JPH0480211A - Preparation of styrenic polymer - Google Patents
Preparation of styrenic polymerInfo
- Publication number
- JPH0480211A JPH0480211A JP19295490A JP19295490A JPH0480211A JP H0480211 A JPH0480211 A JP H0480211A JP 19295490 A JP19295490 A JP 19295490A JP 19295490 A JP19295490 A JP 19295490A JP H0480211 A JPH0480211 A JP H0480211A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- weight
- reactor
- polymerization reactor
- polymer
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 230000000379 polymerizing effect Effects 0.000 claims abstract 4
- 238000006116 polymerization reaction Methods 0.000 claims description 195
- 150000001451 organic peroxides Chemical class 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000012662 bulk polymerization Methods 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 45
- 150000002978 peroxides Chemical class 0.000 abstract description 7
- 238000010924 continuous production Methods 0.000 abstract 2
- 230000003068 static effect Effects 0.000 description 26
- 239000003999 initiator Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- -1 ethylhenzene Chemical compound 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- 238000012668 chain scission Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- SNRYPISWKNTUOS-UHFFFAOYSA-N 2,2-bis(butylperoxy)butane Chemical compound CCCCOOC(C)(CC)OOCCCC SNRYPISWKNTUOS-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 210000002257 embryonic structure Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、塊状又は溶液重合法によるスチレン系重合体
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing styrenic polymers by bulk or solution polymerization.
詳しくは、本発明は、前半の重合段階で特定の有機過酸
化物を用いてスチレン系高分子量重合体をつくり、重合
後半に重合率を高めることにより強度、成形性の優れた
スチレン系重合体を製造する方法に関するものである。Specifically, the present invention creates a styrenic high molecular weight polymer using a specific organic peroxide in the first half of the polymerization stage, and increases the polymerization rate in the second half of the polymerization to produce a styrenic polymer with excellent strength and moldability. The present invention relates to a method for manufacturing.
（従来の技術）
スチレン系重合体は、透明性、成形性、剛性に優れた樹
脂であるところから、以前から家庭用品、電気製品など
の成形材料として広く用いられてきた。近年、原材料の
高謄から他の高品位樹脂を比較的コストの安い樹脂へ切
り替える方向にあり、スチレン系重合体に対する需要は
一層増大の傾向にある。これとともに、利用分野を拡大
する為、及び製品の生産性を高める為スチレン系重合体
の強度、成形性の改良の要望が高まっている。(Prior Art) Styrenic polymers are resins with excellent transparency, moldability, and rigidity, and have long been widely used as molding materials for household goods, electrical products, and the like. In recent years, due to the high quality of raw materials, there has been a trend to replace other high quality resins with relatively inexpensive resins, and the demand for styrenic polymers is on the rise. Along with this, there is an increasing demand for improvements in the strength and moldability of styrenic polymers in order to expand the field of use and increase product productivity.
これまで、強度の高いスチレン系重合体を得るためには
、重合体の平均分子量を大きくすればよいことが広く知
られている。スチレン系重合体の平均分子量を大きくす
る手段としては、重合温度を低くしたり、あるいは、重
合開始剤の使用量を減少させる方法が知られているが、
このような方法は重合速度を遅くするため、生産性が低
下することを免れず、工業的には好ましくない。It has been widely known that in order to obtain a styrenic polymer with high strength, it is sufficient to increase the average molecular weight of the polymer. As a means to increase the average molecular weight of styrenic polymers, methods such as lowering the polymerization temperature or reducing the amount of polymerization initiator used are known.
Such a method slows down the polymerization rate, inevitably lowering productivity, and is not industrially preferred.
生産性を損なうこと無くスチレン系樹脂の平均分子量を
大きくする方法として例えば、１分子中にペルオキシド
結合を３個以上有する一般式（）：
％式％（）
で示される特定のジアンル型ポリメリックペルオキシド
を用いるスチレン系樹脂の製造方法が特開昭６０−８３
０４号公報、特開昭６０−１３８０５号公報ムこ開示さ
れている。As a method for increasing the average molecular weight of styrenic resin without impairing productivity, for example, a specific diane-type polymeric peroxide having three or more peroxide bonds in one molecule and having the general formula (): % formula % () can be used. The method for manufacturing the styrene resin used was published in JP-A-60-83.
No. 04 and Japanese Unexamined Patent Application Publication No. 13805/1982.
また、特開平１−１５６３２５号公報ではポリメリック
ペルオキソエステルが示され、同公報参考例中にはこの
開始剤を用いたスチレンの重合が記載されている。この
時、平均分子量８３．０万、８７．２万のポリスチレン
が得られることが示されている。Further, JP-A-1-156325 discloses a polymeric peroxoester, and the reference examples of the same publication describe the polymerization of styrene using this initiator. It has been shown that at this time, polystyrene with an average molecular weight of 830,000 and 872,000 can be obtained.
（発明が解決しようとするｙＡｌり
しかしながら、前記の特定のシアツル型ペルオキシドを
用いる方法は高分子量化は図れるもののこの開始剤は分
解温度が低く、取り扱いに危険が伴う。かつ、重合初期
に低温で重合することにより高分子量化の効果を発現す
るため、生産性を低下させることを免れない。生産性を
さらムこ高めるためには、開始剤量を多くするか、ある
いは、重合温度を高めなければならず、いずれの方法を
用いても重合体の分子量を逆に低下させてしまうという
問題点があった。However, although the method using the specific sheatzyl peroxide described above can achieve high molecular weight, this initiator has a low decomposition temperature and is dangerous to handle. Polymerization produces the effect of increasing the molecular weight, which inevitably reduces productivity.In order to further increase productivity, it is necessary to increase the amount of initiator or raise the polymerization temperature. However, no matter which method is used, there is a problem in that the molecular weight of the polymer is reduced.
また、特開平１−１５６３２５号公報によればポリメリ
ックペルオキソエステルを開始剤として用いることによ
り高分子量ポリスチレンを与えることは理解できるが、
得られたポリスチレンは分子量が高すぎ、実用的な成形
性−強度ハランスに優れたポリマーを得る方法について
は何等明らかとなっていない。Furthermore, according to JP-A-1-156325, it is understood that high molecular weight polystyrene can be obtained by using a polymeric peroxoester as an initiator.
The molecular weight of the obtained polystyrene is too high, and it is not clear at all how to obtain a polymer with excellent moldability and strength properties for practical use.
（課題を解決するための手段）
本発明者らは、かかる現状に鑑み、＃Ａ意検討を重ねた
結果、前半の重合段階で特定の有機過酸化物を用いてス
チレン系高分子量重合体をつくり、後半の重合で重合率
を高めることにより、良好な成形性を有するスチレン系
樹脂から高い強度を与える高分子量スチレン系樹脂まで
、すなわち、重量平均分子量が２０万〜５０万の範囲の
スチレン系樹脂を、生産性よく製造することができるこ
とを見出し、本発明を完成するに至った。(Means for Solving the Problems) In view of the current situation, the present inventors have repeatedly considered #A, and as a result, the present inventors have determined that a styrene-based high molecular weight polymer is produced using a specific organic peroxide in the first half polymerization step. By increasing the polymerization rate in the second half of the polymerization process, we range from styrenic resins with good moldability to high molecular weight styrene resins that provide high strength. The inventors have discovered that resin can be manufactured with high productivity, and have completed the present invention.
すなわち、本発明は；
スチレン系単量体を塊状重合又は溶液重合してスチレン
系重合体を連続的に製造する方法において、一般式：
％式％
で示される繰り返し単位を３個以上有する有機過酸化物
をスチレン系単量体１００重量部当たり活性酸素量換算
で０．０００２〜０．０５重量部の割合で添加し、重合
温度８５以上１３０°Ｃ未満の温度範囲で反応溶液中の
ポリマー濃度が】５重量％を越える迄予備重合を行った
後、後段重合反応器での重合温度が１７０ ’Ｃを越え
ない温度で重合を行い、最終反応器出口の反応／８液中
のポリマー濃度が７０重量％以上になる迄重合すること
を特徴とするスチレン系重合体の製造方法に関するもの
である。That is, the present invention provides: A method for continuously producing a styrenic polymer by bulk polymerization or solution polymerization of styrenic monomers, in which an organic filtrate having three or more repeating units represented by the general formula: The oxide is added at a ratio of 0.0002 to 0.05 parts by weight in terms of active oxygen amount per 100 parts by weight of the styrene monomer, and the polymer concentration in the reaction solution is adjusted at a polymerization temperature of 85 to 130°C. After prepolymerizing until the concentration exceeds 5% by weight, polymerization is carried out at a temperature that does not exceed 170'C in the subsequent polymerization reactor, and the polymer concentration in the reaction/8 solution at the exit of the final reactor is The present invention relates to a method for producing a styrenic polymer, which is characterized in that it is polymerized to a concentration of 70% by weight or more.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いるスチレン系単量体はスチレン単独、又は
スチレンとスチレン誘導体の混合物である。スチレン系
誘導体の代表的なものとしてはαメチルスチレン、ｐ−
メチルスチレン、ｐターシャリブチルスチレン等である
。また、スチレンと共重合可能な単量体、例えば、アク
リロニトリル、メチルメタアクリレート、ブチルアクリ
レート、ブチルメタアクリシート、メタクリル酸、無水
マレイン酸等とスチレン系単量体との混合物であっても
よい。The styrenic monomer used in the present invention is styrene alone or a mixture of styrene and a styrene derivative. Typical styrene derivatives include α-methylstyrene, p-
These include methylstyrene and p-tert-butylstyrene. It may also be a mixture of a monomer copolymerizable with styrene, such as acrylonitrile, methyl methacrylate, butyl acrylate, butyl methacrylate, methacrylic acid, maleic anhydride, and a styrene monomer.
本発明は分子量調整、そして／又は重合溶液の粘度調整
のために、適当量の溶媒、分子量調整剤を使用すること
も可能である。溶媒としては、トルエン、エチルヘンゼ
ン、キシレン等である。分子量調整剤としては、メルカ
プタン類、α−メチルスチレンダイマー等が使用できる
。溶媒の使用量は特に限定されるものではないが、０重
量％〜１５重量％の範囲の使用が好ましい。In the present invention, it is also possible to use an appropriate amount of a solvent and a molecular weight modifier in order to adjust the molecular weight and/or the viscosity of the polymerization solution. Examples of the solvent include toluene, ethylhenzene, xylene, and the like. As the molecular weight modifier, mercaptans, α-methylstyrene dimer, etc. can be used. Although the amount of the solvent used is not particularly limited, it is preferably used in a range of 0% to 15% by weight.
本発明においては、前段重合反応機で特定の有機過酸化
物からなる開始剤の存在下で重合することが必要である
。この有機過酸化物は前記の一般式（Ａ）で示される繰
り返し単位を少なくとも３個、好ましくは５〜３０個含
有するものであり、このような有機過酸化物としては、
例えば、次に示す繰り返し単位を有するものを挙げるこ
とができる。このような有機過酸化物は公知の方法、例
えば、特開平１−１５６３２５号に開示されている方法
によって合成すればよい。In the present invention, it is necessary to perform polymerization in the presence of an initiator made of a specific organic peroxide in the first stage polymerization reactor. This organic peroxide contains at least 3, preferably 5 to 30, repeating units represented by the general formula (A), and such organic peroxides include:
For example, those having the following repeating units can be mentioned. Such an organic peroxide may be synthesized by a known method, for example, the method disclosed in JP-A-1-156325.
ＣＨ３ ＣＨ３ ＣＨ。CH3 CH3 CH.
Ｌ ＣＨ。L CH.
ＣＨ３ ＣＨ。CH3 CH.
ＣＨ８
本発明において用いる有機過酸化物の１０時間半減期温
度は７５〜９０°Ｃの温度範囲にある。このような有機
過酸化物を用いることにより重合温度を高め、かつ、生
成するスチレン系重合体の高分子量化を図ることができ
る。CH8 The 10-hour half-life temperature of the organic peroxide used in the present invention is in the temperature range of 75-90°C. By using such an organic peroxide, it is possible to increase the polymerization temperature and increase the molecular weight of the produced styrenic polymer.
本発明に使用される一般式（Ａ）で示される有機過酸化
物は単独、あるいは２種以上を混合して用いることも可
能である。また、スチレン系重合体の製法で一般的に用
いられる有機過酸化物を併用することもできる。The organic peroxides represented by the general formula (A) used in the present invention can be used alone or in combination of two or more. Furthermore, organic peroxides commonly used in the production of styrenic polymers can also be used.
本発明においては、一般式（Ａ）で示される有機過酸化
物の使用量はスチレン系単量体１００重量部当たり、活
性酸素量換算で０．０００２〜０゜０５重量部の範囲で
ある。ここで言う活性酸素量とは有機過酸化物中に存在
する過酸化物結合中の活性酸素（−〇−）の量を意味す
る。有機過酸化物のスチレン系単量体１００重量部当た
りの量が活性酸素量換算で０．０００２重量部未満では
重合に要する時間が著しく長くなるので生産性が低下し
、かつ、生成する超高分子量スチレン系重合体の量も少
なくなる。また、０．０５重量部を越えると超高分子量
スチレン系重合体の生成が不十分になり、強度の優れた
スチレン系重合体を得ることができない。In the present invention, the amount of the organic peroxide represented by the general formula (A) used is in the range of 0.0002 to 0.05 parts by weight in terms of active oxygen amount per 100 parts by weight of the styrene monomer. The active oxygen amount here means the amount of active oxygen (-〇-) in peroxide bonds present in the organic peroxide. If the amount of organic peroxide per 100 parts by weight of styrene monomer is less than 0.0002 parts by weight in terms of active oxygen amount, the time required for polymerization will be significantly longer, resulting in decreased productivity and The amount of molecular weight styrenic polymer is also reduced. On the other hand, if the amount exceeds 0.05 parts by weight, the formation of an ultra-high molecular weight styrenic polymer will be insufficient, making it impossible to obtain a styrenic polymer with excellent strength.
本発明における重合は、通常のスチレン系重合体の製造
に際して用いられる塊状重合法または溶液重合法に従い
、原料スチレン系単量体に開始剤及び所望に応し溶媒そ
の他必要な添加剤を加えた混合物を反応容器に挿入し、
必要に応じ加圧しながら加熱することによって行うこと
ができる。The polymerization in the present invention is carried out using a mixture of raw styrenic monomers, an initiator, and optionally a solvent and other necessary additives, according to the bulk polymerization method or solution polymerization method used in the production of ordinary styrenic polymers. Insert into the reaction vessel,
This can be done by heating while applying pressure if necessary.
本発明の前半の重合はこのようにして８５°Ｃ〜］ ３
０ ’Ｃの温度で、より好ましくは、９０°Ｃ〜１２５
°Ｃの温度で反応溶液中のポリマー濃度カ月５重量％以
上、好ましくは、２０重重量以上、より好ましくは２５
重量％以上になるまで行う必要がある。この段階におい
である程度の超高分子量スチレン系重合体を含む反応混
合物が生成する。The polymerization in the first half of the present invention is carried out in this manner at 85°C ~] 3
At a temperature of 0'C, more preferably between 90°C and 125°C
The polymer concentration in the reaction solution at a temperature of 5% by weight or more, preferably 20% by weight or more, more preferably 25% by weight or more.
It is necessary to do this until it reaches a weight percent or higher. At this stage a reaction mixture containing some ultra-high molecular weight styrenic polymer is produced.
重合温度が１３０°Ｃ以上の温度では超高分子量スチレ
ン系重合体が生成せず目的とする強度の優れたスチレン
系重合体が得られない。また、８５°Ｃ以下の低温では
生産性が低下し好ましくない。If the polymerization temperature is 130° C. or higher, an ultra-high molecular weight styrenic polymer will not be produced, and the desired styrenic polymer with excellent strength will not be obtained. Furthermore, low temperatures below 85°C are undesirable because productivity decreases.
また、前半の重合では反応溶液中のスチレン系重合体の
ポリマー濃度が１５重量％になるまで重合を行う必要が
ある。１５重量％未満では最終スチレン系重合体に高い
強度を与えるのに充分な量の超高分子量体を含む反応混
合物を得ることができない。In addition, in the first half of the polymerization, it is necessary to carry out the polymerization until the polymer concentration of the styrene polymer in the reaction solution reaches 15% by weight. If the amount is less than 15% by weight, it is not possible to obtain a reaction mixture containing a sufficient amount of ultra-high molecular weight material to impart high strength to the final styrenic polymer.
前段重合反応器としては、公知の反応器、例えば、完全
混合型反応器、置型反応器等が使用できる。また、複数
個の反応器を直列あるいは並列ムこ並べて使用すること
も可能である。As the first stage polymerization reactor, a known reactor such as a complete mixing type reactor, a stationary type reactor, etc. can be used. It is also possible to use a plurality of reactors in series or in parallel.
次に、前段重合反応器から出た重合液を後段重合反応器
に導く、後段重合器は押出し流れに近い流動パターンを
与える反応器であることが好ましい。この反応器として
は空間部を有する横型二軸反応器、静的混合器を内蔵し
た反応器、攪拌式基型反応器が使用できる。あるいはこ
れらの反応器を組み合わせて使用することも可能である
。特に静的混合器を内蔵した反応器または横型二軸反応
器を使用することが好ましい。Next, the polymerization liquid discharged from the first stage polymerization reactor is introduced into the second stage polymerization reactor, and the second stage polymerization reactor is preferably a reactor that provides a flow pattern close to the extrusion flow. As this reactor, a horizontal twin-shaft reactor with a space, a reactor with a built-in static mixer, and a stirred base reactor can be used. Alternatively, it is also possible to use a combination of these reactors. In particular, it is preferable to use a reactor equipped with a static mixer or a horizontal twin-screw reactor.
完全混合特性に近い流動パターンを与える反応器を使用
すると、重合率が高くなるにつれて、攪拌動力が異常に
大きくなり経済的でない。また、反応溶液の粘度が高く
なるにつれて、混合特性、除熱能力が悪くなり、重合反
応を制御するのが困難となり、結果として低分子量重合
体を多量に生成するので好ましくない。If a reactor that provides a flow pattern close to perfect mixing characteristics is used, as the polymerization rate increases, the stirring power becomes abnormally large, which is not economical. Furthermore, as the viscosity of the reaction solution increases, the mixing characteristics and heat removal ability deteriorate, making it difficult to control the polymerization reaction, and as a result, a large amount of low molecular weight polymer is produced, which is undesirable.
後段重合器では開始剤を後段重合器の最初又は途中一箇
所以上の場所に添加することが好ましい。In the second-stage polymerization vessel, it is preferable to add the initiator at one or more locations at the beginning or in the middle of the second-stage polymerization vessel.
開始剤の添加量は１０００００≧ａ ／ ｂ≧３０００
の範囲であることが好ましい。より好ましくは、６００
００≧ａ ／ ｂ≧５０００の範囲である。The amount of initiator added is 100000≧a/b≧3000
It is preferable that it is in the range of . More preferably 600
The range is 00≧a/b≧5000.
添加する開始剤量が１０００００ ＜ ａ ／ ｂであ
るときは本発明の効果が発現しに（く、ａ ／ ｂ ＜
３０００であるときは低分子量重合体が多量に止成し
本発明の効果が発現しにくい。また、開始剤濃度が高い
ため重合反応を制御することが非常に困難になる。When the amount of initiator added is 100,000 < a / b, the effect of the present invention is not expressed (a / b <
When it is 3,000, a large amount of low molecular weight polymer is stopped and the effects of the present invention are difficult to exhibit. Also, the high initiator concentration makes it very difficult to control the polymerization reaction.
ここで言うａは、後段重合反応器で生成するポリマー重
量％〔最終反応器出口の重合溶液中のポリマー濃度（重
量％）−前段重合反応器出口の重合溶液中のポリマー濃
度（重量％）〕を表す。ｂは反応系に供給される全スチ
レン系単量体１００重量部に対する活性酸素量換算での
開始剤の重量部数を表す。Here, a is the weight percent of the polymer produced in the second-stage polymerization reactor [polymer concentration (weight %) in the polymerization solution at the exit of the final reactor - polymer concentration (weight %) in the polymerization solution at the exit of the first-stage polymerization reactor] represents. b represents the number of parts by weight of the initiator in terms of the amount of active oxygen based on 100 parts by weight of the total styrene monomers supplied to the reaction system.
開始剤の添加場所は特に限定されることはないが、後段
重合反応器の最初または途中添加の場合は、（後段反応
器全容積／（開始剤添加場所数＋１）の値が同し程度に
なるところに添加場所を決めるのがよい。The location where the initiator is added is not particularly limited, but if it is added at the beginning or midway through the second stage polymerization reactor, the value of (total volume of the second stage reactor/(number of initiator addition locations + 1)) should be approximately the same. It is best to decide where to add it.
開始剤と反応溶液を混合するにあたり、混合器として静
的混合器を用いることが好ましい。静的混合器としては
、ケエックス弐スクティノクミキサー、スルーザー式ス
タティックミキサー、東し式スタティックミキサーが使
用できる。動的混合器、例えば、攪拌羽根式完全混合器
では撹拌による剪断応力によって局部的に過熱状態にな
り、低分子量重合体を生成したり、分子鎖切断が生し品
質低下にフながり好ましくない。横型二輪反応器の途中
に開始剤を添加する場合は反応器自身の混合性が優れて
いる故、開始剤溶液を反応溶液表面に滴下するだけでよ
い。In mixing the initiator and the reaction solution, it is preferable to use a static mixer as the mixer. As the static mixer, a KEX Niskutinok mixer, a Sluzer type static mixer, or an Toshi type static mixer can be used. Dynamic mixers, such as stirring blade-type complete mixers, are undesirable because they cause local overheating due to shear stress caused by stirring, which may generate low molecular weight polymers or cause molecular chain scission, leading to quality deterioration. . When adding an initiator midway through a horizontal two-wheeled reactor, the reactor itself has excellent mixing properties, so it is sufficient to simply drop the initiator solution onto the surface of the reaction solution.
均一混合時間も特に限定される物ではないが、３０分以
内で均一混合することが好ましい。均混合に長時間かけ
ることは高濃度開始剤が長時間局在化することになり、
低分子量重合体を生成し本発明の効果が発現せず強度低
下を招くため好ましくない。Although the uniform mixing time is not particularly limited, it is preferable to uniformly mix within 30 minutes. If homogeneous mixing takes a long time, the high concentration initiator will be localized for a long time.
This is not preferable because it produces a low molecular weight polymer, which prevents the effects of the present invention from manifesting and leads to a decrease in strength.
開始剤の添加方法としては開始剤を単独添加してもよい
し、あるいはスチレン単量体あるいは重合溶媒に希釈し
て添加してもよい。As for the method of adding the initiator, the initiator may be added alone, or it may be diluted with styrene monomer or a polymerization solvent and added.
開始剤の種類としては、１０時間半減期の温度が８０〜
＋４０°Ｃの範囲の有８！過酸化物が使用できる。この
ような有機過酸化物の具体例を挙げれば、例えば、２，
２−ビス（−１−ブチルパーオキシ）ブタン、２２−ビ
ス）も−ブチルパーオキシ）オクタン、１．１−ビス（
ｔ−ブチルパーオキシ）−３，３，５−トリメチルシク
ロヘキサン、１．１−ビス（ｔ−ブチルパーオキシ）吉
草酸ｎ−ブチルのようなパーオキシケタール類、２゜５
−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキ
シン−３のようなジアルキルパーオキシド類：ｔ−ブチ
ルパーオキシアテート、ｔ−ブチルパーオキシ−３，３
，５−）リメチルヘキサノエート、ｔ−プチルパーオキ
シヘンゾエート、ジｔ−ブチルパーオキシイソフタレー
ト、２，５ジメチル−２，５−ジ（ヘンシイルバーオキ
シ）ヘキサン、ｔ−ブチルパーオキシイソプロピルカー
ボネートのようなパーオキシエステル類二メチルエチル
ケトンバーオキンド、シクロヘキサノンパーオキシドの
ようなケトンパーオキシド類：ジイソプロビルヘンゼン
ヒドロパーオキシト、ｐ−メタンヒドロパーオキンドの
ようなヒドロパーオキシド類を挙げることができる。The type of initiator has a 10-hour half-life temperature of 80~
+40°C range available! Peroxide can be used. Specific examples of such organic peroxides include 2,
2-bis(-1-butylperoxy)butane, 22-bis-butylperoxy)octane, 1,1-bis(
peroxyketals such as n-butyl tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)valerate, 2°5
-Dialkyl peroxides such as dimethyl-2,5-di(t-butylperoxy)hexyne-3: t-butylperoxyate, t-butylperoxy-3,3
,5-)limethylhexanoate, t-butylperoxyhenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(hensilveroxy)hexane, t-butylperoxy Peroxy esters such as isopropyl carbonate Ketone peroxides such as dimethyl ethyl ketone peroxide and cyclohexanone peroxide; Hydroperoxides such as diisopropyrhenzene hydroperoxide and p-methane hydroperoxide. can be mentioned.
８０°Ｃ以下の１０時間半減期温度を有する開始剤では
短時間で分解反応が生し、局部的にラジカル濃度が高く
なり低分子量重合体を生成し好ましくない。また、１４
０°Ｃ以上の１０時間半減期温度を有する開始剤では、
反応器内で完全に消費されず高温に曝される回収工程ま
で残り、回収工程で低分子量重合体を生成したり、分子
鎖切断を生しさせ品質低下を招くので好ましくない。An initiator having a 10-hour half-life temperature of 80° C. or less causes a decomposition reaction in a short period of time, locally increases the radical concentration, and produces a low molecular weight polymer, which is undesirable. Also, 14
For initiators with a 10 hour half-life temperature above 0°C,
It is undesirable because it is not completely consumed in the reactor and remains until the recovery process where it is exposed to high temperatures, producing low molecular weight polymers or causing molecular chain scission in the recovery process, resulting in quality deterioration.
ここで言う有機過酸化物の１０時間半減期を示す分解温
度は、これをラジカルに対して比較的不活性な溶剤、例
えば、トルエン、ヘンゼンに０゜１モル／１の濃度で溶
解し、この溶液を窒素置換したガラス管中に密封し、恒
温槽に浸漬し、熱分解させると言う実験を恒温槽の温度
を変えて繰り返し行い、以下のようにして求めることが
できる。The decomposition temperature indicating a 10-hour half-life for the organic peroxide mentioned here is determined by dissolving it in a solvent relatively inert to radicals, such as toluene or Hensen, at a concentration of 0.1 mol/1. It can be determined as follows by repeating an experiment in which a solution is sealed in a nitrogen-substituted glass tube, immersed in a constant temperature bath, and thermally decomposed while changing the temperature of the constant temperature bath.
すなわち、この分解反応は近似的ζニー次反応として取
り扱うことができるのでり解有機過酸化物の量を（Ｘ）
と分解速度定数（Ｋ）と時間（１）と有機過酸化物の初
期濃度（Ｃ）の間には、次の式が成り立つ。In other words, this decomposition reaction can be treated as an approximate ζ-nine reaction, so the amount of decomposed organic peroxide can be expressed as (X)
The following equation holds between , decomposition rate constant (K), time (1), and initial concentration of organic peroxide (C).
ｄＸ／ｄ ｔ＝Ｋ （Ｃ−Ｘ） −・−（ｆ
）Ｉ ｎ （Ｃ／ （Ｃ−Ｘ） ） −Ｋｘｔ ＨＨ
Ｈ■従って、ｔと（Ｃ／ （Ｃ−Ｘ））とを−軸対数目
盛りのグラフとしてプロットすると得られる直線の勾配
から分解速度定数（Ｋ）を求めることができる。dX/d t=K (C-X) −・−(f
)I n (C/ (C-X) ) -Kxt HH
H■ Therefore, the decomposition rate constant (K) can be determined from the slope of the straight line obtained by plotting t and (C/(C-X)) as a graph on a -axis logarithmic scale.
他方においてＫに関しては、
Ｋ＝ＡｘＥｘｐ （−△Ｅ／ＲＴ） ・・・■（但し
、Ａば頻度因子、△Ｅは活性化エネルギー、Ｒは気体定
数、Ｔは絶対温度）
の関係式が成り立つので、異なった温度についてＫを計
算し、Ｉｎ（ｔ）＋ｚ２と１／Ｔの関係式をグラフにプ
ロットし、得られた直線から１０時間半減期（Ｄ）＋ｚ
□）を示す分解温度を得ることができる。On the other hand, regarding K, the following relational expression holds true: K=AxExp (-△E/RT)...■ (where A is the frequency factor, △E is the activation energy, R is the gas constant, and T is the absolute temperature) Therefore, calculate K for different temperatures, plot the relational expression between In(t) + z2 and 1/T on a graph, and use the resulting straight line to calculate the 10-hour half-life (D) + z
□) can be obtained.
後段重合反応器での重合温度は、製造すべき重合体の分
子量によって決まるが、いがなる分子量のスチレン系重
合体であっても１７０″Ｃ以下、好ましくは１６０°Ｃ
以下で重合する必要がある。１７０°Ｃを越えて重合す
ると、低分子量重合体が多量に生成して好ましくない。The polymerization temperature in the second stage polymerization reactor is determined by the molecular weight of the polymer to be produced, but even if the styrenic polymer has a certain molecular weight, it should be 170"C or less, preferably 160°C.
It is necessary to polymerize in the following steps. If the polymerization temperature exceeds 170°C, a large amount of low molecular weight polymer will be produced, which is not preferable.
目標分子量が重合温度のみで調整できない場合は、添加
する開始剤量、分子量調整剤あるいは溶媒量等で制御し
なければならない。If the target molecular weight cannot be adjusted only by the polymerization temperature, it must be controlled by the amount of initiator, molecular weight regulator, or solvent added.
最終反応器出口の重合溶液中のポリマー濃度は７０重量
％以上、好ましくは７５重量％以上まで重合する必要が
ある。ポリマー濃度が７０重量％未満であれば強度の優
れたスチレン系重合体は得られない。It is necessary to polymerize the polymer concentration in the polymerization solution at the final reactor outlet to 70% by weight or more, preferably 75% by weight or more. If the polymer concentration is less than 70% by weight, a styrenic polymer with excellent strength cannot be obtained.
最終反応器を出た重合溶液は通常のスチレン系重合体の
塊状または溶液重合において使用されている回収工程に
送られ、脱揮発され、ベレット化される。The polymerization solution leaving the final reactor is sent to a recovery step used in conventional bulk or solution polymerization of styrenic polymers, where it is devolatilized and pelletized.
本発明で言うスチレン系重合体の分子量は特に限定され
るものではないが、重量平均分子量で２０〜５０万程度
のスチレン系重合体の製造に本発明の製造方法及び装置
を適応するのが好ましい。Although the molecular weight of the styrenic polymer referred to in the present invention is not particularly limited, it is preferable to apply the production method and apparatus of the present invention to the production of a styrenic polymer having a weight average molecular weight of about 200,000 to 500,000. .
ここで言う重量平均分子量とは３８°Ｃ、テトラヒトロ
フランヲン各課としてゲルパーミエーションクロマトグ
ラフィーにより測定される。通常行われている如く、単
分散ポリスチレンの溶出時間により検量線を作成し、サ
ンプルの溶出曲線より各溶出時間における分子量を算出
し、重量平均分子量を算出すればよい。The weight average molecular weight referred to herein is measured by gel permeation chromatography at 38°C using tetrahydrofuranone. As is commonly done, a calibration curve is created using the elution time of monodisperse polystyrene, the molecular weight at each elution time is calculated from the elution curve of the sample, and the weight average molecular weight is calculated.
（実施例） 以下、実施例で本発明を更に詳しく説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
但し、本発明はこれらの実施例によって何ら限定される
ものではない。However, the present invention is not limited to these Examples in any way.
なお、実施例中の物性試験は以下の測定方法を用いて行
った。Note that the physical property tests in the examples were conducted using the following measurement method.
■重量平均分子量：
東ソー■製ＧＰＣ（ＨＬＣ−８０２Ａ、同社製ＧＰＣカ
ラム（ＴＳＫ−ＧＥＬＧＭＨ６２本）を用いて測定。■Weight average molecular weight: Measured using Tosoh ■ GPC (HLC-802A, Tosoh GPC column (TSK-GELGMH62)).
■メルト・フロー・レート： ＩＳＯＲ１１３３の方法に準して測定。■Melt flow rate: Measured according to the method of ISOR1133.
■−撃面衝撃強度
：縮成形法（２００°Ｃ）で厚さ２ｍｍ、直径１Ｏｃｕ
の円盤状試験片を作成し、半径７Ｃｍから半径１０ｃｍ
の環状部分を金具で固定し、２０ｃｍの高さから、６．
５ｋｇの鋼球を試験片の中心に落下させて、試験片が破
壊する際の最大応力を測定。- Impact strength on impact surface: 2mm thick, 1Ocu in diameter by contraction molding method (200°C)
Create a disk-shaped test piece with a radius of 7 cm to 10 cm.
6. Fix the annular part of with metal fittings and hold it from a height of 20 cm.
A 5 kg steel ball was dropped into the center of the test piece and the maximum stress at which the test piece broke was measured.
■繰り返し衝撃強度：
圧縮成形法（２００°Ｃ）で厚さ２胚、９ｃｍＸ５ｃｍ
の角状試験片を作成し、中心より縮方向に２５ＣＩ＋の
所を金具で固定し、３／４Ｒ１１３０ｇのミサイルを５
Ｃ１１の高さから試験片の中心に落下させ、クラ、り発
生までの回数を測定。■Repetitive impact strength: 2 embryos thick, 9cm x 5cm by compression molding method (200°C)
Create a square specimen of
Drop the test piece from a height of C11 onto the center of the test piece, and measure the number of times until cracking occurs.
（実施例１）
添付の第１図に記載した装置により、ポリスチレンの重
合を行った。(Example 1) Polystyrene was polymerized using the apparatus shown in the attached FIG. 1.
前段の重合反応器−１は完全混合型反応器であり、容量
は６！である。後段の重合反応器−２，３は静的混合器
を内蔵した背型反応器であり、容量は各々６Ｐである。The first stage polymerization reactor-1 is a complete mixing type reactor and has a capacity of 6! It is. The latter polymerization reactors 2 and 3 are back type reactors with a built-in static mixer, and each has a capacity of 6P.
又、３！毎の二段の温度制御が可能である。Again, 3! Two-stage temperature control is possible.
スチレン９０重量部、エチルヘンゼン９．９７重量部お
よび式：
％式％
で示される繰り返し単位８個を含む有機過酸化物（１０
時間半減期温度８０．４°Ｃ１活性酸素量０．１０ｇ／
Ｉｇ）０．０３重量部からなる原料溶液を２ ｆｆｉ／
Ｈの流量で重合反応器−１へ連続的に供給し、１１０”
Ｃの温度で重合する。重合反応器−１での重合溶液中の
ポリマー濃度は３１重量％である。この反応溶液は重合
反応器−２に導かれ、重合反応器−２では１１５°Ｃ−
１２５°Ｃで重合する。重合反応器−２を出た重合溶液
中のポリマー濃度は、５７重量％である。90 parts by weight of styrene, 9.97 parts by weight of ethylhenzene and an organic peroxide (10
Time Half-life Temperature 80.4°C1 Active oxygen amount 0.10g/
Ig) 0.03 parts by weight of a raw material solution
Continuously supply H to the polymerization reactor-1 at a flow rate of 110"
Polymerizes at a temperature of C. The polymer concentration in the polymerization solution in polymerization reactor-1 is 31% by weight. This reaction solution is led to polymerization reactor-2, where it is heated to a temperature of 115°C.
Polymerize at 125°C. The polymer concentration in the polymerization solution exiting the polymerization reactor-2 is 57% by weight.
続いて、重合反応器−３に導かれ、重合反応器３では１
３０℃−１５０’Ｃで重合する。重合反応器−３を出た
重合溶液中のポリマー濃度は７６重量％である。Subsequently, it is introduced into the polymerization reactor-3, and in the polymerization reactor 3, 1
Polymerize at 30°C-150'C. The polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 76% by weight.
重合反応器−３を出た重合溶液は予熱器で２４０°Ｃ迄
加熱された後脱揮発されベレット化される。The polymerization solution exiting the polymerization reactor-3 is heated to 240°C in a preheater, then devolatilized and pelletized.
重合開始後４８時間目から製品を採取し、物性を評価し
た。評価結果を表−１に示す。The product was collected 48 hours after the start of polymerization and its physical properties were evaluated. The evaluation results are shown in Table-1.
（実施例２）
実施例１と同し装置を用いて、スチレン９３重量部、エ
チルヘンゼン６．９５重量部、実施例１で用いたと同し
有機過酸化物０．０５重置部からなる原料溶液を２．５
１７Ｈの流量で重合反応器１へ連続的に供給し、１０７
°Ｃの温度で重合する。重合反応器−１での重合７８ａ
中のポリマー濃度は３６重量％である。(Example 2) Using the same equipment as in Example 1, a raw material solution consisting of 93 parts by weight of styrene, 6.95 parts by weight of ethylhenzene, and 0.05 parts by weight of the same organic peroxide as used in Example 1 was prepared. 2.5
Continuously supplied to the polymerization reactor 1 at a flow rate of 17H,
Polymerizes at a temperature of °C. Polymerization 78a in polymerization reactor-1
The polymer concentration therein is 36% by weight.
続いて、実施例１と同様に、重合反応器−２では１１０
°Ｃ−１２０°Ｃ１重合反応器−３では１３０°Ｃ−１
５０°Ｃで重合する。重合反応器−２を出た重合溶液中
のポリマー濃度は６１重量％である。Subsequently, as in Example 1, in polymerization reactor-2, 110
°C-120°C1 130°C-1 in polymerization reactor-3
Polymerize at 50°C. The polymer concentration in the polymerization solution exiting the polymerization reactor-2 is 61% by weight.
重合反応器−３を出た重合溶液中のポリマー濃度は７５
重量％である。重合反応器−３を出た重合溶液は実施例
１と同様に処理し、製品を採取する。評価結果を表−１
に示す。The polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 75
Weight%. The polymerization solution exiting the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected. Table 1 shows the evaluation results.
Shown below.
（比較例１）
実施例１と同し装置を用いて、スチレン９０重量部、エ
チルヘン上２９．９０重量部、式：％式％
で示される有機過酸化物（１０時間半減期温度６４．４
°Ｃ１活性酸素量０．０４ｇ／Ｉｇ）０゜１０重量部か
らなる原料溶液を１．５４２／Ｈの流星で重合反応器−
１へ連続的に供給し、１００°Ｃの温度で重合する。重
合反応器−１の重合溶液中のポリマー濃度は２１重量％
である。(Comparative Example 1) Using the same equipment as in Example 1, 90 parts by weight of styrene, 29.90 parts by weight of ethylhene, and an organic peroxide represented by the formula: % (10 hour half-life temperature: 64.4
A raw material solution containing 10 parts by weight of active oxygen (0.04g/Ig) was heated to a polymerization reactor using a meteor at 1.542/H.
1 and polymerized at a temperature of 100°C. The polymer concentration in the polymerization solution in polymerization reactor-1 was 21% by weight.
It is.
続いて実施例１と同様に、重合反応器−２では１１５°
Ｃ−１２５°Ｃ１重合反応器−３では１３０’Ｃ−１５
０°Ｃで重合する。重合反応器−２を出た重合溶液中の
ポリマー濃度は５２重量％で、重合反応器−３を出た重
合溶液中のポリマー濃度は、７４重量％である。重合反
応器−３を出た重合溶液は実施例１と同様に処理し、製
品を採取する。Subsequently, in the same manner as in Example 1, the temperature was set at 115° in polymerization reactor-2.
C-125°C1 130'C-15 in polymerization reactor-3
Polymerizes at 0°C. The polymer concentration in the polymerization solution exiting the polymerization reactor-2 was 52% by weight, and the polymer concentration in the polymerization solution exiting the polymerization reactor-3 was 74% by weight. The polymerization solution exiting the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected.
評価結果を（表−１）に示す。The evaluation results are shown in (Table-1).
（比較例２）
実施例１と同し装置を用いて、スチレン９５１ｉ量部、
エチルヘンガフ４．９フ重量部、１．１ビス〜（ｔ−ブ
チルパーオキソ）シクロヘキサン（１０時間半減期温度
９１°Ｃ１活性酸素量０．０８６ｇ／Ｉｇ）０．０３重
量部からなる原料溶液を２１／Ｈの流量で重合反応器−
１へ連続的に供給し、１０５°Ｃの温度で重合する。重
合反応器１の重合溶液中のポリマー濃度は２６重量％で
ある。(Comparative Example 2) Using the same equipment as in Example 1, parts of styrene 951i,
A raw material solution consisting of 4.9 parts by weight of ethylhengaf and 0.03 parts by weight of 1.1 bis-(t-butylperoxo)cyclohexane (10 hours half-life temperature 91°C1 active oxygen amount 0.086 g/Ig) Polymerization reactor at a flow rate of /H
1 and polymerized at a temperature of 105°C. The polymer concentration in the polymerization solution in polymerization reactor 1 is 26% by weight.
続いて、実施例１と同様に、重合反応器−２では１１５
°Ｃ−１３０°Ｃ１重合反応器−３では１３５°Ｃ−１
４５°Ｃで重合する。重合反応器−２を出た重合溶液中
のポリマー濃度は５６重量％で、重合反応器−３を出た
重合？ｇｆｌ中のポリマー濃度は７５重量％である。Subsequently, as in Example 1, in polymerization reactor-2, 115
°C-130°C1 135°C-1 in polymerization reactor-3
Polymerize at 45°C. The polymer concentration in the polymerization solution exiting the polymerization reactor-2 was 56% by weight, and the polymer concentration in the polymerization solution exiting the polymerization reactor-3 was 56% by weight. The polymer concentration in gfl is 75% by weight.
重合反応器−３を出た重合溶液は実施例１と同様に処理
し、製品を採取する。評価結果を（表１）に示す。The polymerization solution exiting the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected. The evaluation results are shown in (Table 1).
（実施例３）
添付の第２図に記載した装置により、ポリスチレンの重
合を行った。(Example 3) Polystyrene was polymerized using the apparatus shown in the attached FIG. 2.
重合反応器−２、重合反応器−３の容量が各々５１であ
り、２．５ｆ毎の二段の温度制御が可能であり、重合反
応器−３の入口に重合溶液と重合開始剤溶液を混合する
ために、容積１１の静的混合器を設置した以外、実施例
１で用いた装置と同しである。The capacities of polymerization reactor-2 and polymerization reactor-3 are each 51, and two-stage temperature control is possible at 2.5 f intervals. The apparatus was the same as that used in Example 1, except that a static mixer with a volume of 11 was installed for mixing.
スチレン９２重量部、エチルベンゼン７．９７重量部、
実施例１で用いたと同し有機過酸化物０゜０３重蓋部か
らなる原料溶液を２１／ＨＯ）流星で重合反応１−１へ
連続的に供給し、１１０’Ｃの温度で重合する。重合溶
液中のポリマー濃度は３１重量％である。92 parts by weight of styrene, 7.97 parts by weight of ethylbenzene,
A raw material solution consisting of 0.03 layers of organic peroxide as used in Example 1 was continuously supplied to the polymerization reaction 1-1 using a 21/HO) meteor and polymerized at a temperature of 110'C. The polymer concentration in the polymerization solution is 31% by weight.
続いて、実施例１と同様に、重合反応器−２では１２０
°Ｃ−１４０°Ｃで重合する。重合反応器２を出た重合
溶液中のポリマー濃度は６４重量％である。Subsequently, as in Example 1, in polymerization reactor-2, 120
Polymerize at -140°C. The polymer concentration in the polymerization solution leaving the polymerization reactor 2 is 64% by weight.
重合反応機−２を出た重合溶液は静的混合器に導かれる
。一方、１．１−ビス−（ｔ−ブチルパーオキソ）シク
ロヘキサンの１重量％エチルヘンゼン溶液を０．０３β
／Ｈの流量で静的混合器乙こ供給する。重合溶液と重合
開始剤溶液は静的７Ｈ合器で均一混合された後、重合反
応器−３へ導かれる。重合反応器−３では１３５°Ｃ〜
１５０ ’Ｃで重合する。重合反応器−３を出た重合溶
液中のポリマー濃度は８１重量％である。The polymerization solution exiting the polymerization reactor-2 is led to a static mixer. On the other hand, a 1% by weight ethylhensen solution of 1.1-bis-(t-butylperoxo)cyclohexane was
A static mixer is supplied at a flow rate of /H. The polymerization solution and the polymerization initiator solution are uniformly mixed in a static 7H mixer and then introduced into the polymerization reactor-3. 135°C ~ in polymerization reactor-3
Polymerize at 150'C. The polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 81% by weight.
重合反応器−３を出た重合／８液は実施例１と同様に処
理し、製品を採取する。評価結果を表−１に示す。The polymerization/8 liquid discharged from the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected. The evaluation results are shown in Table-1.
（実施例４）
実施例３と同し装置を用いて、スチレン９２重量部、エ
チルヘンゼン７．９７重量部、実施例］で用いたと同し
有機過酸化物０．０２重量部、１゜ｌ−ビス−（１−ブ
チルパーオキソ）シクロヘキサン０．０１重り部からな
る原料？８液を２Ｌ／Ｈの流量で重合反応器−１へ連続
的ムこ供給し、１１０′Ｃの温度で重合する。重合／８
液中のポリマー濃度は２９重量％である。(Example 4) Using the same equipment as in Example 3, 92 parts by weight of styrene, 7.97 parts by weight of ethylhenzene, 0.02 parts by weight of the same organic peroxide used in Example], and 1°l- Raw material consisting of 0.01 part by weight of bis-(1-butylperoxo)cyclohexane? The 8 liquid was continuously fed to the polymerization reactor-1 at a flow rate of 2 L/H, and polymerized at a temperature of 110'C. Polymerization/8
The polymer concentration in the liquid was 29% by weight.
続いて、実施例１と同様ムこ、重合反応器−２では］
２０ ’Ｃ−］ ４０ ’Ｃで重合する。重合反応器２
を出た重合溶液中のポリマー濃度は６２重量％である。Next, in the same manner as in Example 1, in the polymerization reactor-2]
20'C-] Polymerize at 40'C. Polymerization reactor 2
The polymer concentration in the polymerization solution exiting is 62% by weight.
重合反応器−２を出た重合溶液は静的混合器に導かれる
。一方、１．１−ビス−（ｔ−ブチルパーオキシ）シク
ロヘキサンの１重量％エチルベンゼン溶液を０．０３ｊ
２／Ｈの流量で静的混合器に供給する。重合溶液と重合
開始剤溶液は静的混合器で均一混合された後、重合反応
器−３へ導かれる。重合反応器−３では１３５°Ｃ〜１
５０°Ｃで重合する。重合反応器−３を出た重合溶液中
のポリマー濃度は８０重量％である。The polymerization solution exiting the polymerization reactor-2 is led to a static mixer. On the other hand, 0.03j of a 1% by weight ethylbenzene solution of 1.1-bis-(t-butylperoxy)cyclohexane
Feed into the static mixer at a flow rate of 2/H. The polymerization solution and the polymerization initiator solution are uniformly mixed in a static mixer and then introduced into the polymerization reactor-3. Polymerization reactor-3: 135°C ~ 1
Polymerize at 50°C. The polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 80% by weight.
重合反応器−３を出た重合溶液は実施例１と同様に処理
し、製品を採取する。評価結果を表−１に示す。The polymerization solution exiting the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected. The evaluation results are shown in Table-1.
（比較例３）
実施例３と同し装置を用いて、スチレン９２重量部、エ
チルヘンゼン７．９０重量部、比較例１で用いたと同し
有機過酸化物０．１０重量部からなる原料溶液を１．５
１７Ｈの流量で重合反応器１へ連続的に供給し、１００
°Ｃの温度で重合する。重合？８液中のポリマー濃度は
２２重量％である。(Comparative Example 3) Using the same equipment as in Example 3, a raw material solution consisting of 92 parts by weight of styrene, 7.90 parts by weight of ethylhenzene, and 0.10 parts by weight of the same organic peroxide used in Comparative Example 1 was prepared. 1.5
Continuously supplied to the polymerization reactor 1 at a flow rate of 17H,
Polymerizes at a temperature of °C. polymerization? The polymer concentration in liquid 8 was 22% by weight.
続いて、実施例１と同様に、重合反応器−２では１１０
°Ｃ〜１３０°Ｃで重合する。重合反応器２を出た重合
溶液中のポリマー濃度は６０重量％である。Subsequently, as in Example 1, in polymerization reactor-2, 110
Polymerizes between °C and 130 °C. The polymer concentration in the polymerization solution leaving the polymerization reactor 2 is 60% by weight.
重合反応器−２を出た重合溶液は静的混合器に導かれる
。一方、１．１−ビス−（Ｌ−ブチルパーオキシ）シク
ロヘキサンの１重量％エチルヘンゼン溶液を０．０３４
２７Ｈの流量で静的混合器に供給する。重合溶液と重合
開始剤溶液は静的混合器で均一混合された後、重合反応
器−３へ導かれる。重合反応器−３では１３５°Ｃ〜１
５０°Ｃで重合する。重合反応器−３を出た重合溶液中
のポリマー濃度は７６重量％である。The polymerization solution exiting the polymerization reactor-2 is led to a static mixer. On the other hand, a 1% by weight ethylhensen solution of 1.1-bis-(L-butylperoxy)cyclohexane was added to 0.034%
Feed into the static mixer at a flow rate of 27H. The polymerization solution and the polymerization initiator solution are uniformly mixed in a static mixer and then introduced into the polymerization reactor-3. Polymerization reactor-3: 135°C ~ 1
Polymerize at 50°C. The polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 76% by weight.
重合反応器−３を出た重合溶液は実施例１と同様に処理
し、製品を採取する。評価結果を表−１に示す。The polymerization solution exiting the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected. The evaluation results are shown in Table-1.
（比較例４）
実施例３と同し装置を用いて、スチレン９０重量部、エ
チルベンゼン９．９６重量部、実施例１で用いたと同し
有機過酸化物０．０４重量部からなる原料溶液を２．５
１７Ｈの流量で重合反応器１へ連続的に供給し、１０８
°Ｃの温度で重合する。重合溶液中のポリマー濃度は２
８重量％である。(Comparative Example 4) Using the same equipment as in Example 3, a raw material solution consisting of 90 parts by weight of styrene, 9.96 parts by weight of ethylbenzene, and 0.04 parts by weight of the same organic peroxide used in Example 1 was prepared. 2.5
Continuously supplied to the polymerization reactor 1 at a flow rate of 17H,
Polymerizes at a temperature of °C. The polymer concentration in the polymerization solution is 2
It is 8% by weight.
重合反応器−２では１２０°Ｃ−１３０°Ｃ１重合反応
器−３では１３５°Ｃ−１４５°Ｃで重合する。Polymerization is carried out at 120°C-130°C in polymerization reactor-2 and 135°C-145°C in polymerization reactor-3.
重合反応器−２を出た重合溶液中のポリマー濃度は４８
重量％であり、重合反応器−３を出た重合溶液中のポリ
マー濃度は６７重量％である。The polymer concentration in the polymerization solution exiting the polymerization reactor-2 was 48
% by weight, and the polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 67% by weight.
重合反応器−３を出た重合？８ｅ、は実施例１と同様に
処理し、製品を採取する。評価結果を（表１）に示す。Polymerization that came out of polymerization reactor-3? 8e is treated in the same manner as in Example 1, and the product is collected. The evaluation results are shown in (Table 1).
は４８重量％であり、重合反応器−３を出た重合溶液中
のポリマー濃度は６７重量％である。is 48% by weight, and the polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 67% by weight.
重合反応器−３を出た重合溶液は実施例１と同様に処理
し、製品を採取する。評価結果を（表１）に示す。The polymerization solution exiting the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected. The evaluation results are shown in (Table 1).
（比較例５）
実施例３と同し装置を用いて、スチレン９５重量部、エ
チルベンゼン４．９７重量部、実施例１で用いたと同し
有機過酸化物０．０３重量部からなる原料溶液を３１／
Ｈの流量で重合反応器−１へ連続的に供給し、１０２°
Ｃの温度で重合する。(Comparative Example 5) Using the same equipment as in Example 3, a raw material solution consisting of 95 parts by weight of styrene, 4.97 parts by weight of ethylbenzene, and 0.03 parts by weight of the same organic peroxide used in Example 1 was prepared. 31/
Continuously supply H to the polymerization reactor-1 at a flow rate of 102°
Polymerizes at a temperature of C.
重合溶液中のポリマー濃度は１３重量％である。The polymer concentration in the polymerization solution is 13% by weight.
続いて、実施例１と同様に、重合反応器−２では１３５
°Ｃ〜１４０°Ｃで重合する。重合反応器２を出た重合
溶液中のポリマー濃度は６０重量％である。重合反応器
−２を出た重合溶液は静的混合器に導かれる。Subsequently, in the same manner as in Example 1, 135
Polymerizes between °C and 140 °C. The polymer concentration in the polymerization solution leaving the polymerization reactor 2 is 60% by weight. The polymerization solution exiting the polymerization reactor-2 is led to a static mixer.
一方、１，１−ビス−（ｔ−ブチルパーオキシ）シクロ
ヘキサンの１重量％エチルヘンゼンン容液を０．０３ｆ
／Ｈの流量で静的混合器に供給する。重合溶液と重合開
始剤溶液は静的混合器で均一混合された後重合反応器−
３へ導かれる。重合反応器−３では１４０°Ｃ−１４５
°Ｃで重合する。On the other hand, add 0.03 f of a 1% by weight ethyl hexane solution of 1,1-bis-(t-butylperoxy)cyclohexane.
A flow rate of /H is fed to the static mixer. The polymerization solution and polymerization initiator solution are mixed uniformly in a static mixer and then transferred to the polymerization reactor.
Leads to 3. 140°C-145 in polymerization reactor-3
Polymerizes at °C.
重合反応器−３を出た重合溶液中のポリマー濃度は７５
重量％である。The polymer concentration in the polymerization solution exiting the polymerization reactor-3 is 75
Weight%.
重合反応器−３を出た重合溶液は実施例１と同様に処理
し、製品を採取する。評価結果を表−１に示す。The polymerization solution exiting the polymerization reactor-3 is treated in the same manner as in Example 1, and the product is collected. The evaluation results are shown in Table-1.
（比較例６）
実施例３と同し装置を用いて、スチレン９６重量部、エ
チルヘンガフ３，９フ重量部、実施例１で用いたと同し
有機過酸化物０．０３重量部からなる原料溶液を３Ｉ！
、／Ｈの流量で重合反応器−１へ連続的に供給し、１２
０°Ｃの温度で重合する。(Comparative Example 6) Using the same equipment as in Example 3, a raw material solution consisting of 96 parts by weight of styrene, 3.9 parts by weight of ethylhengaf, and 0.03 parts by weight of the same organic peroxide used in Example 1 was prepared. 3I!
,/H to the polymerization reactor-1, and 12
Polymerizes at a temperature of 0°C.
重合溶液中のポリマー濃度は２９重量％である。The polymer concentration in the polymerization solution is 29% by weight.
続いて、実施例１と同様に、重合反応器−２では１３０
°Ｃ〜１４０°Ｃで重合する。重合反応器２を出た重合
？８１中のポリマー濃度は６０重量％である。重合反応
器−２を出た重合？８液は静的混合器に導かれる。Subsequently, as in Example 1, in polymerization reactor-2, 130
Polymerizes between °C and 140 °C. Polymerization leaving polymerization reactor 2? The polymer concentration in 81 is 60% by weight. Polymerization that came out of polymerization reactor-2? 8 liquid is led to a static mixer.
方、１．１−ビス〜（ｔ−ブチルパーオキシ）シクコヘ
キサンの１重量％エチルヘンゼン溶液を０．０３ｆ／Ｈ
の流量で静的混合器に供給する。重合溶液と重合開始剤
溶液は静的混合器で均一混合された後、重合反応器−３
へ導かれる。重合反応器−３では１５０°Ｃ〜１７５°
Ｃで重合する。On the other hand, a 1% by weight ethylhensen solution of 1.1-bis-(t-butylperoxy)cyclohexane was added at 0.03f/H.
feed into the static mixer at a flow rate of . After the polymerization solution and the polymerization initiator solution are uniformly mixed in a static mixer, they are transferred to polymerization reactor-3.
be led to. 150°C to 175° in polymerization reactor-3
Polymerizes with C.
重合反応器−３を出た重合７８液中のポリマー濃度は８
６重量％である。The polymer concentration in the polymerization 78 liquid that exited the polymerization reactor-3 was 8.
It is 6% by weight.
重合反応器−３を出た重合？８液は実施例１と同様に処
理し、製品を採取する。評価結果を表−１に示す。Polymerization that came out of polymerization reactor-3? The 8th liquid was treated in the same manner as in Example 1, and the product was collected. The evaluation results are shown in Table-1.
（発明の効果）
実施例１．２と比較例１：実施例３．４と比較例３の生
産性を比べると、特開昭６０−８３０．１、特開昭６０
−１３８０５号公報記載の低温分解型有機過酸化物を用
いるよりも本発明の有機過酸化物を用いることにより、
３０％〜５０％生産性向上がｌれることが解る。得られ
た重合体の強度は低温分解型有機過酸化物を用いた場合
と同等の強度を有する。(Effect of the invention) Example 1.2 and Comparative Example 1: Comparing the productivity of Example 3.4 and Comparative Example 3, it is found that JP-A-60-830.1 and JP-A-60
By using the organic peroxide of the present invention rather than using the low-temperature decomposition type organic peroxide described in Publication No.-13805,
It can be seen that productivity can be improved by 30% to 50%. The strength of the obtained polymer is equivalent to that when a low-temperature decomposition type organic peroxide is used.
一方、スチレン系重合体の製造に広く使用されている有
機過酸化物を用いた場合（比較例２）と比べると、生産
性向上効果は小さいが、得られた重合体の強度は著しく
改良されていることが理解できる。On the other hand, compared to the case where organic peroxides, which are widely used in the production of styrenic polymers, are used (Comparative Example 2), the productivity improvement effect is small, but the strength of the obtained polymer is significantly improved. I can understand that.
本発明の開始剤を用いても最適な重合条件を設定しなけ
れば、例えば、最終反応器を出た重合溶液中のポリマー
濃度が低い場合（比較例４）、重合温度が１７０°Ｃを
越えた場合で重合した場合（比較例６）、前段での重合
率が低い場合（比較例５）等は強度の向上が殆ど認めら
石ない。Even if the initiator of the present invention is used, if the optimum polymerization conditions are not set, for example, if the polymer concentration in the polymerization solution leaving the final reactor is low (Comparative Example 4), the polymerization temperature will exceed 170°C. In the case where the polymerization was carried out at a low temperature (Comparative Example 6), and when the polymerization rate in the first stage was low (Comparative Example 5), almost no improvement in strength was observed.
以上のように、本発明の特定の有機過酸化物を用いて、
本発明で規定する重合条件でスチレン系重合体を製造す
ることにより、生産性を犠牲にすることなく強度の向上
が圓れる。As mentioned above, using the specific organic peroxide of the present invention,
By producing a styrenic polymer under the polymerization conditions specified in the present invention, strength can be improved without sacrificing productivity.
【図面の簡単な説明】
第１〜２図は、本発明の実施例で使用される装置の説明
Ｖである。
１：前段重合反応器（完全混合型）
２：後段重合反応Ｆｉ−１（静的混合器内蔵）３：後段
重合反応器−２（静的混合器内蔵）４：脱揮槽
５：原料溶液フィートポンプ
５゛ ：開始剤？ｇ’／Ｆｌフィードポンプ６．６’
：重合７容液移送ポンプ
６゛：溶融樹脂移送ポンプ
７・予熱器
８：真空ライン
９：溶融樹脂移送ライン
１０、静的混合器BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1-2 are an illustration V of an apparatus used in an embodiment of the invention. 1: First-stage polymerization reactor (complete mixing type) 2: Second-stage polymerization reaction Fi-1 (built-in static mixer) 3: Second-stage polymerization reactor-2 (built-in static mixer) 4: Devolatilization tank 5: Raw material solution Foot pump 5゛: Initiator? g'/Fl feed pump 6.6'
: Polymerization 7 Volume transfer pump 6゛: Molten resin transfer pump 7/preheater 8: Vacuum line 9: Molten resin transfer line 10, static mixer
Claims (1)
系重合体を連続的に製造する方法において、一般式： ▲数式、化学式、表等があります▼（Ａ） （式中、Ｒ＾１は▲数式、化学式、表等があります▼あ
るいは▲数式、化学式、表等があります▼ＣＨ＿３を表
し、Ｒ＾２は−ＣＨ＿２ＣＨ＿２−、−Ｃ≡Ｃ−、▲数
式、化学式、表等があります▼を表す。）で示される繰
り返し単位を３個以上有する有機過酸化物をスチレン系
単量体１００重量部当たり活性酸素量換算で０．０００
２〜０．０５重量部の割合で添加し、重合温度８５以上
１３０℃未満の温度範囲で反応溶液中のポリマー濃度が
１５重量％を越える迄重合を行った後、後段重合反応器
での重合温度が１７０℃を越えない温度で重合を行い、
最終反応器出口の反応溶液中のポリマー濃度が７０重量
％以上になる迄重合することを特徴とする、スチレン系
重合体の製法。[Claims] In a method for continuously producing styrenic polymers by bulk polymerization or solution polymerization of styrenic monomers, the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) (Formula In the middle, R^1 represents ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ represents CH_3, and R^2 is -CH_2CH_2-, -C≡C-, ▲ mathematical formulas, chemical formulas, There is a table, etc. ▼ represents an organic peroxide having three or more repeating units shown in 0.000 active oxygen amount per 100 parts by weight of styrenic monomer.
2 to 0.05 parts by weight, and polymerization is carried out at a polymerization temperature range of 85 to 130°C until the polymer concentration in the reaction solution exceeds 15% by weight, and then polymerization is carried out in a subsequent polymerization reactor. Polymerization is carried out at a temperature not exceeding 170°C,
A method for producing a styrenic polymer, which comprises polymerizing until the polymer concentration in the reaction solution at the outlet of the final reactor reaches 70% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19295490A JPH0480211A (en) | 1990-07-23 | 1990-07-23 | Preparation of styrenic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19295490A JPH0480211A (en) | 1990-07-23 | 1990-07-23 | Preparation of styrenic polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0480211A true JPH0480211A (en) | 1992-03-13 |
Family
ID=16299790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19295490A Pending JPH0480211A (en) | 1990-07-23 | 1990-07-23 | Preparation of styrenic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0480211A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005248002A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Heat-resistant styrene resin stretched sheet |
| JP2005248003A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Manufacturing method of heat-resistant styrene resin and its composition |
-
1990
- 1990-07-23 JP JP19295490A patent/JPH0480211A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005248002A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Heat-resistant styrene resin stretched sheet |
| JP2005248003A (en) * | 2004-03-04 | 2005-09-15 | Ps Japan Corp | Manufacturing method of heat-resistant styrene resin and its composition |
| JP4721645B2 (en) * | 2004-03-04 | 2011-07-13 | Ｐｓジャパン株式会社 | Method for producing heat-resistant styrenic resin and composition thereof |
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