JPH0714967B2 - Method for producing methacrylic resin - Google Patents
Method for producing methacrylic resinInfo
- Publication number
- JPH0714967B2 JPH0714967B2 JP60227739A JP22773985A JPH0714967B2 JP H0714967 B2 JPH0714967 B2 JP H0714967B2 JP 60227739 A JP60227739 A JP 60227739A JP 22773985 A JP22773985 A JP 22773985A JP H0714967 B2 JPH0714967 B2 JP H0714967B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polymer composition
- volatile components
- methacrylic resin
- methacrylic
- 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 - Fee Related
Links
- 239000000113 methacrylic resin Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 7
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は溶液重合もしくは塊状重合によつてメタクリル
系樹脂の成形材料あるいは押出板等を製造するプロセス
に関する。さらに詳しくは溶液重合もしくは塊状重合に
よつて製造されたメタクリル系樹脂組成物からそれに含
まれる25〜70重量％の未反応モノマー、溶剤および重合
副生成物を除去する方法に関する。TECHNICAL FIELD The present invention relates to a process for producing a molding material of methacrylic resin, an extruded plate or the like by solution polymerization or bulk polymerization. More specifically, it relates to a method for removing 25 to 70% by weight of unreacted monomer, solvent and polymerization by-products contained in a methacrylic resin composition produced by solution polymerization or bulk polymerization.
メタクリル系樹脂はその卓越した透明性、良好な機械的
性質、加工性並びに成形品における外観の美麗さなどに
よつて照明器具、看板、各種装飾品及び銘板などに広く
用いられている。また自動車部品、テーブルウエアー等
に用いられている。The methacrylic resin is widely used for lighting equipment, signboards, various ornaments, nameplates, etc. due to its excellent transparency, good mechanical properties, processability, and beautiful appearance of molded products. It is also used in automobile parts and tableware.
特に最近レンズ、光デイスク、光繊維等の光学用途に用
途が拡大されており上記特性に加えて、光学純度に優れ
た材料すなわち微小異物の低減、残存モノマー等の揮発
成分の低減、高分子量ゲルの極少化が要求されている。In particular, its applications have recently been expanded to optical applications such as lenses, optical disks, and optical fibers. In addition to the above properties, materials with excellent optical purity, that is, reduction of minute foreign substances, reduction of volatile components such as residual monomers, and high molecular weight gel The minimization of is required.
光学純度に優れたメタクリル系樹脂を製造する方法とし
ては溶液重合、塊状重合が優れた方法として知られてい
る。As a method for producing a methacrylic resin having excellent optical purity, solution polymerization and bulk polymerization are known as excellent methods.
溶液重合、塊状重合においては、25〜70重量％の多量の
未反応モノマー、および／または溶剤、重合反応副生成
物を含むメタクリル系樹脂組成物から、それらの揮発性
成分を除去することは非常に重要な技術である。In solution polymerization and bulk polymerization, it is extremely difficult to remove the volatile components from a methacrylic resin composition containing a large amount of unreacted monomer of 25 to 70% by weight, a solvent, and a by-product of a polymerization reaction. Is an important technology.
（従来の技術及び問題点） 未反応モノマー、溶剤及び重合反応副生成物等の揮発性
成分を除去する基本的な方法は、重合体組成物を高温に
加熱した状態で真空雰囲気中に導き揮発分離する方法で
ある。揮発成分が10重量％未満程度の場合には、多段ベ
ント付き二軸押出機等によつて効率的に分離可能であ
り、最終的に得られたメタクリル系樹脂中に残存する揮
発成分は1.0重量％以下であり、物性の良好なメタクリ
ル系樹脂成形材料、あるいは押出板を得ることが出来
る。(Prior art and problems) The basic method for removing volatile components such as unreacted monomer, solvent and by-products of polymerization reaction is to evaporate the polymer composition in a vacuum atmosphere while heating it at a high temperature. It is a method of separating. When the volatile component is less than about 10% by weight, it can be efficiently separated by a twin-screw extruder with a multistage vent, etc., and the volatile component remaining in the finally obtained methacrylic resin is 1.0% by weight. % Or less, and a methacrylic resin molding material having good physical properties or an extruded plate can be obtained.
揮発成分が10重量％をこえる多量の場合には、多段ベン
ト付き押出機を用いた場合、揮発成分のガス化に伴う樹
脂の発泡が激しく、ベント孔が発泡したポリマーにより
閉塞するというトラブルが度々起こり、長時間安定運転
をすることは困難であつた。When the amount of volatile components exceeds 10% by weight, when a multi-stage vented extruder is used, the foaming of the resin due to the gasification of the volatile components is severe, and the vent holes are often blocked by the foamed polymer. It happened and it was difficult to operate stably for a long time.
また多段ベント付き押出機を用いない場合においては重
合体組成物を昇温することが困難であること、揮発成分
を除去した後の高粘度流体の搬送方法、さらに高温、長
時間滞留によるポリマーの劣化、副反応生成物等の問題
を生じる。Further, it is difficult to raise the temperature of the polymer composition when an extruder with a multi-stage vent is not used, a method for transporting a high-viscosity fluid after removing volatile components, a high temperature, a long-term residence time Problems such as deterioration and side reaction products occur.
高温長時間滞留によるポリマーと劣化、着色および副反
応生成物は本発明の目的である光学純度に優れたメタク
リル系樹脂に対して致命的な欠点になり、工業的使用の
場合に問題を生ずる。The polymer and deterioration, coloration and side reaction products due to long-term residence at high temperature become a fatal defect for the methacrylic resin excellent in optical purity which is the object of the present invention, and causes a problem in industrial use.
従来より塊状重合、溶液重合によつて製造した重合体組
成物から未反応単量体、および／または溶剤、副生成物
等の揮発成分を除去して成形材料を製造する方法はスチ
レン系樹脂を中心に検討が進んでおり、例えば特公昭35
−8557号公報、特公昭38−120号公報、特公昭44−20097
号公報、特公昭45−31678号公報、特開昭47−2787号公
報などに開示されている。メタクリル系樹脂に関しても
特公昭52−17555号公報、特開昭50−88197号公報などに
開示されている。Conventionally, a method for producing a molding material by removing volatile components such as unreacted monomers and / or solvents and by-products from a polymer composition produced by bulk polymerization or solution polymerization is a styrene resin. Discussions are progressing mainly, for example, Japanese Patent Publication Sho 35
-8557, JP 38-120, JP 44-20097
It is disclosed in, for example, Japanese Patent Publication No. 45-31678, Japanese Patent Publication No. 47-2787. Methacrylic resins are also disclosed in JP-B-52-17555 and JP-A-50-88197.
（問題点を解決するための手段） 本発明は、高温長時間滞留によるポリマーの劣化、着色
および副反応生成物の少ない脱揮プロセス方法を提供す
るものである。(Means for Solving Problems) The present invention provides a devolatilization process method in which deterioration of a polymer due to residence at a high temperature for a long time, coloring, and a small amount of side reaction products are caused.
すなわち、本発明はメタクリル系重合体組成物から揮発
成分を除去するにあたり、該重合体組成物を温度200〜3
00℃に加熱し、大気圧ないし2.0kg/cm2ゲージの状態に
維持された上部に充分なる空間を有する脱揮タンクに流
延落下し、大部分の揮発成分を除去した後、タンク下部
に接続したベント付き押出機に供給することによつて重
合体組成物の残存揮発分を1.0重量％以下にする事を特
徴とするメタクリル系樹脂の製造方法に関するものであ
る。That is, the present invention, when removing the volatile components from the methacrylic polymer composition, the polymer composition at a temperature of 200 ~ 3
After heating to 00 ° C and casting to a devolatilization tank with sufficient space at the top maintained at atmospheric pressure or 2.0 kg / cm 2 gauge, most of the volatile components were removed, and then at the bottom of the tank. The present invention relates to a method for producing a methacrylic resin, characterized in that the residual volatile content of a polymer composition is reduced to 1.0% by weight or less by supplying it to a connected vented extruder.
本発明のメタクリル系重合体組成物としてはメタクリル
系重合体と未反応モノマー、溶剤及び重合副生成物を主
成分としそのほかに、重合時に添加した開始剤分解物、
連鎖移動剤、添加剤等である。メタクリル系重合体とし
ては、単量体としてメタクリル酸メチル単独またはメタ
クリル酸メチルを主体とする単量体混合物を重合して得
られる。メタクリル酸メチル以外の単量体としてはメタ
クリル酸エチル、メタクリル酸ブチル、メタクリル酸ヘ
キシル、メタクリル酸２エチルヘキシル、アクリル酸メ
チル、アクリル酸エチル、アクリル酸ブチル、アクリロ
ニトリル、メタクリロニトリル、スチレン等が好まし
い。特に好ましくはメタクリル酸メチルとアクリル酸メ
チル、メタクリル酸メチルとスチレンの組み合わせを用
いる。As the methacrylic polymer composition of the present invention, a methacrylic polymer and unreacted monomers, a solvent and a polymerization by-product as the main components, in addition, an initiator decomposition product added at the time of polymerization,
Examples include chain transfer agents and additives. The methacrylic polymer can be obtained by polymerizing methyl methacrylate alone as a monomer or a monomer mixture mainly containing methyl methacrylate. As a monomer other than methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, acrylonitrile, methacrylonitrile, styrene and the like are preferable. Particularly preferably, a combination of methyl methacrylate and methyl acrylate and a combination of methyl methacrylate and styrene are used.
メタクリル酸メチルは40重量％以上用いる事が好まし
く、メタクリル酸メチルが40重量％未満の場合には本発
明の特徴である、無色透明な樹脂を得ることは困難にな
る。It is preferable to use 40% by weight or more of methyl methacrylate, and when the amount of methyl methacrylate is less than 40% by weight, it becomes difficult to obtain a colorless and transparent resin, which is a feature of the present invention.
すなわち本発明の特徴はメタクリル樹脂の熱劣化を軽減
しかつ残存揮発成分の脱揮効率を高くするために脱揮タ
ンクを用いる第一脱揮ゾーンとベントつき押出機による
第二脱揮ゾーンを併用する事にある。That is, the feature of the present invention is that the first devolatilization zone using a devolatilization tank and the second devolatilization zone using a vented extruder are used in combination to reduce the thermal deterioration of methacrylic resin and increase the devolatilization efficiency of residual volatile components. There is something to do.
第一脱揮ゾーンにおいては重合体組成物の加熱は予熱器
を用いて行い、予熱器の温度条件を200〜300℃にする。In the first devolatilization zone, the heating of the polymer composition is performed using a preheater, and the temperature condition of the preheater is set to 200 to 300 ° C.
昇温された重合体組成物は予熱器の狭い出口を通して脱
揮タンクに流延落下せしめる。The heated polymer composition is cast and dropped into a devolatilization tank through a narrow outlet of a preheater.
脱揮タンクの圧力は大気圧ないし2.0kg/cm2ゲージに維
持し、瞬間的に急激な揮発とそれによる発泡を生じせし
めその結果非常に大きな蒸発面積を形成し、揮発分を除
去する。The pressure of the devolatilization tank is maintained at atmospheric pressure or 2.0 kg / cm 2 gauge, and instantaneously causes rapid volatilization and thereby foaming, resulting in formation of a very large evaporation area and removal of volatile components.
発泡した重合体組成物の体積は急激に膨張するので脱揮
タンクの上部空間は発泡前の重合体組成物の３〜５倍の
容積が必要である。Since the volume of the foamed polymer composition expands rapidly, the volume above the devolatilization tank needs to be 3 to 5 times the volume of the polymer composition before foaming.
流延落下時には、ポリマーは蒸発潜熱により冷却され、
180〜280℃になる。When cast and dropped, the polymer is cooled by latent heat of vaporization,
It reaches 180-280 ℃.
脱揮タンクの圧力は揮発成分の除去および重合体組成物
をベント付き押出機に供給する駆動力としてコントロー
ルされる。通常大気圧ないし2.0kg/cm2ゲージに維持し
運転する。大気圧より圧力が低い場合には脱揮効率が高
すぎて重合体組成物中の揮発成分が少なくなり結果とし
て粘度が上昇し排出が困難になる。2.0kg/cm2ゲージを
越えた場合には脱揮効率不足となりベント付き押出機で
ベント閉塞等のトラブルを生ずる。The pressure in the devolatilization tank is controlled as a driving force for removing the volatile components and supplying the polymer composition to the vented extruder. Operate at atmospheric pressure or 2.0kg / cm 2 gauge. When the pressure is lower than the atmospheric pressure, the devolatilization efficiency is too high and the volatile components in the polymer composition are reduced, resulting in an increase in viscosity and difficulty in discharge. If it exceeds 2.0 kg / cm 2 gauge, devolatilization efficiency becomes insufficient, and troubles such as vent clogging occur in the vented extruder.
脱揮タンクから排出される重合体組成物中の残存揮発成
分は好ましくは３〜10重量％であり、特に10重量％以上
にならないようにコントロールする。残存揮発分が10重
量％以上になつた場合には脱揮タンクの工程であるベン
ト付き押出機の運転が、多量の揮発成分の発泡体による
ベント部閉塞等のトラブルによ実質的に不可能になる。
また３重量％以下の場合には樹脂の分子量にもよるが粘
度が数千ポイズから数万ポイズに変化し、非常に粘稠に
なり排出が非常に困難になる場合がある。その結果、滞
留時間が長くなり樹脂の着色劣化が生じ易く問題とな
る。The residual volatile component in the polymer composition discharged from the devolatilization tank is preferably 3 to 10% by weight, and particularly controlled so as not to exceed 10% by weight. When the residual volatile content reaches 10% by weight or more, it is practically impossible to operate the extruder with a vent, which is the process of the devolatilization tank, due to troubles such as clogging of the vent due to the foam of a large amount of volatile components. become.
On the other hand, if the amount is 3% by weight or less, the viscosity may change from several thousand poises to tens of thousands poises depending on the molecular weight of the resin, and it may become very viscous and discharge may be very difficult. As a result, the residence time becomes long, and deterioration of the color of the resin easily occurs, which is a problem.
本発明の特徴は脱揮ゾーンを二段に設けることにより第
一段の高温脱揮における重合体組成物の滞留時間をでき
うる限り短縮の樹脂の着色および重合副成物の生成を防
ぐことにある。滞留時間は好ましくは10〜30分が良い。The feature of the present invention is to prevent the coloring of the resin and the formation of polymerization by-products which can shorten the residence time of the polymer composition in the high-temperature devolatilization in the first stage as much as possible by providing the devolatilization zone in two stages. is there. The residence time is preferably 10 to 30 minutes.
本発明の第二脱揮ゾーンとして用いるベント付き押出機
としては二軸多段ベント付き押出機が好ましい。特に好
ましくは三段ベントつき二軸押出機を用いる。As the vented extruder used as the second devolatilization zone of the present invention, a twin-screw multistage vented extruder is preferable. Particularly preferably, a twin-screw extruder with a three-stage vent is used.
押出機のL/Dは通常20〜40である 第二脱揮ゾーンの押出機の加熱は第一段ベント部の温度
において200〜220℃、圧力は大気圧ないし1.0kg/cm2ゲ
ージで運転する。特に圧力は、スクリユウ軸封部のグラ
ンドからの空気の漏れ込みを防ぐために必要であり負圧
で運転した場合には、空気の漏れ込みのためポリマーの
酸化劣化がおこり得られたポリマーが着色し好ましくな
い。The L / D of the extruder is usually 20 to 40.The heating of the extruder in the second devolatilization zone is 200 to 220 ° C at the temperature of the first stage vent, and the pressure is atmospheric pressure or 1.0 kg / cm 2 gauge. To do. In particular, the pressure is necessary to prevent air from leaking from the gland of the screw shaft seal.When operating at a negative pressure, oxidative deterioration of the polymer occurs due to air leak, and the obtained polymer is colored. Not preferable.
第二ベント部、第三ベント部以降は温度230〜280℃、好
ましくは240〜270℃、圧力は100mmHg以下が好ましい。
温度が230℃未満の場合には粘度が非常に高くなり揮発
分の除去が困難になる。圧力が100mmHgを越えると揮発
分の除去効率が極端に低下し好ましくない。After the second vent portion and the third vent portion, the temperature is 230 to 280 ° C, preferably 240 to 270 ° C, and the pressure is preferably 100 mmHg or less.
If the temperature is lower than 230 ° C, the viscosity becomes so high that it becomes difficult to remove volatile components. When the pressure exceeds 100 mmHg, the removal efficiency of volatile components is extremely reduced, which is not preferable.
（効果） 本発明は、高温長時間によるポリマーの劣化、着色おび
副反応生成物の少ない脱揮プロセス方法である。(Effect) The present invention is a devolatilization process method in which polymer deterioration due to high temperature and long time, and coloring and side reaction products are small.
実施例１ 通常の溶液重合を第１図に示すように完全撹拌槽１を用
いて行いメタクリル酸メチル99重量％、アクリル酸メチ
ル１重量％からなりGPCで測定した平均分子量11万のメ
タクリル樹脂50％と未反応モノマー、開始剤、連鎖移動
剤の残留物、分解物、溶剤50％を含む重合体組成物を得
た。Example 1 Ordinary solution polymerization was carried out using a complete stirring tank 1 as shown in FIG. 1, and was 99% by weight of methyl methacrylate and 1% by weight of methyl acrylate, and a methacrylic resin having an average molecular weight of 110,000 measured by GPC. %, An unreacted monomer, an initiator, a residue of a chain transfer agent, a decomposition product, and a solvent of 50% were obtained.
これを定量ポンプ２により定常的に取り出して、予熱器
３で260℃に加熱し脱揮タンク４に流延落下せしめる。
脱揮タンクは圧力0.8kg/cm2ゲージ、温度200℃に維持し
残存揮発成分を除去する。残存揮発成分が7.5重量％の
重合体を脱揮タンク下部より排出し二軸押出機５の供給
部に落下せしめる。二軸押出機５の第一段脱揮部６は圧
力約0.5kg/cm2ゲージ、温度220℃に維持され、第二脱揮
部７は50mmHg、250℃の条件、第三脱揮部８は30mmHg、2
50℃の条件で残存揮発成分を除去した。押出ダイス９か
ら押し出された樹脂の最終残存揮発成分は0.34重量％で
あつた。This is constantly taken out by the metering pump 2, heated to 260 ° C. by the preheater 3 and cast and dropped into the devolatilization tank 4.
The devolatilization tank is maintained at a pressure of 0.8 kg / cm 2 gauge and a temperature of 200 ° C to remove residual volatile components. A polymer having a residual volatile component of 7.5% by weight is discharged from the lower part of the devolatilization tank and dropped into the supply part of the twin-screw extruder 5. The first stage devolatilization section 6 of the twin-screw extruder 5 is maintained at a pressure of about 0.5 kg / cm 2 gauge and a temperature of 220 ° C, and the second devolatilization section 7 is at 50 mmHg and 250 ° C, and the third devolatilization section 8 is used. Is 30mmHg, 2
The residual volatile components were removed at 50 ° C. The final residual volatile component of the resin extruded from the extrusion die 9 was 0.34% by weight.
３オンス射出成形機で3mm厚の試験片を成形した所、外
観は無色透明で非常に良好であつた。When a 3 mm thick test piece was molded with a 3 ounce injection molding machine, the appearance was colorless and transparent and was very good.
実施例２ 通常の溶液重合を第１図に示す完全撹拌槽１を用いて行
いメタクリル酸メチル70重量％、スチレン30重量％から
なり、GPCで測定した重量平均分子量が15万のメタクリ
ル系樹脂45％と開始剤、連鎖移動剤の残留物、分解物、
溶剤55％を含む重合体組成物を得た。これを定量ポンプ
２により定常的に取り出して、予熱器３で240℃に加熱
し脱揮タンク４に流延落下せしめる。脱揮タンクは1.1k
g/cm2ゲージ、200℃に維持し残存揮発成分を除去する。
残存揮発成分が9.0重量％の重合体を脱揮タンク下部よ
り排出し二軸押出機５の供給部に落下せしめる。Example 2 Ordinary solution polymerization was carried out using the complete stirring tank 1 shown in FIG. 1 and consisting of 70% by weight of methyl methacrylate and 30% by weight of styrene, and a methacrylic resin having a weight average molecular weight of 150,000 measured by GPC. %, Initiator, residue of chain transfer agent, degradation product,
A polymer composition containing 55% solvent was obtained. This is taken out constantly by the metering pump 2, heated to 240 ° C. by the preheater 3 and cast and dropped into the devolatilization tank 4. The devolatilization tank is 1.1k
Keep the g / cm 2 gauge at 200 ° C to remove residual volatile components.
A polymer having a residual volatile component of 9.0% by weight is discharged from the lower part of the devolatilization tank and dropped into the supply part of the twin-screw extruder 5.
脱揮押出機５の第一段脱揮部６は圧力約0.5kg/cm2、温
度220℃に維持され、第二脱揮部７は50mmHg、250℃の条
件、第三脱揮部８は30mmHg、250℃の条件で残存揮発成
分を除去した。押出ダイス９から押し出された樹脂の最
終残存揮発成分は0.24重量％であつた。The first-stage devolatilizing section 6 of the devolatilizing extruder 5 is maintained at a pressure of about 0.5 kg / cm 2 and a temperature of 220 ° C., the second devolatilizing section 7 is at 50 mmHg and 250 ° C., and the third devolatilizing section 8 is Residual volatile components were removed under the conditions of 30 mmHg and 250 ° C. The final residual volatile component of the resin extruded from the extrusion die 9 was 0.24% by weight.
３オンス射出成形機で3mm厚の試験片を形成した所、外
観は無色透明で非常に良好であつた。When a 3 mm-thick test piece was formed with a 3 ounce injection molding machine, the appearance was colorless and transparent and was very good.
第１図は、本発明の一実施態様のフロシートである。 第１図において、１は完全混合重合反応機、２は定量ポ
ンプ、３は予熱器、４は脱揮タンク、５は二軸押出機、
6,7,8は押出機ベント口（第一，第二，第三）、９はス
トランドダイスを示す。FIG. 1 is a flow sheet according to an embodiment of the present invention. In FIG. 1, 1 is a completely mixed polymerization reactor, 2 is a metering pump, 3 is a preheater, 4 is a devolatilization tank, 5 is a twin-screw extruder,
6, 7 and 8 are extruder vents (first, second and third), and 9 is a strand die.
Claims (3)
除去するにあたり、該重合体組成物を温度200〜300℃に
加熱し、大気圧ないし2.0kg/cm2ゲージの状態に維持さ
れた上部に充分なる空間を有する脱揮タンクに流延落下
し、大部分の揮発成分を除去した後、タンク下部に接続
したベント付き押出機に供給することによつて重合体組
成物の残存揮発分を1.0重量％以下にする事を特徴とす
るメタクリ系樹脂の製造方法1. When removing volatile components from a methacrylic polymer composition, the polymer composition is heated to a temperature of 200 to 300 ° C., and an upper portion maintained at atmospheric pressure or 2.0 kg / cm 2 gauge. After being cast and dropped into a devolatilization tank having a sufficient space to remove most of the volatile components, the residual volatile components of the polymer composition can be removed by feeding the extruder with a vent connected to the bottom of the tank. A method for producing a methacrylic resin, characterized in that the content is 1.0% by weight or less
メチル単位80重量％以上含みGPCで測定した分子量が７
〜15万の重合体と、25〜70重量％の未反応モノマー、溶
剤および重合副生成物からなる揮発性成分である特許請
求の範囲第（１）項記載のメタクリル系樹脂の製造方法2. A methacrylic polymer composition containing 80% by weight or more of methyl methacrylate units and having a molecular weight of 7 measured by GPC.
The method for producing a methacrylic resin according to claim (1), which is a volatile component consisting of ˜150,000 polymer, 25 to 70% by weight of unreacted monomer, solvent and polymerization by-product.
メチル単位40〜70重量％およびスチレン単位30〜60重量
％からなりGPCで測定した分子量が７〜15万の共重合体
と、25〜70重量％の未反応モノマー、溶剤および重合副
生成物からなる揮発性成分である特許請求の範囲第
（１）項記載のメタクリル系樹脂の製造方法3. A copolymer having a methacrylic polymer composition of 40 to 70% by weight of methyl methacrylate unit and 30 to 60% by weight of styrene unit and having a molecular weight of 70 to 150,000 as measured by GPC, and 25 to 70%. The method for producing a methacrylic resin according to claim (1), which is a volatile component composed of a non-reacted monomer by weight, a solvent and a polymerization by-product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60227739A JPH0714967B2 (en) | 1985-10-15 | 1985-10-15 | Method for producing methacrylic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60227739A JPH0714967B2 (en) | 1985-10-15 | 1985-10-15 | Method for producing methacrylic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6289710A JPS6289710A (en) | 1987-04-24 |
| JPH0714967B2 true JPH0714967B2 (en) | 1995-02-22 |
Family
ID=16865605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60227739A Expired - Fee Related JPH0714967B2 (en) | 1985-10-15 | 1985-10-15 | Method for producing methacrylic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0714967B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3508780B2 (en) * | 1993-11-09 | 2004-03-22 | 三菱瓦斯化学株式会社 | Method for producing methacrylate polymer |
| JP2003075648A (en) * | 2001-09-07 | 2003-03-12 | Denki Kagaku Kogyo Kk | Light guide plate |
| JP4323406B2 (en) | 2004-10-04 | 2009-09-02 | 住友化学株式会社 | Continuous polymerization apparatus and continuous polymerization method using the same |
| JP5150708B2 (en) | 2010-11-08 | 2013-02-27 | 住友化学株式会社 | Continuous polymerization apparatus and method for producing polymer composition |
| JP5249366B2 (en) | 2011-01-26 | 2013-07-31 | 住友化学株式会社 | Continuous polymerization apparatus and method for producing polymer composition |
| JP5431376B2 (en) | 2011-01-26 | 2014-03-05 | 住友化学株式会社 | Continuous polymerization apparatus and method for producing polymer composition |
| JP2012207203A (en) | 2011-03-17 | 2012-10-25 | Sumitomo Chemical Co Ltd | Process for production of polymer composition |
| JP5901361B2 (en) | 2011-11-18 | 2016-04-06 | 住友化学株式会社 | Continuous polymerization apparatus and method for producing polymer composition |
| JP2014012781A (en) | 2012-07-05 | 2014-01-23 | Sumitomo Chemical Co Ltd | Method for producing methacrylic polymer composition |
| JP6002017B2 (en) | 2012-12-03 | 2016-10-05 | 住友化学株式会社 | Method for producing methacrylic polymer composition |
| JP6228225B2 (en) * | 2013-10-28 | 2017-11-08 | 株式会社クラレ | Method for producing methacrylic resin composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4935640B2 (en) * | 1971-08-19 | 1974-09-25 | ||
| JPS5550483B2 (en) * | 1973-08-08 | 1980-12-18 | ||
| JPS5217555A (en) * | 1975-08-01 | 1977-02-09 | Asahi Glass Co Ltd | Fluorine-containing copolymer compositions containing carbonaceous mat erials |
| JPS5430428A (en) * | 1977-08-10 | 1979-03-06 | Fuji Electric Co Ltd | Pulse width modulation control system for three-phase inverter |
| JPS5850644B2 (en) * | 1980-08-27 | 1983-11-11 | 住友化学工業株式会社 | Continuous manufacturing method for methyl methacrylate resin molding material |
| JPS5938216A (en) * | 1982-08-27 | 1984-03-02 | Asahi Chem Ind Co Ltd | Purification of polymethyl methacrylate |
-
1985
- 1985-10-15 JP JP60227739A patent/JPH0714967B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6289710A (en) | 1987-04-24 |
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