 50 mL glass sealed brown bottle to 70% of the volume, and the hue after storing in a constant temperature bath at 40 ° C. for 3 months was measured (APHA).
did.
(Measurement of presence or absence of gel formation) A 75% aqueous solution of a quaternary salt of N, N-dimethylaminopropylacrylamide containing a polymerization inhibitor was placed in a sealed brown bottle made of 50 mL glass immediately after the reaction.
After injecting to 0% and storing in a constant temperature bath at 40 ° C. for 3 months, each was put in a 20 parts by mass stainless steel metal container and dissolved in 25 parts by mass of distilled water. Next, nitrogen gas was blown at room temperature, the inside of the system was replaced with nitrogen, and the presence or absence of adhesion gel generation on the wall surface of the stainless metal container was examined.
合成例：Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド４級塩の合成
窒素雰囲気下で、１Ｌの耐圧容器に、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド
２５０ｇ、反応溶媒としてアセトン６３ｇ、蒸留水１１０ｇ、及び重合禁止剤としてハイ
ドロキノンモノメチルエーテルを表１に記載の濃度になるように添加し、内温２０℃以下
に調整、撹拌しながら塩化メチルを注入し、四級化反応を実施した。
反応液中の残存遊離アミン（残存Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド）が
０．２％以下になったところで、反応液中のアセトンを減圧留去し、カチオン性ビニルモ
ノマー７５％含有水溶液３９０ｇを得た。
なお、反応中、終始撹拌への負荷は確認されなかった。
Synthesis example: Synthesis of quaternary salt of N, N-dimethylaminopropyl acrylamide In a nitrogen atmosphere, 250 g of N, N-dimethylaminopropyl acrylamide, 63 g of acetone as a reaction solvent, 110 g of distilled water, and polymerization are prohibited in a 1 L pressure vessel. Hydroquinone monomethyl ether as an agent was added so as to have a concentration shown in Table 1, and the internal temperature was adjusted to 20 ° C. or lower, and methyl chloride was injected while stirring to carry out a quaternization reaction.
When the remaining free amine (residual N, N-dimethylaminopropylacrylamide) in the reaction solution became 0.2% or less, acetone in the reaction solution was distilled off under reduced pressure to obtain 390 g of an aqueous solution containing 75% cationic vinyl monomer. Obtained.
During the reaction, no load on stirring was confirmed throughout.
実施例１〜３及び比較例１
合成例で得た水溶液に、酢酸を添加し表１に記載のｐＨとし、本発明の水系溶液を得た
。
なお、比較例１として、ｐＨを酸性にしたもの、比較例２として、酢酸を添加しないも
の（ｐＨ：なりゆき）を表示した。
結果を表１に示す。
Examples 1 to 3 and Comparative Example 1
Acetic acid was added to the aqueous solution obtained in the synthesis example to obtain the pH shown in Table 1, and the aqueous solution of the present invention was obtained.
In addition, as Comparative Example 1, the acidified pH, and as Comparative Example 2, no acetic acid was added (pH: Naruki).
The results are shown in Table 1.
表１より、水溶液のｐＨを７〜８とした場合に、ｐＨを調整しない場合と比較して色相
劣化の進行が飛躍的に抑制されていることが明らかである。また、重合防止剤であるハイ
ドロキノンモノメチルエーテルの添加量を適切化することにより、さらに保存時の着色が
少ない溶液となることがわかる。また、ｐＨを酸性にした場合には、色相劣化の進行は抑
制されるが、経時的にゲル生成による変質が見られた。
From Table 1, it is clear that when the pH of the aqueous solution is 7 to 8, the progress of hue deterioration is drastically suppressed as compared with the case where the pH is not adjusted. Moreover, it turns out that it becomes a solution with little coloring at the time of a preservation | save by optimizing the addition amount of the hydroquinone monomethyl ether which is a polymerization inhibitor. Further, when the pH was acidified, the progress of hue deterioration was suppressed, but deterioration due to gel formation was observed over time.
以上説明してきたように、本発明のカチオン性ビニルモノマー水系溶液は、製造、運搬
、または保管時の外温、光、衝撃等による色相の劣化及び微量の金属イオン（特に鉄など
）等による重合を抑制し、長期にわたる着色及び増粘やポプコン重合、または重合体製造
時のゲル化による変質を防ぐことができる。したがって、着色や重合により商品価値を損
なう、シャンプー等の香粧品・化粧品等のカチオン性ポリマーの原料として好適に用いる
ことができる。
As described above, the cationic vinyl monomer aqueous solution of the present invention is polymerized by a deterioration in hue due to external temperature, light, impact, etc. during manufacture, transportation, or storage, and a trace amount of metal ions (especially iron). Can be prevented, and deterioration due to long-term coloration and thickening, popcon polymerization, or gelation during polymer production can be prevented. Therefore, it can be suitably used as a raw material for cationic polymers such as cosmetics and cosmetics such as shampoos that impair the commercial value due to coloring or polymerization.
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| US4166828A (en) * | 1977-12-02 | 1979-09-04 | The Dow Chemical Company | Preparation of N-(aminomethyl)-α,β-ethylenically unsaturated carboxamides and their polymers |
| DE3108622A1 (en) * | 1981-03-06 | 1982-09-16 | Wacker-Chemie GmbH, 8000 München | "METHOD FOR STABILIZING AQUEOUS SOLUTIONS OF ACETOACETAMIDES" |
| CA1261334A (en) * | 1985-06-03 | 1989-09-26 | Dodd W. Fong | Water soluble monomers |
| JPH01117850A (en) * | 1987-10-30 | 1989-05-10 | Dia Furotsuku Kk | Method for stabilizing cationic vinyl monomer |
| JP2908515B2 (en) * | 1989-07-07 | 1999-06-21 | 株式会社日本触媒 | Method for producing quaternary ammonium salt |
| JP2872813B2 (en) * | 1990-12-11 | 1999-03-24 | 三井化学株式会社 | Method for producing unsaturated quaternary ammonium salt |
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