JPH0463082B2 - - Google Patents
Info
- Publication number
- JPH0463082B2 JPH0463082B2 JP8337885A JP8337885A JPH0463082B2 JP H0463082 B2 JPH0463082 B2 JP H0463082B2 JP 8337885 A JP8337885 A JP 8337885A JP 8337885 A JP8337885 A JP 8337885A JP H0463082 B2 JPH0463082 B2 JP H0463082B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- parts
- emulsion
- monomer
- methyl methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000178 monomer Substances 0.000 claims description 41
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- 238000004132 cross linking Methods 0.000 claims description 23
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920006037 cross link polymer Polymers 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920003169 water-soluble polymer Polymers 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000010556 emulsion polymerization method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- -1 alkyl methacrylate Chemical compound 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000193 polymethacrylate Polymers 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=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
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明はメチルメタクリレート系の架橋重合体
粒子を含有する水性エマルジヨンの製造法に関す
るものであつて、さらに詳しくは、界面活性剤を
全く使用しない所謂ソープフリー乳化重合法に
て、メチルメタクリレートモノマー又はメチルメ
タクリレートを含有するビニルモノマーと、架橋
性モノマーとを共重合させることにより、架橋重
合体粒子の安定なエマルジヨンを製造する方法に
係る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an aqueous emulsion containing methyl methacrylate crosslinked polymer particles, and more specifically to a so-called soap-free emulsion polymerization method that does not use any surfactant. The present invention relates to a method for producing a stable emulsion of crosslinked polymer particles by copolymerizing a methyl methacrylate monomer or a vinyl monomer containing methyl methacrylate with a crosslinkable monomer.
メチルメタクリレートをソープフリー乳化重合
法にて、他のビニルモノマーと共重合させること
は、他のモノマーが架橋性でない限り比較的容易
であつて、事実、従来技術にもその実例を多数見
ることができる。ところが、メチルメタクリレー
トに反応させしめるモノマーが架橋性モノマーで
ある場合、ソープフリー乳化重合法ではモノマー
並びに生長過程にあるポリマーの分散が不充分で
あることに起因して架橋重合体が凝塊となりやす
く、この傾向は架橋性モノマーの使用量の増加に
伴つて一層増長されるので、ソープフリー乳化重
合法では架橋重合体粒子の安定なエマルジヨンを
製造できないのが通例である。 Copolymerizing methyl methacrylate with other vinyl monomers by soap-free emulsion polymerization is relatively easy unless the other monomers are crosslinkable, and in fact, many examples can be found in the prior art. can. However, when the monomer reacted with methyl methacrylate is a crosslinking monomer, the crosslinked polymer tends to form agglomerates due to insufficient dispersion of the monomer and the polymer during the growth process in the soap-free emulsion polymerization method. Since this tendency is further exacerbated as the amount of crosslinking monomer used increases, it is generally not possible to produce stable emulsions of crosslinked polymer particles using the soap-free emulsion polymerization method.
従つて、メチルメタクリレートと架橋性モノマ
ーを乳化重合させる場合には、モノマー並びに生
成ポリマーの分散を良好ならしめる目的で反応系
に界面活性剤を添加し、状況によつてはさらに分
散安定剤として水溶性高分子を添加して重合を行
わせる方法が一般に慣用されており、この方法に
よれば、一応満足できる均質性と安定性を備えた
架橋重合体のエマルジヨンを得ることができる。
しかしながら、エマルジヨンに界面活性剤が含ま
れていることは、次の点で好ましくない。 Therefore, when emulsion polymerizing methyl methacrylate and a crosslinking monomer, a surfactant is added to the reaction system in order to improve the dispersion of the monomer and the resulting polymer, and depending on the situation, a water-soluble dispersion stabilizer may also be added. A commonly used method is to carry out polymerization by adding a polymer, and according to this method, it is possible to obtain an emulsion of a crosslinked polymer having satisfactory homogeneity and stability.
However, the inclusion of a surfactant in the emulsion is unfavorable for the following reasons.
すなわち、架橋重合体のエマルジヨンは、これ
を例えば噴霧乾燥などの手段で乾燥し、さらにジ
エツト粉砕などの適宜な手段で一次粒子に解砕し
て、顔料、フイラーなどに用いられるが、エマル
ジヨンに界面活性剤が含まれていると、一次粒子
への解砕が困難になるばかりでなく、たとえ解砕
できても粒子に界面活性剤が付着しているため、
粒子の使途によつては、界面活性剤の影響を懸念
しなければならないのである。 In other words, an emulsion of a crosslinked polymer is dried by a method such as spray drying, and then crushed into primary particles by an appropriate method such as jet pulverization to be used for pigments, fillers, etc.; If an activator is included, not only will it be difficult to disintegrate into primary particles, but even if the particles can be disintegrated, the surfactant will still be attached to the particles.
Depending on the intended use of the particles, one must be concerned about the influence of surfactants.
而して本発明は界面活性剤を全く使用しないソ
ープフリー乳化重合法で、架橋重合体粒子の安定
なエマルジヨンを製造する方法を提供するもので
あり、その方法はメチルメタクリレート単独又は
メチルメタクリレートを含有するビニルモノマー
を界面活性剤の不存在下に乳化重合せしめ、その
重合率が１〜40％の範囲に到達した時点で、少な
くとも２個のビニル基を有する架橋性モノマーを
連続的又は間欠的に反応系に添加して重合を続行
させ、前記の重合率が55〜90％の範囲に到達した
時点で、架橋性モノマーの添加を終了し、しかる
後重合反応を完結させることを特徴とする。 Therefore, the present invention provides a method for producing a stable emulsion of crosslinked polymer particles by a soap-free emulsion polymerization method that does not use any surfactant. When the polymerization rate reaches a range of 1 to 40%, a crosslinking monomer having at least two vinyl groups is continuously or intermittently polymerized in the absence of a surfactant. It is characterized in that it is added to the reaction system to continue the polymerization, and when the polymerization rate reaches the range of 55 to 90%, the addition of the crosslinkable monomer is terminated, and then the polymerization reaction is completed.
本発明の方法によれば、乳化重合は界面活性剤
及び架橋性モノマーが一切存在しない条件下で、
メチルメタクレート又はメチルメタクリレートを
含有するビニルモノマーによつて開始され、重合
触媒（開始剤）としては、通常の乳化重合の場合
と同様、有機過酸化物、アゾ化合物、過硫酸塩な
どが使用される。反応開始時に使用されるモノマ
ーはメチルメタクリレート単独であつても差支え
ないが、架橋能を持たない限り他のビニルモノマ
ーも併用可能であつて、そうしたビニルモノマー
にはスチレン、酢酸ビニル、アクリル酸、メタク
リル酸、アクリル酸アルキル、メタクリル酸アル
キル、アクリル酸アミド、メタクリル酸アミド、
アクリロニトリル、Ｎ−メチロールアクリルアミ
ドなどが包含される。これらビニルモノマーを併
用する場合、その使用量は任意に選ぶことができ
るが、一般にはメチルメタクリレート量の50％以
下程度とするのが通例である。本発明は界面活性
剤を含まない条件下で乳化重合を実施することを
要件とするが、分散安定剤として機能する水溶性
高分子の使用までをも排除するものではなく、実
用上はむしろ水溶性高分子を使用する方が好まし
い。この場合、水溶性高分子の使用量は、本発明
で使用するモノマー全量の１重量％以下程度とす
ることを可とし、水溶性高分子としてはポリビニ
ルアルコール、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、高重合度ポリエ
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、ポリスチレンスルホン酸アルカリ属塩など
が使用可能である。 According to the method of the present invention, emulsion polymerization is carried out in the absence of any surfactant and crosslinking monomer.
The polymerization is initiated by a vinyl monomer containing methyl methacrylate or methyl methacrylate, and organic peroxides, azo compounds, persulfates, etc. are used as polymerization catalysts (initiators), as in the case of ordinary emulsion polymerization. Ru. The monomer used at the start of the reaction may be methyl methacrylate alone, but other vinyl monomers can also be used in combination as long as they do not have crosslinking ability; such vinyl monomers include styrene, vinyl acetate, acrylic acid, and methacrylate. acid, alkyl acrylate, alkyl methacrylate, acrylamide, methacrylic acid amide,
Acrylonitrile, N-methylolacrylamide, and the like are included. When these vinyl monomers are used together, the amount used can be arbitrarily selected, but is generally about 50% or less of the amount of methyl methacrylate. Although the present invention requires emulsion polymerization to be carried out under surfactant-free conditions, this does not preclude the use of water-soluble polymers that function as dispersion stabilizers; It is preferable to use a polymer with a high molecular weight. In this case, the amount of water-soluble polymer used can be about 1% by weight or less of the total amount of monomers used in the present invention, and examples of water-soluble polymers include polyvinyl alcohol, alkali metal salt of polyacrylate,
Alkali metal polymethacrylates, highly polymerized polyethylene glycols, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, alkali metal polystyrene sulfonates, and the like can be used.
反応系への架橋性モノマーの添加は、上記した
メチルメタクリレート単独又はメチルメタクリレ
ート含有ビニルモノマーの重合率が１〜40％の範
囲に到達した時点で開始され、55〜90％の範囲に
到達した時点で終了される。つまり、架橋性モノ
マーは重合反応が進行しつつある反応系に、連続
的又は間欠的に添加され、一挙に添加されること
はない。本発明で使用される架橋性モノマーは、
ジビニルベンゼン、ジビニルトルエン、エチレン
グリコールジメタクリレート、トリメタクリル酸
トリメチロールプロパン、アリルメタクリレート
などで例示される如く、１分子中に少なくとも２
個のビニル基を有するモノマーであつて、典型的
にはジビニルベンゼン及びエチレングリコールジ
メタクリレートが使用される。架橋性モノマーの
使用量は本発明で使用する非架橋性モノマー全量
（重量）と同量以下の範囲で任意に選ぶことがで
きる。上記した通り、本発明の方法では架橋性モ
ノマーが連続的又は間欠的に反応系に添加される
が、この場合、架橋性モノマーを非架橋性モノマ
ー又は酢酸エチル、トルエンなどの有機溶剤で稀
釈しておくことができ、こうすることは、添加す
る架橋性モノマーが少量である場合とか、固体で
ある場合に有効である。架橋性モノマーの添加終
了後は、系内の未反応モノマーが消費されるまで
反応を継続してこれを完結させることにより、本
発明の目的生成物たる架橋重合体粒子のエマルジ
ヨンを得ることができる。 Addition of the crosslinking monomer to the reaction system is started when the polymerization rate of the above-mentioned methyl methacrylate alone or vinyl monomer containing methyl methacrylate reaches a range of 1 to 40%, and when it reaches a range of 55 to 90%. It ends with. That is, the crosslinking monomer is added continuously or intermittently to the reaction system in which the polymerization reaction is progressing, and is not added all at once. The crosslinking monomer used in the present invention is
As exemplified by divinylbenzene, divinyltoluene, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc., at least two
Monomers having vinyl groups, typically divinylbenzene and ethylene glycol dimethacrylate, are used. The amount of the crosslinking monomer to be used can be arbitrarily selected within a range equal to or less than the total amount (weight) of the non-crosslinking monomer used in the present invention. As mentioned above, in the method of the present invention, a crosslinking monomer is added continuously or intermittently to the reaction system, but in this case, the crosslinking monomer is diluted with a non-crosslinking monomer or an organic solvent such as ethyl acetate or toluene. This is effective when the crosslinking monomer to be added is small or solid. After the addition of the crosslinking monomer is completed, the reaction is continued until the unreacted monomer in the system is consumed to complete the reaction, thereby obtaining an emulsion of crosslinked polymer particles, which is the desired product of the present invention. .
以上の通り、本発明の方法は界面活性剤を全く
使用しない所謂ソープフリー乳化重合法に、架橋
性モノマーを関与させるが、関与の時期はメタク
リレートモノマー又はメチルメタクリレート含有
ビニルモノマーの重合が或る程度進行し、その重
合率が１〜40％に到達する以後、55〜90％に到達
する以前であり、しかも架橋性モノマーは一挙に
添加されることがないので、本発明によれば架橋
重合体粒子の安定なエマルジヨンを製造すること
ができる。そして本発明で得られるエマルジヨン
は、これを乾燥後一次粒子に解砕すれば、得られ
る微粉末は界面活性剤の影響を全く心配すること
なく、顔料、フイラーなどに利用することができ
る。 As described above, the method of the present invention involves a crosslinking monomer in the so-called soap-free emulsion polymerization method that does not use any surfactant. After the polymerization rate reaches 1 to 40%, but before it reaches 55 to 90%, and the crosslinking monomer is not added all at once, according to the present invention, the crosslinked polymer Stable emulsions of particles can be produced. If the emulsion obtained by the present invention is dried and then crushed into primary particles, the fine powder obtained can be used for pigments, fillers, etc. without worrying about the influence of surfactants.
次に実施例を比較例と共に示して本発明の効果
を具体的に説明するが、実施例及び比較例に示す
「部」はすべて「重量部」を意味する。 Next, the effects of the present invention will be specifically explained by showing Examples and Comparative Examples, and all "parts" shown in Examples and Comparative Examples mean "parts by weight."
実施例 １
還流冷却器、温度計、窒素吹き込み管、滴下ロ
ート及びすり合わせ方式のかきまぜ装置を付した
１の５口フラスコに、蒸留水400部、ポリエチ
レングリコール0.5部、チオ硫酸ナトリウム0.5
部、メタクリレート200部を入れ、窒素気流下、
一定のかきまぜ速度（400rpm）に保ちながら50
℃に昇温する。続いて50℃になつた時点で過硫酸
カリウム１部を加え重合を開始させる。重合を開
始させてから１時間経過後、重合率が10％になつ
たところでスチレン30部、エチレングリコールジ
メタクリレート70部、酢酸エチル50部の混合物を
滴下し始め、重合率が70％になつた時点で滴下を
終える様にする。滴下終了後、50±３℃で３時間
反応を継続して反応を完結させる。Example 1 400 parts of distilled water, 0.5 parts of polyethylene glycol, and 0.5 parts of sodium thiosulfate were placed in a 5-neck flask equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a mixing device.
and 200 parts of methacrylate, and under a nitrogen stream,
50 while maintaining a constant stirring speed (400 rpm).
Increase temperature to ℃. Subsequently, when the temperature reached 50°C, 1 part of potassium persulfate was added to initiate polymerization. One hour after starting the polymerization, when the polymerization rate reached 10%, a mixture of 30 parts of styrene, 70 parts of ethylene glycol dimethacrylate, and 50 parts of ethyl acetate was started dropwise, and the polymerization rate reached 70%. Make sure to finish dripping at this point. After the dropwise addition is completed, the reaction is continued for 3 hours at 50±3°C to complete the reaction.
こうして得られたエマルジヨンは安定で凝集生
成物はほとんどなく、分散粒子の平均粒径は
0.45μであつた。 The emulsion thus obtained is stable, with almost no agglomeration products, and the average particle size of the dispersed particles is
It was 0.45μ.
実施例 ２
還流冷却器、温度計、窒素吹き込み管、滴下ロ
ート及びすり合わせ方式のかきまぜ装置を付した
１の５口フラスコに、蒸留水400部、ポリメタ
クリル酸ソーダ0.5部、チオ硫酸ナトリウム0.5
部、メチルメタクリレート200部を入れ、窒素気
流下、一定のかきまぜ速度（400ppm）に保ちな
がら50℃に昇温する。続いて50℃になつた時点で
過硫酸カリウム１部を加えて重合を開始させる。
重合を開始させてから30分経過後の重合率５％に
なつたところで、メチルメタクリレート20部とジ
ビニルベンゼン80部の混合物を滴下し始め、重合
率が60％になつた時点で滴下を終える様にする。
滴下を終えてから50±３℃で３時間反応を継続し
て反応を完結させる。こうして得られたエマルジ
ヨンは非常に安定で、凝集生成物や撹拌バネへの
付着もほとんど認められず、分散粒子の平均粒径
は0.55μであつた。Example 2 400 parts of distilled water, 0.5 parts of sodium polymethacrylate, and 0.5 parts of sodium thiosulfate were placed in a 5-necked flask equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a mixing device.
and 200 parts of methyl methacrylate, and the temperature was raised to 50°C under a nitrogen stream while maintaining a constant stirring rate (400 ppm). Subsequently, when the temperature reaches 50°C, 1 part of potassium persulfate is added to initiate polymerization.
When the polymerization rate reached 5% 30 minutes after starting the polymerization, a mixture of 20 parts of methyl methacrylate and 80 parts of divinylbenzene was started to be added dropwise, and the dropping was stopped when the polymerization rate reached 60%. Make it.
After the dropwise addition was completed, the reaction was continued for 3 hours at 50±3°C to complete the reaction. The emulsion thus obtained was very stable, with almost no agglomerated products or adhesion to the stirring spring, and the average particle size of the dispersed particles was 0.55μ.
実施例 ３
還流冷却器、温度計、窒素吹き込み管、滴下ロ
ート及びすり合わせ方式のかきまぜ装置を付した
１の５口フラスコに、蒸留水400部、ポリエチ
レングリコール１部、亜硫酸水素ナトリウム１
部、メチルメタクリレート100部、スチレン50部
を入れ、窒素気流下、一定のかきまぜ速度
（400rpm）に保ちながら55℃に昇温する。続いて
55℃になつた時点で過硫酸カリウム２部を加え重
合を開始させる。重合を開始させてから１時間後
の重合率12％になつたところで、ジビニルベンゼ
ン150部とトルエン50部の混合物を滴下し始め、
重合率が80％になつた時点で滴下を終える様にす
る。滴下を終えてから55±３℃で３時間反応を継
続し、反応を完結させる。こうして得たエマルジ
ヨンは安定であり、凝集生成物がほとんどなく、
分散粒子の平均粒径は0.65μであつた。Example 3 400 parts of distilled water, 1 part of polyethylene glycol, and 1 part of sodium bisulfite were placed in a 5-necked flask equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a mixing device.
100 parts of methyl methacrylate, and 50 parts of styrene were added, and the temperature was raised to 55°C under a nitrogen stream while maintaining a constant stirring speed (400 rpm). continue
When the temperature reached 55°C, 2 parts of potassium persulfate was added to initiate polymerization. One hour after starting the polymerization, when the polymerization rate reached 12%, a mixture of 150 parts of divinylbenzene and 50 parts of toluene was started dropwise.
Stop dropping when the polymerization rate reaches 80%. After finishing the dropwise addition, the reaction was continued for 3 hours at 55±3°C to complete the reaction. The emulsion thus obtained is stable and has almost no agglomeration products;
The average particle size of the dispersed particles was 0.65μ.
実施例 ４
還流冷却器、温度計、窒素吹き込み管、滴下ロ
ート及びすり合わせ方式のかきまぜ装置を付した
１の５口フラスコに、蒸留水400部、ポリエチ
レングリコール１部、亜硫酸水素ナトリウム１
部、メチルメタクリレート150部、メチルアクリ
レート50部、アクリロニトリル50部を入れ、窒素
気流下、一定のかきまぜ速度（300rpm）に保ち
ながら55℃に昇温する。続いて55℃になつた時点
で過硫酸カリウム２部を加えて重合を開始させ
る。重合を開始させてから45分後の重合率28％に
なつた時点でジビニルベンゼン50部の滴下を開始
し、重合率が85％になつた時点で滴下を終える様
にする。架橋性モノマーの滴下を終えてから55±
３℃で３時間反応を継続し反応を完結させる。こ
うして得たエマルジヨンは安定であり凝集物がほ
とんどなく、分散粒子の平均粒径は0.35μであつ
た。Example 4 400 parts of distilled water, 1 part of polyethylene glycol, and 1 part of sodium bisulfite were placed in a 5-necked flask equipped with a reflux condenser, thermometer, nitrogen blowing pipe, dropping funnel, and mixing device.
150 parts of methyl methacrylate, 50 parts of methyl acrylate, and 50 parts of acrylonitrile and heated to 55°C under a nitrogen stream while maintaining a constant stirring speed (300 rpm). Subsequently, when the temperature reached 55°C, 2 parts of potassium persulfate was added to initiate polymerization. When the polymerization rate reaches 28%, 45 minutes after starting the polymerization, dropwise addition of 50 parts of divinylbenzene is started, and the dropwise addition is stopped when the polymerization rate reaches 85%. 55± after finishing dropping the crosslinking monomer
The reaction was continued at 3°C for 3 hours to complete the reaction. The emulsion thus obtained was stable and had almost no aggregates, and the average particle size of the dispersed particles was 0.35μ.
比較例 １
実施例１において滴下用架橋性モノマー混合物
を重合初期からフラスコ内に入れて一括仕込の重
合方法で行なつたところ、触媒を添加してから80
分後に粘度が著しく上昇しフラスコ内容物が流動
しない状態になつた。Comparative Example 1 In Example 1, the cross-linking monomer mixture for dropping was put into the flask from the initial stage of polymerization and the polymerization was carried out in bulk.
After a few minutes, the viscosity increased significantly and the contents of the flask became immobile.
比較例 ２
実施例２において添加用架橋性モノマー混合物
を重合初期からフラスコ内に入れて一括仕込の重
合方法で行なつたところ、触媒を加えて90分後に
粘度が著しく上昇しフラスコ内容物が流動しない
状態になり重合の継続は不可能であつた。Comparative Example 2 In Example 2, the crosslinking monomer mixture for addition was put into the flask from the initial stage of polymerization and the polymerization was carried out using a batch charging method. However, 90 minutes after adding the catalyst, the viscosity increased significantly and the contents of the flask became fluid. It became impossible to continue the polymerization.
比較例 ３
実施例４において重合率35％でジビニルベンゼ
ンを一度に加えて重合を６時間継続したところ、
フラスコ内のエマルジヨンは凝集生成物が多く、
しかもフラスコ、撹拌バネへのスケール付着も著
しく多かつた。この凝集生成物とスケール付着物
を削つて200メツシユの金網で過し、乾燥した
後、その重量を測定したところ仕込モノマーの45
％が凝集生成及びスケール付着物になつているこ
とが分つた。Comparative Example 3 In Example 4, divinylbenzene was added at once at a polymerization rate of 35% and polymerization was continued for 6 hours.
The emulsion in the flask contains many agglomerated products,
Furthermore, there was a significant amount of scale adhesion to the flask and stirring spring. The agglomerated products and scale deposits were scraped off, passed through a 200-mesh wire mesh, dried, and weighed.
% was found to result in agglomeration and scale deposits.
比較例 ４
還流冷却後、温度計、窒素吹き込み管、滴下ロ
ート及びすり合わせ方式のかきまぜ装置を付した
１の５口フラスコに、蒸留水400部、ポリエチ
レングリコール１部、亜硫酸水素ナトリウム１
部、メチルメタクリレート285部、ジビニルベン
ゼン15部を入れ、窒素気流下、一定のかきまぜ速
度（400rpm）に保ちながら55℃に昇温する。続
いて55℃になつた時点で過硫酸カリウム２部を加
えて重合を開始させる。55±３℃で８時間保ち反
応を完結させる。こうして得られたエマルジヨン
は凝集生成物が非常に多く、凝集生成物とスケー
ル付着物をけずつて、200メツシユの金網で過
し、乾燥した後、その重量を測定したところ、仕
込モノマーの48％が凝集生成物及びスケール付着
物になつている事が分つた。Comparative Example 4 After cooling under reflux, 400 parts of distilled water, 1 part of polyethylene glycol, and 1 part of sodium hydrogen sulfite were placed in a 5-necked flask equipped with a thermometer, nitrogen blowing tube, dropping funnel, and mixing device.
1 part, 285 parts of methyl methacrylate, and 15 parts of divinylbenzene, and the temperature was raised to 55°C under a nitrogen stream while maintaining a constant stirring speed (400 rpm). Subsequently, when the temperature reached 55°C, 2 parts of potassium persulfate was added to initiate polymerization. The reaction was completed by keeping at 55±3°C for 8 hours. The emulsion thus obtained contained a large amount of agglomerated products, and after scraping off the agglomerated products and scale deposits, it was filtered through a 200-mesh wire mesh, dried, and its weight was measured. was found to have become agglomerated products and scale deposits.
比較例 ５
実施例４においてジビニルベンゼンの滴下開始
を重合率70％のところで行なつたところジビニル
ベンゼンの滴下中に反応系内の増粘が起こり、フ
ラスコ内の撹拌が出来ない状態になつた。Comparative Example 5 In Example 4, when the dropwise addition of divinylbenzene was started at a polymerization rate of 70%, the reaction system increased in viscosity during the dropwise addition of divinylbenzene, making it impossible to stir the inside of the flask.
Claims (1)
リレートを含有するビニルモノマーを界面活性剤
の不存在下に乳化重合させ、その重合率が１〜40
％の範囲に到達した時点で、少なくとも２個のビ
ニル基を有する架橋性モノマーを連続的又は間欠
的に添加して反応を続行し、前記の重合率が55〜
90％の範囲に到達した時点で、架橋性モノマーの
添加を終了し、しかる後反応を完結させることを
特徴とする架橋重合体エマルジヨンの製造法。 ２ 前記の乳化重合を水溶性高分子の存在下で行
う特許請求の範囲第１項記載の方法。 ３ 前記の架橋性モノマーがエチレングリコール
ジメタクリレート又はジビニルベンゼンである特
許請求の範囲第１項記載の方法。[Claims] 1. Methyl methacrylate alone or a vinyl monomer containing methyl methacrylate is emulsion polymerized in the absence of a surfactant, and the polymerization rate is 1 to 40.
%, the reaction is continued by continuously or intermittently adding a crosslinking monomer having at least two vinyl groups until the polymerization rate reaches 55 to 50%.
A method for producing a crosslinked polymer emulsion, characterized in that the addition of the crosslinkable monomer is stopped when the concentration reaches 90%, and the reaction is then completed. 2. The method according to claim 1, wherein the emulsion polymerization is carried out in the presence of a water-soluble polymer. 3. The method according to claim 1, wherein the crosslinking monomer is ethylene glycol dimethacrylate or divinylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8337885A JPS61241310A (en) | 1985-04-18 | 1985-04-18 | Production of emulsion of crosslinked polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8337885A JPS61241310A (en) | 1985-04-18 | 1985-04-18 | Production of emulsion of crosslinked polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61241310A JPS61241310A (en) | 1986-10-27 |
| JPH0463082B2 true JPH0463082B2 (en) | 1992-10-08 |
Family
ID=13800752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8337885A Granted JPS61241310A (en) | 1985-04-18 | 1985-04-18 | Production of emulsion of crosslinked polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61241310A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002156780A (en) * | 2000-09-11 | 2002-05-31 | Mitsubishi Chemicals Corp | Electrostatic charge image developing toner, method for producing the same, and method for fixing the toner |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0335029B1 (en) * | 1988-03-30 | 1994-03-16 | Japan Synthetic Rubber Co., Ltd. | Highly crosslinked polymer particles and process for producing the same |
| JP2722661B2 (en) * | 1989-05-15 | 1998-03-04 | 日本合成ゴム株式会社 | Method for producing aqueous dispersion of reactive polymer particles |
| US6458501B1 (en) * | 1999-09-30 | 2002-10-01 | Xerox Corporation | Forming a toner using surfactant-free emulsion polymerization |
| JP5808552B2 (en) * | 2011-03-10 | 2015-11-10 | 株式会社日本触媒 | Polymer particles |
| TWI582154B (en) * | 2013-02-04 | 2017-05-11 | Japan Exlan Co Ltd | Composite agglomerated resin particles and compositions containing the particles |
| CN105189567B (en) * | 2013-07-24 | 2019-03-26 | 日本A&L株式会社 | The manufacturing method and copolymer emulsion of copolymer emulsion |
| WO2017022423A1 (en) * | 2015-07-31 | 2017-02-09 | 綜研化学株式会社 | (meth)acrylic crosslinked particles and method for producing same |
-
1985
- 1985-04-18 JP JP8337885A patent/JPS61241310A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002156780A (en) * | 2000-09-11 | 2002-05-31 | Mitsubishi Chemicals Corp | Electrostatic charge image developing toner, method for producing the same, and method for fixing the toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61241310A (en) | 1986-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5395903A (en) | Conjugated diene chain-transfer agents for polymerization of olefinically unsaturated (co)monomers | |
| JPH0463082B2 (en) | ||
| JPS5964635A (en) | Production of water-absorptive resin | |
| JP3162367B2 (en) | Protective colloid-based redispersible acrylic resin emulsion powder and method for producing the same | |
| JPS5919127B2 (en) | Method for increasing the molecular weight of vinylpyrrolidone polymers | |
| JP3321209B2 (en) | Method for producing cross-linked carboxyl group-containing polymer | |
| JPS6339606B2 (en) | ||
| JPS62243607A (en) | Soap-free emulsion polymerization of vinyl monomer containing basic nitrogen atom | |
| JPS6028286B2 (en) | Suspension polymerization method for vinyl compounds | |
| US3707585A (en) | Suspension polymerization of vinyl monomers | |
| JPS6139619B2 (en) | ||
| JP3466301B2 (en) | Method for producing monodisperse polystyrene-based particles | |
| JP3658032B2 (en) | Method for producing sodium polyacrylate | |
| JPH028602B2 (en) | ||
| JPS5846122B2 (en) | Chemical modification method of acrylamide polymer | |
| JPH0791348B2 (en) | Method for producing crosslinked polymer particles | |
| JPH0515777A (en) | Production of swellable oil absorbent | |
| JPS6031329B2 (en) | Hydrosol production method | |
| JP3417583B2 (en) | Method for producing high acid value acrylic resin | |
| TWI303251B (en) | Production of polymer | |
| JPS6124047B2 (en) | ||
| US6025443A (en) | Process for the production of spherical polymers | |
| JP2002003511A (en) | Method for producing polymer particle | |
| JPH0586403B2 (en) | ||
| JPS59136305A (en) | Production of water-soluble spherical polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |