JPH0576962B2 - - Google Patents
Info
- Publication number
- JPH0576962B2 JPH0576962B2 JP1922986A JP1922986A JPH0576962B2 JP H0576962 B2 JPH0576962 B2 JP H0576962B2 JP 1922986 A JP1922986 A JP 1922986A JP 1922986 A JP1922986 A JP 1922986A JP H0576962 B2 JPH0576962 B2 JP H0576962B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization initiator
- resin beads
- radical polymerization
- peroxide
- temperature
- 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 - Fee Related
Links
- 239000012508 resin bead Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 239000007870 radical polymerization initiator Substances 0.000 claims description 24
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 150000001451 organic peroxides Chemical class 0.000 claims description 18
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- 238000012673 precipitation polymerization Methods 0.000 claims description 9
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 12
- 235000019400 benzoyl peroxide Nutrition 0.000 description 12
- 239000002612 dispersion medium Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- -1 azo compound Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 239000003999 initiator Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- WJRSLHBOQIOTES-UHFFFAOYSA-N tetradecoxycarbonyl tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OC(=O)OCCCCCCCCCCCCCC WJRSLHBOQIOTES-UHFFFAOYSA-N 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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- ZIZMLIPKURGKPM-UHFFFAOYSA-N 1-tetradecylperoxytetradecane Chemical group CCCCCCCCCCCCCCOOCCCCCCCCCCCCCC ZIZMLIPKURGKPM-UHFFFAOYSA-N 0.000 description 1
- JPOUDZAPLMMUES-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)octane Chemical compound CCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C JPOUDZAPLMMUES-UHFFFAOYSA-N 0.000 description 1
- VDQNOOZIDCTAPX-UHFFFAOYSA-N 3-butylperoxycarbonylbenzenecarboperoxoic acid Chemical compound CCCCOOC(=O)C1=CC=CC(C(=O)OO)=C1 VDQNOOZIDCTAPX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- JTUSQSYFVVBAED-UHFFFAOYSA-N ditetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OCCCCCCCCCCCCCC JTUSQSYFVVBAED-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はラジカル重合開始剤をビニルモノマー
の重合物でコーテイングすることによつて得られ
る重合開始剤含有樹脂ビーズを製造する方法に関
する。この樹脂ビーズは安定化された重合開始剤
として種々の用途に用いられる。例えば、歯科用
即時重合レジン等の重合開始剤と樹脂ビーズとを
ドライブレンドしてモノマー液と混和使用する用
途等に特に有用である。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing polymerization initiator-containing resin beads obtained by coating a radical polymerization initiator with a polymerized vinyl monomer. These resin beads are used for various purposes as a stabilized polymerization initiator. For example, it is particularly useful for uses such as instant polymerization resins for dentistry, in which a polymerization initiator and resin beads are dry blended and mixed with a monomer solution.
従来の技術
ラジカル重合開始剤を含有する樹脂ビーズの製
造法としては、従来、多量のベンゾイルパーオキ
サイドをビニルモノマーに混合分散したスラリー
溶液を分散媒中に滴下し60〜68℃で懸濁又は沈澱
重合する方法（特開昭58−152003号公報）が知ら
れている。Conventional technology As a method for producing resin beads containing a radical polymerization initiator, a slurry solution in which a large amount of benzoyl peroxide is mixed and dispersed in vinyl monomer is dropped into a dispersion medium and suspended or precipitated at 60 to 68°C. A polymerization method (Japanese Unexamined Patent Publication No. 152003/1983) is known.
しかし、この方法は、重合開始に必要な一次ラ
ジカルを十分に供給するためにビニルモノマーに
対して50wt％以上もの多量のラジカル重合開始
剤を用いる必要があり、ラジカル重合開始剤含量
が比較的少量の樹脂ビーズを製造する場合には、
ラジカル重合開始剤を、得られる樹脂ビーズ中に
有効に残存させようとすると、ビニルモノマーの
重合に多大の時間を要するばかりではなく、一次
ラジカルの供給が十分でないために重合途中で分
散不良をおこして重合物が凝集して、モチ状とな
り、樹脂ビーズが得られないという欠点があつ
た。 However, in this method, it is necessary to use a large amount of radical polymerization initiator of 50 wt% or more based on the vinyl monomer in order to sufficiently supply the primary radicals necessary for polymerization initiation, and the radical polymerization initiator content is relatively small. When manufacturing resin beads,
If a radical polymerization initiator is to remain effectively in the resulting resin beads, not only does it take a long time to polymerize the vinyl monomer, but the insufficient supply of primary radicals causes poor dispersion during polymerization. The disadvantage was that the polymer aggregated and became sticky, making it impossible to obtain resin beads.
発明が解決しようとする問題点
本発明は、前記した従来の方法の欠点を解消
し、比較的少量のラジカル重合開始剤を効率よく
ビニルモノマーの重合物でコーテイングして重合
開始剤含有樹脂ビーズを製造する方法を提供しよ
うとするものである。Problems to be Solved by the Invention The present invention solves the drawbacks of the conventional methods described above, and forms polymerization initiator-containing resin beads by efficiently coating a relatively small amount of radical polymerization initiator with a vinyl monomer polymer. The aim is to provide a manufacturing method.
問題点を解決するための手段
本発明の方法は、ラジカル重合開始剤及びそれ
よりも低い温度を有する有機過酸化物の存在下に
ビニルモノマーを懸濁重合又は沈澱重合すること
により、重合中に分散不良をおこすことなく、重
合開始剤含有樹脂ビーズを効率よく製造する方法
である。Means for Solving the Problems The method of the present invention involves suspension or precipitation polymerization of vinyl monomers in the presence of a radical polymerization initiator and an organic peroxide having a lower temperature. This is a method for efficiently producing polymerization initiator-containing resin beads without causing poor dispersion.
（ビニルモノマー）
本発明に用いられるビニルモノマーは、懸濁重
合あるいは沈澱重合により樹脂ビーズを製造する
のに用いられるラジカル重合性のビニルモノマー
であり、例えばメタクリル酸エステル類、アクリ
ル酸エステル類、及びスチレン類や酢酸ビニル等
のビニルモノマーの少なくとも１種が用いられ
る。これらの中でもメタクリル酸メチルが特に好
んで用いられる。(Vinyl Monomer) The vinyl monomer used in the present invention is a radically polymerizable vinyl monomer used to produce resin beads by suspension polymerization or precipitation polymerization, and includes, for example, methacrylic esters, acrylic esters, and At least one type of vinyl monomer such as styrenes and vinyl acetate is used. Among these, methyl methacrylate is particularly preferably used.
（ラジカル重合開始剤）
樹脂ビーズに含有されるラジカル重合開始剤
は、熱あるいは光により分解してラジカルを生成
し、連鎖機構によりラジカル重合を開始させるこ
とができるような物質であつて、懸濁又は沈澱重
合に用いられる分散媒に不溶な、有機過酸化物や
アゾ化合物である。具体的には、例えば、ベンゾ
イルパーオキサイド等のジアシルパーオキサイ
ド、２・２−ビス（ｔ−ブチルパーオキシ）オク
タン等のパーオキシケタール、メチルシクロヘキ
サノンパーオキサイド等のケトンパーオキサイ
ド、２・５−ジメチルヘキサン−２・５−ジハイ
ドロパーオキサイド等のハイドロパーオキサイ
ド、ジクミルパーオキサイド等のジアルキルパー
オキサイド、ジミリチルパーオキシジカーボネー
ト等のパーオキシジカーボネート、およびジｔ−
ブチルジパーオキシイソフタレート等のパーオキ
シエステル等の各種の有機過酸化物及び２，2′−
アゾビスイソブチロニトリル等のアゾ化合物が挙
げられる。これらの中でも実用性及び共存させる
これより分解温度の低い有機過酸化物との組合せ
の点から、分解温度が比較的高い、例えば、10時
間半滅期温度が74℃のベンゾイルパーオキサイド
等が好んで用いられる。(Radical polymerization initiator) The radical polymerization initiator contained in the resin beads is a substance that can be decomposed by heat or light to generate radicals and initiate radical polymerization through a chain mechanism. Alternatively, it is an organic peroxide or an azo compound that is insoluble in the dispersion medium used in precipitation polymerization. Specifically, for example, diacyl peroxide such as benzoyl peroxide, peroxyketal such as 2,2-bis(t-butylperoxy)octane, ketone peroxide such as methylcyclohexanone peroxide, 2,5-dimethyl Hydroperoxides such as hexane-2,5-dihydroperoxide, dialkyl peroxides such as dicumyl peroxide, peroxydicarbonates such as dimylytyl peroxydicarbonate, and di-t-
Various organic peroxides such as peroxy esters such as butyl diperoxyisophthalate and 2,2'-
Examples include azo compounds such as azobisisobutyronitrile. Among these, preferred are benzoyl peroxide, which has a relatively high decomposition temperature, such as benzoyl peroxide, which has a 10-hour half-life temperature of 74°C, from the viewpoint of practicality and coexistence with an organic peroxide having a lower decomposition temperature. It is used in
これらのラジカル重合開始剤の量は、ビニルモ
ノマー100重量部に対して30重量部以下、好まし
くは１〜20重量部である。１重量部未満では得ら
れる樹脂ビーズ中のラジカル重合開始剤量が少な
すぎて実用的でなく、又30重量部を越えると得ら
れた樹脂ビーズの透明性が失なわれ、また粒径も
ばらつくので好ましくない。 The amount of these radical polymerization initiators is 30 parts by weight or less, preferably 1 to 20 parts by weight, based on 100 parts by weight of the vinyl monomer. If it is less than 1 part by weight, the amount of radical polymerization initiator in the resulting resin beads is too small to be practical, and if it exceeds 30 parts by weight, the resulting resin beads will lose their transparency and the particle size will vary. So I don't like it.
（有機過酸化物）
前記ラジカル重合開始剤と共存させる、より低
い分解温度を有する有機過酸化物は、ビニルモノ
マーの懸濁又は沈澱重合反応に開始剤として用い
られるものであり、前記したラジカル重合開始剤
に含まれる有機過酸化物の中から選ばれるもので
あつて、樹脂ビーズに含有されるラジカル重合開
始剤と組合せにおいて、該ラジカル重合開始剤よ
り分解温度が５℃以上、好ましくは10℃以上低い
ものである。(Organic peroxide) The organic peroxide having a lower decomposition temperature and coexisting with the radical polymerization initiator is used as an initiator in the suspension or precipitation polymerization reaction of vinyl monomers, and is used as an initiator in the suspension or precipitation polymerization reaction of vinyl monomers. An initiator selected from organic peroxides that, when combined with the radical polymerization initiator contained in the resin beads, has a decomposition temperature of 5°C or higher, preferably 10°C, than the radical polymerization initiator. This is lower than that.
このような有機過酸化物の例としては、例え
ば、ラジカル重合開始剤として10時間半滅期温度
が74℃のベンゾイルパーオキサイドを含有する樹
脂ビーズを製造する場合には、ジミリスチルパー
オキシーボネート（10時間半滅期温度41℃）、ｔ
−ブチルパーオキシビバレート（同55℃）、及び
ラウロイルパーオキサイド（同62℃）等の、又、
ジクミルパーオキサイド（10時間半滅期温度117
℃）を含有する樹脂ビーズの場合には、ｔ−ブチ
ルパーオキシイソプロピルカーボネート（同98
℃）、ベンゾイルパーオキサイド、及びラウロイ
ルパーオキサイド等の、樹脂ビーズに含有される
ラジカル重合開始剤より５℃以上低い分解温度を
有する有機過酸化物が選らばれる。これらの有機
過酸化物は、分解温度の異なる２種以上を併用す
ることにより、ビニルモノマーの重合をより速や
かに進めることも出来る。 Examples of such organic peroxides include, for example, when producing resin beads containing benzoyl peroxide, which has a half-life temperature of 74°C for 10 hours, as a radical polymerization initiator, dimyristyl peroxybonate ( 10 hours half-life temperature 41℃), t
-Butyl peroxybivalate (55℃) and lauroyl peroxide (62℃), etc.
Dicumyl peroxide (10 hours half-life temperature 117
In the case of resin beads containing t-butyl peroxyisopropyl carbonate (98 °C)
An organic peroxide having a decomposition temperature lower than the radical polymerization initiator contained in the resin beads by 5°C or more is selected, such as benzoyl peroxide, and lauroyl peroxide. By using two or more of these organic peroxides having different decomposition temperatures in combination, the polymerization of the vinyl monomer can proceed more quickly.
有機過酸化物の使用量は、ビニルモノマー100
重量部に対し、0.5〜５重量部である。有機過酸
化物量が少なすぎるとビニルモノマーの重合を開
始するのに十分な一次ラジカルが供給されず、
又、多すぎると反応コントロールが難かしく好ま
しくない。 The amount of organic peroxide used is vinyl monomer 100
The amount is 0.5 to 5 parts by weight. If the amount of organic peroxide is too small, sufficient primary radicals will not be supplied to initiate polymerization of vinyl monomers,
On the other hand, if the amount is too large, it becomes difficult to control the reaction, which is not preferable.
（反応）
ビニルモノマーの懸濁又は沈澱重合反応は、通
常分散媒中にラジカル重合開始剤及びそれより低
い分解温度を有する有機過酸化物を溶解したモノ
マー液を添加し、撹拌条件下、不活性気体雰囲気
中で加熱して行われる。(Reaction) Suspension or precipitation polymerization reactions of vinyl monomers are usually carried out by adding a monomer solution in which a radical polymerization initiator and an organic peroxide having a lower decomposition temperature are dissolved in a dispersion medium, and under stirring conditions, inert This is done by heating in a gas atmosphere.
重合温度は樹脂ビーズに含有されるラジカル重
合開始剤の分解温度よりも低い温度で、且つそれ
より低い分解温度を有する有機過酸化物が有効に
一次ラジカルを発生する温度、具体的には、樹脂
ビーズ中に含有されるラジカル重合開始剤の10時
間半滅期温度よりも５℃以上好ましくは10℃以上
低い温度で、用いられる有機過酸化物の分解温度
により適当な温度が選らばれる。例えば、ベンゾ
イルパーオキサイドに対してジミリスチルパーオ
キシカーボネートを用いる場合には、40〜65℃、
好ましくは50〜60℃である。 The polymerization temperature is a temperature lower than the decomposition temperature of the radical polymerization initiator contained in the resin beads, and a temperature at which an organic peroxide having a lower decomposition temperature effectively generates primary radicals, specifically, a temperature lower than the decomposition temperature of the radical polymerization initiator contained in the resin beads. The temperature is 5° C. or more, preferably 10° C. or more lower than the 10-hour half-life temperature of the radical polymerization initiator contained in the beads, and an appropriate temperature is selected depending on the decomposition temperature of the organic peroxide used. For example, when using dimyristyl peroxy carbonate for benzoyl peroxide, 40 to 65°C,
Preferably it is 50-60°C.
懸濁又は沈澱重合に用いられる分散媒は、ビニ
ルモノマーは溶かしても溶かさなくてもかまわな
いが、重合した樹脂は分散媒に不溶なものであ
る。即ち、ビニルモノマーが分散媒に可溶な場合
には樹脂ビーズ中に含有されるラジカル重合開始
剤への沈澱重合系となり、不溶の場合には懸濁重
合系となる。一般に、ビニルモノマー及びアゾ化
合物や有機過酸化物は油溶性であるため、分散媒
として水を用いるのが一般的であるが、水以外に
もラジカル重合開始剤が不溶性のものである場合
にはメタノール等のアルコール類も使用可能であ
る。又、分散媒の量は熱除去の容易さからビニル
モノマーと同量以上を用いる。 The dispersion medium used in suspension or precipitation polymerization may or may not dissolve the vinyl monomer, but the polymerized resin is insoluble in the dispersion medium. That is, when the vinyl monomer is soluble in the dispersion medium, it becomes a precipitation polymerization system to the radical polymerization initiator contained in the resin beads, and when it is insoluble, it becomes a suspension polymerization system. Generally, vinyl monomers, azo compounds, and organic peroxides are oil-soluble, so water is generally used as a dispersion medium. However, if the radical polymerization initiator is insoluble in addition to water, Alcohols such as methanol can also be used. Further, the amount of dispersion medium used is at least the same amount as the vinyl monomer in order to facilitate heat removal.
分散媒として水を用いる場合、通常ポリビニル
アルコール、ゼラチン等の水溶性高分子や、リン
酸カルシウム、炭酸マグネシウム、及びタルク等
の難水溶性無機物の微粉末等が分散安定剤として
用いられる。更に、必要に応じてアルキルベンゼ
ンスルフオン酸塩、Na2SO4、食塩、および
EDTA等の分散安定助剤を用いることもできる。 When water is used as a dispersion medium, water-soluble polymers such as polyvinyl alcohol and gelatin, and fine powders of poorly water-soluble inorganic substances such as calcium phosphate, magnesium carbonate, and talc are usually used as dispersion stabilizers. Furthermore, alkylbenzene sulfonate, Na 2 SO 4 , salt, and
Dispersion stabilizing aids such as EDTA can also be used.
実験例
以下、実験例により本発明をさらに具体的に説
明する。EXPERIMENTAL EXAMPLE The present invention will be explained in more detail below using experimental examples.
実施例 １
撹拌器付２セパラブルフラスコにリン酸三カ
ルシウム10g、ドデシルベンゼンスルフオン酸ナ
トリウム0.03g、及び水1000gを仕込み、300gのメ
タクリル酸メチルにベンゾイルパーオキサイド
70g及びジミリスチルジカーボネート3gを混合溶
解したモノマー液を加え、撹拌条件下、窒素雰囲
気中で55℃で４時間懸濁重合させた。反応液を冷
却後ステンレス製金鋼（200メツシユ）でろ過し、
生成物を３回水洗後、通風乾燥して樹脂ビーズ
337.2gを得た。この樹脂ビーズのベンゾイルパー
オキサイド含有量は18.3wt％であつた。Example 1 10 g of tricalcium phosphate, 0.03 g of sodium dodecylbenzenesulfonate, and 1000 g of water were placed in two separable flasks equipped with a stirrer, and benzoyl peroxide was added to 300 g of methyl methacrylate.
A monomer solution prepared by mixing and dissolving 70 g of dimyristyl dicarbonate and 3 g of dimyristyl dicarbonate was added, and suspension polymerization was carried out at 55° C. for 4 hours in a nitrogen atmosphere under stirring conditions. After cooling the reaction solution, filter it through stainless steel (200 mesh).
After washing the product three times with water, it is dried with ventilation and made into resin beads.
Obtained 337.2g. The benzoyl peroxide content of these resin beads was 18.3 wt%.
実施例 ２
ベンゾイルパーオキサイド3.1gを用いた他は全
て実施例１と同様にして、ベンゾイルパーオキサ
イド1.0wt％を含む樹脂ビーズ287.8gを得た。こ
の樹脂ビーズ14gを1.0wt％ジメチルパラトルイ
ジン含有メタクリル酸メチル溶液5gと混和し歯
科用トレーレジン用に用いたところ約６分で硬化
し、硬化後のトレーの機械的物性も良好であつ
た。Example 2 287.8 g of resin beads containing 1.0 wt% of benzoyl peroxide were obtained in the same manner as in Example 1 except that 3.1 g of benzoyl peroxide was used. When 14 g of these resin beads were mixed with 5 g of a methyl methacrylate solution containing 1.0 wt% dimethyl para-toluidine and used for a dental tray resin, it cured in about 6 minutes, and the mechanical properties of the cured tray were also good.
実施例 ３
実施例１において、ジミリスチルカーボネート
の量を1.5gとし、ラウロイルパーオキサイド1.5g
を加えた他は実施例と同様に行つた。ベンゾイル
パーオキサイド含有量18.5wt％の樹脂ビーズ
337.7gを得た。Example 3 In Example 1, the amount of dimyristyl carbonate was 1.5 g, and the amount of lauroyl peroxide was 1.5 g.
The procedure was the same as in the example except that . Resin beads with benzoyl peroxide content of 18.5wt%
Obtained 337.7g.
比較例
実施例１において、ジミリスチルジカーボネー
トを用いない他は実施例１と同様に行つたが、重
合中分散不良をおこし重合物はモチ状となつて樹
脂ビーズは得られなかつた。Comparative Example Example 1 was carried out in the same manner as in Example 1 except that dimyristyl dicarbonate was not used, but poor dispersion occurred during polymerization, the polymerized product became sticky, and no resin beads were obtained.
Claims (1)
温度を有する有機過酸化物の存在下に該有機過酸
化物が有効に一次ラジカルを発生する温度でビニ
ルモノマーを懸濁重合又は沈殿重合させることを
特徴とする重合開始剤含有樹脂ビーズの製造法。1. Vinyl monomers are subjected to suspension or precipitation polymerization in the presence of a radical polymerization initiator and an organic peroxide having a lower decomposition temperature than the radical polymerization initiator at a temperature at which the organic peroxide effectively generates primary radicals. A method for producing resin beads containing a polymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1922986A JPS62177001A (en) | 1986-01-31 | 1986-01-31 | Production of resin beads containing polymerization initiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1922986A JPS62177001A (en) | 1986-01-31 | 1986-01-31 | Production of resin beads containing polymerization initiator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62177001A JPS62177001A (en) | 1987-08-03 |
| JPH0576962B2 true JPH0576962B2 (en) | 1993-10-25 |
Family
ID=11993547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1922986A Granted JPS62177001A (en) | 1986-01-31 | 1986-01-31 | Production of resin beads containing polymerization initiator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62177001A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5085500A (en) * | 1989-11-28 | 1992-02-04 | Tsi Incorporated | Non-imaging laser particle counter |
| US7173075B2 (en) | 2004-08-30 | 2007-02-06 | Ultradent Products, Inc. | Gas releasing sealing and filling compositions |
| JP5144982B2 (en) * | 2007-07-27 | 2013-02-13 | 積水化成品工業株式会社 | Method for producing monodisperse particles |
-
1986
- 1986-01-31 JP JP1922986A patent/JPS62177001A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62177001A (en) | 1987-08-03 |
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