JPS6047037A - Production of expandable styrene resin particle - Google Patents
Production of expandable styrene resin particleInfo
- Publication number
- JPS6047037A JPS6047037A JP15465883A JP15465883A JPS6047037A JP S6047037 A JPS6047037 A JP S6047037A JP 15465883 A JP15465883 A JP 15465883A JP 15465883 A JP15465883 A JP 15465883A JP S6047037 A JPS6047037 A JP S6047037A
- Authority
- JP
- Japan
- Prior art keywords
- blowing agent
- polymerization
- resin particles
- weight
- cyclohexane
- 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.)
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Links
Abstract
Description
【発明の詳細な説明】
本発明は発泡性スチレン系樹脂粒子の製造法に関し、さ
らに詳しくは成形品の強度に優れ、かつ製造時間の短縮
化を図った発泡性スチレン系樹脂粒子の製造法に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing expandable styrenic resin particles, and more particularly to a method for manufacturing expandable styrenic resin particles that provides molded articles with excellent strength and reduces manufacturing time. .
従来、成形品の強度は基材樹脂の分子１２発泡剤の組成
、セル数等により影響を受けることが知られている。本
発明者らは発泡剤の圧入時期について種々検討したとこ
ろ９重合初期から発泡剤を圧入する方法や１重合転化率
５０〜９８チと粒子径が決定された後発泡剤を圧入する
方法は２重合が完結した後発泡剤を圧入する方法に比較
して。Conventionally, it has been known that the strength of a molded article is affected by the composition of the molecular 12 blowing agent in the base resin, the number of cells, etc. The present inventors have studied various methods of injecting the blowing agent and found that there are two methods: one is to inject the blowing agent from the early stage of polymerization, and the other is to inject the blowing agent after the single polymerization conversion rate is 50 to 98 inches and the particle size has been determined. Compared to the method of press-injecting the blowing agent after the polymerization is completed.
得られる樹脂粒子の強度が低下することがわかった。こ
の原因としては９発泡剤が連鎖移動剤となシ、ビーズ表
面の分子量の低下が発生し、成形品の強度を低下させる
ことが判明した。従って、短い製造時間で生産性を上げ
るために９重合途中で発泡剤を圧入しても高強度の成形
品が得られる製造方法が要望されている。It was found that the strength of the resulting resin particles decreased. It has been found that the reason for this is that the blowing agent 9 does not act as a chain transfer agent, which causes a decrease in the molecular weight of the bead surface, resulting in a decrease in the strength of the molded product. Therefore, in order to increase productivity in a short manufacturing time, there is a need for a manufacturing method that allows a molded article with high strength to be obtained even if a blowing agent is press-injected during the 9-polymerization.
本発明の目的は、上記に鑑み、短い製造時間で高強度の
成形品が得られる発泡性−スチレン系樹脂粒子の製造法
を提供することにある。In view of the above, an object of the present invention is to provide a method for producing expandable styrenic resin particles that allows a molded article with high strength to be obtained in a short production time.
本発明者らは、前記目的達成のため９種々研究の結果、
懸濁重合の重合開始剤として、２官能遊離基を有する化
合物を含む、特定の３成分系混合物を用いることにより
２重合転化率５０〜９８％の時点で１発泡剤を圧入して
も、高強度の成形品が得られ、かつ製造時間の短縮化も
達成できることを見出し９本発明に到達した。As a result of nine different studies to achieve the above objective, the present inventors found that
By using a specific three-component mixture containing a compound having a difunctional free radical as a polymerization initiator for suspension polymerization, even if one blowing agent is injected at a double polymerization conversion rate of 50 to 98%, high The inventors have discovered that it is possible to obtain a molded article with high strength and to shorten the manufacturing time, and have thus arrived at the present invention.
本発明は、スチレン系単量体を懸濁重合させ。The present invention involves suspension polymerization of styrenic monomers.
重合途中で発泡剤を添加して発泡性岬スチレン系樹脂粒
子を製造する方法において、前記懸濁重合の重合開始剤
として、スチレン系単量体に対して、Ｌ＃福〜０，１重
量％の過酸化ベンゾイル。In a method for producing expandable Misaki styrenic resin particles by adding a blowing agent during polymerization, as a polymerization initiator for the suspension polymerization, L#Fuku~0.1% by weight is added to the styrene monomer. benzoyl peroxide.
０．０５〜０．６重量−のシクロヘキサン系ノ（−オキ
シケタールおよび０．０δ〜０．２重量−のｔ−ブチル
パーベンゾエートからなる混合物を用い、かつ発泡剤の
添加を重合転化率５０〜９８チの時点で行なうことを特
徴とする。A mixture consisting of 0.05 to 0.6 weight of cyclohexane-based oxyketal and 0.0δ to 0.2 weight of t-butyl perbenzoate was used, and the blowing agent was added at a polymerization conversion rate of 50 to 50. It is characterized by being carried out at the 98th point.
本発明方法に用いられるスチレン系単量体とは。What is the styrenic monomer used in the method of the present invention?
スチレン、若しくハα−メチルスチレン、クロロスチレ
ン、ｔ−ブチルスチレン等の置換スチレンまたはスチレ
ン、若しくは置換スチレンとこれらと共重合可能な単量
体【例えばα−メチルスチレン、アクリロニトリル、メ
チルメタアクリレート。Styrene, substituted styrene such as α-methylstyrene, chlorostyrene, t-butylstyrene, styrene, or substituted styrene and monomers copolymerizable therewith (for example α-methylstyrene, acrylonitrile, methyl methacrylate).
エチルアクリレート、ジメチルマレ−１・、ジエチル７
−ｑレート、ジビニルベンゼン等）との混合物が用いら
れる。スチレンと共重合可能な単量体は１種または２種
以上混合して用いられる。また。Ethyl acrylate, dimethyl male-1, diethyl 7
-q rate, divinylbenzene, etc.). Monomers copolymerizable with styrene may be used alone or in combination of two or more. Also.
スチレン系単量体としては、スチレンが５００重量％上
含ｉれるものが好ましい。The styrene monomer preferably contains 500% by weight or more of styrene.
懸濁重合においては１分散剤として難溶性無機物、水溶
性高分子保護コロイド等を重合系に添加することができ
る。In suspension polymerization, sparingly soluble inorganic substances, water-soluble polymeric protective colloids, etc. can be added to the polymerization system as dispersants.
水溶性高分子保護コロイドとしては、ポリビニルアルコ
ール、メチルセルロース等カ６ 、Ｄ 、 難溶性無機
物としては、燐酸カルシウム、ピロ燐酸マグネシウム、
ベントナイトがある。Water-soluble polymeric protective colloids include polyvinyl alcohol, methyl cellulose, etc., and sparingly soluble inorganic substances include calcium phosphate, magnesium pyrophosphate,
There's bentonite.
難溶性無機物を分散剤とした場合は、ドデシルベンゼン
スルホン酸ナトリウム等の界面活性剤が少量併用される
のが好ましい。使用量は難溶性無機物が水に対し０．０
１〜１重量％、界面活性剤は１〜２ ｏ ｏ ｐｐｍの
範囲で選ばれるのが好ましい。When a poorly soluble inorganic substance is used as a dispersant, it is preferable to use a small amount of a surfactant such as sodium dodecylbenzenesulfonate. The amount used is 0.0 of poorly soluble inorganic substances relative to water.
Preferably, the surfactant is selected in the range of 1 to 1% by weight, and the surfactant is in the range of 1 to 2 o ppm.
本発明に使用される発泡剤としては、生成される樹脂の
軟化点よりも低い沸点を有し、かつビニル系樹脂粒子を
溶解しないか、または僅かに膨潤させる性質を持ったも
のが好適である。これらの発泡剤としては１例えばプロ
パン、ブタン、べ、：ブタン等の脂肪族炭化水素類、シ
クロブタン、シクロベンクン、シクロヘキサン等の環式
脂肪族炭化水素類、メチルクロライド、ジクロロジフル
オロメタン等の・・ロゲン化炭化水素類等を挙げること
ができる。発泡剤の使用量は２通常ス丙しン系単量体の
重量に対して３〜１２重量裂、好ましくは６〜８重量％
の割合である。前記発泡剤のうちプロパンおよびブタン
を単独または併用して用いるときには２発泡剤の含浸時
にビニル系重合体を溶解する有機溶剤を少量（好ましく
はスチレン系単量体に対し、０．２〜０，３重量％）併
用することが好ましい。このような溶剤としては９例え
ばエチレンジクロライド、トリクロロエチレン、テトラ
クロロエチレン、ベンゼン、トルエン、キシレン。The blowing agent used in the present invention is preferably one that has a boiling point lower than the softening point of the resin to be produced and has the property of not dissolving the vinyl resin particles or causing them to swell slightly. . Examples of these blowing agents include aliphatic hydrocarbons such as propane, butane, and butane, cycloaliphatic hydrocarbons such as cyclobutane, cyclobencune, and cyclohexane, and methyl chloride, dichlorodifluoromethane, etc. Hydrocarbons and the like can be mentioned. The amount of blowing agent to be used is usually 3 to 12% by weight, preferably 6 to 8% by weight based on the weight of the carbon monomer.
This is the percentage of When propane and butane are used alone or in combination among the blowing agents, a small amount of an organic solvent that dissolves the vinyl polymer (preferably 0.2 to 0.0 3% by weight) is preferably used in combination. Examples of such solvents include ethylene dichloride, trichlorethylene, tetrachloroethylene, benzene, toluene, and xylene.
エチルベンゼン等を挙げることができる。Examples include ethylbenzene.
発泡剤の添加（含浸）は９重合途中に水性媒体中に発泡
剤を圧入することによって行なうことができるが１重合
転化率５０〜９８チの時点で行なうことが重合系の安定
性および生産性の面から必要である。重合初期から発泡
剤を存在させると。Addition (impregnation) of the blowing agent can be carried out by pressurizing the blowing agent into the aqueous medium during the polymerization, but it is best to add the blowing agent at a point where the conversion rate of one polymerization is 50 to 98 degrees to improve the stability and productivity of the polymerization system. It is necessary from this point of view. When a blowing agent is present from the initial stage of polymerization.
粒子径の調節が難しく、また分散系を不安定にする。一
方９重合が完結した後９発泡剤を圧入する場合は９合成
時間が長くなシ、生産性が低下する。It is difficult to control the particle size and makes the dispersion system unstable. On the other hand, when the blowing agent is press-injected after the polymerization is completed, the synthesis time is longer and the productivity is lowered.
本発明方法においては、懸濁重合の重合開始剤として、
過酸化ベンゾイル、シクロヘキサン系パーオキシケター
ルおよびｔ−ブチルパーベンゾエートからなる混合物が
用いられる。これらの重合開始剤の使用量は、目的とす
る分子量により決定されたものである。In the method of the present invention, as a polymerization initiator for suspension polymerization,
A mixture consisting of benzoyl peroxide, cyclohexane peroxyketal and t-butyl perbenzoate is used. The amount of these polymerization initiators to be used is determined depending on the desired molecular weight.
シクロヘキサン系パーオキシケタールとしては。As a cyclohexane peroxyketal.
１．１−ジ−ｔ−ブチルペルオキシ−３，３，５−トリ
メチル−シクロヘキサン、１．１−ジ−ｔ−ブチルペル
オキシ−シクロヘキサン等がある。Examples include 1.1-di-t-butylperoxy-3,3,5-trimethyl-cyclohexane and 1.1-di-t-butylperoxy-cyclohexane.
Ｏ１／２−キ
過酸化ベンゾイルの使用量は、＃存１〜Ｏ１＃重牛
りすぎ、Ｏｌ−重ｔＳを越える場合には分子量が低下す
る。またシクロヘキサン系パーオキシケタールの使用量
は、０．０５〜０．６重量％、好ましくは０．０５〜０
．３重量％である。０．０５重量−未満では分子量的に
効果が少なく、また重合時間が長くなる欠点があｐ、０
１重量％を越える場合には。The amount of O1/2-benzoyl peroxide to be used is from #1 to O1 #heavy, and if it exceeds Ol-heavy tS, the molecular weight will decrease. The amount of cyclohexane peroxyketal used is 0.05 to 0.6% by weight, preferably 0.05 to 0.
．． It is 3% by weight. If it is less than 0.05% by weight, the molecular weight will be less effective and the polymerization time will be longer.
If it exceeds 1% by weight.
分子量が低下する。ｔ−ブチルパーベンゾエートの使用
量は、０．０２〜０．２重量％、好ましくは０．０５〜
０．２重量％である。０．ＯＲ重量％未滴の場合には、
残存単量体を減少させるのに長時間を要し、０，１重量
％を越える場合には基材樹脂の分子量を低下させる傾向
があり、また残存単量体の減少も平衡に達する。Molecular weight decreases. The amount of t-butyl perbenzoate used is 0.02 to 0.2% by weight, preferably 0.05 to 0.2% by weight.
It is 0.2% by weight. 0. If OR weight% is not dropped,
It takes a long time to reduce the residual monomer, and if it exceeds 0.1% by weight, the molecular weight of the base resin tends to decrease, and the reduction of the residual monomer also reaches an equilibrium.
本発明方法全実施するに際しては、まずスチレン系単量
体を、特定量の前記３成分系重合開始剤の存在下に１通
常９０〜１００℃で行ない、このとき５〜６時間懸濁重
合させる。When carrying out all of the methods of the present invention, first, styrene monomers are subjected to suspension polymerization in the presence of a specified amount of the three-component polymerization initiator, usually at 90 to 100°C, for 5 to 6 hours. .
次いで重合転化率５０〜９８チの時点で９反応液に２発
泡剤を圧入して９発泡剤の含浸が行なわれる。この際の
発泡剤圧入温度は１ｏｏ〜１１５℃である。さらに発泡
剤を圧入後、１００〜１２０℃で反応液を加熱して９発
泡剤の含浸と重合を完結させると、目的とする発泡性−
スチレン系樹脂粒子が得られる。Next, when the polymerization conversion rate is 50 to 98 degrees, two blowing agents are pressure-injected into the reaction solution No. 9 to impregnate the blowing agent No. 9. The blowing agent injection temperature at this time is 100 to 115°C. After pressurizing the blowing agent, the reaction solution is heated at 100 to 120°C to complete the impregnation and polymerization of the blowing agent.
Styrenic resin particles are obtained.
本発明方法においては、得られる樹脂の重量平均分子量
（Ｍ ｗ ）は２８００００〜３７００００゜数平均分
子量（Ｍｎ）は１０５０００〜１３５０００の範囲に調
整することが好ましい。分子量がこれらの範囲を越える
場合には、基材としては強度が上がるが２通常の発泡や
成形時のスチーム加熱条件では充分な発泡、成形融着が
得られないことがある。またこれらの分子量の下限に達
しない場合には１機械特性が低下し、低分子量物はブロ
ッキング、成形加工時金型高温部での表皮溶解（いわゆ
るケロイド状）の原因となることがある。In the method of the present invention, it is preferable that the weight average molecular weight (Mw) of the resulting resin is adjusted to a range of 280,000 to 370,000 degrees and the number average molecular weight (Mn) of the resin to be adjusted to a range of 105,000 to 135,000. When the molecular weight exceeds these ranges, the strength of the base material increases, but sufficient foaming and molding fusion may not be obtained under normal steam heating conditions during foaming and molding. In addition, if the lower limit of these molecular weights is not reached, the mechanical properties deteriorate, and low molecular weight substances may cause blocking and skin melting (so-called keloid-like) in the high temperature part of the mold during molding.
本発明方法によれば、懸濁重合における重合開始剤の種
類および使用量ならびに発泡剤の圧入時期を上記のよう
に規定することより、高強度の成形品を得ることができ
、しかも製造時間の短縮化をも達成することができる。According to the method of the present invention, by specifying the type and amount of polymerization initiator used in suspension polymerization and the injection timing of blowing agent as described above, it is possible to obtain a molded article with high strength and to reduce the production time. Shortening can also be achieved.
すなわち、従来９重合途中で発泡剤を圧入する場合には
９重合完結後に発泡剤を圧入する場合に比較して、成形
品の強度の低下がみられたが９本発明方法によれば３・
成分系重合開始剤のうち１成分として２官能遊離基ヲ有
する化合物を使用することにより９重合転化率５０〜９
８チで発泡剤を圧入しても重合完結後の発泡剤圧入と同
等以上の成形品の強度を有するものが得られる。しかも
この際合成に要する時間は１重合完結後に発泡剤を圧入
する場、合の合成時間（例えば約１８時間）に比較して
、１０チ以上（例えば約２時間）短縮させることができ
、生産性向上の点で非常に有利である。In other words, conventionally, when a blowing agent was injected midway through polymerization, the strength of the molded product decreased compared to when a blowing agent was injected after completion of polymerization, but with the method of the present invention, 3.
By using a compound having a difunctional free radical as one component of the component-based polymerization initiator, a polymerization conversion rate of 50 to 9 can be achieved.
Even if the blowing agent is press-fitted with 8 holes, a molded article having strength equal to or higher than that obtained by press-fitting the blowing agent after polymerization is completed can be obtained. Moreover, the time required for synthesis can be reduced by more than 10 hours (for example, about 2 hours) compared to the synthesis time (for example, about 18 hours) when a blowing agent is press-injected after one polymerization is completed, and production It is very advantageous in terms of improving sex.
次に本発明の実施例を示、す。下記部は重量部を意゛味
する。Next, examples of the present invention will be shown. The following parts refer to parts by weight.
実施例１〜７
攪拌機付きオートクレーブ中で、第３リン酸カルシウム
０．１ 部およびドデシルベンゼンスルホン酸すトリウ
ム１％水溶液０．５部を蒸留水１００部に分散または溶
解させた。次いでこれに過酸化ベンソイル、１，１−ジ
−ｔ−ブチルペル、ｔキシ−３゜３、５− ）リメチル
シクロヘキサンおよびｔ−ブチルハーヘンゾエ“−トを
第１表に示す量で溶解させ。Examples 1 to 7 In an autoclave equipped with a stirrer, 0.1 part of tertiary calcium phosphate and 0.5 part of a 1% aqueous solution of thorium dodecylbenzenesulfonate were dispersed or dissolved in 100 parts of distilled water. Then, benzoyl peroxide, 1,1-di-t-butyl peroxide, t-x-3,3,5-)limethylcyclohexane and t-butylhachenzoate were dissolved in this in the amounts shown in Table 1. .
これにセル調整剤としてヒドロキシステアリン酸アマイ
ド０．１部分散させたスチレン１００部を攪拌しながら
添加し、窒素雰囲気下に９５±１°Ｃで懸濁重合全開始
させた。２時間１０１分後に２反応液に第３リン酸カル
シウム０．０５部金加え、更に重合転化率９５チに達し
た時点で第３リン酸カルシウム０．３部を加えた後、１
０５℃に昇温し、シクロヘキサン２部およびブタ７７部
全１時間かけて導入した。その後４０分間かけて１１５
℃に昇温し９同温度に２時間３０分保った後、室温まで
冷却すると１発泡性ポリスチレン粒子が得られた。To this, 100 parts of styrene in which 0.1 part of hydroxystearamide was dispersed as a cell conditioner was added with stirring, and suspension polymerization was completely initiated at 95±1°C under a nitrogen atmosphere. After 2 hours and 101 minutes, 0.05 part of tribasic calcium phosphate was added to the reaction solution 2, and when the polymerization conversion rate reached 95%, 0.3 part of tribasic calcium phosphate was added, and then 1
The temperature was raised to 0.05°C, and 2 parts of cyclohexane and 77 parts of pork were introduced over a total of 1 hour. 115 over the next 40 minutes
The temperature was raised to 9°C, kept at the same temperature for 2 hours and 30 minutes, and then cooled to room temperature to obtain expandable polystyrene particles.
得られた発泡性ポリスチレンの分子量をＩＩ Ｌ Ｃに
より測定した結果およびＪＩＳ−Ａ−９５１１による曲
げ強度試験（密度０．１６６ ｇ／ｃｃ）の結果をあわ
せて第１表に示す。Table 1 shows the molecular weight of the obtained expandable polystyrene measured by IILC and the results of a bending strength test (density 0.166 g/cc) according to JIS-A-9511.
以下余白
第１表 配合と物性
比較例１および２
過酸化ベンゾイル、１，１−ジ−ｔ−ブチルペルオキシ
−３，３，５−） ’）メチルシクロヘキサンおよびｔ
−ブチルパーベンゾエート第２表に示す量で用い、その
他は実施例１と同様に処理した。結果を第２表に示す。Table 1 with blank space below Comparative Examples 1 and 2 of formulation and physical properties Benzoyl peroxide, 1,1-di-t-butylperoxy-3,3,5-)') Methylcyclohexane and t
-Butyl perbenzoate was used in the amount shown in Table 2, and the other conditions were the same as in Example 1. The results are shown in Table 2.
第２表 配合と物性
比較例１および２はいずれも実施例１に比較して９強度
が１．８ Ｋｆ・ｆ／ｃｍ２と低いが、これは比較例１
においては高分子量化したためと考えられる。Table 2: Formulation and physical properties Comparative Examples 1 and 2 both have a lower strength of 1.8 Kf・f/cm2 than Example 1;
This is thought to be due to the higher molecular weight.
また比較例２においては、Ｍｗ／Ｍｎの比が太きく、す
なわち分子量がブロードであったためと考過酸化ヘンソ
イル、１．１−ジーｔ−ブチルペルオキシ−３，３，５
−）リメチルシクロヘキサンおよびｔ−ブチルパーベン
ゾエートを第３表に示す量で用い、その他は実施例１と
同様に処理した。結果を第３表に示す。In addition, in Comparative Example 2, the Mw/Mn ratio was large, that is, the molecular weight was broad.
-) Limethylcyclohexane and t-butyl perbenzoate were used in the amounts shown in Table 3, and otherwise the procedure was as in Example 1. The results are shown in Table 3.
以下余白
第３表 配合と物性
’Ｏｎ”
て２強度がＺ Ｏ〜２．１ Ｋｆ ・ｆ／ｃｍ２と低い
。これは数平均分子量が示すように低分子：叶物の発生
が強度を低下させているものと考えられる。Below is a blank table 3. Formulation and physical properties 'On' 2 The strength is low at ZO ~ 2.1 Kf・f/cm2.This is because the number average molecular weight indicates that the low molecular weight: The occurrence of leaves reduces the strength. It is thought that the
比較例０
重合開始剤として過酸化ベンゾイル０．２０ ｓ＋１．
１−ジ−ｔ−ブチルペルオキシ−３，３，５−）リメチ
ルゾクロヘキサン０．０５部およびｔ−ブチルパーベン
ゾニー） ０．０５部（実施例４と同じ）を用い、ガス
の含浸を次のように変更し、その他は実施例１と同様に
処理した。すなわち重合転化率９５％の時点で、９３℃
から１２５℃に４０分間で昇温し、同温度で３０分間保
温することにより重合を９９．８ ％完結させた。次い
でこの反応液に１０５℃に４０分間で冷却し、シクロヘ
キサン２部およびブタン７部を１時間かけて導入した。Comparative Example 0 Benzoyl peroxide was used as a polymerization initiator at 0.20 s+1.
Impregnation with gas using 0.05 part of 1-di-t-butylperoxy-3,3,5-)limethylzoclohexane and 0.05 part of t-butylperbenzony (same as in Example 4). The process was carried out in the same manner as in Example 1 except for the following changes. That is, at a polymerization conversion rate of 95%, the temperature is 93°C.
The polymerization was completed by 99.8% by raising the temperature from 125° C. over 40 minutes and keeping it at the same temperature for 30 minutes. The reaction solution was then cooled to 105° C. over 40 minutes, and 2 parts of cyclohexane and 7 parts of butane were introduced over 1 hour.
その後４０分間かけて１１５℃に昇温し、同温度に２時
、間３０分保った後、室温まで冷却した。得られた発泡
性ポリスチレンについて実施例１と同様に測定すると、
数平均分子量１２．３Ｘ１０’、重量平均分子量３３．
３ Ｘｉ Ｏ’、 Ｍｗ／Ｍｎ 〜２．７ 、曲げ強度
２．９ Ｋｇ・ｆ／■２と、実施例４とほぼ同等の特性
であった。Thereafter, the temperature was raised to 115° C. over 40 minutes, maintained at the same temperature for 2 hours and 30 minutes, and then cooled to room temperature. When the obtained expandable polystyrene was measured in the same manner as in Example 1,
Number average molecular weight 12.3X10', weight average molecular weight 33.
3 Xi O', Mw/Mn ~2.7, and bending strength of 2.9 Kg·f/■2, which were almost the same characteristics as Example 4.
しかし、比較例ｔは重合を完結させるために。However, in Comparative Example t, in order to complete the polymerization.
１２５℃に昇温したり、保温したため、実施例４に比較
して、１時間５０分合成時間が長くかかつている。Since the temperature was raised to 125° C. and the temperature was maintained, the synthesis time was 1 hour and 50 minutes longer than in Example 4.
Claims (1)
中で発泡剤を添加して発泡性ｍスチレン系樹脂粒子を製
造する方法において、前記懸濁重合の重〜０．．６！ｆ
’ｆ％のシクロヘキサン系パーオキシケタ−ルおよび０
． Ｏｇ −０，２重量％のｔ−ブチルパーベンゾエー
トからなる混合物金柑い、かつ発泡剤の添加を重合転化
率５０〜９８％の時点で行なうことを特徴とする発泡性
スチレン系樹脂粒子の製造法。(1) Styrenic monomer 71i - A method of producing expandable m styrenic resin particles by carrying out suspension polymerization and adding a blowing agent during the polymerization. ．． 6! f
'f% of cyclohexane peroxyketal and 0
．． Og - A method for producing expandable styrenic resin particles, characterized in that a mixture consisting of 0.2% by weight of t-butyl perbenzoate is used, and a blowing agent is added at a polymerization conversion rate of 50 to 98%. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15465883A JPS6047037A (en) | 1983-08-24 | 1983-08-24 | Production of expandable styrene resin particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15465883A JPS6047037A (en) | 1983-08-24 | 1983-08-24 | Production of expandable styrene resin particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6047037A true JPS6047037A (en) | 1985-03-14 |
| JPS6338063B2 JPS6338063B2 (en) | 1988-07-28 |
Family
ID=15589047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15465883A Granted JPS6047037A (en) | 1983-08-24 | 1983-08-24 | Production of expandable styrene resin particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6047037A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403866A (en) * | 1991-03-20 | 1995-04-04 | Hitachi Chemical Co., Ltd. | Foamable resin composition and a thermoplastic foamable pattern and metal casting manufacturing method using said composition |
| JPH08330464A (en) * | 1995-05-31 | 1996-12-13 | Nec Kyushu Ltd | Pin grid array structure lsi |
| JP2002097296A (en) * | 2000-09-26 | 2002-04-02 | Hitachi Chem Co Ltd | Foamable acrylonitrile-styrene resin particle and foamed molding using the same |
| JP2006522844A (en) * | 2003-04-14 | 2006-10-05 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Peroxide distribution to suspension process where styrene is polymerized |
| JP2010222490A (en) * | 2009-03-24 | 2010-10-07 | Kaneka Corp | Foamable styrenic resin particle |
| JP2013032449A (en) * | 2011-08-02 | 2013-02-14 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particle, foamed particle, and foamed molding |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4915634A (en) * | 1972-06-06 | 1974-02-12 | ||
| JPS54107994A (en) * | 1978-02-14 | 1979-08-24 | Denki Kagaku Kogyo Kk | Preparation of styrene resin |
| JPS55123631A (en) * | 1979-03-14 | 1980-09-24 | Kanegafuchi Chem Ind Co Ltd | Production of foaming thermoplastic resin particle |
| JPS57145133A (en) * | 1981-03-04 | 1982-09-08 | Hitachi Chem Co Ltd | Production of foamable styrene resin particle |
-
1983
- 1983-08-24 JP JP15465883A patent/JPS6047037A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4915634A (en) * | 1972-06-06 | 1974-02-12 | ||
| JPS54107994A (en) * | 1978-02-14 | 1979-08-24 | Denki Kagaku Kogyo Kk | Preparation of styrene resin |
| JPS55123631A (en) * | 1979-03-14 | 1980-09-24 | Kanegafuchi Chem Ind Co Ltd | Production of foaming thermoplastic resin particle |
| JPS57145133A (en) * | 1981-03-04 | 1982-09-08 | Hitachi Chem Co Ltd | Production of foamable styrene resin particle |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403866A (en) * | 1991-03-20 | 1995-04-04 | Hitachi Chemical Co., Ltd. | Foamable resin composition and a thermoplastic foamable pattern and metal casting manufacturing method using said composition |
| JPH08330464A (en) * | 1995-05-31 | 1996-12-13 | Nec Kyushu Ltd | Pin grid array structure lsi |
| JP2002097296A (en) * | 2000-09-26 | 2002-04-02 | Hitachi Chem Co Ltd | Foamable acrylonitrile-styrene resin particle and foamed molding using the same |
| JP2006522844A (en) * | 2003-04-14 | 2006-10-05 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Peroxide distribution to suspension process where styrene is polymerized |
| JP2010222490A (en) * | 2009-03-24 | 2010-10-07 | Kaneka Corp | Foamable styrenic resin particle |
| JP2013032449A (en) * | 2011-08-02 | 2013-02-14 | Sekisui Plastics Co Ltd | Foamable polystyrene-based resin particle, foamed particle, and foamed molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6338063B2 (en) | 1988-07-28 |
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