JPH01161004A - Suspension polymerization of styrene - Google Patents
Suspension polymerization of styreneInfo
- Publication number
- JPH01161004A JPH01161004A JP31862087A JP31862087A JPH01161004A JP H01161004 A JPH01161004 A JP H01161004A JP 31862087 A JP31862087 A JP 31862087A JP 31862087 A JP31862087 A JP 31862087A JP H01161004 A JPH01161004 A JP H01161004A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- organic peroxide
- suspension polymerization
- fatty acid
- aliphatic organic
- 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.)
- Pending
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 5
- -1 fatty acid perester Chemical group 0.000 claims abstract description 16
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 7
- 229930195729 fatty acid Natural products 0.000 claims abstract description 7
- 239000000194 fatty acid Substances 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 abstract description 9
- 229920002223 polystyrene Polymers 0.000 abstract description 9
- 150000002976 peresters Chemical class 0.000 abstract 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 abstract 1
- HLGNQSCJUXGFRV-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis[(2-methylpropan-2-yl)oxy]cyclohexane Chemical compound CC1CC(C)(C)CC(OC(C)(C)C)(OC(C)(C)C)C1 HLGNQSCJUXGFRV-UHFFFAOYSA-N 0.000 abstract 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 abstract 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 150000001451 organic peroxides Chemical class 0.000 description 6
- 239000004794 expanded polystyrene Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- MSIJNEPFXZFULB-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)CC(C)(C)C MSIJNEPFXZFULB-UHFFFAOYSA-N 0.000 description 1
- OTCSXIBBGZJGSY-UHFFFAOYSA-N 2-ethyl-2-(2-methylbutan-2-ylperoxy)butanoic acid Chemical compound CCC(C)(C)OOC(CC)(CC)C(O)=O OTCSXIBBGZJGSY-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010558 suspension polymerization method Methods 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
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、スチレンの重合方法に関するもので。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for polymerizing styrene.
脂肪族有機過酸化物を重合開始剤に使用することにより
耐変色性に優れたポリスチレンや発泡ポリスチレンを製
造することができる。By using an aliphatic organic peroxide as a polymerization initiator, polystyrene and expanded polystyrene with excellent color fastness can be produced.
ポリスチレンや発泡ポリスチレン等は、一般に懸濁重合
により生産されているが１重合開始剤として有機過酸化
物が使用されている。Polystyrene, foamed polystyrene, etc. are generally produced by suspension polymerization, and organic peroxides are used as monopolymerization initiators.
有機過酸化物として、その分解温度と歴史的背ｌｔＫよ
りベンゾイルパーオキサイド（ＢＰＯ）が使用されてき
た。さらに近年では、ＢＰＯに比較して分解温度が高い
ｔ−プチルバーオキシベンゾ工−）（ＴＢＰＢ）を併用
しポリマーの残存スチレンを減少させる方法が行われて
いる。Benzoyl peroxide (BPO) has been used as an organic peroxide due to its decomposition temperature and historical backlash. Furthermore, in recent years, a method has been used to reduce residual styrene in polymers by using t-butylbaroxybenzobenzoyl (TBPB), which has a higher decomposition temperature than BPO.
しかしながら両有機過酸化物共にベンゼン環を持つてお
り、これまでの方法で製造されたポリスチレンや発泡ポ
リスチレンは、長期問屋外で使用すると黄色に変色する
欠点を持っている。However, both organic peroxides have benzene rings, and polystyrene and expanded polystyrene produced by conventional methods have the disadvantage of turning yellow when used outdoors for a long period of time.
ポリスチレンや発泡ポリスチレンの耐変色性を向上させ
るため、ＢＰＯやＴＢＰＢに変わる有機過酸化物を開発
する。In order to improve the color fastness of polystyrene and expanded polystyrene, we will develop an organic peroxide to replace BPO and TBPB.
上記の問題点を解決するために鋭意検討した結果１本発
明者等は脂肪族の有機過酸化物を使用すれば耐変色性に
優れたポリスチレンや発泡ポリスチレンが製造できるこ
とを見いだした。As a result of extensive studies to solve the above problems, the present inventors have discovered that polystyrene and expanded polystyrene with excellent discoloration resistance can be produced by using an aliphatic organic peroxide.
またＢＰＯにかわる有機過酸化物として二級脂肪酸のパ
ーエステルが適していることを見いだした。It has also been found that peresters of secondary fatty acids are suitable as organic peroxides in place of BPO.
即ち本発明は下記一般式で示される二級脂肪酸パーエス
テルと１０時間半減期温度が９０〜１０５℃の脂肪族有
機過酸化物とを使用することを特徴とするスチレンの懸
濁重合方法である。That is, the present invention is a styrene suspension polymerization method characterized by using a secondary fatty acid perester represented by the following general formula and an aliphatic organic peroxide having a 10-hour half-life temperature of 90 to 105°C. .
一般式
Ｒ１−Ｒ５はアルキル基でＲ１＋ Ｒ２の炭素数は２〜
１ｏ 、Ｒ，十Ｒ４＋ ’Ｒ５の炭素数は３−８である
。The general formula R1-R5 is an alkyl group, and the number of carbon atoms in R1+R2 is 2 to
The number of carbon atoms in 1o, R, 10R4+'R5 is 3-8.
本発明に使用する二級脂肪酸パーエステルはいずれも１
０時間半減期温度が６５〜８０℃でありＢＰＯＫ：近い
値を有しており、ポリマーの物性に与える影響も少ない
。The secondary fatty acid peresters used in the present invention are all 1
The 0-hour half-life temperature is 65 to 80°C, which is close to BPOK, and there is little influence on the physical properties of the polymer.
具体的には、ｔ−ブチルパーオキシオクトエ−） （Ｔ
ＢＰＯ）、ｔ−アミルパーオキシオクトエート、１−オ
クチルパーオキシオクトニート、 ｔ−プチルパーオ
キシインプチレー）（ＴＢＰ工）。Specifically, t-butylperoxyoctoate) (T
BPO), t-amyl peroxy octoate, 1-octyl peroxy octonite, t-butyl peroxy octoate) (TBP Engineering).
ｔ−アミルパーオキシインブチレート、ｔ−オクチルパ
ーオキシイソブチレート、ｔ−ブチルパーオキシ−２−
エチルブチレート、ｔ−アミルパーオキシ−２−エチル
ブチレート、ｔ−オクチルパーオキシ−２−エチルブチ
レートがあげられる。t-Amylperoxyin butyrate, t-octylperoxyisobutyrate, t-butylperoxy-2-
Examples include ethyl butyrate, t-amylperoxy-2-ethylbutyrate, and t-octylperoxy-2-ethylbutyrate.
ＴＢＰＢにかわる高温活性の本発明に使用する脂肪族有
機過酸化物は、１０時間半減期温度が９０〜１０５℃の
もので、１，１−ジ−ｔ−ブチルオキシ−３，３，５−
）リメチルシクロヘキサン。The high-temperature active aliphatic organic peroxide used in the present invention to replace TBPB has a 10-hour half-life temperature of 90 to 105°C, and is 1,1-di-t-butyloxy-3,3,5-
) Limethylcyclohexane.
１ｔ１−ジ−ｔ−ブチルパーオキシシクロヘキサン。1t1-di-t-butylperoxycyclohexane.
２．２−ジ−ｔ−ブチルパーオキシブタンなどのパーオ
キシケタール類、ｔ−アミルパーオキシ−３゜５．５−
）リメチルヘキサノエート、ｔ−ブチルパーオキシ−３
，５，５−トリメチルヘキサノエートなどの一級脂肪酸
のパーエステル、ｔ−アミルパーオキシインプロピルカ
ーボネート、ｔ−ブチルパーオキシインプロビルカーボ
ネートなどのパーオキシモノカーボネートが使用できる
。2. Peroxyketals such as 2-di-t-butylperoxybutane, t-amylperoxy-3°5.5-
) Limethylhexanoate, t-butylperoxy-3
, 5,5-trimethylhexanoate, and peroxymonocarbonates such as t-amylperoxyimpropyl carbonate and t-butylperoxyimpropyl carbonate can be used.
また、２′ａ類以上を組み合わせて使用することもでき
る。Moreover, 2'a or more can also be used in combination.
重合系の配合や温度スキームは従来のまま重合を行うこ
とができる。Polymerization can be carried out using conventional polymerization formulations and temperature schemes.
次に本発明のスチレンの重合例を例示する。 Next, an example of the polymerization of styrene of the present invention will be illustrated.
実施例１ １ｔオートクレーブ中に脱イオン水３００ ｆ。Example 1 300 f of deionized water in a 1 t autoclave.
リン酸三カルシウム４２、α−オレフィンスルフオン酸
ナトリウムの１チ水溶液１２１表−１中の有機過酸化物
を入れ攪拌分散させ、さらにスチレンモノマー３０ Ｏ
ｆ、大豆油５２を加え窒素置換後９ａ℃に昇温し重合を
開始した。Tricalcium phosphate 42, 121 aqueous solution of sodium α-olefin sulfonate, organic peroxides listed in Table 1 were added, stirred and dispersed, and styrene monomer 30 O
f. Soybean oil 52 was added, and after nitrogen purging, the temperature was raised to 9 a° C. to start polymerization.
４時間後、１℃／分で昇温を始め１５０℃とし。After 4 hours, the temperature was started to increase at 1°C/min to 150°C.
さらに２時間重合を続けた。Polymerization was continued for an additional 2 hours.
生成したポリスチレンは、希塩酸で２回、脱イオン水で
２回洗浄したのち乾燥させた。The produced polystyrene was washed twice with dilute hydrochloric acid and twice with deionized water, and then dried.
このようにして重合したポリスチレンは板状に成形し、
３力月間の屋外暴露試験を行った。The polystyrene polymerized in this way is formed into a plate shape,
A three-month outdoor exposure test was conducted.
結果は１表−１にまとめだ。The results are summarized in Table 1-1.
本発明により、耐変色性に優れた商品価値の高いポリス
チレンや発泡ポリスチレンを製造する事ができる。According to the present invention, polystyrene and expanded polystyrene with excellent color fastness and high commercial value can be produced.
特許出願人 化薬ヌーリー株式会社Patent applicant: Kayaku Nouri Co., Ltd.
Claims (1)
時間半減期温度が９０〜１０５℃の脂肪族有機過酸化物
とを使用することを特徴とするスチレンの懸濁重合方法
。 一般式 ▲数式、化学式、表等があります▼ Ｒ＿１〜Ｒ＿５はアルキル基でＲ＿１＋Ｒ＿２の炭素数
は２〜１０、Ｒ＿３＋Ｒ＿４＋Ｒ＿５の炭素数は３〜８
である。[Claims] Secondary fatty acid perester represented by the following general formula and 10
A method for suspension polymerization of styrene, characterized in that an aliphatic organic peroxide having a time half-life temperature of 90 to 105°C is used. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R_1 to R_5 are alkyl groups, R_1 + R_2 has 2 to 10 carbon atoms, and R_3 + R_4 + R_5 has 3 to 8 carbon atoms.
It is.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31862087A JPH01161004A (en) | 1987-07-24 | 1987-12-18 | Suspension polymerization of styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31862087A JPH01161004A (en) | 1987-07-24 | 1987-12-18 | Suspension polymerization of styrene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01161004A true JPH01161004A (en) | 1989-06-23 |
Family
ID=18101167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31862087A Pending JPH01161004A (en) | 1987-07-24 | 1987-12-18 | Suspension polymerization of styrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01161004A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680708A (en) * | 1992-06-13 | 1994-03-22 | Huels Ag | Discontinuous production of pearly foamable styrene homo- or copolymer |
| JP2004250656A (en) * | 2002-10-08 | 2004-09-09 | Atofina Chemicals Inc | Method for producing foamable styrene polymer |
-
1987
- 1987-12-18 JP JP31862087A patent/JPH01161004A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680708A (en) * | 1992-06-13 | 1994-03-22 | Huels Ag | Discontinuous production of pearly foamable styrene homo- or copolymer |
| JP2004250656A (en) * | 2002-10-08 | 2004-09-09 | Atofina Chemicals Inc | Method for producing foamable styrene polymer |
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