JP3300541B2 - Suspension polymerization stabilizer - Google Patents
Suspension polymerization stabilizerInfo
- Publication number
- JP3300541B2 JP3300541B2 JP21289794A JP21289794A JP3300541B2 JP 3300541 B2 JP3300541 B2 JP 3300541B2 JP 21289794 A JP21289794 A JP 21289794A JP 21289794 A JP21289794 A JP 21289794A JP 3300541 B2 JP3300541 B2 JP 3300541B2
- Authority
- JP
- Japan
- Prior art keywords
- suspension polymerization
- stabilizer
- suspension
- particle size
- polymerization
- 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
- 239000003381 stabilizer Substances 0.000 title claims description 40
- 238000010557 suspension polymerization reaction Methods 0.000 title claims description 37
- 239000002245 particle Substances 0.000 claims description 33
- 239000000725 suspension Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 7
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 6
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 235000012255 calcium oxide Nutrition 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 238000010558 suspension polymerization method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ビニル系単量体の懸濁
重合法で使用する微細なヒドロキシアパタイトである懸
濁重合用安定剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizer for suspension polymerization, which is a fine hydroxyapatite used in a suspension polymerization method for vinyl monomers.
【０００２】[0002]
【従来の技術】懸濁重合法は重合物がビーズ状として得
られるために別名パール重合又はビーズ重合法として長
い歴史を持った、粒状の重合物を得る方法として有用で
ある。この種の重合においては、重合可能なビニルモノ
マー、懸濁分散剤または懸濁安定剤、および触媒の存在
下で水のような分散媒に分散または懸濁させる。このよ
うに、懸濁重合法において、懸濁安定剤が必要であり水
難溶性の無機物質のような微粉末固体である場合と水溶
性高分子物質の場合に大別され、また両者を併用するこ
とも周知である。2. Description of the Related Art A suspension polymerization method is useful as a method for obtaining a granular polymer having a long history as a pearl polymerization or a bead polymerization since a polymer is obtained in the form of beads. In this type of polymerization, the polymer is dispersed or suspended in a dispersion medium such as water in the presence of a polymerizable vinyl monomer, a suspension dispersant or a suspension stabilizer, and a catalyst. As described above, in the suspension polymerization method, a suspension stabilizer is necessary, and it is roughly classified into a case of a fine powder solid such as a poorly water-soluble inorganic substance and a case of a water-soluble polymer substance. It is also well known.
【０００３】[0003]
【発明が解決しようとする課題】懸濁重合用安定剤の使
用目的は、 重合工程中の懸濁安定性をよくすること、 重合物中への懸濁重合用安定剤の混入が微量であるこ
と、 目的の粒子径の重合物が得られること、 などである。The purpose of use of the suspension polymerization stabilizer is to improve the suspension stability during the polymerization process, and the amount of the suspension polymerization stabilizer mixed into the polymer is very small. And that a polymer having a desired particle size can be obtained.
【０００４】即ち、懸濁安定剤の使用により重合操作が
円滑に行え、かつ目的の粒子径の重合物を効率良く得る
ことにあるが、この種の懸濁安定剤において水難溶性の
無機物質のうち代表的なものとしてヒドロキシアパタイ
ト（以下ＨＡＰという）が最も優れた懸濁安定剤として
知られている。しかしながら、懸濁安定剤として性能の
高いとされるＨＡＰであっても、一般に懸濁重合法はそ
の遂行と効果の点で予知できず、また不規則であったり
して再現性に欠けることが多いため、懸濁安定性および
重合反応器壁面スケール生成の抑制などについては満足
できる結果は得られていない。[0004] That is, the use of a suspension stabilizer allows the polymerization operation to be carried out smoothly and to efficiently obtain a polymer having a desired particle size. Among these, hydroxyapatite (hereinafter referred to as HAP) is known as the most excellent suspension stabilizer. However, even with HAP, which is considered to have high performance as a suspension stabilizer, the suspension polymerization method is generally unpredictable in terms of its performance and effect, and is irregular and lacks reproducibility. Therefore, satisfactory results have not been obtained with respect to suspension stability and suppression of formation of scale on the wall of the polymerization reactor.
【０００５】例えば、微粒子化されていないＨＡＰで
は、上記の理由からビーズが合一化してモチ状になった
り、または目的の粒子径の重合物が再現性良く得られな
い、といった問題点、さらに重合反応器壁面にスケール
生成などがしばしば起こり、これを防止するために使用
量を多くしなければならない。しかしながら、使用量を
多くすることにより生成重合物中に懸濁安定剤が混入し
て製品の品質劣化の原因となるとともに、コストアップ
になり好ましくない。また、懸濁安定性を図るために水
対単量体の比率を大きくすることも考えられるがこれは
生産性の低下のため好ましくない。[0005] For example, in the case of HAP which has not been made into fine particles, there is a problem that beads are coalesced into a sticky shape or a polymer having a desired particle size cannot be obtained with good reproducibility for the above reasons. Scale formation often occurs on the wall of the polymerization reactor, and the amount used must be increased to prevent this. However, if the amount used is increased, the suspension stabilizer is mixed into the produced polymer, which causes deterioration of the quality of the product and undesirably increases the cost. In addition, it is conceivable to increase the ratio of water to monomer in order to achieve suspension stability, but this is not preferable because productivity is reduced.
【０００６】従って、水難溶性の固体粉末、特にＨＡＰ
の懸濁安定剤について、従来より、上記の欠点を排除す
べく多くの提案がなされている。例えば、ＨＡＰを用い
て懸濁重合するに当たり、超音波照射処理により微粉化
する方法（特公昭４７−３８９３１）あるいは助剤とし
て燐酸カリウムを添加する方法（特公昭４８−４２２２
０）などＨＡＰを使用するに当たって後処理の工夫や助
剤の添加がなされているがいずれの方法も本質的な問題
解決に至っておらず工業的にみても不利である点が多
い。また、固体粉末のＨＡＰに替えて、予め水に微粉末
ＨＡＰが分散したスラリーまたはペースト状にして使用
する方法（特開昭５３−９０３８６）が提案されている
が、プロセスの転換が避けられないという問題点を包含
している。Accordingly, hardly water-soluble solid powders, especially HAP
Many suspension stabilizers have been hitherto proposed to eliminate the above-mentioned disadvantages. For example, in suspension polymerization using HAP, a method of pulverizing by ultrasonic irradiation (JP-B-47-38931) or a method of adding potassium phosphate as an auxiliary agent (JP-B-48-222)
In the case of using HAP such as 0), post-treatment is devised and an auxiliary agent is added, but none of these methods has essentially solved the problem and is disadvantageous from an industrial point of view. Also, a method has been proposed in which instead of solid powder HAP, a slurry or paste in which fine powder HAP is dispersed in water in advance (JP-A-53-90386) has been proposed, but a process change cannot be avoided. The problem is included.
【０００７】[0007]
【課題を解決するための手段】本発明者等はこの問題を
解決すべく鋭意研究を重ねた結果、ＨＡＰを特定の粉砕
機を用いて微粉化することにより上記問題点を実質的に
解決できることを見出だし、本発明を完成するに至った
ものである。Means for Solving the Problems As a result of intensive studies to solve this problem, the present inventors have found that the above problem can be substantially solved by pulverizing HAP using a specific crusher. Have been found, and the present invention has been completed.
【０００８】即ち、本発明は消石灰、炭酸カルシウムお
よび／または生石灰と燐酸を反応して得られたヒドロキ
シアパタイトスラリーを濾過し、乾燥した後、ジェット
ミルで粉砕して得ることを特徴とする懸濁重合用安定剤
に関する。That is, the present invention provides a suspension characterized in that a hydroxyapatite slurry obtained by reacting slaked lime, calcium carbonate and / or quick lime with phosphoric acid is filtered, dried and pulverized by a jet mill. It relates to a stabilizer for polymerization.
【０００９】本発明を更に詳細に説明する。本発明に用
いる消石灰、炭酸カルシウムおよび／または生石灰は、
耐不溶解物の少ないものが好ましく、また、粒子径が小
さいほど燐酸との反応性が高く好適である。燐酸は、市
販の精製されたものであれば、特に制限されるものでは
ない。ヒドロキシアパタイトスラリーの濾過は、通常の
方法で行うことができる。例えば、フィルタープレスが
用いられるが、特には圧搾式が好適である。濾過した後
の乾燥は、バンド式乾燥機を用い、２００℃程度の温度
で乾燥させるのが一般的である。The present invention will be described in more detail. Slaked lime, calcium carbonate and / or quicklime used in the present invention are:
It is preferable that the amount of insoluble matter is small, and that the smaller the particle size is, the higher the reactivity with phosphoric acid is. Phosphoric acid is not particularly limited as long as it is commercially available and purified. Filtration of the hydroxyapatite slurry can be performed by a usual method. For example, a filter press is used, and a squeeze type is particularly preferable. Drying after filtration is generally performed at a temperature of about 200 ° C. using a band dryer.
【００１０】本発明に用いるジェットミルは、カウンタ
ージェットミル、シングルトラックジェットミル、Ｊｅ
ｔ−Ｏ−Ｍｉｚｅｒ，Ｍｉｃｒｏｎｉｚｅｒ，Ｂｌａｗ
−Ｋｎｏｘ，Ｔｒｏｓｔ Ｊｅｔ Ｍｉｌｌ、ニューマ
チックジェットミルなどが知られている。本発明では、
ジェットミルを用いて粉砕することにより、得られるＨ
ＡＰの粒子径が小さく、粒度分布がシャープであること
から好適である。しかしながら、これらのジェットミル
に特に限定はされるものではない。The jet mill used in the present invention is a counter jet mill, a single track jet mill, Je.
t-O-Mizer, Micronizer, Blow
-Knox, Trost Jet Mill, pneumatic jet mill and the like are known. In the present invention,
H obtained by grinding using a jet mill
It is preferable because the particle diameter of AP is small and the particle size distribution is sharp. However, these jet mills are not particularly limited.
【００１１】消石灰、炭酸カルシウムおよび／または生
石灰と燐酸を反応する温度は、７０℃以上が好ましい。
更に好ましくは、８０℃以上が好適である。反応温度が
７０℃未満では、ジェットミルを用いて粉砕した場合、
この水懸濁させたときのｐＨが８．０を超え、懸濁重合
結果に不都合をきたすことがしばしば見られる。即ち、
懸濁重合法での重合生成物の粒度分布が大きくなり収率
が低下する。また粒子の形状が真球ではない等の不都合
を生じる。ｐＨが８．０を超えるのは、ＨＡＰ粒子の表
面部と中心部の組成が異なり、ジェットミルを用いて粉
砕した際、中心部の組成が表面に露出することによりｐ
Ｈに異常をきたすものと推察する。The temperature at which slaked lime, calcium carbonate and / or quicklime is reacted with phosphoric acid is preferably 70 ° C. or higher.
More preferably, the temperature is 80 ° C. or higher. When the reaction temperature is lower than 70 ° C., when pulverized using a jet mill,
The pH of this aqueous suspension exceeds 8.0, which often causes inconvenience in suspension polymerization results. That is,
The particle size distribution of the polymerization product in the suspension polymerization method becomes large and the yield decreases. Further, inconvenience such that the shape of the particles is not a true sphere is caused. The reason that the pH exceeds 8.0 is that the composition of the surface portion and the center portion of the HAP particles are different, and when pulverized by using a jet mill, the composition of the center portion is exposed on the surface, so that p
It is presumed that H is abnormal.
【００１２】目的の粒子径の重合物を再現性良く得るた
めには、懸濁重合用安定剤として用いられるＨＡＰの平
均粒子径が小さく、粒度分布がシャープであるとともに
水懸濁させたときのｐＨが７．０〜８．０であることが
望ましい。In order to obtain a polymer having a desired particle size with good reproducibility, the average particle size of HAP used as a stabilizer for suspension polymerization is small, the particle size distribution is sharp, and the HAP used when suspended in water. It is desirable that the pH be 7.0 to 8.0.
【００１３】懸濁重合用安定剤の平均粒子径が４μｍ以
下で、かつ粒子径が０．９μｍ以下のものを１５重量％
以上含有する必要がある。平均粒子径が４μｍを超える
場合、懸濁重合法で得られる重合物の粒子径が大きくな
り、懸濁重合用安定剤の添加量を増加する必要性が発生
し経済的でない。また、粒子径が０．９μｍ未満のもの
が１５重量％未満では、上記した現象が顕著となるため
好ましくない。When the average particle diameter of the suspension polymerization stabilizer is 4 μm or less and the particle diameter is 0.9 μm or less, 15% by weight
It is necessary to contain the above. When the average particle size exceeds 4 μm, the particle size of the polymer obtained by the suspension polymerization method becomes large, and it becomes necessary to increase the amount of the stabilizer for suspension polymerization, which is not economical. If the particle diameter is less than 0.9 μm and less than 15% by weight, the above-mentioned phenomenon becomes remarkable, which is not preferable.
【００１４】然して、本発明者等は種々の実験と観察に
より、本発明のジェットミルを用いて粉砕した懸濁重合
用安定剤は、懸濁重合液に添加される以前から微粒子で
あり、単量体の表面に界面活性剤を介して多くの微粒子
ＨＡＰが吸着し、安定した重合反応がなされるものと推
察している。However, the present inventors have found from various experiments and observations that the suspension polymerization stabilizer pulverized using the jet mill of the present invention is fine particles before being added to the suspension polymerization solution, It is presumed that many fine particles HAP are adsorbed on the surface of the monomer via a surfactant and a stable polymerization reaction is performed.
【００１５】このように反応温度を高くして得られたＨ
ＡＰをジェットミルを用いて粉砕した懸濁重合用安定剤
は、従来の懸濁重合用安定剤と比較して、より小粒子の
重合物を得る場合でも添加量を少なくすることが可能で
あり、低コスト化が可能な懸濁重合用安定剤である。The H obtained by increasing the reaction temperature in this manner
The suspension polymerization stabilizer obtained by pulverizing the AP using a jet mill can reduce the amount of addition even when obtaining a polymer of smaller particles as compared with a conventional suspension polymerization stabilizer. Is a stabilizer for suspension polymerization that can be reduced in cost.
【００１６】[0016]
【実施例】以下、実施例を挙げて本発明を具体的に説明
するが、本発明の要旨をそれらに限定するものではな
い。以下、部および％は総て重量部および重量％を示
す。 実施例１ ３００Ｌの攪拌機を備えた、ジャケット付き反応器に水
１２５．８ｋｇと消石灰２２．２ｋｇを仕込み９０℃に
加熱した。これに２３．８％燐酸６８．３ｋｇを３００
分で添加した。得られたヒドロキシアパタイトスラリー
をフィルタープレスで濾過した後、熱風乾燥機で２００
℃、５時間乾燥した。該乾燥品をシングルトラックジェ
ットミル（セイシン企業社製）で粉砕し、平均粒子径
２．８μｍ、０．９μｍ以下の粒子径２３％の懸濁重合
用安定剤を得た。該懸濁重合用安定剤を水に１０％懸濁
させたときのｐＨは、７．５１であった。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the gist of the present invention is not limited thereto. Hereinafter, all parts and percentages are by weight. Example 1 In a jacketed reactor equipped with a 300 L stirrer, 125.8 kg of water and 22.2 kg of slaked lime were charged and heated to 90 ° C. To this, 68.3 kg of 23.8% phosphoric acid was added to 300
Minutes. The obtained hydroxyapatite slurry was filtered with a filter press, and then dried with a hot air drier.
C. and dried for 5 hours. The dried product was pulverized with a single-track jet mill (manufactured by Seishin Enterprise Co., Ltd.) to obtain a suspension polymerization stabilizer having an average particle size of 2.8 μm and a particle size of 23% or less having a particle size of 0.9 μm or less. The pH when the suspension polymerization stabilizer was suspended at 10% in water was 7.51.
【００１７】該懸濁重合用安定剤を用いて、下記の原料
を用いスチレンの重合を行った。 （原料名） 水 １００部 懸濁重合用安定剤 ０．３部 ドデシルベンゼンスルホン酸ソーダ ０．０００２部 スチレンモノマー １００部 過酸化ベンゾイル ０．２部 攪拌機付きステンレス製オートクレーブに、水、懸濁重
合用安定剤及びドデシルベンゼンスルホン酸ソーダを上
記の割合で仕込み、反応器内を窒素ガスで置換しながら
攪拌した。充分に攪拌した後、予め混合しておいたスチ
レンモノマーと過酸化ベンゾイルの混合物を３０分間で
投入した。次いで３５０ｒｐｍの攪拌速度で攪拌しなが
ら９０℃で１０時間重合を行った。更に、常法により重
合物を遠心分離機で脱水し、塩酸で洗浄後、水洗および
乾燥して重合物を得た。得られた重合物の４０〜６０メ
ッシュの間にある含有量は、９８．６％であり、平均粒
子径は０．８ｍｍであった。Using the suspension polymerization stabilizer, styrene was polymerized using the following raw materials. (Raw material name) Water 100 parts Suspension polymerization stabilizer 0.3 parts Sodium dodecylbenzenesulfonate 0.0002 parts Styrene monomer 100 parts Benzoyl peroxide 0.2 parts Water and suspension polymerization in a stainless steel autoclave with a stirrer The stabilizer and sodium dodecylbenzenesulfonate were charged at the above ratios and stirred while replacing the inside of the reactor with nitrogen gas. After sufficient stirring, a premixed mixture of styrene monomer and benzoyl peroxide was added for 30 minutes. Next, polymerization was carried out at 90 ° C. for 10 hours while stirring at a stirring speed of 350 rpm. Further, the polymer was dehydrated by a centrifugal separator by a conventional method, washed with hydrochloric acid, washed with water and dried to obtain a polymer. The content of the polymer obtained between 40 and 60 mesh was 98.6%, and the average particle size was 0.8 mm.
【００１８】実施例２ 実施例１の粉砕機をカウンタージェットミル（ホソカワ
ミクロン社製）に変更し、実施例１と同様に懸濁重合用
安定剤を得た。得られた懸濁重合用安定剤の平均粒子径
は３．３μｍ、０．９μｍ以下１８％、１０％スラリー
ｐＨ７．４０であった。該懸濁重合用安定剤を用いて、
実施例１と同様の原料を用いてスチレンの重合を行っ
た。得られた重合物の４０〜６０メッシュの間にある含
有量は、９８．１％であり、平均粒子径は０．８５ｍｍ
であった。Example 2 A pulverizer of Example 1 was changed to a counter jet mill (manufactured by Hosokawa Micron), and a stabilizer for suspension polymerization was obtained in the same manner as in Example 1. The average particle diameter of the obtained stabilizer for suspension polymerization was 3.3 μm, not more than 0.9 μm, 18%, and 10% slurry pH was 7.40. Using the stabilizer for suspension polymerization,
Using the same raw materials as in Example 1, styrene was polymerized. The content of the polymer obtained between 40 and 60 mesh is 98.1%, and the average particle size is 0.85 mm.
Met.
【００１９】実施例３ 実施例１の消石灰を炭酸カルシウム３０．６ｋｇ、に変
更した以外は実施例１と同様に行った。得られた懸濁重
合用安定剤は、平均粒子径３．１μｍ、０．９μｍ以下
の粒子径２１％であった。該懸濁重合用安定剤を水に１
０％懸濁させたときのｐＨは、７．５５であった。該懸
濁重合用安定剤を用い実施例１と同様にスチレンの重合
を行った。その結果、得られた重合物の４０〜６０メッ
シュの間にある含有量は、９８．８％であり、平均粒子
径は０．９ｍｍであった。Example 3 The procedure of Example 1 was repeated except that the slaked lime of Example 1 was changed to 30.6 kg of calcium carbonate. The obtained stabilizer for suspension polymerization had an average particle diameter of 3.1 μm and a particle diameter of 0.9% or less of 21%. Add the suspension polymerization stabilizer to water
The pH when suspended at 0% was 7.55. Using the suspension polymerization stabilizer, styrene was polymerized in the same manner as in Example 1. As a result, the content of the obtained polymer between 40 and 60 mesh was 98.8%, and the average particle size was 0.9 mm.
【００２０】比較例１ 実施例１の粉砕機を自由ミル（奈良機械社製）に変更し
た以外は、実施例１と同様に行い懸濁重合用安定剤を得
た。得られた懸濁重合用安定剤の平均粒子径は６．７μ
ｍ、０．９μｍ以下１２％、１０％スラリーｐＨ７．５
３であった。この懸濁重合用安定剤を用いて、実施例１
と同様にスチレンの重合を行った。その結果、重合物が
モチ状となり、粒子状のものが得られなかった。Comparative Example 1 A stabilizer for suspension polymerization was obtained in the same manner as in Example 1 except that the pulverizer of Example 1 was changed to a free mill (manufactured by Nara Machinery Co., Ltd.). The average particle diameter of the obtained suspension polymerization stabilizer is 6.7 μm.
m, 0.9 μm or less 12%, 10% slurry pH 7.5
It was 3. Using this suspension polymerization stabilizer, Example 1
The polymerization of styrene was carried out in the same manner as described above. As a result, the polymer became sticky, and no particles could be obtained.
【００２１】[0021]
【発明の効果】本発明によれば従来技術では達成されな
かった、重合工程中の懸濁安定性、重合物中への懸
濁安定剤の混入が微量であること、目的の粒子径の重
合物が得られること、の向上が達成される。即ち、本発
明の範囲外である比較例は、重合物がモチ状になり、重
合操作が円滑に行うことができない。これに対し、本発
明の範囲内である実施例は、これらの性能がすべて優れ
ているのが明らかであり、本発明の意義は大きい。According to the present invention, the suspension stability during the polymerization step, the incorporation of a small amount of the suspension stabilizer into the polymer, and the polymerization of the desired particle size, which were not achieved by the prior art, were achieved. The product is improved. That is, in Comparative Examples which are out of the range of the present invention, the polymer becomes sticky and the polymerization operation cannot be performed smoothly. On the other hand, it is clear that Examples within the scope of the present invention are all excellent in these performances, and the present invention is significant.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−222103（ＪＰ，Ａ) 特開 昭53−90386（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 2/18 ────────────────────────────────────────────────── (5) References (56) References JP-A-5-222103 (JP, A) JP-A-53-90386 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08F 2/18
Claims (4)
は生石灰と燐酸を反応して得られたヒドロキシアパタイ
トスラリーを濾過し、乾燥した後、ジェットミルで粉砕
して得ることを特徴とする懸濁重合用安定剤。1. A suspension for suspension polymerization, characterized in that a hydroxyapatite slurry obtained by reacting slaked lime, calcium carbonate and / or quick lime with phosphoric acid is filtered, dried and pulverized by a jet mill. Agent.
は生石灰と燐酸を反応する温度が７０℃以上である請求
項１記載の懸濁重合用安定剤。2. The suspension polymerization stabilizer according to claim 1, wherein the temperature at which slaked lime, calcium carbonate and / or quicklime is reacted with phosphoric acid is 70 ° C. or higher.
重合用安定剤を、水に１０重量％で懸濁させたときのｐ
Ｈが７．０〜８．０である請求項１記載の懸濁重合用安
定剤。3. The suspension polymerization stabilizer obtained by pulverizing with a jet mill has a p value of 10% by weight when suspended in water.
2. The stabilizer for suspension polymerization according to claim 1, wherein H is 7.0 to 8.0.
ｍ以下で、かつ粒子径が０．９μｍ以下のものを１５重
量％以上含有する請求項１記載の懸濁重合用安定剤。4. The suspension polymerization stabilizer has an average particle size of 4 μm.
The stabilizer for suspension polymerization according to claim 1, wherein the stabilizer for suspension polymerization contains 15% by weight or more having a particle size of 0.9 m or less and a particle size of 0.9 m or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21289794A JP3300541B2 (en) | 1994-09-06 | 1994-09-06 | Suspension polymerization stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21289794A JP3300541B2 (en) | 1994-09-06 | 1994-09-06 | Suspension polymerization stabilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0873511A JPH0873511A (en) | 1996-03-19 |
| JP3300541B2 true JP3300541B2 (en) | 2002-07-08 |
Family
ID=16630088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21289794A Expired - Lifetime JP3300541B2 (en) | 1994-09-06 | 1994-09-06 | Suspension polymerization stabilizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3300541B2 (en) |
-
1994
- 1994-09-06 JP JP21289794A patent/JP3300541B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0873511A (en) | 1996-03-19 |
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