JPH0699525B2 - Method for producing copolymer - Google Patents
Method for producing copolymerInfo
- Publication number
- JPH0699525B2 JPH0699525B2 JP59126135A JP12613584A JPH0699525B2 JP H0699525 B2 JPH0699525 B2 JP H0699525B2 JP 59126135 A JP59126135 A JP 59126135A JP 12613584 A JP12613584 A JP 12613584A JP H0699525 B2 JPH0699525 B2 JP H0699525B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- temperature
- copolymer
- methylstyrene
- acrylonitrile
- 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
- 229920001577 copolymer Polymers 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 12
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000003505 polymerization initiator Substances 0.000 description 7
- 239000003999 initiator Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical compound CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- QRMPKOFEUHIBNM-UHFFFAOYSA-N p-dimethylcyclohexane Natural products CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HSMAVZYQDXUJLK-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C)C HSMAVZYQDXUJLK-UHFFFAOYSA-N 0.000 description 1
- JZDHUYKBYNFYAB-UHFFFAOYSA-N 2-(tert-butyldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(C)C JZDHUYKBYNFYAB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はα−メチルスチレンとアクリロニトリルの共重
合体、特に熱変形温度が高くかつ熱安定性の良好な該共
重合体の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a copolymer of α-methylstyrene and acrylonitrile, and more particularly to a method for producing the copolymer having a high heat distortion temperature and good thermal stability. Is.
〔従来の技術及び問題点〕 α−メチルスチレンとアクリロニトリルの共重合体の熱
変形温度を高めるため、2,5−ジメチルヘキサン2,5−ビ
ス（パープロピオネート）または2,5ジメチルヘキサン
2,5ビス（パーラウレート）等のパーオキサイド系ラジ
カル重合開始剤を用いて重合して分子量を高め、共重合
体中の残存単量体を少なくする方法が検討されている。
（特公昭45−1825）かかる方法においては、得られる共
重合体の分子量は高いが、ペレツト化時に分子量の低下
が起こり、成形物とした場合の衝撃強度が低下する。こ
れは、α−メチルスチレンとアクリロニトリルの共重合
体は、解重合性があるため、重合終了時高分子量重合体
を得たにもかかわらず、ペレツト化時又は成形時に分子
量の低下が起こり、熱変形温度を低下させるためと考え
られる。[Prior Art and Problems] In order to raise the heat distortion temperature of the copolymer of α-methylstyrene and acrylonitrile, 2,5-dimethylhexane 2,5-bis (perpropionate) or 2,5-dimethylhexane
A method of increasing the molecular weight by polymerization using a peroxide-based radical polymerization initiator such as 2,5 bis (perlaurate) to reduce the amount of residual monomers in the copolymer has been investigated.
(Japanese Patent Publication No. 45-1825) In such a method, the copolymer obtained has a high molecular weight, but the molecular weight is lowered during pelletization, and the impact strength of the molded product is lowered. This is because the copolymer of α-methylstyrene and acrylonitrile has depolymerizability, so even though a high molecular weight polymer was obtained at the end of the polymerization, the molecular weight was lowered during pelletization or during molding, and It is considered that the deformation temperature is lowered.
〔問題点を解決するための手段〕 本発明者はペレツト化時及び成形時において分子量の低
下を起こさず、かつ実用上有用な機械的性質と成形性、
高い熱変形温度を有するα−メチルスチレンとアクリロ
ニトリルの共重合体を得ることを目的にこれを達成すべ
く、鋭意検討した結果、α−メチルスチレンとアクリロ
ニトリル単量体混合物を特定のアゾ系触媒の存在下に特
定の重合温度で懸濁重合することにより達成できること
を見出し本発明に到達した。[Means for Solving Problems] The present inventor does not cause a decrease in molecular weight during pelletization and during molding, and has practically useful mechanical properties and moldability,
In order to achieve this for the purpose of obtaining a copolymer of α-methylstyrene and acrylonitrile having a high heat distortion temperature, as a result of extensive studies, α-methylstyrene and acrylonitrile monomer mixture of a specific azo catalyst The present inventors have found that the present invention can be achieved by carrying out suspension polymerization at a specific polymerization temperature in the presence of the present invention, and thus reached the present invention.
すなわち、本発明はα−メチルスチレン65〜75重量％と
アクリロニトリル25〜35重量％の混合物を共重合するに
あたり、10時間半減期（ベンゼン中の0.1モル／）70
℃以上90℃未満の２−ターシャリーブチルアゾ系ラジカ
ル重合開始剤の存在下で、20時間半減期温度から５時間
半減期温度の範囲で懸濁重合させることを特徴とするα
−メチルスチレンとアクリロニトリルの共重合体の製造
方法である。That is, according to the present invention, when copolymerizing a mixture of 65-75% by weight of α-methylstyrene and 25-35% by weight of acrylonitrile, a half-life of 10 hours (0.1 mol / benzene in benzene) is 70%.
Suspension polymerization in the range of 20 hours half-life temperature to 5 hours half-life temperature in the presence of a 2-tertiarybutylazo radical polymerization initiator having a temperature of ℃ to less than 90 ℃ α
-A method for producing a copolymer of methylstyrene and acrylonitrile.
この方法により製造された共重合体は、従来のα−メチ
ルスチレンとアクリロニトリルの共重合体に比べ、熱変
形温度が高く、成形時の安定性が良好である。The copolymer produced by this method has a higher heat distortion temperature and better stability during molding than the conventional copolymer of α-methylstyrene and acrylonitrile.
以下、具体的に本発明を説明する。Hereinafter, the present invention will be specifically described.
本発明で単量体混合物の組成はα−メチルスチレン65〜
75重量％、アクリロニトリル25〜35重量％である。α−
メチルスチレンの量が65重量％より少ないと得られる共
重合体の熱変形温度が低くなり、この共重合体の特徴が
失われさらに着色を起こし易くなり好ましくない。75重
量％より多いと重合速度が極端に低下し残存単量体量が
多く、得られる共重合体の熱変形温度が低くなる。In the present invention, the composition of the monomer mixture is α-methylstyrene 65-
75% by weight and 25-35% by weight of acrylonitrile. α-
When the amount of methylstyrene is less than 65% by weight, the heat distortion temperature of the obtained copolymer becomes low, the characteristics of the copolymer are lost, and the coloring is likely to occur, which is not preferable. If it is more than 75% by weight, the polymerization rate will be extremely reduced, the amount of residual monomers will be large, and the heat distortion temperature of the resulting copolymer will be low.
本発明方法において最も特徴とする所は、特定の２−タ
ーシャリーブチルアゾ系重合開始剤を用いて、特定の重
合温度で懸濁重合を行なうことである。すなわち、重合
開始剤としては10時間半減期が70℃以上90℃未満の２−
ターシャリーブチルアゾ系重合開始剤を用い、重合温度
としては、20時間半減期温度から５時間半減期温度の範
囲で重合を行なうことが必須である。The most characteristic feature of the method of the present invention is that suspension polymerization is carried out at a specific polymerization temperature using a specific 2-tertiarybutylazo polymerization initiator. That is, as a polymerization initiator, a 2-hour compound having a 10-hour half-life of 70 ° C or higher and lower than 90 ° C
It is essential to use a tertiary butyl azo-based polymerization initiator and carry out the polymerization at a polymerization temperature of 20 hours to 5 hours.
通常の有機過酸物を開始剤として用いた場合、ペレツト
化時に分子量の低下が起こり、成形物とした場合の衝撃
強度が低下する。２−ターシャリーブチルアゾ系重合開
始剤を開始剤として使用する場合、10時間半減期が70℃
未満の開始剤では重合速度が遅く残存単量体も多い。一
方、10時間半減期が90℃以上の２−ターシャリーブチル
アゾ系重合開始剤を用いると、充分な重合速度が得られ
るが、生成する共重合体の熱変形温度が低下することを
見出した。これは、重合時に生成する低分子量重合体の
含有量の差によるものであり、低分子量重合体の生成は
重合温度にのみ依存するため、低温で活性のある10時間
半減期が90℃未満の開始剤を用いねばならない。When a usual organic peracid is used as an initiator, the molecular weight is lowered during pelletization, and the impact strength of the molded product is lowered. When using a 2-tert-butyl azo polymerization initiator as the initiator, the 10-hour half-life is 70 ° C.
If the amount of the initiator is less than 1, the polymerization rate is slow and the amount of residual monomer is large. On the other hand, it was found that when a 2-tertiarybutylazo polymerization initiator having a 10-hour half-life of 90 ° C. or more is used, a sufficient polymerization rate can be obtained, but the heat distortion temperature of the resulting copolymer decreases. . This is due to the difference in the content of low molecular weight polymer produced during polymerization, the production of low molecular weight polymer depends only on the polymerization temperature, 10 hours half-life active at low temperatures is less than 90 ℃. An initiator must be used.
重合温度としては、20時間半減期温度から５時間半減期
温度の範囲であり、20時間半減期より低温では重合開始
剤が共重合体中に残留し熱変形温度を低下させる。５時
間半減期より高温では重合後半に開始剤が消失してしま
い重合を完結することが困難である。The polymerization temperature is in the range of 20 hours half-life temperature to 5 hours half-life temperature, and at a temperature lower than 20 hours half-life temperature, the polymerization initiator remains in the copolymer to lower the heat distortion temperature. When the temperature is higher than the half-life of 5 hours, the initiator disappears in the latter half of the polymerization and it is difficult to complete the polymerization.
本発明の方法に使用可能な２−ターシャリーブチルアゾ
系重合開始剤の例としては、２−ｔ−ブチルアゾ−２−
シアノ−４−メチルペンタン,2−ｔ−ブチルアゾ−２−
シアノプロパン,2−ｔ−ブチルアゾ−２−シアノブタン
などが挙げられる。Examples of the 2-tert-butylazo-based polymerization initiator that can be used in the method of the present invention include 2-t-butylazo-2-
Cyano-4-methylpentane, 2-t-butylazo-2-
Examples thereof include cyanopropane and 2-t-butylazo-2-cyanobutane.
重合は通常10〜40時間で完遂することができる。また懸
濁重合は水性媒体中で通常知られている懸濁安定剤を使
用して行うことができる。The polymerization can usually be completed in 10 to 40 hours. The suspension polymerization can be carried out in an aqueous medium by using a generally known suspension stabilizer.
本発明により得られる共重合体は従来のものに比較して
極めて高い熱変形温度を有し、しかも優れた機械的性
質、成形性、透明性を有しており成形材料として有用で
ある。特にポリスチレン樹脂、アクリル樹脂、AS樹脂で
は耐熱性が満足されない用途に適している。またABS樹
脂等の他樹脂の改質材としても使用することも可能であ
る。The copolymer obtained by the present invention has an extremely high heat distortion temperature as compared with the conventional ones, and has excellent mechanical properties, moldability and transparency, and is useful as a molding material. It is especially suitable for applications where polystyrene resin, acrylic resin, and AS resin do not have sufficient heat resistance. It can also be used as a modifier for other resins such as ABS resin.
以下、実施例、比較例を挙げて本発明を説明する。Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.
実施例及び比較例 撹拌機付き５オートクレーブに純水2kgと第三リン酸
カルシウウ20gを添加し、窒素ガスを吹き込みながら充
分撹拌した。次にα−メチルスチレン1.4kg、アクリロ
ニトリル0.6kg及び有機過酸化物重合開始剤（表1,表
２）を添加した後、系内を窒素ガス雰囲気とした。オー
トクレーブを加熱し、内容物を所定の温度（表１）まで
昇温し、その温度で20時間重合を行なつた。この様にし
て得られた懸濁重合液を、塩酸にて中和、脱水した後、
80℃にて乾燥し粒状重合物を得た。この重合物を通常の
押出機によりペレツト化した。諸性質を測定した。結果
を表１に示す。Examples and Comparative Examples 2 kg of pure water and 20 g of calcium phosphate tribasic were added to a 5 autoclave equipped with a stirrer and sufficiently stirred while blowing nitrogen gas. Next, 1.4 kg of α-methylstyrene, 0.6 kg of acrylonitrile and an organic peroxide polymerization initiator (Table 1 and Table 2) were added, and then the system was made a nitrogen gas atmosphere. The autoclave was heated, the contents were heated to a predetermined temperature (Table 1), and polymerization was carried out at that temperature for 20 hours. The suspension polymerization solution thus obtained was neutralized with hydrochloric acid and dehydrated,
It was dried at 80 ° C to obtain a granular polymer. The polymer was pelletized by a conventional extruder. Various properties were measured. The results are shown in Table 1.
なお、共重合体の数平均連鎖長（n:ポリスチレン基
準）は粒状重合物とペレツトの両サンプルをGPC〔東洋
曹達工業（株）製HLC−802A〕を用いて以下の条件で測
定した。The number average chain length (n: polystyrene standard) of the copolymer was measured under the following conditions using GPC [Toyo Soda Kogyo Co., Ltd. HLC-802A] for both samples of the granular polymer and pellets.
溶媒≒テトラビドロフラン（THF） カラム≒東洋曹達製 GM−６ 2Feet2本 カラム恒温槽温度≒38℃ 溶媒流量≒1.5ml/min 試料濃度≒0.1重量％ 試料注入量≒0.5ml 検出器：示差屈析計 データ処理装置：東洋曹達製 CP−8000 また、共重合体の熱変形温度はASTM−Ｄ−648、衝撃強
度はASTM−Ｄ−256によつて測定した。Solvent ≒ Tetravidrofuran (THF) column ≒ Toyo Soda GM-6 2Feet 2 columns Constant temperature bath temperature ≈ 38 ℃ Solvent flow rate ≈ 1.5 ml / min Sample concentration ≈ 0.1 wt% Sample injection amount ≈ 0.5 ml Detector: Differential permeation analyzer Data processor: CP-8000 manufactured by Toyo Soda Co., Ltd. The heat distortion temperature of the copolymer was measured by ASTM-D-648, and the impact strength was measured by ASTM-D-256.
Claims (1)
ロニトリル25〜35重量％の混合物を共重合するにあた
り、10時間半減期（ベンゼン中の0.1モル／）の温度
が70℃以上90℃未満の２−ターシャリーブチルアゾ系ラ
ジカル重合開始剤の存在下で、20時間半減期温度から５
時間半減期温度の範囲で懸濁重合させることを特徴とす
るα−メチルスチレンとアクリロニトリルの共重合体の
製造方法。1. When copolymerizing a mixture of 65-75% by weight of α-methylstyrene and 25-35% by weight of acrylonitrile, the temperature of the 10-hour half-life (0.1 mol / in benzene) is 70 ° C or higher and lower than 90 ° C. In the presence of 2-tertiarybutylazo radical polymerization initiator of
A method for producing a copolymer of α-methylstyrene and acrylonitrile, which comprises carrying out suspension polymerization within a time half-life temperature range.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59126135A JPH0699525B2 (en) | 1984-06-19 | 1984-06-19 | Method for producing copolymer |
| CN85104396.8A CN1005633B (en) | 1984-06-19 | 1985-06-10 | Thermoplastic resin blend |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59126135A JPH0699525B2 (en) | 1984-06-19 | 1984-06-19 | Method for producing copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS614709A JPS614709A (en) | 1986-01-10 |
| JPH0699525B2 true JPH0699525B2 (en) | 1994-12-07 |
Family
ID=14927536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59126135A Expired - Lifetime JPH0699525B2 (en) | 1984-06-19 | 1984-06-19 | Method for producing copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0699525B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4831285A (en) * | 1971-08-26 | 1973-04-24 | ||
| US4268652A (en) * | 1980-01-16 | 1981-05-19 | The Dow Chemical Company | Color styrene-acrylonitrile polymers |
| JPS60203611A (en) * | 1984-03-28 | 1985-10-15 | Kanegafuchi Chem Ind Co Ltd | Production of alpha-alkylstyrene based heat-resistant resin |
-
1984
- 1984-06-19 JP JP59126135A patent/JPH0699525B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS614709A (en) | 1986-01-10 |
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