JPS62243607A - Soap-free emulsion polymerization of vinyl monomer containing basic nitrogen atom - Google Patents
Soap-free emulsion polymerization of vinyl monomer containing basic nitrogen atomInfo
- Publication number
- JPS62243607A JPS62243607A JP8765286A JP8765286A JPS62243607A JP S62243607 A JPS62243607 A JP S62243607A JP 8765286 A JP8765286 A JP 8765286A JP 8765286 A JP8765286 A JP 8765286A JP S62243607 A JPS62243607 A JP S62243607A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- polymerization
- water
- nitrogen atom
- soap
- 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.)
- Granted
Links
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 title claims abstract description 23
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 title claims abstract description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 title abstract description 16
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 13
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 4
- 238000010556 emulsion polymerization method Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 21
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003505 polymerization initiator Substances 0.000 abstract description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 27
- 239000002245 particle Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000012153 distilled water Substances 0.000 description 19
- 239000004816 latex Substances 0.000 description 13
- 229920000126 latex Polymers 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007869 azo polymerization initiator Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- PGMMQIGGQSIEGH-UHFFFAOYSA-N 2-ethenyl-1,3-oxazole Chemical compound C=CC1=NC=CO1 PGMMQIGGQSIEGH-UHFFFAOYSA-N 0.000 description 1
- LSSICPJTIPBTDD-UHFFFAOYSA-N 2-ethenyl-1h-indole Chemical compound C1=CC=C2NC(C=C)=CC2=C1 LSSICPJTIPBTDD-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- CKSURTJJJBWBOU-UHFFFAOYSA-N 3-[(3-amino-3-imino-2-methylpropyl)diazenyl]-2-methylpropanimidamide;hydrochloride Chemical compound Cl.NC(=N)C(C)CN=NCC(C)C(N)=N CKSURTJJJBWBOU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はジメチルアミノエチルメタクリレートを代表例
とする塩基性窒素原子含有ビニルモノマーと、他の共重
合可能な七ツマ−２例えばメチルメタクリレートとを、
乳化剤として機能する界面活性剤の不存在下に、乳化重
合させる方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to the use of basic nitrogen atom-containing vinyl monomers, typified by dimethylaminoethyl methacrylate, and other copolymerizable heptamers, such as methyl methacrylate. ,
The present invention relates to a method of emulsion polymerization in the absence of a surfactant that functions as an emulsifier.
［従来の技術］
乳化剤として機能する界面活性剤を使用せずに、ビニル
糸上ツマ−を重合させる所謂ソープフリー乳化重合法は
、特開昭５０−６１４８４号公報や特公昭５９−１０３
６８号公報等で提案されている。これらの従来のソープ
フリー乳化重合法では、いずれも過硫酸カリウムのよう
な水溶性の過硫酸塩系触媒又は過硫酸塩とスルホキシ化
合物からなるレドックス触媒を重合開始剤として使用す
る。[Prior Art] A so-called soap-free emulsion polymerization method for polymerizing vinyl yarn yarn without using a surfactant that functions as an emulsifier is disclosed in Japanese Patent Application Laid-Open No. 50-61484 and Japanese Patent Publication No. 59-103.
This is proposed in Publication No. 68 and the like. In these conventional soap-free emulsion polymerization methods, a water-soluble persulfate-based catalyst such as potassium persulfate or a redox catalyst consisting of a persulfate and a sulfoxy compound is used as a polymerization initiator.
また、乳化剤を使用する点でソープフリー乳化重合法と
は相違するが１重合開始剤としてアゾ系化合物を使用す
る従来例は、特開昭５８−２５３７８号公報に記載され
ている。Furthermore, a conventional method using an azo compound as a polymerization initiator, which is different from the soap-free emulsion polymerization method in that an emulsifier is used, is described in JP-A-58-25378.
［発明が解決しようとする問題点］
乳化剤を使用する乳化重合法と、ソープフリー重合法を
対比すると、前者はその生成物たる重合体ラテックス中
に残存する乳化剤が、重合体ラテックスの用途に悪影響
を及ぼす心配があるのに対して、後者はそうした懸念が
ない点で優れている。[Problems to be Solved by the Invention] Comparing the emulsion polymerization method using an emulsifier and the soap-free polymerization method, it is found that in the former, the emulsifier remaining in the product polymer latex has an adverse effect on the use of the polymer latex. However, the latter is superior in that there is no such concern.
しかしながら、ジメチルアミノエチルメタクリレートの
如き塩基性窒素原子含有ビニルモノマーは、過酸化物と
レドックス反応を起こすために、従来の方法ではソープ
フリー乳化重合させることができない。However, basic nitrogen atom-containing vinyl monomers such as dimethylaminoethyl methacrylate cannot be subjected to soap-free emulsion polymerization by conventional methods because they undergo redox reactions with peroxides.
而して１本発明は従来法では不可能である塩基性窒素原
子含有ビニルモノマーのソープフリー乳化重合を、ソー
プフリー乳化重合法では新規なアゾ系重合開始剤を使用
して、可能ならしめる方法を提供するを目的とする。Therefore, 1. The present invention provides a method for making soap-free emulsion polymerization of basic nitrogen atom-containing vinyl monomers, which is impossible with conventional methods, possible by using a novel azo polymerization initiator in the soap-free emulsion polymerization method. The purpose is to provide.
［問題点を解決するための手段］
本発明の方法は、一般式：
（式中、Ｒ工は水素又は炭素数１〜５のアルキル基を示
し、Ｒ２，Ｒ，は水素又は炭素数１〜６のアルキル基を
示し、ｎは１〜６の整数を示す。）で表わされる塩基性
窒素原子含有ビニルモノマーと他の共重合可能なモノマ
ーの混合物を、水溶性高分子化合物及び水溶性アゾ化合
物の存在下に水系で乳化重合させることからなり、その
最大の特徴は、アゾビスシアノバレリアン酸を、その０
．５〜１．５当量に相当するアルカリ金属水酸化物又は
水溶性アミンで中和した塩を重合開始剤として使用する
ことにある。[Means for Solving the Problems] The method of the present invention is based on the general formula: 6 alkyl group, and n is an integer of 1 to 6. It consists of emulsion polymerization in an aqueous system in the presence of
．． It consists in using a salt neutralized with an alkali metal hydroxide or a water-soluble amine corresponding to 5 to 1.5 equivalents as a polymerization initiator.
［作 用］
既述した通り、アゾビスシアノバレリアン酸は重合開始
剤として公知であるが、これをそのままジメチルアミノ
エチルメタクリレート（ＤＭＡ）のソープフリー乳化重
合に用いた場合には、重合開始剤として用いた酸がＤＭ
Ａの一部と塩を形成するため、開始剤末端のカルボキシ
ル基が生成重合体粒子の分散安定化に寄与できない。[Function] As mentioned above, azobiscyanovaleric acid is known as a polymerization initiator, but when used as it is in the soap-free emulsion polymerization of dimethylaminoethyl methacrylate (DMA), it acts as a polymerization initiator. The acid used was DM
Since it forms a salt with a part of A, the carboxyl group at the end of the initiator cannot contribute to stabilizing the dispersion of the resulting polymer particles.
ところが、開始剤末端のカルボキシル基を予め中和して
マスクしておくと、最早開始剤はＤＭＡと塩を形成する
ことがないので、重合開始剤は生成重合体粒子の分散安
定化にも寄与し、このために、ソープフリー乳化重合が
安定に遂行するものと考えられる。このことはＤＭＡ以
外の塩基性窒素原子含有ビニル七ツマ−をソープフリー
乳化重合する場合も同様である。However, if the carboxyl group at the end of the initiator is neutralized and masked in advance, the initiator will no longer form a salt with DMA, and the polymerization initiator will also contribute to stabilizing the dispersion of the resulting polymer particles. However, it is believed that for this reason, soap-free emulsion polymerization is carried out stably. This also applies to the soap-free emulsion polymerization of basic nitrogen atom-containing vinyl septamers other than DMA.
従って、本発明ではアゾビスシアノバレリアン酸（Ａ
ＣＶ Ａ）を、その０．５〜１．５当量に相当するアル
カリ金属水酸化物又は水溶性アミンで中和した塩が１重
合開始剤として使用される。そしてこの場合の水溶性ア
ミンには、アンモニア。Therefore, in the present invention, azobiscyanovaleric acid (A
A salt obtained by neutralizing CV A) with an alkali metal hydroxide or a water-soluble amine corresponding to 0.5 to 1.5 equivalents thereof is used as a polymerization initiator. And the water-soluble amine in this case is ammonia.
メチルアミン、エチルアミン、プロピルアミン、ブチル
アミン、ジメチルアミン、トリメチルアミン、エチルア
ミン、ジエチルアミン、トリエチルアミン、モノエタノ
ールアミン、ジェタノールアミン、Ｎ−メチルエタノー
ルアミン、２−ジメチルアミノエタノールアミンなどが
使用可能であり、またアルカリ金属水酸化物には、リチ
ウム、カリウム及びす１−リウムの各水酸化物が使用可
能である。中和当量について言えば、その値が０．５未
満では乳化重合を円滑に進行させることができず、１．
５超ではＤＭＡなどの塩基性窒素原子含有ビニルモノマ
ーが加水分解しやすくなるので好ましくない。一般的に
は０．８〜１．１の中和当量を採用するのが好適である
。Methylamine, ethylamine, propylamine, butylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, monoethanolamine, jetanolamine, N-methylethanolamine, 2-dimethylaminoethanolamine, etc. can be used, and alkaline Lithium, potassium, and 1-lium hydroxides can be used as the metal hydroxide. Regarding the neutralization equivalent, if the value is less than 0.5, emulsion polymerization cannot proceed smoothly;
If it exceeds 5, basic nitrogen atom-containing vinyl monomers such as DMA are likely to be hydrolyzed, which is not preferable. Generally, it is suitable to employ a neutralization equivalent of 0.8 to 1.1.
重合開始剤の使用量は、原料モノマー１００重量部当り
０．５〜１５重量部が適当であって、０．５重量部未満
では乳化重合を安定に進めることができない。The appropriate amount of the polymerization initiator to be used is 0.5 to 15 parts by weight per 100 parts by weight of raw material monomers, and if it is less than 0.5 parts by weight, emulsion polymerization cannot proceed stably.
本発明の原料モノマーとしては、一般式：（式中、Ｒ１
は水素又は炭素数１〜５のアルキル基を示し、 Ｒ，、
Ｒ，は水素又は炭素数１〜６のアルキル基を示し、ｎは
１〜６の整数を示す。）で表わされる塩基性窒素原子含
有ビニル七ツマ−と他の共重合可能な七ツマ−が使用さ
れる。The raw material monomer of the present invention has the general formula: (wherein, R1
represents hydrogen or an alkyl group having 1 to 5 carbon atoms, R,,
R represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6. ) and other copolymerizable vinyl heptamers are used.
上記一般式で表わされる塩基性窒素原子含有ビニルモノ
マーの具体例には、ＤＭＡの外、ジエチルアミノエチル
メタクリレート、ジメチルアミノプロピルメタクリレー
ト、ジメチルアミノエチルアクリレート、ジエチルアミ
ノエチルアクリレートなどが包含される。また、「他の
共重合可能な七ツマ−」とは、塩基性窒素原子含有ビニ
ル七ツマ−と共重合可能なモノマーを意味し、そうした
モノマーとしては、メタクリル酸アルキルエステル、ア
クリル酸アルキルエステル、アクリロニトリル、アクリ
ルアマイド、Ｎ−メチロールアクリルアマイド、 ダイ
アセトンアクリルアマイド、スチレン、酢酸ビニルなど
を例示することができる外、ビニルピリジン、アミノス
チレン、 Ｎ、Ｎ’−アルキルアミノスチレン、ビニル
イミダゾール、ビニルオキサゾール、ビニルインドール
の如き窒素含有ビニルモノマーも必要に応じて使用する
ことができる。Specific examples of the basic nitrogen atom-containing vinyl monomer represented by the above general formula include DMA, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, and the like. In addition, "other copolymerizable heptamers" means monomers copolymerizable with the basic nitrogen atom-containing vinyl heptamers, and examples of such monomers include alkyl methacrylates, alkyl acrylates, Examples include acrylonitrile, acrylamide, N-methylol acrylamide, diacetone acrylamide, styrene, vinyl acetate, etc., as well as vinylpyridine, aminostyrene, N,N'-alkylaminostyrene, vinylimidazole, vinyloxazole, Nitrogen-containing vinyl monomers such as vinyl indole can also be used if desired.
本発明方法に於ける原料モノマーは、塩基性窒素原子含
有ビニルモノマーを０．１〜７０重量％含有するのが通
例である。塩基性窒素原子含有ビニルモノマー単独では
、水溶性ポリマーが多量に生成し、乳化重合を安定に実
施できない。The raw material monomer used in the method of the present invention usually contains 0.1 to 70% by weight of a basic nitrogen atom-containing vinyl monomer. If the basic nitrogen atom-containing vinyl monomer is used alone, a large amount of water-soluble polymer will be produced and emulsion polymerization cannot be carried out stably.
本発明のソープフリー乳化重合法では、上に述べたアゾ
系重合開始剤と共に、保護コロイドとして機能する水溶
性高分子化合物が使用される。この水溶性高分子化合物
としては、ポリビニルアルコール、ポリエチレングリコ
ール、ヒドロキシエチルセルロース、カルボキシメチル
セルロース、メチルセルロース、ポリアクリルアマイド
、ポリアクリル酸アルカリ金属塩、ポリメタクリル酸ア
ルカリ金属塩、ポリスチレンスルホン酸アルカリ金属塩
等が使用可能である。In the soap-free emulsion polymerization method of the present invention, a water-soluble polymer compound that functions as a protective colloid is used together with the above-mentioned azo polymerization initiator. As this water-soluble polymer compound, polyvinyl alcohol, polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyacrylamide, alkali metal salt of polyacrylate, alkali metal salt of polymethacrylate, alkali metal salt of polystyrene sulfonate, etc. are used. It is possible.
水溶性高分子化合物の使用は、ソープフリー乳化重合の
安定性を向上させ、生成重合体粒子の粒径を０．１〜１
μの範囲に収め、しかも粒度分布を非常に狭くするうえ
で有効である。しかし。The use of water-soluble polymer compounds improves the stability of soap-free emulsion polymerization and reduces the particle size of the resulting polymer particles by 0.1-1.
It is effective in keeping the particle size within the μ range and making the particle size distribution very narrow. but.
余り多量に使用すると、反応終了後の重合体ラテックス
に残存する水溶性高分子化合物が重合体粒子を凝集させ
てしまう不都合がある。従って、本発明では水溶性高分
子化合物の使用量を、原料モノマー１００重量部当り、
１重量部以下とするものであり、これによって上記のよ
うな不都合を伴うことなく、水溶性高分子化合物特有の
機能を発揮させることができる。If too large a quantity is used, there is a problem that the water-soluble polymer compound remaining in the polymer latex after the reaction ends will aggregate the polymer particles. Therefore, in the present invention, the amount of water-soluble polymer compound to be used per 100 parts by weight of raw material monomer is
The amount is 1 part by weight or less, and thereby allows the water-soluble polymer compound to exhibit its unique functions without the above-mentioned disadvantages.
重合温度は反応媒体である水の沸点以下６０℃以上とす
るのが適当であって、６０℃以下では重合開始剤である
水溶性アゾ化合物の分解速度が遅くなり、ソープフリー
乳化重合を安定に進行させることができない。It is appropriate that the polymerization temperature is below the boiling point of water, which is the reaction medium, and at least 60°C. If it is below 60°C, the decomposition rate of the water-soluble azo compound, which is the polymerization initiator, will be slow, making soap-free emulsion polymerization stable. I can't proceed.
本発明のソープフリー乳化重合法で得られた重合体ラテ
ックスは、そのまま凝集剤や抄紙助剤などとして使用で
きる外１例えば噴霧乾燥によって重合体ラテックスを乾
燥し、必要に応じてジェット粉砕機などで微細化するこ
とにより。The polymer latex obtained by the soap-free emulsion polymerization method of the present invention can be used as it is as a flocculant or papermaking aid. By miniaturization.
重合体微粉末を得ることができる。この重合体微粉末は
臭気がなく、ブローオフ帯電量測定装置でその帯電量を
測定すると、プラス帯電性を示すので、マイナス帯電性
を示す被着体の表面改質剤として使用することができる
。Fine polymer powder can be obtained. This fine polymer powder has no odor, and when its charge amount is measured using a blow-off charge measuring device, it exhibits positive chargeability, so it can be used as a surface modifier for adherends that exhibit negative chargeability.
［実 施 例］
実施例１
攪拌機、温度計、窒素導入管及び還流冷却管を備えたＩ
Ｑのセパラブルフラスコに、蒸留水６４０部（重量、以
下同じ）、ポリビニルアルコール０．２３部、ジメチル
アミノエチルメタクリレート（ＤＭＡ）３．０部及びメ
チルメタクリレート（ＭＭＡ）１１５部を入れ、窒素気
流下一定の攪拌状態で加熱し１反応塩度が７０℃になっ
た時点で１重合開始剤溶液１８．６部〔アゾビスシアノ
バレリアン酸（Ａ ＣＶ Ａ）２．３部、２５％アンモ
ニア水１．３部、蒸留水１５部〕を投入して重合を開始
させ、重合温度を７０℃に保持して１３０３０分間反応
て重合を完結させた。[Example] Example 1 I equipped with a stirrer, thermometer, nitrogen inlet pipe and reflux condenser pipe
Put 640 parts of distilled water (weight, same below), 0.23 parts of polyvinyl alcohol, 3.0 parts of dimethylaminoethyl methacrylate (DMA), and 115 parts of methyl methacrylate (MMA) into a separable flask (Q), and place under a nitrogen stream. When the salinity of 1 reaction reached 70°C by heating under constant stirring, 18.6 parts of polymerization initiator solution [2.3 parts of azobiscyanovaleric acid (ACV A), 1.2 parts of 25% aqueous ammonia]. 3 parts of distilled water and 15 parts of distilled water] to start polymerization, and the polymerization temperature was maintained at 70° C. and the reaction was carried out for 13,030 minutes to complete the polymerization.
得られた重合体ラテックスは分散粒子の平均粒径が０．
４５μｍで、凝集物が少ない分散安定性の良い乳化液で
あった。The obtained polymer latex has an average particle size of dispersed particles of 0.
The emulsion had a diameter of 45 μm and had good dispersion stability with few aggregates.
実施例２ 実施例１と同様な反応装置に蒸留水６４０部。Example 2 640 parts of distilled water was added to the same reaction apparatus as in Example 1.
ポリビニルアルコール０．２３部、ＤＭＡ３８部１ＭＭ
Ａ３７部を入れ、窒素気流下一定の攪拌状態で加熱する
。反応系の温度が７５℃になった時点で実施例１と同一
の重合開始剤溶液を１８．６部投入して重合を開始させ
、重合温度を７５℃に保って１１０分間反応させて重合
を完結させた。Polyvinyl alcohol 0.23 parts, DMA 38 parts 1MM
Add 37 parts of A and heat with constant stirring under a nitrogen stream. When the temperature of the reaction system reached 75°C, 18.6 parts of the same polymerization initiator solution as in Example 1 was added to initiate polymerization, and the polymerization was carried out for 110 minutes while maintaining the polymerization temperature at 75°C. Completed it.
得られた重合体ラテックスは分散粒子の平均粒径が１．
０μ■で、凝集物が少ない分散安定性の良い乳化液であ
った。The obtained polymer latex has dispersed particles with an average particle diameter of 1.
The emulsion was 0μ■ and had good dispersion stability with few aggregates.
実施例３
実施例１と同様な反応装置に蒸留水６４０部、ポリビニ
ルアルコール０．２３部、ＤＭＡ３．０部、Ｍ Ｍ Ａ
１１５部を入れ、窒素気流下一定の攪拌状態で加熱す
る。反応系の温度が７５℃になった時点で、重合開始剤
溶液２３．８部（Ａ ＣＶ Ａ５．５部、２５％アンモ
ニア水３．３部、蒸留水１５部）を投入して重合を開始
させ１重合部度を７５℃に保って１１０分間反応させて
重合を完結させた。Example 3 640 parts of distilled water, 0.23 parts of polyvinyl alcohol, 3.0 parts of DMA, and MMA were added to the same reaction apparatus as in Example 1.
Add 115 parts of the mixture and heat with constant stirring under a nitrogen stream. When the temperature of the reaction system reached 75°C, 23.8 parts of polymerization initiator solution (5.5 parts of ACV A, 3.3 parts of 25% ammonia water, 15 parts of distilled water) was added to start polymerization. One polymerization portion was maintained at 75° C. and reacted for 110 minutes to complete polymerization.
得られた重合体ラテックスは分散粒子の平均粒径が０．
５μｍで、凝集物が少ない分散安定性の良い乳化液であ
った。The obtained polymer latex has an average particle size of dispersed particles of 0.
The emulsion had a particle size of 5 μm and had good dispersion stability with few aggregates.
実施例４
実施例１と同様な反応装置に蒸留水６４０部、ポリビニ
ルアルコール０．２３部、 ジエチルアミノエチルメタ
クリレート３．０部、Ｍ Ｍ Ａ １１５部を入れ、窒
素気流下一定の攪拌状態で加熱する。Example 4 640 parts of distilled water, 0.23 parts of polyvinyl alcohol, 3.0 parts of diethylaminoethyl methacrylate, and 115 parts of MMA were placed in a reaction apparatus similar to that of Example 1, and heated with constant stirring under a nitrogen stream. .
反応系の温度が８０℃になった時点で、重合開始剤溶液
１８．３部（Ａ ＣＶ Ａ２．３部、モノエタノールア
ミン１．０部、蒸留水１５部）を投入して重合を開始さ
せ、重合温度を８０℃に保って１２０２０分間反応て重
合を完結させた。When the temperature of the reaction system reached 80°C, 18.3 parts of a polymerization initiator solution (2.3 parts of ACV A, 1.0 parts of monoethanolamine, 15 parts of distilled water) was added to initiate polymerization. The polymerization temperature was maintained at 80° C. and the reaction was carried out for 12,020 minutes to complete the polymerization.
得られた重合体ラテックスは分散粒子の平均粒径が０．
５μｍで、凝集物が少ない分散安定性の良い乳化液であ
った。The obtained polymer latex has an average particle size of dispersed particles of 0.
The emulsion had a particle size of 5 μm and had good dispersion stability with few aggregates.
実施例５
実施例１と同様な反応装置に蒸留水６４０部、ポリビニ
ルアルコール０．２３部、 ジエチルアミノエチルメタ
クリレート３．０部、ＭＭＡ１１５部を入れ、窒素気流
下一定の攪拌状態で加熱する。Example 5 640 parts of distilled water, 0.23 parts of polyvinyl alcohol, 3.0 parts of diethylaminoethyl methacrylate, and 115 parts of MMA are placed in a reaction apparatus similar to that of Example 1, and heated under constant stirring under a nitrogen stream.
反応系の温度が７８℃になった時点で、重合開始剤溶液
２４．５部（Ａ ＣＶ Ａ５．５部、トリエチルアミン
４部、蒸留水１５部）を投入して重合を開始させ。When the temperature of the reaction system reached 78°C, 24.5 parts of a polymerization initiator solution (5.5 parts of ACV A, 4 parts of triethylamine, 15 parts of distilled water) was added to initiate polymerization.
重合温度を８０℃に保って１１０分間反応させて重合を
完結させた。The polymerization temperature was maintained at 80° C. and the reaction was carried out for 110 minutes to complete the polymerization.
得られた重合体ラテックスは分散粒子の平均粒径が０．
６μｍで、凝集物が少ない分散安定性の良い乳化液であ
った。The obtained polymer latex has an average particle size of dispersed particles of 0.
The emulsion had a particle diameter of 6 μm and had good dispersion stability with few aggregates.
実施例６ 実施例１と同様な反応装置に蒸留水６４０部。Example 6 640 parts of distilled water was added to the same reaction apparatus as in Example 1.
ポリビニルアルコール０．２３部、 ＤＭＡ３．０部、
ＭＭＡ６９部、ｎ−ブチルメタクリレート４６部を入れ
、窒素気流下一定の攪拌状態で加熱する。Polyvinyl alcohol 0.23 parts, DMA 3.0 parts,
Add 69 parts of MMA and 46 parts of n-butyl methacrylate, and heat with constant stirring under a nitrogen stream.
反応系の温度が７５℃↓こなった時点で、重合開始剤溶
液１８部（ＡＣＶＡ２．３部、水酸化ナトリウム０．７
部、蒸留水１５部）を投入して重合を開始させ。When the temperature of the reaction system reached 75°C↓, add 18 parts of polymerization initiator solution (2.3 parts of ACVA, 0.7 parts of sodium hydroxide).
15 parts of distilled water) to start polymerization.
重合温度を８０℃に保って１２０２０分間反応て重合を
完結させた。The polymerization temperature was maintained at 80° C. and the reaction was carried out for 12,020 minutes to complete the polymerization.
得られた重合体ラテックスは分散粒子の平均粒径が０．
７μ醜で、凝集物が少ない分散安定性の良い乳化液であ
った。The obtained polymer latex has an average particle size of dispersed particles of 0.
The emulsion was 7μ ugly, had few aggregates, and had good dispersion stability.
実施例７ 実施例１と同様な反応装置に蒸留水６４０部。Example 7 640 parts of distilled water was added to the same reaction apparatus as in Example 1.
ポリビニルアルコール０．２３部、ＤＭＡ３．０部、Ｍ
Ｍ Ａ ２０部、スチレン６０部、アクリル酸ブチル
３５部を入れ、窒素気流下一定の攪拌状態で加熱する０
反応系の温度が７５℃になった時点で、重合σ汀始剤溶
液２１．５部（Ａ ＣＶ Ａ５．５部、水酸化リチウム
１．０部、蒸留水１５部）を投入して重合を開始させ、
重合温度を８０℃に保って１２０２０分間反応て重合を
完結させた。Polyvinyl alcohol 0.23 parts, DMA 3.0 parts, M
Add 20 parts of MA, 60 parts of styrene, and 35 parts of butyl acrylate, and heat with constant stirring under a nitrogen stream.
When the temperature of the reaction system reached 75°C, 21.5 parts of polymerization σ initiator solution (5.5 parts of ACV A, 1.0 parts of lithium hydroxide, 15 parts of distilled water) was added to initiate polymerization. let it start,
The polymerization temperature was maintained at 80° C. and the reaction was carried out for 12,020 minutes to complete the polymerization.
得られた重合体ラテックスは分散粒子の平均粒径が０．
５μｍで、凝集物が少ない分散安定性の良い乳化液であ
った。The obtained polymer latex has an average particle size of dispersed particles of 0.
The emulsion had a particle size of 5 μm and had good dispersion stability with few aggregates.
比較例１
実施例１と同様な反応装置に蒸留水６４０部、ポリビニ
ルアルコール０．２３部、ＤＭＡ３．０部、ＭＭＡ１１
５部を入れ、窒素気流下一定の攪拌状態で加熱する。反
応系の温度が７５℃になった時点で、ＡＣＶＡ溶液１７
．３部（Ａ ＣＶ Ａ２．３部、蒸留水１５部）を投入
して重合を開始させたところ、反応開始後約３０分で反
応物が増粘し、樹脂が析出して攪拌が困難になったので
、水を投入して実験を中止した。Comparative Example 1 In a reaction apparatus similar to Example 1, 640 parts of distilled water, 0.23 parts of polyvinyl alcohol, 3.0 parts of DMA, and 11 parts of MMA were added.
Add 5 parts of the mixture and heat with constant stirring under a nitrogen stream. When the temperature of the reaction system reached 75°C, ACVA solution 17
．． When polymerization was started by adding 3 parts of ACV (2.3 parts of ACV, 15 parts of distilled water), the reactants thickened approximately 30 minutes after the start of the reaction, and the resin precipitated, making stirring difficult. Therefore, water was added and the experiment was stopped.
比較例２
実施例１と同様な反応装置に蒸留水８００部、ポリビニ
ルアルコール０．２部、ＤＭＡ２部、ＭＭＡ２００部を
入れ、窒素気流下一定の攪拌状態で加熱する１反応系の
温度が７５℃になった時点で。Comparative Example 2 800 parts of distilled water, 0.2 parts of polyvinyl alcohol, 2 parts of DMA, and 200 parts of MMA are placed in the same reaction apparatus as in Example 1, and heated under constant stirring under a nitrogen stream.1 The temperature of the reaction system is 75°C. As soon as it became.
過硫酸カリウム（Ｋ Ｐ Ｓ ）２．０部を投入して重
合を開始させたが１反応が遅いのでＫ Ｐ Ｓ ２．０
部を追加したところ１反応物が増粘し、樹脂が析出して
攪拌が困難になったので、実験を中止した。2.0 parts of potassium persulfate (K P S ) was added to start polymerization, but the reaction was slow, so K P S 2.0
When 1 part of the reactant was added, the viscosity of the reactant increased and the resin precipitated, making stirring difficult, so the experiment was discontinued.
比較例３
実施例１と同様な反応装置に蒸留水６５０部、ポリビニ
ルアルコール０．３部−ＤＭＡ２部、ＭＭＡ１２０部を
入れ、窒素気流下一定の攪拌状態で加熱する。反応系の
温度が７８℃になった時点で、アゾビス（２−アミジノ
プロパン）塩酸塩溶液１７．４部（当該塩酸塩２．４部
、蒸留水１５部）を投入して重合を開始させたところ、
反応開始後約３０分で反応物が増粘し、樹脂が析出して
攪拌が困難になったので、水を投入して実験を中止した
。Comparative Example 3 650 parts of distilled water, 0.3 parts of polyvinyl alcohol-2 parts of DMA, and 120 parts of MMA are placed in a reaction apparatus similar to that of Example 1, and heated under constant stirring under a nitrogen stream. When the temperature of the reaction system reached 78°C, 17.4 parts of azobis(2-amidinopropane) hydrochloride solution (2.4 parts of the hydrochloride, 15 parts of distilled water) was added to initiate polymerization. However,
Approximately 30 minutes after the start of the reaction, the reactant thickened and resin precipitated, making stirring difficult, so water was added and the experiment was stopped.
［発明の効果］
本発明のソープフリー乳化重合法によれば、従来はソー
プフリー乳化重合されることが困難であったジメチルア
ミノエチルメタクリレートなどの塩基性窒素原子含有ビ
ニル七ツマ−を安定に乳化重合されることができる。従
って１本発明の方法で得られる重合体ラテックスは、乳
化剤を含まないので、凝集剤や抄紙助剤などに好適に使
用することができ、また、この重合体ラテックスを常法
通り乾燥すれば、プラス帯電性を示す微細な重合体粉末
を得ることができるので、この粉末はマイナス帯電性を
示すポリエチレン粉末やポリスチレンゲルパウダーの表
面改質剤、流動性改良剤として極めて有用である。[Effects of the Invention] According to the soap-free emulsion polymerization method of the present invention, basic nitrogen atom-containing vinyl hexamers such as dimethylaminoethyl methacrylate, which were conventionally difficult to be subjected to soap-free emulsion polymerization, can be stably emulsified. Can be polymerized. Therefore, since the polymer latex obtained by the method of the present invention does not contain an emulsifier, it can be suitably used as a flocculant or a papermaking aid, and if this polymer latex is dried in a conventional manner, Since it is possible to obtain a fine polymer powder that exhibits positive chargeability, this powder is extremely useful as a surface modifier and fluidity improver for polyethylene powder and polystyrene gel powder that exhibit negative chargeability.
Claims (1)
示し、Ｒ＿２、Ｒ＿３は水素又は炭素数１〜６のアルキ
ル基を示し、ｎは１〜６の整数を示す。）で表わされる
塩基性窒素原子含有ビニルモノマーと他の共重合可能な
モノマーの混合物を、水溶性高分子化合物及び水溶性ア
ゾ化合物の存在下に水系で乳化重合させる塩基性窒素原
子含有ビニルモノマーのソープフリー乳化重合法。 ２、水溶性アゾ化合物が、アゾビスシアノバレリアン酸
を、その０．５〜１．５当量に相当するアルカリ金属水
酸化物又は水溶性アミンで中和した塩である特許請求の
範囲第１項記載の方法。 ３、水溶性アゾ化合物の使用量が、モノマー１００重量
部当り０．５〜１５重量部である特許請求の範囲第１項
記載の方法。 ４、水溶性高分子化合物の使用量が、モノマー１００重
量部当り１重量部以下である特許請求の範囲第１項記載
の方法。[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R_2 and R_3 represent hydrogen or a 6 alkyl group, and n is an integer of 1 to 6. A soap-free emulsion polymerization method of basic nitrogen atom-containing vinyl monomers, which is emulsion polymerized in an aqueous system in the presence of. 2. Claim 1, wherein the water-soluble azo compound is a salt obtained by neutralizing azobiscyanovaleric acid with an alkali metal hydroxide or a water-soluble amine corresponding to 0.5 to 1.5 equivalents thereof. Method described. 3. The method according to claim 1, wherein the amount of the water-soluble azo compound used is 0.5 to 15 parts by weight per 100 parts by weight of the monomer. 4. The method according to claim 1, wherein the amount of water-soluble polymer compound used is 1 part by weight or less per 100 parts by weight of monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8765286A JPH0713111B2 (en) | 1986-04-16 | 1986-04-16 | Soap-free emulsion polymerization method of vinyl monomer containing basic nitrogen atom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8765286A JPH0713111B2 (en) | 1986-04-16 | 1986-04-16 | Soap-free emulsion polymerization method of vinyl monomer containing basic nitrogen atom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62243607A true JPS62243607A (en) | 1987-10-24 |
| JPH0713111B2 JPH0713111B2 (en) | 1995-02-15 |
Family
ID=13920892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8765286A Expired - Fee Related JPH0713111B2 (en) | 1986-04-16 | 1986-04-16 | Soap-free emulsion polymerization method of vinyl monomer containing basic nitrogen atom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0713111B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225505A (en) * | 1989-12-21 | 1993-07-06 | Atochem | Acrylic copolymers and their use as coatings |
| JP2006008561A (en) * | 2004-06-24 | 2006-01-12 | Kao Corp | Polymer emulsion for cosmetic |
| US7960091B2 (en) * | 2008-01-31 | 2011-06-14 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
| WO2012093464A1 (en) * | 2011-01-06 | 2012-07-12 | 株式会社カネカ | Methyl methacrylate polymer production method |
| CN111410714A (en) * | 2020-05-16 | 2020-07-14 | 连云港万泰医药辅料技术有限公司 | Preparation method of gastric-soluble coating material polyacrylic resin IV |
-
1986
- 1986-04-16 JP JP8765286A patent/JPH0713111B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5225505A (en) * | 1989-12-21 | 1993-07-06 | Atochem | Acrylic copolymers and their use as coatings |
| JP2006008561A (en) * | 2004-06-24 | 2006-01-12 | Kao Corp | Polymer emulsion for cosmetic |
| JP4536433B2 (en) * | 2004-06-24 | 2010-09-01 | 花王株式会社 | Polymer emulsion for cosmetics |
| US7960091B2 (en) * | 2008-01-31 | 2011-06-14 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
| WO2012093464A1 (en) * | 2011-01-06 | 2012-07-12 | 株式会社カネカ | Methyl methacrylate polymer production method |
| CN111410714A (en) * | 2020-05-16 | 2020-07-14 | 连云港万泰医药辅料技术有限公司 | Preparation method of gastric-soluble coating material polyacrylic resin IV |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0713111B2 (en) | 1995-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0183466A2 (en) | Process for the production of a water-soluble polymer dispersion | |
| US2524627A (en) | Suspension polymerization of vinyl compounds | |
| US2326078A (en) | Process of polymerizing methacrylic acid | |
| WO2019218607A1 (en) | Method for synthesizing magadiite/pmma nano composite microspheres by using ph value regulation in pickering emulsion | |
| JPS62243607A (en) | Soap-free emulsion polymerization of vinyl monomer containing basic nitrogen atom | |
| US4529782A (en) | High molecular weight water soluble polymers | |
| JPH0463082B2 (en) | ||
| JP3732557B2 (en) | Carboxyl group-containing polymer composition | |
| JP3658032B2 (en) | Method for producing sodium polyacrylate | |
| JP2003516427A (en) | Water-in-oil polymer emulsion and method for producing the same | |
| JP3869898B2 (en) | Method for producing acrylamide polymer dispersion | |
| JP3580397B2 (en) | Method for producing aqueous dispersion of water-soluble cationic polymer | |
| JPH0597931A (en) | Production of n-vinylcarboxylic acid amide polymer | |
| JPH11292908A (en) | Polymerization of n-vinylcarboxylic acid amide, polymer and production of polymer | |
| JP3611000B2 (en) | Method for producing aqueous dispersion of vinylamine polymer | |
| US5475047A (en) | Carboxylic acid thickener having improved performance under alkaline conditions | |
| JPH0672170B2 (en) | Method for producing water-soluble polymer dispersion | |
| JP3580396B2 (en) | Method for producing aqueous dispersion of vinylamine polymer | |
| JPS62235304A (en) | Production of fine powder polymer | |
| JPH0326206B2 (en) | ||
| JP4124288B2 (en) | Aqueous dispersion of vinylamine polymer and method for producing the same | |
| JP2003246909A (en) | High polymer dispersion and method for producing the same | |
| US4568731A (en) | Polyacrylamide and polyacrylic acid polymers | |
| JP3417583B2 (en) | Method for producing high acid value acrylic resin | |
| US4074041A (en) | Process for preparing solid water soluble polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |