JPH0667987B2 - Method for producing styrene-based copolymer - Google Patents
Method for producing styrene-based copolymerInfo
- Publication number
- JPH0667987B2 JPH0667987B2 JP10377086A JP10377086A JPH0667987B2 JP H0667987 B2 JPH0667987 B2 JP H0667987B2 JP 10377086 A JP10377086 A JP 10377086A JP 10377086 A JP10377086 A JP 10377086A JP H0667987 B2 JPH0667987 B2 JP H0667987B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- based copolymer
- dicarboxylic acid
- solvent
- ethylenically unsaturated
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 44
- 229920001577 copolymer Polymers 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000002904 solvent Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000003209 petroleum derivative Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007796 conventional method Methods 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
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000000011 acetone peroxide Substances 0.000 description 1
- 235000019401 acetone peroxide Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- -1 aromatic olefins Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はスチレン系共重合体の製造方法に関し、詳しく
は反応の際に特定の溶媒を用いることにより、高分子量
のスチレン系共重合体、特にエチレン性不飽和ジカルボ
ン酸無水物を含有するスチレン系共重合体を効率よく製
造する方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a styrene-based copolymer, and more specifically, by using a specific solvent during the reaction, a high-molecular-weight styrene-based copolymer, In particular, it relates to a method for efficiently producing a styrene-based copolymer containing an ethylenically unsaturated dicarboxylic acid anhydride.
従来、スチレン−無水マレイン酸共重合体等のスチレン
系共重合体を製造する際に用いる溶媒としては、クメ
ン、シメンなど（特公昭40−15829号）や1,2−ジクロル
エタンなど（特開昭59−187008号）が知られている。し
かしながら、これらの溶媒を用いて製造される共重合体
は、比較的低分子量のものが主であり、高分子量の共重
合体の製造には不向きであった。しかも反応に要する溶
媒の量が多いという問題があった。Conventionally, as a solvent used for producing a styrene-based copolymer such as a styrene-maleic anhydride copolymer, cumene, cymene, etc. (Japanese Patent Publication No. 40-15829), 1,2-dichloroethane, etc. No. 59-187008) is known. However, the copolymers produced using these solvents are mainly those having a relatively low molecular weight, and were not suitable for producing a high molecular weight copolymer. Moreover, there is a problem that the amount of solvent required for the reaction is large.
本発明の目的は、上記問題点を解消し、比較的高分子量
のスチレン−無水マレイン酸共重合体等のスチレン系共
重合体を、少量の溶媒で効率よく製造する方法を提供す
ることである。An object of the present invention is to solve the above problems and provide a method for efficiently producing a styrene-based copolymer such as a relatively high molecular weight styrene-maleic anhydride copolymer with a small amount of solvent. .
すなわち、本発明はスチレンとエチレン性不飽和ジカル
ボン酸無水物とを反応させてスチレン系共重合体を製造
するにあたり、溶媒として石油系炭化水素を熱分解して
得られる熱分解生成物のうち沸点110〜160℃の留分を用
いることを特徴とするスチレン系共重合体の製造方法を
提供するものである。That is, in the present invention, when styrene is reacted with an ethylenically unsaturated dicarboxylic acid anhydride to produce a styrene-based copolymer, a boiling point of a thermal decomposition product obtained by thermally decomposing a petroleum hydrocarbon as a solvent is used. It is intended to provide a method for producing a styrene-based copolymer, which is characterized by using a fraction of 110 to 160 ° C.
本発明における共重合体の製造原料は、 式 で示されるスチレンとエチレン性不飽和ジカルボン酸無
水物、例えば無水マレイン酸，無水イタコン酸，無水シ
トラコン酸である。このエチレン性不飽和ジカルボン酸
無水物のうち特に 式 で示される無水マレイン酸が好ましい。これら製造原料
に関しては特に限定はなく、いかなる製造方法により得
られるものであってもよく、また、市販品を用いること
もできる。たとえばスチレンは熱分解ガソリンから分留
して得られたものであっても良い。The raw material for producing the copolymer in the present invention is represented by the formula: And styrene and an ethylenically unsaturated dicarboxylic acid anhydride represented by, for example, maleic anhydride, itaconic anhydride, and citraconic anhydride. Among the ethylenically unsaturated dicarboxylic acid anhydrides, particularly the formula Maleic anhydride represented by is preferred. There is no particular limitation on these production raw materials, and those obtained by any production method may be used, or commercially available products may be used. For example, styrene may be obtained by fractional distillation from pyrolysis gasoline.
本発明において用いる溶媒は、石油系炭化水素を熱分解
して得られる熱分解生成物のうち沸点110〜160℃の留分
である。上記石油系炭化水素としては特に制限はない
が、比較的軽質な石油系炭化水素が適当であり、特にナ
フサ留分などが好適である。この石油系炭化水素の熱分
解は、常法により行なうことができる。具体的には通常
温度が700℃以上、好ましくは750〜850℃、圧力0.5〜4k
g／cm２Ｇ、好ましくは1.0〜2.0kg／cm２Ｇ、分解時間
0.2〜1.0秒、好ましくは0.3〜0.5秒の条件で行なう。こ
のようにして得られる熱分解生成物の組成は、原料油
（石油系炭化水素）の種類や熱分解の条件によって異な
るが、例えば、エチレンを製造する目的でナフサ等の石
油系炭化水素を温度700℃以上で熱分解する際に副生す
る分解油は、通常は下記組成 飽和脂肪族炭化水素 ５〜15％ 芳香族アルキル類 35〜85％ 不飽和炭化水素 ２〜10％ 芳香族オレフィン類 ２〜15％ の範囲の炭素数５〜15個の混合油である。この熱分解生
成物として具体的には熱分解ガソリン（TCG），カーボ
ンブラックオイル（CBO）などがあり、特に熱分解ガソ
リンが好適である。The solvent used in the present invention is a fraction having a boiling point of 110 to 160 ° C among the thermal decomposition products obtained by thermally decomposing petroleum hydrocarbons. The petroleum hydrocarbon is not particularly limited, but relatively light petroleum hydrocarbon is suitable, and naphtha fraction is particularly preferable. The thermal decomposition of this petroleum hydrocarbon can be carried out by a conventional method. Specifically, the normal temperature is 700 ℃ or more, preferably 750 ~ 850 ℃, pressure 0.5 ~ 4k
g / cm 2 G, preferably 1.0 to 2.0 kg / cm 2 G, decomposition time
The condition is 0.2 to 1.0 second, preferably 0.3 to 0.5 second. The composition of the thermal decomposition product thus obtained varies depending on the type of feedstock (petroleum hydrocarbons) and the conditions of thermal decomposition. The cracked oil produced as a by-product when thermally cracking at 700 ° C or higher is usually the following composition: saturated aliphatic hydrocarbon 5 to 15% aromatic alkyls 35 to 85% unsaturated hydrocarbon 2 to 10% aromatic olefins 2 It is a mixed oil having 5 to 15 carbon atoms in the range of up to 15%. Specific examples of the pyrolysis products include pyrolysis gasoline (TCG) and carbon black oil (CBO), and pyrolysis gasoline is particularly preferable.
このような熱分解生成物（混合油）のうち、本発明で溶
媒として用いるのは沸点110〜160℃、好ましくは125〜1
50℃の留分である。この留分は通常は炭素数６〜９個の
芳香族化合物を主成分として含有するものである。Among such thermal decomposition products (mixed oil), the solvent used in the present invention has a boiling point of 110 to 160 ° C., preferably 125 to 1
It is a fraction at 50 ° C. This fraction usually contains an aromatic compound having 6 to 9 carbon atoms as a main component.
本発明においては以上のような溶媒の存在下に前記した
製造原料、すなわちスチレンとエチレン性不飽和ジカル
ボン酸無水物との反応を行なう。ここで、溶媒以外の反
応条件としては特に制限はなく、常法によって行なうこ
とができる。製造原料の使用量としては、通常はエチレ
ン性不飽和ジカルボン酸無水物１モルに対してスチレン
を0.9〜20モル、好ましくは1.0〜3.0モルの割合で反応
させる。また、溶媒の使用量は製造原料の４〜10倍量
（重量比）、好ましくは4.5〜5.5倍量（重量比）で充分
である。また、反応温度は140〜200℃、好ましくは160
〜180℃、反応圧力は１〜10kg／cm２Ｇ、好ましくは１
〜3kg／cm２Ｇ、反応時間は0.5〜５時間、好ましくは１
〜２時間が適当である。この反応においては、必要に応
じてベンゾイルパーオキサイド，アセトンパーオキサイ
ド，ジクミルパーオキサイド，クメンハイドロジエンパ
ーオキサイド，ジラウリルパーオキサイド，ジ・ターシ
ャリー・ブチルパーオキサイド，ターシャリー・ブチル
クミルパーオキサイドなどの有機過酸化物やアゾビスイ
ソブチロニトリルなどのアゾ化合物などを重合開始剤と
して使用することができる。In the present invention, the above-mentioned raw materials for production, that is, styrene, is reacted with the ethylenically unsaturated dicarboxylic acid anhydride in the presence of the above solvent. Here, the reaction conditions other than the solvent are not particularly limited, and can be carried out by a conventional method. The amount of the raw materials used is usually 0.9 to 20 mol of styrene, preferably 1.0 to 3.0 mol, per 1 mol of the ethylenically unsaturated dicarboxylic acid anhydride. The amount of the solvent used is 4 to 10 times as much as the production raw material (weight ratio), preferably 4.5 to 5.5 times as much (weight ratio). The reaction temperature is 140 to 200 ° C., preferably 160.
~ 180 ° C, reaction pressure 1 ~ 10kg / cm 2 G, preferably 1
~ 3 kg / cm 2 G, reaction time 0.5-5 hours, preferably 1
~ 2 hours is appropriate. In this reaction, benzoyl peroxide, acetone peroxide, dicumyl peroxide, cumene hydrogen peroxide, dilauryl peroxide, di-tert-butyl peroxide, tertiary-butyl cumyl peroxide, etc. The organic peroxides and azo compounds such as azobisisobutyronitrile can be used as the polymerization initiator.
なお、反応終了後、溶媒は適当な条件で蒸留することに
より容易に反応生成物から除去することができる。上記
条件としては通常は温度180〜220℃、圧力１〜20Torrで
ある。After the reaction, the solvent can be easily removed from the reaction product by distillation under appropriate conditions. The above conditions are usually a temperature of 180 to 220 ° C. and a pressure of 1 to 20 Torr.
叙上の如き本発明の方法により製造されるスチレン系共
重合体は、例えばエチレン性不飽和ジカルボン酸無水物
として無水マレイン酸を用いた場合には、下式 で表わされるスチレン単位および下式 で表わされる無水マレイン酸単位を有するものとなり、
これらのランダム共重合体，ブロック共重合体，交互共
重合体など様々なものがある。この共重合体は、具体的
には下記一般式 （式中、ｋｉは１〜３の整数,nは６〜８の整数であり、
ｉは１〜ｎの整数に変化する変数を示す。） で表わすことができる。The styrenic copolymer produced by the method of the present invention as described above has, for example, the following formula when maleic anhydride is used as the ethylenically unsaturated dicarboxylic acid anhydride. Styrene unit represented by Having a maleic anhydride unit represented by
There are various types such as random copolymers, block copolymers, and alternating copolymers. This copolymer is specifically represented by the following general formula (In the formula, k i is an integer of 1 to 3, n is an integer of 6 to 8,
i represents a variable that changes to an integer of 1 to n. ) Can be represented.
本発明により得られる共重合体は比較的高分子量のもの
であり、具体的には重量平均分子量が5,000〜10,000、
好ましくは6,000〜9,000、数平均分子量が1,000〜7,00
0、好ましくは2,000〜5,000の共重合体が得られる。ま
た、本発明により得られる共重合体の酸価の範囲は通常
25〜480mgKOH／ｇ、好ましくは250〜500mgKOH／ｇであ
る。The copolymer obtained by the present invention has a relatively high molecular weight, specifically, a weight average molecular weight of 5,000 to 10,000,
Preferably 6,000 ~ 9,000, number average molecular weight 1,000 ~ 7,00
0, preferably 2,000 to 5,000 copolymers are obtained. The acid value range of the copolymer obtained by the present invention is usually
It is 25 to 480 mgKOH / g, preferably 250 to 500 mgKOH / g.
叙上の如き本発明の方法によると従来の方法に比較して
高分子量のスチレン−マレイン酸共重合体等のスチレン
系共重合体を製造することができる。また、反応に使用
する溶媒の量が従来に比較して少量で良いという利点が
ある。さらに本発明の方法で得られる共重合体は残留溶
媒量が少ないという利点もある。According to the method of the present invention as described above, a styrene-based copolymer such as a styrene-maleic acid copolymer having a high molecular weight can be produced as compared with the conventional method. Further, there is an advantage that the amount of the solvent used for the reaction can be smaller than that in the conventional case. Further, the copolymer obtained by the method of the present invention has an advantage that the residual solvent amount is small.
したがって本発明の方法は石炭スラリー用添加剤，セメ
ント添加剤などの材料として有用なスチレン系共重合体
の製造方法として好適である。Therefore, the method of the present invention is suitable as a method for producing a styrene copolymer useful as a material for coal slurry additives, cement additives and the like.
次に、本発明を実施例により詳しく説明する。 Next, the present invention will be described in detail with reference to Examples.
調製例 第１表に示す組成のTCG750トン／日を蒸留塔（段数16,
還流比Ｒ／Ｄ＝0.5,塔頂温度85℃，塔底温度180℃，圧
力1.3kg／cm２Ｇ）で蒸留し、三段目からのサイドカッ
ト留分を20トン／日の割合で得た。さらにこのサイドカ
ット留分を蒸留塔（段数28,還流比Ｒ／Ｄ＝3.0,塔頂温
度87℃，塔底温度148℃，圧力1.2kg／cm２Ｇ）で蒸留
し、目的留分を11トン／日の割合で得た。Preparation Example 750 tons / day of TCG having the composition shown in Table 1 was used in a distillation column (16 plates,
Distillation at reflux ratio R / D = 0.5, tower top temperature 85 ° C, tower bottom temperature 180 ° C, pressure 1.3kg / cm 2 G) to obtain a side cut fraction from the third stage at a rate of 20 tons / day. It was Further, this side cut fraction is distilled in a distillation column (28 plates, reflux ratio R / D = 3.0, column top temperature 87 ° C., column bottom temperature 148 ° C., pressure 1.2 kg / cm 2 G) to obtain a target fraction of 11 Obtained at the rate of tons / day.
実施例１ 無水マレイン酸49gを調製例で得た目的留分250gに加
え、約45℃になるまで加熱撹拌して溶解させた。次にス
チレン52gと触媒（ジ・ターシャリー・ブチル・パーオ
キサイド）1.0gを加え、均一なモノマー溶液（調合液）
とした。 Example 1 49 g of maleic anhydride was added to 250 g of the target fraction obtained in Preparation Example, and the mixture was dissolved by heating and stirring until it reached about 45 ° C. Next, 52 g of styrene and 1.0 g of catalyst (di-tert-butyl-peroxide) were added, and a uniform monomer solution (prepared solution) was added.
And
別にオートクレーブに調製例で得た目的留分250gを仕込
み175℃になるまで加熱撹拌した後ポンプで上部から上
記調合液を滴下し、１時間かけて滴下を終了させた。滴
下終了後さらに30分間175℃で加熱撹拌して反応を終結
させた。反応終了後ロータリーエバポレーターで200℃,
5Torrの条件で溶媒（目的留分）を留去してスチレン−
無水マレイン酸共重合体を得た。以上の反応条件および
得られた共重合体の性状を第２表に示す。Separately, 250 g of the target fraction obtained in Preparation Example was charged into an autoclave, and the mixture was heated and stirred until it reached 175 ° C., and then the above-mentioned preparation liquid was dropped from the upper part with a pump, and the dropping was completed over 1 hour. After the dropping was completed, the reaction was terminated by heating and stirring at 175 ° C. for another 30 minutes. After the reaction is completed, use a rotary evaporator at 200 ℃,
The solvent (target fraction) was distilled off under the condition of 5 Torr to remove styrene-
A maleic anhydride copolymer was obtained. Table 2 shows the above reaction conditions and the properties of the resulting copolymer.
実施例２ 実施例１において反応に使用するスチレンを目的留分中
のスチレン・モノマーに換えたことおよび触媒の使用量
を1.0gにしたこと以外は実施例１と同様にした。結果を
第２表に示す。Example 2 Example 1 was repeated except that the styrene used in the reaction in Example 1 was changed to the styrene monomer in the target fraction and the amount of the catalyst used was 1.0 g. The results are shown in Table 2.
実施例３ 実施例１においてスチレン，無水マレイン酸および触媒
の使用量を第２表に示す量にしたこと以外は実施例１と
同様にして行なった。結果を第２表に示す。Example 3 The procedure of Example 1 was repeated, except that the amounts of styrene, maleic anhydride and catalyst used in Example 1 were changed to those shown in Table 2. The results are shown in Table 2.
比較例1,2 実施例１において溶媒として目的留分250g（溶媒全量50
0g）に代えてクメン300g（溶媒全量600g）を用い、かつ
触媒量，反応圧力を第１表に示す通りにしたこと以外は
実施例１と同様にして行なった。結果を第２表に示す。Comparative Examples 1 and 2 250 g of a target fraction as a solvent in Example 1 (total amount of solvent: 50
The same procedure as in Example 1 was repeated except that 300 g of cumene (total amount of solvent: 600 g) was used instead of 0 g), and the amount of catalyst and the reaction pressure were as shown in Table 1. The results are shown in Table 2.
Claims (6)
無水物とを反応させてスチレン系共重合体を製造するに
あたり、溶媒として石油系炭化水素を熱分解して得られ
る熱分解生成物のうち沸点110〜160℃の留分を用いるこ
とを特徴とするスチレン系共重合体の製造方法。1. A boiling point among thermal decomposition products obtained by thermally decomposing petroleum hydrocarbons as a solvent in producing a styrene-based copolymer by reacting styrene with an ethylenically unsaturated dicarboxylic acid anhydride. A method for producing a styrene-based copolymer, which comprises using a fraction at 110 to 160 ° C.
ルに対してスチレン0.9〜20モルの割合で反応させる特
許請求の範囲第１項記載の製造方法。2. The production method according to claim 1, wherein the reaction is carried out in a proportion of 0.9 to 20 mol of styrene with respect to 1 mol of the ethylenically unsaturated dicarboxylic acid anhydride.
の範囲第１項記載の製造方法。3. The production method according to claim 1, wherein the petroleum hydrocarbon is naphtha.
許請求の範囲第１項記載の製造方法。4. The method according to claim 1, wherein the pyrolysis product is pyrolysis gasoline.
芳香族炭化水素を主成分とするものである特許請求の範
囲第１項記載の製造方法。5. The process according to claim 1, wherein the fraction having a boiling point of 110 to 160 ° C. is mainly composed of an aromatic hydrocarbon having 6 to 9 carbon atoms.
無水マレイン酸である特許請求の範囲第１項記載の製造
方法。6. An ethylenically unsaturated dicarboxylic acid anhydride,
The method according to claim 1, which is maleic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10377086A JPH0667987B2 (en) | 1986-05-08 | 1986-05-08 | Method for producing styrene-based copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10377086A JPH0667987B2 (en) | 1986-05-08 | 1986-05-08 | Method for producing styrene-based copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62260805A JPS62260805A (en) | 1987-11-13 |
| JPH0667987B2 true JPH0667987B2 (en) | 1994-08-31 |
Family
ID=14362696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10377086A Expired - Lifetime JPH0667987B2 (en) | 1986-05-08 | 1986-05-08 | Method for producing styrene-based copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0667987B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5392642B2 (en) * | 2000-09-28 | 2014-01-22 | コニカミノルタケミカル株式会社 | Method for producing styrene-maleic anhydride copolymer |
-
1986
- 1986-05-08 JP JP10377086A patent/JPH0667987B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62260805A (en) | 1987-11-13 |
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