JPH01146910A - Preparation of fine spherical polymer particle - Google Patents
Preparation of fine spherical polymer particleInfo
- Publication number
- JPH01146910A JPH01146910A JP30723887A JP30723887A JPH01146910A JP H01146910 A JPH01146910 A JP H01146910A JP 30723887 A JP30723887 A JP 30723887A JP 30723887 A JP30723887 A JP 30723887A JP H01146910 A JPH01146910 A JP H01146910A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylate
- suspension
- polymn
- polymerization
- particle size
- 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000007127 saponification reaction Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000010419 fine particle Substances 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- -1 methacrylate ester Chemical class 0.000 abstract description 5
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 abstract description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 abstract description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000002537 cosmetic Substances 0.000 abstract description 2
- 239000010687 lubricating oil Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229940007550 benzyl acetate Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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、メタクリル酸エステルの懸濁重合により球状
ポリマー微粒子を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing spherical polymer fine particles by suspension polymerization of methacrylic acid ester.
（従来の技術）
従来、メタクリル酸エステルを懸濁重合してポリマー粒
子を製造する際、懸濁安定剤としてメタクリル酸とメタ
クリル酸メチルの共重合体や、鹸化度の高いポリビニル
アルコールなどの水溶性高分子を使用する方法が知られ
ている。(Prior art) Conventionally, when producing polymer particles by suspension polymerization of methacrylic acid ester, a copolymer of methacrylic acid and methyl methacrylate or a water-soluble material such as polyvinyl alcohol with a high degree of saponification was used as a suspension stabilizer. Methods using polymers are known.
（発明が解決しようとする問題点）
しかしながら、これらの方法のうち、前者の場合は、直
径５０μｍより小さい微粒子ができす、懸濁液の安定性
が悪いなどの欠点があり、また後者の場合は、粒径分布
が広くなってしまい、かつ重合後の濾過速度が著しく遅
く（後述の比較例参照）、工業的実施が不可能であるな
どの欠点を有していた。(Problems to be Solved by the Invention) However, among these methods, the former method has drawbacks such as the formation of fine particles smaller than 50 μm in diameter and poor suspension stability, and the latter method had disadvantages such as a wide particle size distribution and a significantly slow filtration rate after polymerization (see Comparative Examples below), making industrial implementation impossible.
本発明は、これらの欠点を解決したもので、メタクリル
酸エステルの懸濁重合により、直径１〜２０μｍの間で
、狭い粒径分布を有し、重合後の脱水時の？過速度が速
い、ポリマー徹粒子の製造方法を提供するものである。The present invention solves these drawbacks, and has a narrow particle size distribution between 1 and 20 μm in diameter by suspension polymerization of methacrylic acid ester, and has a narrow particle size distribution during dehydration after polymerization. The present invention provides a method for producing polymer particles with high overspeed.
（問題を解決するための手段）
本発明は、メタクリル酸エステルの懸濁重合において、
重合度１５００以上でかつ鹸化度７５〜８５モル％のポ
リビニルアルコールを懸濁安定剤として用いる球状ポリ
マー微粒子の製造方法である。(Means for solving the problem) The present invention provides the following steps in suspension polymerization of methacrylic acid ester:
This is a method for producing spherical polymer fine particles using polyvinyl alcohol having a degree of polymerization of 1500 or more and a degree of saponification of 75 to 85 mol% as a suspension stabilizer.
本発明で使用されるメタクリル酸エステルとしては、メ
タクリル酸メチル、メタクリル酸オクチル、メタクリル
酸ステアリルなどの直鎖脂肪族エステル、メタクリル酸
ｔｅｒｔ−ブチル、メタクリル酸２−エチルヘキシルな
どの分岐脂肪族エステル、メタクリル酸アリルなどの不
飽和エステルなどである。The methacrylic esters used in the present invention include straight chain aliphatic esters such as methyl methacrylate, octyl methacrylate, and stearyl methacrylate; branched aliphatic esters such as tert-butyl methacrylate and 2-ethylhexyl methacrylate; These include unsaturated esters such as allyl acids.
本発明においては、上記一官能性のメタクリレートのほ
かに二官能性のジメタクリレートを併用することができ
、それにより多孔性のポリマー粒子を得ることが出来、
かつ耐熱性や粒子硬度を上げることが可能となる。その
際の二官能性ジメタクリル酸エステルとしては、エチレ
ングリコールジメタクリレート、ネオペンチルグリコー
ルジメタクリレートなどが使用でき、これらはいかなる
割合でもよいが、好ましくは全モノマーに対し５〜５０
％の範囲である。In the present invention, in addition to the monofunctional methacrylate described above, a difunctional dimethacrylate can be used in combination, thereby making it possible to obtain porous polymer particles.
Moreover, it becomes possible to increase heat resistance and particle hardness. As the difunctional dimethacrylic ester in this case, ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc. can be used, and these may be used in any proportion, but preferably 5 to 50% of the total monomers.
% range.
メタクリル酸エステルの重合は、５０〜１００℃の温度
で開裂反応が始まり、水への溶解性のないラジカル重合
開始剤を使うことができる。この重合開始剤として、過
酸化ベンゾイル、過酸化ラウロイル、２．２−一アゾビ
スイソブチロニトリル、２，２゛−アゾビス−２，４−
ジメチルバレロニトリルなどが使用できる。これらはメ
タクリル酸エステルに対し０．１〜３．０重量％、望ま
しくは０．２〜０．４重量％の濃度で使用される。In the polymerization of methacrylic acid ester, a cleavage reaction starts at a temperature of 50 to 100°C, and a radical polymerization initiator that is not soluble in water can be used. As the polymerization initiator, benzoyl peroxide, lauroyl peroxide, 2,2-1 azobisisobutyronitrile, 2,2'-azobis-2,4-
Dimethylvaleronitrile etc. can be used. These are used in a concentration of 0.1 to 3.0% by weight, preferably 0.2 to 0.4% by weight, based on the methacrylic ester.
本発明は、懸濁重合の分散媒として、重合度１５００以
上で鹸化度７５〜８５モル％のポリビニルアルコールを
用いることに特徴を有する。それによりポリマー粒子の
粒径を小さくすることができ、しかも粒径分布を狭くす
ることが可能となり、さらに重合後の脱水に際して濾過
速度を高めることができるようになる。重合度が１５０
０未満のポリビニルアルコールでは分散時に、粒子の直
径が１〜２μｍと小さくなり過ぎたり、重合反応中にモ
ノマー液滴同志の凝集が発生したりするし、ポリビニル
アルコールの鹸化度が８５％以上のものでは、分散の際
に粒径分布が広くなり、重合後の濾過の際に、Ｐ紙の目
詰りを起し、濾過に長時間を要する等の問題を生ずる。The present invention is characterized in that polyvinyl alcohol having a degree of polymerization of 1500 or more and a degree of saponification of 75 to 85 mol % is used as a dispersion medium for suspension polymerization. This makes it possible to reduce the particle size of the polymer particles, narrow the particle size distribution, and increase the filtration rate during dehydration after polymerization. Degree of polymerization is 150
If the polyvinyl alcohol has a saponification degree of less than 0, the diameter of the particles may become too small (1 to 2 μm) during dispersion, or agglomeration of monomer droplets may occur during the polymerization reaction. In this case, the particle size distribution becomes wide during dispersion, which causes problems such as clogging of P paper during filtration after polymerization and a long filtration time.
またメタクリル酸−メタクリル酸メチル共重合体のよう
なポリビニルアルコール以外の水溶性高分子を用いた場
合、直径５０μｍ以下の微粒子ができず、さらにｇ濁液
の安定性が劣り撹拌を停止すると、水層とモノマー層に
すぐに分液してしまって微粒子の重合が不可能となる。Furthermore, when water-soluble polymers other than polyvinyl alcohol, such as methacrylic acid-methyl methacrylate copolymer, are used, fine particles with a diameter of 50 μm or less cannot be formed, and the stability of the suspension is poor, and when stirring is stopped, water The liquid immediately separates into the monomer layer and the monomer layer, making it impossible to polymerize the fine particles.
本発明の分散剤は、蒸溜水に対して０．３〜１．０重量
％、好ましくは０．５〜０．７重量％の濃度で溶解させ
た水溶液として用いるのが有効である。The dispersant of the present invention is effectively used as an aqueous solution dissolved in distilled water at a concentration of 0.3 to 1.0% by weight, preferably 0.5 to 0.7% by weight.
本発明の方法により、表面積が大で、かさ比重の小さい
多孔質の微粒子を得ることができる。それは懸濁重合時
に、重合性モノマーのほかに、重合反応に関与しない化
合物（以下希釈剤という）を加えておき、重合後に減圧
乾燥、溶媒洗浄などを行うことにより除去し、希釈剤が
存在していた部分を微細な孔として残すことにより行な
われる。By the method of the present invention, porous fine particles with a large surface area and a small bulk specific gravity can be obtained. During suspension polymerization, in addition to the polymerizable monomer, a compound that does not participate in the polymerization reaction (hereinafter referred to as diluent) is added, and after polymerization, it is removed by drying under reduced pressure, solvent washing, etc., and the diluent is removed. This is done by leaving the areas that were previously covered in tiny holes.
その際の希釈剤としては、ベンゼン、トルエンのような
芳香族炭化水素、ヘプタン、ドデカンのような脂肪族炭
化水素、酢酸ブチル、酢酸ベンジルのようなエステル類
、等の、分散媒として用いる水への溶解度が低い化合物
が用いられる。これらの希釈剤は、全モノマーに対して
０．５〜２．０倍の範囲で使用するのが望ましく、多過
ぎると機械的強度が不足し、少な過ぎると表面積、かな
比重などの性質が不足する結果となる。Examples of diluents include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as heptane and dodecane, and esters such as butyl acetate and benzyl acetate. Compounds with low solubility are used. It is desirable to use these diluents in an amount of 0.5 to 2.0 times the total monomer. If it is too large, mechanical strength will be insufficient, and if it is too small, properties such as surface area and specific gravity will be insufficient. The result is
重合反応は、懸濁分散剤水溶液に、一官能性メタクリレ
ート、二官能性メタクリレート、希釈剤、重合開始剤の
混合液を、水系：モノマー系の比が１０：１から１．５
：ｌ好ましくは４．５：１から２．０：１の割合で加え
、市販の高速分散装置で任意の粒径になるまで分散させ
５０″Ｃ〜１００負゛Ｃの温度で２．０〜２０時間重合
することにより行われる。In the polymerization reaction, a mixed solution of a monofunctional methacrylate, a difunctional methacrylate, a diluent, and a polymerization initiator is added to an aqueous solution of a suspension dispersant at an aqueous:monomer ratio of 10:1 to 1.5.
:l Preferably in a ratio of 4.5:1 to 2.0:1, dispersed with a commercially available high-speed dispersion device until a desired particle size is obtained, and then dispersed at a temperature of 50"C to 100% negative C. This is carried out by polymerizing for 20 hours.
反応後は、微粒子を戸別し、付着しているポリビニルア
ルコールを水で洗浄し、そののち溶剤洗浄または減圧乾
燥を行い希釈剤を除去することにより球状ポリマー微粒
子が精製される。After the reaction, the fine particles are separated, the attached polyvinyl alcohol is washed with water, and the diluent is removed by washing with a solvent or drying under reduced pressure, thereby purifying the spherical polymer particles.
（実施例）
実施例１
５βのセパラブルフラスコに、懸濁分散剤として、重合
度２１２０、鹸化度７９．４％のポリビー：／ｌｚ７’
ル：ｚ−ル（＠１り−ｙ Ｌ／製ＰＶＡ４２０ ）１８
．３７ｔｒを２６２５ｍβの蒸溜水に溶解させ、モノマ
ー系としてメタクリル酸ステアリル３００ｍβ、エチレ
ングリコールジメタクリレート３００ｍ１、トルエン４
５０ｍＪ！、ラウロイルパーオキサイド１．２００ｇの
溶液を加えた。この混合液をラボディスパーザ−（三田
村理研＠Ｊ製Ｘ−１０２０型）を用い、顕微鏡で観察し
な粒径が最大のらので約７，０μｍになるまで分散させ
た。(Example) Example 1 Polybyte with a degree of polymerization of 2120 and a degree of saponification of 79.4% was added to a 5β separable flask as a suspension dispersant.
Le:z-le (@1ri-y L/PVA420) 18
．． 37tr was dissolved in 2625mβ of distilled water, and the monomer system was 300mβ of stearyl methacrylate, 300ml of ethylene glycol dimethacrylate, and 4 toluene.
50mJ! , a solution of 1.200 g of lauroyl peroxide was added. This mixed solution was dispersed using a laboratory spazer (Model X-1020, manufactured by Mitamura Riken @ J) until the particle size, which could not be observed under a microscope, reached a maximum particle size of about 7.0 μm.
フラスコに温度計、撹拌装置、冷却管をとりつけ、窒素
気流下、８０℃で６時間重合反応を行った。得られたス
ラリーを吸引濾過し、戸別した微粒子を再び蒸溜水に分
散させて付着しているポリビニルアルコールを洗浄し濾
過しな。これを１００℃で２日間真空乾燥して希釈剤の
トルエンを蒸発させ光学顕微鏡で観察したところ粒径が
２〜７μｍの多孔性ポリマー微粒子５４０ｇを得た。A thermometer, a stirrer, and a cooling tube were attached to the flask, and the polymerization reaction was carried out at 80° C. for 6 hours under a nitrogen stream. The resulting slurry is filtered by suction, the separated fine particles are dispersed again in distilled water, the polyvinyl alcohol adhering to the slurry is washed away, and the slurry is filtered. This was vacuum dried at 100° C. for 2 days to evaporate the diluent toluene, and when observed under an optical microscope, 540 g of porous polymer fine particles with a particle size of 2 to 7 μm were obtained.
重合反応後のスラリーの濾過は、直径９（！Ｏのヌッチ
ェと濾紙（東洋Ｐ紙■製Ｎｏ、２）を用いたところ、７
５０ｍＪ２のスラリーの水流ポンプによる吸引濾過が、
２４．０分で終了した。The slurry after the polymerization reaction was filtered using a Nutsche with a diameter of 9 (!O) and a filter paper (No. 2 manufactured by Toyo P Paper ■).
Suction filtration of 50mJ2 slurry using a water pump
It ended in 24.0 minutes.
比較例
懸濁分散剤として、重合度２４００、鹸化Ｊ斐８８．０
％のポリビニルアルコール（クラレ（…製ＰＶＡ２２４
）を用いる以外は、実施例１と同様の方法によりポリマ
ー微粒子を重合したところ、重合反応後のスラリ７５０
ｍρを吸引濾過するのに実施例１と同様の装置で２０時
間以上を要しな。Comparative suspension dispersant: degree of polymerization 2400, saponification J 88.0
% polyvinyl alcohol (PVA224 manufactured by Kuraray)
) was used, except that polymer fine particles were polymerized in the same manner as in Example 1. After the polymerization reaction, the slurry 750
It took more than 20 hours to suction-filter mρ using the same apparatus as in Example 1.
実施例２
希釈剤として酢酸ベンジル４５０ｍｊ！を用いる以外は
実施例１と同様の処方、方法により分散させ、９２℃で
４時間重合反応を行なった。懸濁分散剤を蒸溜水で洗浄
したのち、微粒子をアセトンで洗浄し酢酸ベンジルを置
換してから真空乾燥し、実施例１と同様の多孔性ポリマ
ー微粒子（粒径２〜７．＋ｚｍ）５７０ｇを得た。重合
反応後のスラリー７５０ ｍ Ｊ２の濾過は、実施例１
と同様の装置を用いて２２．０分で終了した。Example 2 450 mj of benzyl acetate as a diluent! The dispersion was carried out using the same recipe and method as in Example 1, except that the following was used, and the polymerization reaction was carried out at 92° C. for 4 hours. After washing the suspension dispersant with distilled water, the fine particles were washed with acetone to replace benzyl acetate, and then vacuum dried to obtain 570 g of porous polymer fine particles (particle size 2 to 7.+zm) similar to Example 1. Obtained. Filtration of slurry 750 m J2 after polymerization reaction was carried out in Example 1.
The test was completed in 22.0 minutes using the same equipment as above.
実施例３
二官能性メタクリレートとしてジメチルアリルメタクリ
レ−） Ｈ２Ｃ＝Ｃ（ＣＨ３）Ｃｏｏ−ＣＨ２−ＣＨ
＝Ｃ＜ＣＨｓ ）２ ３００ｍ（１、二官能性ジメタク
リレートとしてネオペンチルグリコールジメタクリレー
ト Ｈ２Ｃ＝Ｃ（ＣＨｓ ）Ｃｏｏ−ＣＨ２Ｃ（ＣＨｓ
）ｚ ＣＨ２−０ＣＯＣ（ＣＨ３）−ＣＨ２３００ｍ
Ｊ２を用いる以外は実施例１と同様の方法により、多孔
性ポリマー微粒子（粒径２〜７μｍ）５５０ｇを得た。Example 3 Dimethylallyl methacrylate as difunctional methacrylate H2C=C(CH3)Coo-CH2-CH
=C<CHs)2 300m(1, neopentyl glycol dimethacrylate as difunctional dimethacrylate H2C=C(CHs)Coo-CH2C(CHs
)z CH2-0COC(CH3)-CH2300m
550 g of porous polymer fine particles (particle size 2 to 7 μm) were obtained in the same manner as in Example 1 except that J2 was used.
重合反応後のスラリー７５０ｍＪ２の濾過には実施例１
と同様の装置を用いて３０．０分を要した。Example 1 was used for filtration of 750 mJ2 of slurry after polymerization reaction.
It took 30.0 minutes using the same equipment as above.
実Ｉ＠例４
二官能性メタクリレートとしてメタクリル酸メチル３０
０ｍＪ２、二官能性メタクリレートとして、エチレング
リコールジメタクリレート３００ｍρを用い、希釈剤を
入れずに、実施例１の分散装置により、最大粒径のもの
が２０μｍになるまで分散し、８０℃で４時間重合した
。そののち、蒸溜水で洗浄し、真空乾燥して、非多孔性
ポリマー微粒子（粒径４〜２０μｍ）５６５ｇを得た。Example I @ Example 4 Methyl methacrylate 30 as difunctional methacrylate
0 mJ2, using 300 mρ of ethylene glycol dimethacrylate as the difunctional methacrylate, without adding a diluent, dispersed with the dispersion device of Example 1 until the maximum particle size was 20 μm, and polymerized at 80 ° C. for 4 hours. did. Thereafter, it was washed with distilled water and vacuum dried to obtain 565 g of non-porous polymer fine particles (particle size: 4 to 20 μm).
重合後のスラリー７５０ｍＪ２の濾過は実施例１と同様
の装置を用いて１５．０分で終了した。Filtration of 750 mJ2 of the slurry after polymerization was completed in 15.0 minutes using the same device as in Example 1.
〈発明の効果）
本発明の製造方法により真珠の形状をもち、直径１．０
〜２０．０μｍの間で狭い粒径分布を有するメタクリル
酸エステルのポリマー微粒子が得られ、かつ重合後には
効率的な濾過速度で洗浄と戸別が可能となる。<Effects of the invention> The manufacturing method of the present invention has a pearl shape and a diameter of 1.0 mm.
Polymer fine particles of methacrylic acid ester having a narrow particle size distribution between 20.0 μm and 20.0 μm are obtained, and after polymerization, it is possible to wash and distribute the product from house to house at an efficient filtration rate.
本発明によるポリマー微粒子は、顔料または潤滑油等へ
の添加剤や化粧品素材等に好適に用いられる。The polymer fine particles according to the present invention are suitably used as additives for pigments or lubricating oils, cosmetic materials, and the like.
Claims (3)
分散剤として重合度１５００以上で、かつ鹸化度７５〜
８５モル％のポリビニルアルコールを使用することを特
徴とする球状ポリマー微粒子の製造方法。(1) In the suspension polymerization of methacrylic acid ester, the polymerization degree is 1500 or more and the saponification degree is 75 to 75 as a suspension dispersant.
A method for producing spherical polymer fine particles, characterized in that 85 mol% of polyvinyl alcohol is used.
ートと二官能性のジメタクリレートの混合物である、特
許請求の範囲第１項に記載の球状ポリマー微粒子の製造
方法。(2) The method for producing spherical polymer fine particles according to claim 1, wherein the methacrylic acid ester is a mixture of a monofunctional methacrylate and a difunctional dimethacrylate.
囲第１項または第２項記載の球状ポリマー微粒子の製造
方法。(3) The method for producing spherical polymer particles according to claim 1 or 2, wherein the spherical polymer particles are porous.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30723887A JPH01146910A (en) | 1987-12-04 | 1987-12-04 | Preparation of fine spherical polymer particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30723887A JPH01146910A (en) | 1987-12-04 | 1987-12-04 | Preparation of fine spherical polymer particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01146910A true JPH01146910A (en) | 1989-06-08 |
Family
ID=17966698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30723887A Pending JPH01146910A (en) | 1987-12-04 | 1987-12-04 | Preparation of fine spherical polymer particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01146910A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1602670A1 (en) * | 2004-06-04 | 2005-12-07 | Nitto Denko Corporation | Production method of porous spherical particles of vinyl polymer |
| DE102012216081A1 (en) | 2012-09-11 | 2013-03-14 | Evonik Industries Ag | Manufacturing light diffusing molded part useful e.g. in a light-emitting diodes-lighting control system, comprises injecting a molding composition comprising a polymethyl methacrylate matrix and spherical plastic particles, into a tool |
| US8609011B2 (en) | 2003-05-06 | 2013-12-17 | Evonik Roehm Gmbh | Method for the production of light-diffusing moulded items with excellent optical characteristics |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62215604A (en) * | 1986-03-17 | 1987-09-22 | Mitsubishi Chem Ind Ltd | Production of crosslinked polymer particle |
-
1987
- 1987-12-04 JP JP30723887A patent/JPH01146910A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62215604A (en) * | 1986-03-17 | 1987-09-22 | Mitsubishi Chem Ind Ltd | Production of crosslinked polymer particle |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8609011B2 (en) | 2003-05-06 | 2013-12-17 | Evonik Roehm Gmbh | Method for the production of light-diffusing moulded items with excellent optical characteristics |
| EP1602670A1 (en) * | 2004-06-04 | 2005-12-07 | Nitto Denko Corporation | Production method of porous spherical particles of vinyl polymer |
| JP2005344066A (en) * | 2004-06-04 | 2005-12-15 | Nitto Denko Corp | Method for producing porous spherical particle of vinyl-based polymer |
| US7122582B2 (en) | 2004-06-04 | 2006-10-17 | Nitto Denko Corporation | Production method of porous spherical particles of vinyl polymer |
| AU2005202436B2 (en) * | 2004-06-04 | 2010-12-23 | Nitto Denko Corporation | Production method of porous spherical particles of vinyl polymer |
| DE102012216081A1 (en) | 2012-09-11 | 2013-03-14 | Evonik Industries Ag | Manufacturing light diffusing molded part useful e.g. in a light-emitting diodes-lighting control system, comprises injecting a molding composition comprising a polymethyl methacrylate matrix and spherical plastic particles, into a tool |
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