JPH0637525B2 - Method for producing spherical particles - Google Patents
Method for producing spherical particlesInfo
- Publication number
- JPH0637525B2 JPH0637525B2 JP8236189A JP8236189A JPH0637525B2 JP H0637525 B2 JPH0637525 B2 JP H0637525B2 JP 8236189 A JP8236189 A JP 8236189A JP 8236189 A JP8236189 A JP 8236189A JP H0637525 B2 JPH0637525 B2 JP H0637525B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerizable monomer
- particles
- dispersed
- aqueous medium
- soluble initiator
- 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 この発明は球状粒子の製造方法に関する。さらに詳しく
は皺状表面を有する球状粒子の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing spherical particles. More specifically, it relates to a method for producing spherical particles having a wrinkled surface.
（ロ）従来の技術及び課題 従来、球状粒子の表面積を大きくする方法として特に多
孔性粒子とするものが多数提案されており、吸着剤やイ
オン交換樹脂として重用されている。しかしながらこれ
ら多孔性粒子ではほぼ中心部まで穴があいているために
強度的に大変脆いという欠点がある。(B) Conventional Techniques and Problems Conventionally, many methods for increasing the surface area of spherical particles, particularly those using porous particles, have been proposed, and they are widely used as adsorbents and ion exchange resins. However, these porous particles have a drawback in that they are very brittle in terms of strength because they have a hole in almost the center thereof.
一方、粒子表面に凹凸状にして表面積を大きくする方法
が若干知られている。この方法としては、例えば特開昭
60-28402号公報に記載のものが挙げられる。On the other hand, there are some known methods for increasing the surface area by making the particle surface uneven. As this method, for example, Japanese Patent Laid-Open No.
Examples thereof include those described in JP-A No. 60-28402.
しかしながら、上記方法による粒子の製造には有機溶剤
を使用するため、その有機溶剤の除去に困難を要してい
る。However, since the organic solvent is used for producing the particles by the above method, it is difficult to remove the organic solvent.
この発明は上記問題点に鑑みてなされたものであり、有
機溶剤を用いることなく強度的に強くかつ表面積の大き
な粒子を製造する方法を提供しようとするものである。The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing particles having a strong strength and a large surface area without using an organic solvent.
（ハ）課題を解決するための手段及び作用 かくしてこの発明によれば、リン酸カルシウムを含有す
る水性媒体中に、油相としての重合性単量体が分散さ
れ、かつこの水性媒体中に水溶性開始剤が、及び分散さ
れた重合性単量体中に油溶性開始剤が各々含有されてな
る懸濁液を調製し、この懸濁液を高速撹拌下で上記重合
性単量体の重合条件に付すことにより、重合性単量体の
重合を分散状態で進行させて表面に多数の皺が形成され
た重合体球状粒子を得ることを特徴とする球状粒子の製
造方法が提供される。(C) Means and Actions for Solving the Problems Thus, according to the present invention, a polymerizable monomer as an oil phase is dispersed in an aqueous medium containing calcium phosphate, and water-soluble initiation in the aqueous medium is started. Agent, and a suspension in which the oil-soluble initiator is contained in each of the dispersed polymerizable monomer, and the suspension is subjected to high-speed stirring under the polymerization conditions of the polymerizable monomer. The method for producing spherical particles is characterized in that the polymerization of the polymerizable monomer is allowed to proceed in a dispersed state to obtain polymer spherical particles having many wrinkles formed on the surface.
この発明の方法においてリン酸カルシウムは分散剤とし
て用いられる。Calcium phosphate is used as a dispersant in the method of this invention.
この発明に用いられる重合性単量体としては、重合性ビ
ニル系単量体が好ましく、例えばアクリロニトリル、メ
タクリロニトリル等のニトリル系単量体、スチレン、α
−メチルスチレン等のスチレン系単量体、ビニルトルエ
ン、塩化ビニル、アクリルアミド等が挙げられる。これ
らの単量体は単独または２種以上の混合物で用いられて
もよい。The polymerizable monomer used in the present invention is preferably a polymerizable vinyl-based monomer, for example, acrylonitrile, nitrile-based monomers such as methacrylonitrile, styrene, α
-Styrene-based monomers such as methylstyrene, vinyltoluene, vinyl chloride, acrylamide and the like. These monomers may be used alone or as a mixture of two or more kinds.
この発明に用いられる水溶性開始剤としては、過硫酸ア
ンモニウム、過硫酸カリウム、過硫酸ナトリウム等が挙
げられる。Examples of the water-soluble initiator used in this invention include ammonium persulfate, potassium persulfate, sodium persulfate and the like.
この発明に用いられる油溶性開始剤としては、上記重合
性単量体に可溶なものであればよく、例えば通常使用さ
れる2,2′−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）等のアゾ系
化合物、過酸化ベンゾイル、過酸化ラウロイル等の過酸
化物等が挙げられる。The oil-soluble initiator used in the present invention may be any one that is soluble in the above-mentioned polymerizable monomer, for example, 2,2′-azobis (isobutyronitrile) which is usually used, 2,2 ′ −
Examples thereof include azo compounds such as azobis (2,4-dimethylvaleronitrile) and peroxides such as benzoyl peroxide and lauroyl peroxide.
この発明において、上記リン酸カルシウム、重合性単量
体、水溶性開始剤及び油溶性開始剤は、それぞれが所定
量で水性媒体中に混合される。上記リン酸カルシウムは
重合性単量体に対して0.1〜20重量％、好ましくは１〜1
5重量％の範囲で用いられる。この場合0.1重量％に満た
ないときは得られる粒子表面に所望の皺が生じなく、一
方20重量％を越えると液の粘度が高くなりすぎて重合性
単量体の分散が不良になる。上記水溶性開始剤は重合性
単量体に対して0.01〜0.3重量％、好ましくは0.05〜0.2
重量％の範囲で用いられる。この場合0.01重量％に満た
ないときは最終的に得られる粒子表面に所望の皺が生じ
なく、一方0.3重量％を越えると粒子が中空状態でかつ
粒子表面に所望の皺が生じない。In the present invention, the calcium phosphate, the polymerizable monomer, the water-soluble initiator and the oil-soluble initiator are mixed in a predetermined amount in an aqueous medium. The calcium phosphate is 0.1 to 20 wt% with respect to the polymerizable monomer, preferably 1 to 1
Used in the range of 5% by weight. In this case, if it is less than 0.1% by weight, desired wrinkles do not occur on the surface of the obtained particles, while if it exceeds 20% by weight, the viscosity of the liquid becomes too high and the dispersion of the polymerizable monomer becomes poor. The water-soluble initiator is 0.01 to 0.3 wt% with respect to the polymerizable monomer, preferably 0.05 to 0.2
Used in the range of wt%. In this case, if the amount is less than 0.01% by weight, desired wrinkles do not occur on the surface of the finally obtained particles, whereas if it exceeds 0.3% by weight, the particles are hollow and desired wrinkles do not occur on the particle surface.
この発明において水系媒体中への上記リン酸カルシウ
ム、重合性単量体、水溶性開始剤及び油溶性開始剤の添
加・混合は、リン酸カルシウムを含有する水性媒体中
に、油相としての重合性単量体が分散され、かつこの水
性媒体中に水溶性開始剤が、及び分散された重合性単量
体中に油溶性開始剤が各々含有されてた懸濁液が調製さ
れるように行われる。この場合、水系媒体中に分散され
た重合性単量体が重合条件に付される前に、この水系媒
体中に上記リン酸カルシウム、重合性単量体、水溶性開
始剤及び油溶性開始剤の各所定量が混合されてさえいれ
ばよく、従って水系媒体中に上記リン酸カルシウム、重
合性単量体、水溶性開始剤及び油溶性開始剤が一度に混
合されるものであってもよく、また、水系媒体中にまず
リン酸カルシウムを添加した後、重合性単量体、水溶性
開始剤及び油溶性開始剤を添加するものであってもよ
く、さらにまた、リン酸カルシウム及び水溶性開始剤を
水性媒体中に添加しておき、ここに油溶性開始剤を含む
重合性開始剤を添加するものであってもよい。上記懸濁
液における重合性単量体の分散は、高速撹拌により達成
される。この高速撹拌の条件は最終的に得られる粒子の
表面状態に影響を及ぼす１因と考えられるので、撹拌翼
の先端の周速度が少なくとも2.3m/s以上である高速撹拌
が適している。詳しくは実施例の記載が参照される。In the present invention, the calcium phosphate, the polymerizable monomer, the water-soluble initiator and the oil-soluble initiator are added to and mixed with the aqueous medium in the aqueous medium containing calcium phosphate, and the polymerizable monomer as an oil phase is used. Is dispersed, and a water-soluble initiator is contained in the aqueous medium, and an oil-soluble initiator is contained in the dispersed polymerizable monomer. In this case, before the polymerizable monomer dispersed in the aqueous medium is subjected to polymerization conditions, the calcium phosphate in the aqueous medium, the polymerizable monomer, the water-soluble initiator and the oil-soluble initiator at various positions. It suffices that a fixed amount is mixed, and therefore the calcium phosphate, the polymerizable monomer, the water-soluble initiator and the oil-soluble initiator may be mixed at once in the aqueous medium, or the aqueous medium. First, calcium phosphate may be added therein, and then a polymerizable monomer, a water-soluble initiator and an oil-soluble initiator may be added, and further, calcium phosphate and a water-soluble initiator may be added to an aqueous medium. Alternatively, a polymerizable initiator containing an oil-soluble initiator may be added here. Dispersion of the polymerizable monomer in the suspension is achieved by high speed stirring. This high-speed stirring condition is considered to be one factor that influences the surface condition of the finally obtained particles, so high-speed stirring with a peripheral velocity at the tip of the stirring blade of at least 2.3 m / s or more is suitable. For details, the description of the examples is referred to.
上記のごとく得られる懸濁液は、分散された油相である
重合性単量体の重合条件に付される。この条件として
は、懸濁液を50〜90℃、好ましくは55〜80℃の温度に加
熱する等が挙げられる。The suspension obtained as described above is subjected to the polymerization conditions of the dispersed oil phase polymerizable monomer. Examples of this condition include heating the suspension to a temperature of 50 to 90 ° C, preferably 55 to 80 ° C.
この発明の方法において、上記懸濁重合終了後常法に従
って、ロ別、水洗浄、脱水、乾燥することにより、皺状
の表面を有する球状粒子が得られる。In the method of the present invention, spherical particles having a wrinkled surface are obtained by filtration, washing with water, dehydration, and drying according to a conventional method after the suspension polymerization is completed.
（ニ）実施例 以下実施例によりこの発明を詳細に説明するが、これに
よりこの発明は限定されるものではない。(D) Examples The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.
実施例１ ５オートクレーブ中に、水3200ｇ、リン酸カルシウム
32ｇ、過硫酸カリウム0.80ｇ、アゾビスイソブチロニト
リル８ｇ、スチレン800ｇを仕込み、温度70℃の条件
下、周速度3.7m/sにおいて10時間懸濁重合に付した。40
℃に冷却後、ロ過、洗浄、乾燥を行い、球状粒子を得
た。Example 1 5 3200 g water, calcium phosphate in an autoclave
32 g, potassium persulfate 0.80 g, azobisisobutyronitrile 8 g and styrene 800 g were charged and subjected to suspension polymerization for 10 hours at a peripheral speed of 3.7 m / s under a temperature of 70 ° C. 40
After cooling to ° C, filtration, washing and drying were performed to obtain spherical particles.
上記球状粒子を電子顕微鏡写真（倍率2000倍）で観察し
たところ、規則正しく皺が刻まれた表面を有するもので
あった。この写真を第１図として添付する。またこの皺
の深さは５〜10μｍであった。When the above spherical particles were observed by an electron micrograph (magnification: 2000), they had a regularly wrinkled surface. This photograph is attached as Figure 1. The depth of the wrinkles was 5 to 10 μm.
実施例２ リン酸カルシウムの使用量を80ｇに変える以外は実施例
１と同様にして粒子を製造した。Example 2 Particles were produced in the same manner as in Example 1 except that the amount of calcium phosphate used was changed to 80 g.
得られた粒子は表面に皺を有するものであり、平均粒径
35μｍで、実施例１で得られたものよりも皺の数が多い
ものであった。The obtained particles have wrinkles on the surface and have an average particle size.
At 35 μm, the number of wrinkles was larger than that obtained in Example 1.
実施例３ 過硫酸カリウムの使用量を0.40ｇに変える以外は実施例
１と同様にして粒子を製造した。Example 3 Particles were produced in the same manner as in Example 1 except that the amount of potassium persulfate used was changed to 0.40 g.
得られた粒子は表面に皺を有するものであり、平均粒径
50μｍで、実施例１で得られたものよりも皺の深さが浅
いものであった。The obtained particles have wrinkles on the surface and have an average particle size.
At 50 μm, the wrinkles were shallower than those obtained in Example 1.
実施例４ 過硫酸カリウム0.80ｇに変えて、過硫酸アンモニウム0.
80ｇを用いる以外は実施例１と同様にして粒子を製造し
た。Example 4 Ammonium persulfate was changed to 0.80 g of potassium persulfate to give 0.
Particles were prepared in the same manner as in Example 1 except that 80 g was used.
得られた粒子は表面に皺を有するものであり、平均粒径
30μｍで、表面状態は実施例１で得られたものとほぼ同
様なものであった。The obtained particles have wrinkles on the surface and have an average particle size.
At 30 μm, the surface condition was almost the same as that obtained in Example 1.
比較例１ リン酸カルシウムの使用量を0.4ｇ変える以外は実施例
１と同様にして粒子を製造した。Comparative Example 1 Particles were produced in the same manner as in Example 1 except that the amount of calcium phosphate used was changed to 0.4 g.
得られた粒子には、その表面に皺が形成されていなかっ
た。No wrinkles were formed on the surface of the obtained particles.
比較例２ 過硫酸カリウムの使用量を４ｇに変える以外は実施例１
と同様にして粒子を製造した。Comparative Example 2 Example 1 except that the amount of potassium persulfate used was changed to 4 g.
The particles were produced in the same manner as in.
得られた粒子には、その表面に皺が形成されていなく、
さらに強度の弱い中空粒子であった。The obtained particles do not have wrinkles formed on their surface,
The hollow particles were weaker in strength.
比較例３ 周速度を1.8m/sに変更する以外は実施例１同様にして粒
子を製造した。Comparative Example 3 Particles were produced in the same manner as in Example 1 except that the peripheral speed was changed to 1.8 m / s.
得られた粒子には、その表面に皺が形成されていなかっ
た。No wrinkles were formed on the surface of the obtained particles.
以上のことから、この実施例１〜４の方法によれば、表
面に皺が形成されかつ内部が充填された強度のつよい球
状粒子を得ることができる。From the above, according to the methods of Examples 1 to 4, it is possible to obtain strong spherical particles having wrinkles formed on the surface and filled inside.
（ホ）発明の効果 この発明によれば、皺状の表面を有する表面積の大きい
球状粒子を得ることができる。またこの方法によれば有
機溶剤を用いないので、極めて簡便に皺状粒子を得るこ
とができる。またさらにこの発明によれば、内部が充填
された強度の強い皺状粒子を得ることができる。(E) Effect of the Invention According to the present invention, it is possible to obtain spherical particles having a wrinkled surface and a large surface area. Further, according to this method, since no organic solvent is used, wrinkled particles can be obtained very easily. Furthermore, according to the present invention, it is possible to obtain wrinkle-like particles having high strength filled inside.
第１図はこの発明の方法により製造される球状粒子の一
例の表面構造を写真で示す図である。FIG. 1 is a photograph showing a surface structure of an example of spherical particles produced by the method of the present invention.
Claims (1)
に、油相としての重合性単量体が分散され、かつこの水
性媒体中に水溶性開始剤が、及び分散された重合性単量
体中に油溶性開始剤が各々含有されてなる懸濁液を調製
し、この懸濁液を高速撹拌下で上記重合性単量体の重合
条件に付すことにより、重合性単量体の重合を分散状態
で進行させて表面に多数の皺が形成された重合体球状粒
子を得ることを特徴とする球状粒子の製造方法。1. A polymerizable monomer as an oil phase is dispersed in an aqueous medium containing calcium phosphate, and a water-soluble initiator is dispersed in the aqueous medium and the dispersed polymerizable monomer is dispersed in the aqueous medium. A suspension containing oil-soluble initiators was prepared, and the suspension was subjected to polymerization conditions of the above-mentioned polymerizable monomer under high-speed stirring, whereby the polymerization of the polymerizable monomer was dispersed. A method for producing spherical particles, characterized in that the spherical polymer particles having a large number of wrinkles formed on the surface thereof are obtained by advancing in step 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8236189A JPH0637525B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing spherical particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8236189A JPH0637525B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing spherical particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02261804A JPH02261804A (en) | 1990-10-24 |
| JPH0637525B2 true JPH0637525B2 (en) | 1994-05-18 |
Family
ID=13772442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8236189A Expired - Lifetime JPH0637525B2 (en) | 1989-03-31 | 1989-03-31 | Method for producing spherical particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637525B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5214923B2 (en) * | 2007-07-27 | 2013-06-19 | 株式会社ジェイエスピー | Method for producing vinyl resin particles |
| JP6520139B2 (en) * | 2015-01-22 | 2019-05-29 | コニカミノルタ株式会社 | Method for producing hollow resin particles |
-
1989
- 1989-03-31 JP JP8236189A patent/JPH0637525B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02261804A (en) | 1990-10-24 |
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