JPH0448802B2 - - Google Patents
Info
- Publication number
- JPH0448802B2 JPH0448802B2 JP58087152A JP8715283A JPH0448802B2 JP H0448802 B2 JPH0448802 B2 JP H0448802B2 JP 58087152 A JP58087152 A JP 58087152A JP 8715283 A JP8715283 A JP 8715283A JP H0448802 B2 JPH0448802 B2 JP H0448802B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- temperature
- polymerization
- transfer
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 44
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 29
- 239000006188 syrup Substances 0.000 description 19
- 235000020357 syrup Nutrition 0.000 description 19
- 229920001169 thermoplastic Polymers 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000012662 bulk polymerization Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- -1 alkyl methacrylates Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002904 solvent Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical class ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction 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
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】
本発明は高温の重合性液状組成物を重合閉塞を
起すことなく移送する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for transferring high temperature polymerizable liquid compositions without polymerization blockage.
更に詳しくは、本発明は高温の重合性液状組成
物を、内内壁面が規定の温度に加熱された移送区
域を液相状態を保持して通過させて重合閉塞を防
止する高温の重合性液状組成物の移送方法に関す
る。 More specifically, the present invention provides a high-temperature polymerizable liquid composition that prevents polymerization blockage by passing the high-temperature polymerizable liquid composition through a transfer zone whose inner wall surface is heated to a predetermined temperature while maintaining a liquid phase state. The present invention relates to a method for transferring a composition.
重合可能な単量体を塊状で予備重合してシロツ
プを製造すること、塊状重合法あるいは溶液重合
法によつて複数の反応器を用いて重合体含有率を
高めて熱可塑性重合体組成物を製造すること、お
よび／または未反応単量体、溶剤、副生成物ある
いは不純物等の揮発成分を含有する熱可塑性重合
体組成物から揮発成分を分離して熱可塑性重合体
を製造することはいずれも公知である。いずれの
場合においても、重合工程、溶解工程などの先行
する処理工程から排出されるシロツプ、高重合率
の反応混合物あるいは揮発成分を含有する熱可塑
性重合体組成物（以下これらを総称して重合性液
状組成物という）は後続する処理工程に移送され
必要な処理が行なわれた後、製品であるシロツプ
あるいは熱可塑性重合体として取り出される。こ
のような処理工程としては冷却工程、後段の重合
工程および／または脱揮工程が挙げられる。これ
らの処理工程に付される重合性液状組成物は重合
反応などが加熱条件下で行なわれるため通常高温
条件を保持しており、かつ、未反応単量体を相当
量含有しているため更に重合可能な状態にあるに
もかかわわらず重合禁止剤を実質的に含有しない
ので、該処理工程への移送過程において徐々に重
合が進行したり、既に生成した重合体が移送区域
の内壁面に付着し、徐々に成長すると共に不溶性
の重合体に変化して該移送区域を閉塞させるに到
るなどいずれも連続運転を不可能にする問題が発
生する。このような現象はメチルメタクリレート
など特定の単量体を含有する場合に特に著しい。 The production of syrup by prepolymerizing polymerizable monomers in bulk, or the preparation of thermoplastic polymer compositions by increasing the polymer content using multiple reactors by bulk polymerization or solution polymerization. producing a thermoplastic polymer and/or separating volatile components from a thermoplastic polymer composition containing volatile components such as unreacted monomers, solvents, by-products or impurities. is also publicly known. In either case, syrups discharged from preceding processing steps such as polymerization and dissolution steps, reaction mixtures with high polymerization rates, or thermoplastic polymer compositions containing volatile components (hereinafter collectively referred to as polymerizable The liquid composition (referred to as liquid composition) is transferred to subsequent processing steps, subjected to necessary treatments, and then extracted as a product, syrup or thermoplastic polymer. Such treatment steps include a cooling step, a subsequent polymerization step, and/or a devolatilization step. The polymerizable liquid compositions subjected to these treatment steps usually maintain high temperature conditions because the polymerization reaction is carried out under heating conditions, and also contain a considerable amount of unreacted monomers. Even though it is in a polymerizable state, it does not substantially contain a polymerization inhibitor, so polymerization may progress gradually during the transfer process to the treatment process, or the already formed polymer may be deposited on the inner wall surface of the transfer area. Problems such as adhesion, gradual growth, and transformation into insoluble polymers that clog the transfer zone occur, making continuous operation impossible. This phenomenon is particularly remarkable when specific monomers such as methyl methacrylate are contained.
懸濁重合ないし乳化重合をを連続的に行なう場
合の槽列重合装置における重合体の排出、移送過
程における塊状重合物の付着による重合槽間の連
結パイプの閉塞を防止する方法としては、例えば
移送パイプ中に反応液の温度より低温の水、また
は連鎖移動剤を含む水を注入する方法（特公昭45
−18465）、移送パイプを外部よりこの反応液の温
度より低温に冷却する方法（特公昭49−2339）が
提案されているが、これらの方法を塊状重合法あ
るいは連続重合法によつて製造される重合性液状
組成物の移送に適用することは不可能である。す
なわち、前者の方法では反応液と混合して均一液
を形成することができず重合体の析出や反応液の
停滞が生じてかえつて付着を助長して閉塞の原因
となり、一方後者では反応液の粘度が低温側で著
しく増大する性質があるため移送パイプ内壁面付
近での停滞が生じて付着が増大し、あるいは高粘
度のため移送自体が不可能となる欠点を有してい
た。 When suspension polymerization or emulsion polymerization is carried out continuously, methods for preventing clogging of connecting pipes between polymerization tanks due to adhesion of bulk polymers during the discharge and transfer process of polymer in a series polymerization apparatus include transfer, for example. A method of injecting water at a temperature lower than the temperature of the reaction solution or water containing a chain transfer agent into the pipe (Special Publication Act 1977).
-18465), and a method of externally cooling the transfer pipe to a temperature lower than the temperature of this reaction liquid (Japanese Patent Publication No. 49-2339), but these methods are not suitable for production by bulk polymerization or continuous polymerization. It is not possible to apply this method to the transfer of polymerizable liquid compositions. In other words, in the former method, it is not possible to mix with the reaction liquid to form a homogeneous liquid, resulting in polymer precipitation and stagnation of the reaction liquid, which promotes adhesion and causes blockage, whereas in the latter method, the reaction liquid is mixed with the reaction liquid to form a homogeneous liquid. Because the viscosity of the material increases significantly at low temperatures, it has the disadvantage that stagnation occurs near the inner wall of the transfer pipe, resulting in increased adhesion, or the high viscosity makes transfer itself impossible.
本発明者らはこれらの欠点を克服する方法につ
いて鋭意検討した結果、高温の重合性液状組成物
を、内壁面が規定の温度に加熱された移送区域を
液相状態で通過させる簡便な方法により移送区域
の内壁面への重合体の付着や閉塞を防止できるこ
とを見出し本発明に到達した。 The inventors of the present invention have conducted extensive studies on ways to overcome these drawbacks, and have found that a simple method in which a high-temperature polymerizable liquid composition is passed in a liquid phase through a transfer zone whose inner wall surface is heated to a specified temperature is used. The inventors have discovered that it is possible to prevent the polymer from adhering to the inner wall surface of the transfer zone and from blocking it, and have arrived at the present invention.
すなわち、本発明は70〜250℃、好ましくは90
〜250℃の温度条件下にある重合性液状組成物を
後続する処理工程へ移送するに当り、移送区域の
内壁面を150〜290℃、好ましくは180〜250℃であ
り、かつ、該組成物の温度より低くない温度に加
熱し、かつ、該移送区域内の組成物を１〜20気
圧、好ましくは４〜10気圧の圧力条件下に維持し
て実質的に液相状態で通過させることを特徴とす
る高温の重合性液状組成物の移送方である。本発
明の方法によりこのように重合体の付着が防止さ
れる理由は明確ではないが、移送区域の内壁面に
沿つて通過する組成物の粘度が低下することによ
り内壁面付近での流速が上昇し、該区域内、例え
ば管内の半径方向の流速分布が平均化して停滞が
起り難く付着速度よりも脱着速度の方が速くなつ
て重合体の付着が回避されるため、あるいは内壁
面上での重合反応の進行による重合体の生成速度
よりも該壁面上での重合反応が進行しても付着あ
るいは閉塞の原因とはならないためと推察され
る。 That is, the temperature of the present invention is 70 to 250°C, preferably 90°C.
When transferring a polymerizable liquid composition under a temperature condition of ~250°C to a subsequent processing step, the temperature of the inner wall surface of the transfer zone is 150-290°C, preferably 180-250°C, and the composition is and maintaining the composition in the transfer zone under pressure conditions of 1 to 20 atmospheres, preferably 4 to 10 atmospheres, so that it passes substantially in a liquid phase. This is a characteristic method of transferring a high temperature polymerizable liquid composition. Although it is not clear why the method of the present invention prevents polymer deposition in this way, the flow rate near the inner wall is increased by reducing the viscosity of the composition passing along the inner wall of the transfer zone. However, the flow velocity distribution in the radial direction within the area, for example inside the pipe, is averaged, making it difficult for stagnation to occur, and the desorption rate is faster than the deposition rate, avoiding polymer deposition, or polymer deposition on the inner wall surface. This is presumed to be because the progress of the polymerization reaction on the wall does not cause adhesion or blockage, rather than the rate of polymer production due to the progress of the polymerization reaction.
次に本発明について詳細に説明する。 Next, the present invention will be explained in detail.
本発明の方法による移送に適する重合性液状組
成物の形態としては、重合可能な単量体を塊状で
予備重合して得られるシロツプ、塊状重合法ある
いは溶液重合法によつて熱可塑性重合体を製造す
る場合の未反応単量体、溶剤、副生成物あるいは
不純物等の揮発成分を含有する熱可塑性重合体組
成物などが挙げられる。また、本発明の方法に適
する重合性液状組成物の組成としては単量体100
〜80重量％とゴム状重合体０〜20重量％からなる
単量体溶液に必要に応じて溶剤などを含有する原
料液またはこれを重合してなる重合転化率が３〜
80重量％の単量体−重合体混合物が挙げられる。
特に適する単量体としてはメチルメタクリレー
ト、エチルメタクリレートなどのアルキルメタク
リレート類、およびスチレン、α−メチルスチレ
ン、核置換アルキルスチレン、核置換クロルスチ
レンなどのビニル芳香族化合物を挙げることがで
き、これらの１種または２種以上を60重量％以上
含有してなる単量体または単量体混合物が用いら
れる。ゴム状重合体としてははポリブタジエン、
ポリイソプレン、ポリイソブチレンなどの単独重
合体、ブタジエン／スチレン、ブタジエン／アク
リロニトリル、ブタジエン／メチルメタクリレー
ト、ブタジエン／アルキルアクリレートなどのジ
エン系共重合体、エチレン／酢酸ビニル共重合
体、エチレンアルキルアクリレート（アルキル基
の炭素数１〜８個）共重合体、ゴム状ポリアルキ
ルアクリレートまたはその共重合体、ポリウレタ
ン、塩素化ポリエチレンおよびEPDMなどを挙
げることができ、これらの１種または２種以上が
最終製品に耐衝撃性などを付与する目的で用いら
れる。 Examples of the form of the polymerizable liquid composition suitable for transport by the method of the present invention include syrup obtained by prepolymerizing polymerizable monomers in bulk, and thermoplastic polymers prepared by bulk polymerization or solution polymerization. Examples include thermoplastic polymer compositions containing volatile components such as unreacted monomers, solvents, by-products, and impurities during production. Furthermore, the composition of the polymerizable liquid composition suitable for the method of the present invention is as follows:
A raw material solution containing a monomer solution consisting of ~80% by weight and a rubbery polymer of 0 to 20% by weight, and a solvent etc. as necessary, or a raw material solution obtained by polymerizing this and having a polymerization conversion rate of 3 to 20% by weight.
Mention may be made of 80% by weight monomer-polymer mixtures.
Particularly suitable monomers include alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, and vinyl aromatic compounds such as styrene, α-methylstyrene, nuclear-substituted alkylstyrene, and nuclear-substituted chlorostyrene; A monomer or a monomer mixture containing at least 60% by weight of the species or two or more species is used. Rubbery polymers include polybutadiene,
Homopolymers such as polyisoprene and polyisobutylene, diene copolymers such as butadiene/styrene, butadiene/acrylonitrile, butadiene/methyl methacrylate, butadiene/alkyl acrylate, ethylene/vinyl acetate copolymers, ethylene alkyl acrylate (alkyl group Copolymers (having 1 to 8 carbon atoms), rubber-like polyalkyl acrylates or copolymers thereof, polyurethanes, chlorinated polyethylenes, and EPDM, and one or more of these may be used to improve the resistance of the final product. Used for the purpose of imparting impact properties, etc.
先行する処理工程より排出される通常70〜250
℃、好ましくは90〜200℃の重合性液状組成物が
移送区域に供給される。温度がこの範囲より低い
ときは、特別な配慮を行なうことなく比較的容易
に重合閉塞を防止して移送することができず、一
方、この範囲より高いときには、元来重合性液状
組成物自体が分解、着色を生じる欠点を有してい
るため、いずれも本発明の方法による移送には適
さない。 Usually 70 to 250 discharged from the preceding treatment process
A polymerizable liquid composition at a temperature of 0.degree. C., preferably from 90 to 200.degree. C., is supplied to the transfer zone. When the temperature is lower than this range, polymerization blockage cannot be prevented and transferred relatively easily without special consideration, whereas when the temperature is higher than this range, the polymerizable liquid composition itself is Since they have the disadvantage of causing decomposition and coloring, they are not suitable for transportation by the method of the present invention.
移送区域の内壁面は150〜290℃、好ましくは
180〜290℃であり、かつ、該前の処理工程より流
入する組成物の温度より低くない温度に加熱され
る。内壁面の温度がこの範囲より低いときは移送
区域の内壁面に重合体が付着し、徐々に成長する
と共に不溶性の重合体に変化して該区域内を閉塞
させ、一方、この範囲より高いときは熱による分
解、着色が生じて最終製品を変質、劣化させる欠
点を有している。また、該区域の内壁面の温度が
流入する該組成物の温度より低いときは該組成物
の温度が前記範囲内であつても重合閉塞の原因と
なり易い欠点を有する。 The inner wall surface of the transfer zone is 150-290℃, preferably
It is heated to a temperature of 180 to 290°C and not lower than the temperature of the incoming composition from the previous treatment step. When the temperature of the inner wall surface is lower than this range, the polymer adheres to the inner wall surface of the transfer zone and gradually grows and turns into an insoluble polymer, clogging the area, while when it is higher than this range. has the disadvantage that thermal decomposition and coloration occur, altering and deteriorating the final product. Further, when the temperature of the inner wall surface of the zone is lower than the temperature of the composition flowing into the zone, there is a drawback that polymerization clogging is likely to occur even if the temperature of the composition is within the above range.
該移送区域は内壁面を規定の温度範囲内に加熱
する機能を有し、液の停滞の少ない構造であれば
いかなる装置形状であつてもよいが、例えば無撹
拌の細長い管状であり、外部に熱媒体の流路が設
けられた二重管が適する。加熱されていない箇所
への重合体の付着を回避するため、加熱は該区域
を画する器壁の実質的に全面積に実施されるのが
好ましい。管状区域のＬ／Ｄは先行する処理工程
と後続する処理工程との間の該組成物の逆混合の
影響を避ける意味で通常３以上、好ましくは10以
上に選ばれ、また該区域内を流れる該組成物の平
均線速度は通常10cm／分以上、好ましくは50cm／
分以上に選ばれる。この範囲より遅いときは内壁
面に重合体が付着成長し易い欠点が表われる。ま
た、該移送区域内における該組成物の蒸気圧は通
常大気圧よりも高いので、該区域の内壁面上にお
ける単量体の蒸発と、これに伴なう重合体の器壁
への付着を抑える目的で、該組成物が実質的に液
相を保持するに十分な圧力が加えられ、通常１〜
20気圧、好ましくは４〜10気圧に維持される。ま
た該組成物の温度は、変質、劣化を避けるため、
通常220℃以下、好ましくは200℃以下に保持され
る。 The transfer zone has the function of heating the inner wall surface within a specified temperature range, and may have any shape as long as it has a structure that minimizes stagnation of liquid. A double pipe provided with a flow path for the heat medium is suitable. To avoid deposition of polymer in unheated areas, heating is preferably carried out over substantially the entire area of the vessel wall delimiting the area. The L/D of the tubular section is usually selected to be 3 or more, preferably 10 or more, in order to avoid the effect of back mixing of the composition between the preceding treatment step and the subsequent treatment step, and the L/D of the tubular section is selected to be 3 or more, preferably 10 or more, and the The average linear velocity of the composition is usually 10 cm/min or more, preferably 50 cm/min.
Chosen by more than a minute. When the temperature is slower than this range, a drawback appears in that the polymer tends to adhere and grow on the inner wall surface. In addition, since the vapor pressure of the composition in the transfer zone is usually higher than atmospheric pressure, evaporation of the monomer on the inner wall surface of the zone and accompanying adhesion of the polymer to the vessel wall are prevented. For purposes of restraining, a pressure sufficient to maintain the composition in a substantially liquid phase is applied, usually between 1 and 2.
The pressure is maintained at 20 atmospheres, preferably between 4 and 10 atmospheres. In addition, the temperature of the composition should be adjusted to avoid deterioration and deterioration.
It is usually kept at 220°C or lower, preferably 200°C or lower.
本発明の方法によれば、重合工程などの先行す
る処理工程と、冷却工程、後段の重合工程およ
び／または脱揮工程などの後続する処理工程とを
組み合わせて構成される一連の製造工程によりシ
ロツプあるいは熱可塑性重合体を製造するに当
り、両工程間の重合性液状組成物の移送区域にお
ける重合閉塞を防止できて長時間の連続運転に耐
えると共に、該組成物の変質、劣化のない簡便で
効率的な移送方法が提供される。 According to the method of the present invention, syrup is produced by a series of manufacturing steps consisting of a combination of a preceding treatment step such as a polymerization step and a subsequent treatment step such as a cooling step, a subsequent polymerization step and/or a devolatilization step. Alternatively, when producing a thermoplastic polymer, it is possible to prevent polymerization clogging in the transfer area of the polymerizable liquid composition between both processes, and to withstand long-term continuous operation, and to provide a simple and convenient method that does not cause deterioration or deterioration of the composition. An efficient transport method is provided.
また、移送区域は撹拌機などの設置が不要であ
るから構造自体が極めて単純であるのみならず、
曲線状であつてもよいから各工程の配置上の制約
がない利点がある。 In addition, since there is no need to install a stirrer in the transfer area, the structure itself is not only extremely simple, but also
Since it may be curved, there is an advantage that there are no restrictions on the arrangement of each step.
本発明の方法を適用して製造されたシロツプは
更に重合開始剤を加えて加熱重合せしめて樹脂板
や成形材料などを製造するのに用いられ、一方、
熱可塑性重合体はそのまま成形材料として用いら
れるか、押出板などに加工して使用に供される。 The syrup produced by applying the method of the present invention is used to further add a polymerization initiator and heat polymerize it to produce resin plates, molding materials, etc.
Thermoplastic polymers can be used as they are as molding materials, or they can be processed into extruded plates and the like.
つぎに本発明を実施例によつて具体的に説明す
るが、本発明はこれらによつて限定されるもので
はない。なお、実施例中の％は重量％である。 EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. In addition, % in an example is weight %.
実施例 １
前段にダブルヘリカルリボン翼を設置した撹拌
槽型反応器、後段に撹拌軸を有し、該撹拌軸上に
軸と垂直方向に設置したピンが管壁に垂直に軸に
向つて設置した固定ピンと互いに拭い合うように
配置してなる管型反応器を配列してなる二段式連
続反応装置を使用してシロツプを製造し、出口に
接続した移送配管を介して加圧条件下にあるシロ
ツプ受槽に捕集した。槽型反応器の容積は0.5
で、槽型反応器と管型反応器の容積比は１：0.25
であり、移送配管としては内径６mm、長さ1.6m
の二重管を使用し、ジヤケツトには熱媒油を循環
した。Example 1 A stirred tank reactor with double helical ribbon blades installed in the front stage, a stirring shaft in the rear stage, and a pin installed on the stirring shaft in a direction perpendicular to the shaft and facing the axis perpendicular to the tube wall. Syrup is produced using a two-stage continuous reactor consisting of an array of tubular reactors arranged in such a way as to wipe each other with fixing pins, and the syrup is produced under pressurized conditions via a transfer pipe connected to the outlet. It was collected in a syrup tank. The volume of the tank reactor is 0.5
The volume ratio of the tank reactor and tube reactor is 1:0.25.
The transfer piping has an inner diameter of 6 mm and a length of 1.6 m.
A double pipe was used to circulate heat transfer oil through the jacket.
アゾビスイソブチロニトリル0.047％を含有す
るメチルメタクリレート単量体を槽型反応器にお
ける平均滞留時間147秒、両反応器の反応温度160
℃、圧力６気圧で連続塊状重合して得られるシロ
ツプの管型反応器出口における重合体含有率は
26.6％、25℃における粘度は21.0ポイズ、シロツ
プ中の重合体の数平均重合度は745であり、残留
開始剤濃度は0.01ppm以下であつた。移送配管の
ジヤケツトに220℃の熱媒油を循環し、シロツプ
受槽を窒素で加圧して該配管の内圧を６気圧に維
持して120時間連続運転を行なつた。該配管内の
シロツプの平均線速度は約720cm／分、シロツプ
の該配管出口での温度は180℃であり、該配管内
での重合体含有率および粘度の伸びは認められな
かつた。また全期間を通じて該配管内における圧
力損失は実質的に０であり、最終シロツプの性状
も実質的に一定で、分解、着色は全く認められな
かつた。 The average residence time of methyl methacrylate monomer containing 0.047% azobisisobutyronitrile in a tank reactor was 147 s, and the reaction temperature of both reactors was 160 s.
The polymer content at the outlet of the tubular reactor of the syrup obtained by continuous bulk polymerization at ℃ and 6 atm pressure is
26.6%, the viscosity at 25°C was 21.0 poise, the number average degree of polymerization of the polymer in the syrup was 745, and the residual initiator concentration was 0.01 ppm or less. Thermal oil at 220°C was circulated through the jacket of the transfer pipe, and the syrup receiving tank was pressurized with nitrogen to maintain the internal pressure of the pipe at 6 atmospheres, and continuous operation was performed for 120 hours. The average linear velocity of the syrup in the pipe was about 720 cm/min, the temperature of the syrup at the outlet of the pipe was 180°C, and no increase in polymer content or viscosity was observed in the pipe. Further, the pressure loss in the pipe was substantially zero throughout the entire period, and the properties of the final syrup were also substantially constant, with no decomposition or coloration observed.
また、連続運転を停止した後、移送配管を開放
点検したところ、内壁面および反応器との接続部
への重合体の付着は全く認められなかつた。 Further, after stopping the continuous operation, the transfer piping was opened and inspected, and no polymer was observed to adhere to the inner wall surface or the connection to the reactor.
比較例 １
移送配管のジヤケツトに循環する熱媒油の温度
を180℃としたほかは実施例１と同一の装置およ
び反応条件で重合および移送を行なつた。反応開
始８時間後に該配管内の圧力損失が１気圧を超え
なお急激に増大する傾向を認めたため運転を停止
して該配管内を開放点検したところ、管内の入口
から1/3付近を中心に内壁に環状に重合体が付着
し、閉塞寸前の状態であつた。Comparative Example 1 Polymerization and transfer were carried out using the same equipment and reaction conditions as in Example 1, except that the temperature of the heat transfer oil circulating in the jacket of the transfer pipe was 180°C. Eight hours after the start of the reaction, we observed a tendency for the pressure loss in the pipe to exceed 1 atm and to increase rapidly.We stopped the operation and opened and inspected the pipe.We found that the pressure loss in the pipe exceeded 1 atm, and when we opened and inspected the pipe, we found that the pressure loss in the pipe was around 1/3 from the inlet. Polymer was attached to the inner wall in a ring shape, and it was on the verge of being blocked.
比較例 ２
移送配管のジヤケツトに循環する熱媒油の温度
を360℃、該配管内の圧力を12気圧としたほかは
実施例１と同一の装置および反応条件で重合およ
び移送を行なつたところ、該配管出口でのシロツ
プ温度は約280℃であつた。最終シロツプの重合
転化率は27.3％、25℃における粘度は15.5ポイ
ズ、数平均重合度は670であり、ゲル浸透クロマ
トグラフイーにより重合度分布を測定したとこ
ろ、分解に基づく重合度100前後の低重合度重合
体の生成が認められた。また最終シロツプは淡褐
色に着色していた。この条件で60時間連続運転し
た後、移送配管を開放点検したところ、内壁面へ
の重合体の付着は認められなかつた。Comparative Example 2 Polymerization and transfer were carried out using the same equipment and reaction conditions as in Example 1, except that the temperature of the thermal oil circulating in the jacket of the transfer pipe was 360°C and the pressure inside the pipe was 12 atm. The syrup temperature at the outlet of the pipe was approximately 280°C. The polymerization conversion rate of the final syrup was 27.3%, the viscosity at 25°C was 15.5 poise, and the number average degree of polymerization was 670. When the polymerization degree distribution was measured by gel permeation chromatography, it was found that the degree of polymerization due to decomposition was around 100. Formation of polymerization degree polymer was observed. The final syrup was colored light brown. After continuous operation for 60 hours under these conditions, the transfer piping was opened and inspected, and no polymer was found to have adhered to the inner wall surface.
実施例 ２
メチルメタクリレート70％、α−メチルスチレ
ン30％からなる単量体混合物を塊状重合して得た
重合体含有率が32％で、160℃、６気圧の条件下
にある重合体成物を、ジヤケツトに200℃の熱媒
油を循環させた内径６mm、長さ1.6mの二重管式
の移送配管に導びいて平均線速度180cm／分でシ
ロツプ受槽に移送した。120時間連続運転した後、
移送配管を開放点検したところ、内壁面への重合
体の付着は全く認められなかつた。Example 2 A polymer composition with a polymer content of 32% obtained by bulk polymerizing a monomer mixture consisting of 70% methyl methacrylate and 30% α-methylstyrene under conditions of 160°C and 6 atm. was introduced into a double-pipe transfer pipe with an inner diameter of 6 mm and a length of 1.6 m, which circulated thermal oil at 200°C through a jacket, and was transferred to a syrup receiving tank at an average linear velocity of 180 cm/min. After 120 hours of continuous operation,
When the transfer piping was opened and inspected, no polymer was observed to adhere to the inner wall surface.
実施例 ３
撹拌槽型反応器と特開昭57−42308号公報実施
例１に記載の回転円盤脱揮押出機との間を、内径
13mm、長さ2mの二重管式の移送配管で接続して
なる反応装置を使用した。該配管のジヤケツトに
220℃の熱媒油を循環して加熱し、連続塊状重合
法によつて調製したスチレン重合体65％、スチレ
ン単量体35％からなる160℃、15気圧の条件下に
ある重合体組成物を４Kg／時の割合で移送して前
記脱揮押出機に供給し、該脱揮押出機の中心部よ
り重合体を取り出すと共に外周方向より単量体を
回収した。該配管は脱揮に必要な加熱機の役目も
兼ねさせることができ、該組成物は該配管出口で
200℃まで昇温した。脱揮押出機の回転数
300rpm、内圧260Torr、ジヤケツト熱媒温度220
℃の条件で120時間連続運転した後、開放点検し
たところ、移送配管の内壁面のほか、重合反応
器、脱揮押出機のいずれにも重合体の付着は全く
認められかつた。Example 3 The inner diameter was
A reactor was used, which was connected by a double-pipe transfer pipe measuring 13 mm and 2 m in length. on the jacket of the piping
A polymer composition prepared by continuous bulk polymerization by circulating heat transfer oil at 220°C and containing 65% styrene polymer and 35% styrene monomer under conditions of 160°C and 15 atm. was transferred at a rate of 4 kg/hour and supplied to the devolatilizing extruder, the polymer was taken out from the center of the devolatilizing extruder, and the monomer was recovered from the outer circumferential direction. The piping can also serve as a heater necessary for devolatilization, and the composition is heated at the outlet of the piping.
The temperature was raised to 200℃. Revolution speed of devolatilizing extruder
300rpm, internal pressure 260Torr, jacket heat medium temperature 220
After 120 hours of continuous operation at ℃, an open inspection revealed that no polymer was observed at all on the inner wall of the transfer pipe, the polymerization reactor, or the devolatilizing extruder.
Claims (1)
リレート、スチレン、α−メチルスチレンおよび
ｐ−メチルスチレンから選ばれた１種または２種
以上を少なくとも60重量％含有してなる単量体
100〜80重量％とゴム状重合体０〜20重量％から
なる原料液を部分重合してなる重合転化率が３〜
80重量％の単量体−重合体混合物である重合性液
状組成物を後続する処理工程へ移送するに当り、
移送区域の内壁面を150〜290℃であり、かつ、該
組成物の温度より低くない温度に加熱し、かつ、
該移送区域内の組成物を１〜20気圧の圧力条件下
に維持して実質的に液相状態で通過させることを
特徴とする高温の重合性液状組成物の移送方法。 ２ 移送区域内の組成物の流れが実質的に押出流
れである特許請求の範囲第１項に記載の方法。 ３ 移送区域がＬ／Ｄが３以上の管状路であり、
かつ、該区域内の組成物の平均線速度が10cm／分
以上である特許請求の範囲第１項に記載の方法。[Claims] 1 Contains at least 60% by weight of one or more selected from methyl methacrylate, styrene, α-methylstyrene and p-methylstyrene under a temperature condition of 70 to 250°C. monomer
Partially polymerized raw material liquid consisting of 100 to 80% by weight and 0 to 20% by weight of rubbery polymer, with a polymerization conversion rate of 3 to 3.
In transferring the polymerizable liquid composition, which is an 80% by weight monomer-polymer mixture, to a subsequent processing step,
heating the inner wall surface of the transfer zone to a temperature of 150 to 290 °C and no lower than the temperature of the composition, and
A method for transferring a high temperature polymerizable liquid composition, characterized in that the composition in the transfer zone is maintained under a pressure condition of 1 to 20 atmospheres and is passed in a substantially liquid phase. 2. The method of claim 1, wherein the flow of composition in the transfer zone is substantially an extrusion flow. 3. The transfer area is a tubular path with L/D of 3 or more,
The method according to claim 1, wherein the average linear velocity of the composition in the area is 10 cm/min or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8715283A JPS59210910A (en) | 1983-05-17 | 1983-05-17 | Transfer of high-temperature polymerizable liquid composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8715283A JPS59210910A (en) | 1983-05-17 | 1983-05-17 | Transfer of high-temperature polymerizable liquid composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59210910A JPS59210910A (en) | 1984-11-29 |
| JPH0448802B2 true JPH0448802B2 (en) | 1992-08-07 |
Family
ID=13907004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8715283A Granted JPS59210910A (en) | 1983-05-17 | 1983-05-17 | Transfer of high-temperature polymerizable liquid composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59210910A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1642638A1 (en) | 2004-10-04 | 2006-04-05 | Sumitomo Chemical Company, Limited | Apparatus for continuous polymerization and method for continuous polymerizing using the same |
| EP1655309A1 (en) | 2004-11-09 | 2006-05-10 | Sumitomo Chemical Company, Limited | Process for stopping continuous polymerization |
| EP2450101A1 (en) | 2010-11-08 | 2012-05-09 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| EP2481477A1 (en) | 2011-01-26 | 2012-08-01 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| EP2481476A1 (en) | 2011-01-26 | 2012-08-01 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| WO2013073595A1 (en) | 2011-11-18 | 2013-05-23 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| WO2014007271A1 (en) | 2012-07-05 | 2014-01-09 | Sumitomo Chemical Company, Limited | Process for producing methacrylic polymer composition |
| WO2014088082A1 (en) | 2012-12-03 | 2014-06-12 | 住友化学株式会社 | Method for producing methacrylic polymer composition, and molded article |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017163158A1 (en) | 2016-03-21 | 2017-09-28 | Sabic Global Technologies B.V. | Method for processing an oligomerization product stream |
| WO2021117903A1 (en) * | 2019-12-12 | 2021-06-17 | 株式会社クラレ | Methacrylic copolymer and manufacturing method suitable for manufacturing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS492335A (en) * | 1972-04-22 | 1974-01-10 | ||
| JPS49114689A (en) * | 1973-03-07 | 1974-11-01 | ||
| JPS51105384A (en) * | 1975-02-13 | 1976-09-17 | Solvay | |
| JPS5454188A (en) * | 1977-10-06 | 1979-04-28 | Sumitomo Chem Co Ltd | Continuous preparation of methyl methacrylate syrup |
-
1983
- 1983-05-17 JP JP8715283A patent/JPS59210910A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS492335A (en) * | 1972-04-22 | 1974-01-10 | ||
| JPS49114689A (en) * | 1973-03-07 | 1974-11-01 | ||
| JPS51105384A (en) * | 1975-02-13 | 1976-09-17 | Solvay | |
| JPS5454188A (en) * | 1977-10-06 | 1979-04-28 | Sumitomo Chem Co Ltd | Continuous preparation of methyl methacrylate syrup |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1642638A1 (en) | 2004-10-04 | 2006-04-05 | Sumitomo Chemical Company, Limited | Apparatus for continuous polymerization and method for continuous polymerizing using the same |
| EP1655309A1 (en) | 2004-11-09 | 2006-05-10 | Sumitomo Chemical Company, Limited | Process for stopping continuous polymerization |
| EP2450101A1 (en) | 2010-11-08 | 2012-05-09 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| EP2481477A1 (en) | 2011-01-26 | 2012-08-01 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| EP2481476A1 (en) | 2011-01-26 | 2012-08-01 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| WO2013073595A1 (en) | 2011-11-18 | 2013-05-23 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| US9266975B2 (en) | 2011-11-18 | 2016-02-23 | Sumitomo Chemical Company, Limited | Continuous polymerization apparatus and process for producing polymer composition |
| WO2014007271A1 (en) | 2012-07-05 | 2014-01-09 | Sumitomo Chemical Company, Limited | Process for producing methacrylic polymer composition |
| WO2014088082A1 (en) | 2012-12-03 | 2014-06-12 | 住友化学株式会社 | Method for producing methacrylic polymer composition, and molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59210910A (en) | 1984-11-29 |
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