JPH04146903A - Production of sheetlike polymer - Google Patents
Production of sheetlike polymerInfo
- Publication number
- JPH04146903A JPH04146903A JP27122690A JP27122690A JPH04146903A JP H04146903 A JPH04146903 A JP H04146903A JP 27122690 A JP27122690 A JP 27122690A JP 27122690 A JP27122690 A JP 27122690A JP H04146903 A JPH04146903 A JP H04146903A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- polymer
- polymerization reaction
- reaction product
- product
- 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 52
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 33
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000002954 polymerization reaction product Substances 0.000 claims description 40
- 238000007872 degassing Methods 0.000 claims description 17
- 238000007493 shaping process Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract 8
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000003068 static effect Effects 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- -1 MEC propyl 1-nolate Chemical compound 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NFPBWZOKGZKYRE-UHFFFAOYSA-N 2-propan-2-ylperoxypropane Chemical group CC(C)OOC(C)C NFPBWZOKGZKYRE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- KXVOHRRVZLJSCW-UHFFFAOYSA-N COC(C(=C)C)=O.[N] Chemical compound COC(C(=C)C)=O.[N] KXVOHRRVZLJSCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-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
- 229920000297 Rayon Polymers 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 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
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 239000006187 pill Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- JJQPJEWSKYMIDU-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC(C)(C)C JJQPJEWSKYMIDU-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、メタクリル酸メチルを主成分とする板状重合
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 a plate-shaped polymer containing methyl methacrylate as a main component.
［従来の技術〕
板状重合物を製造する方法としては、上下に相対するよ
うに配置された回転ベルトおよびその両側辺部でベルト
間に挾まれたシール材とで形成される空間部に、ビニル
単量体またはこれらの重合体を含有するシロップを封入
し、ベルトを移行させながら重合を進める方法が、特公
昭４６−４１６０２号公報、同４７−３４８１５号公報
、同５２−３０９８５号公報等で知られている。[Prior Art] As a method for producing a plate-like polymer, in a space formed by rotating belts arranged vertically facing each other and a sealing material sandwiched between the belts on both sides thereof, A method of enclosing a syrup containing vinyl monomers or these polymers and proceeding with polymerization while moving a belt is disclosed in Japanese Patent Publication No. 46-41602, Japanese Patent Publication No. 47-34815, Japanese Patent Publication No. 52-30985, etc. It is known for.
［発明が解決しようとする課題］
しかしながら、これらの方法は、ベルト重合装置が大が
かりとなり高価であるために、製造コスト的に不利とな
る欠点を有していた。また、得られる板状重合物の厚み
は、２個の回転ベルトの間隔で制御することになるが、
このベルトの間隔の制御が困難であるため、板状重合物
の厚み精度に劣るという問題もあった。[Problems to be Solved by the Invention] However, these methods have disadvantages in terms of manufacturing costs because the belt polymerization apparatus is large-scale and expensive. In addition, the thickness of the obtained plate-shaped polymer is controlled by the interval between the two rotating belts,
Since it is difficult to control the interval between the belts, there is also the problem that the thickness accuracy of the plate-shaped polymer is poor.
一方、単量体を実質的に含有しない重合体をタイスより
溶融押し出して板状重合物を製造する方法も知られてい
る。この方法は、装置が比較的安価であるという点では
有利であるが、重合体をダイスより押し出して板状に賦
型するときに内部歪が発生するために、後で加熱加工す
る場合に板状重合物の縦方向や横方向の熱収縮率が大幅
に異なるという欠点を有している。更には、押出賦型の
加工をする上で、重合体の高分子量化か難しく、その結
果、機械特性や耐溶剤性等の品質特性に劣るものとなる
。On the other hand, a method is also known in which a polymer plate containing substantially no monomer is melt-extruded from a Tice to produce a plate-like polymer. This method is advantageous in that the equipment is relatively inexpensive, but internal strain occurs when extruding the polymer from a die and forming it into a plate shape, so when heat-processing is performed later, the The disadvantage is that the heat shrinkage rates of the polymer in the longitudinal and transverse directions are significantly different. Furthermore, it is difficult to increase the molecular weight of the polymer during extrusion mold processing, resulting in poor quality properties such as mechanical properties and solvent resistance.
［課題を解決するための手段］
そこで、本発明者らは上記の問題点に鑑み、安価な装置
で、経済的に有利な製造方法を提供するへく鋭意検討し
た結果、本発明を完成するに到りた。[Means for Solving the Problems] Therefore, in view of the above-mentioned problems, the present inventors have completed the present invention as a result of intensive studies to provide an economically advantageous manufacturing method using inexpensive equipment. It arrived.
即ち、本発明は下記（１）〜（５）までの工程からなり
、かつ（４）以降の工程を連続的に行うことを特徴とす
る板状重合物の製造方法である。That is, the present invention is a method for producing a plate-shaped polymer, which comprises the following steps (1) to (5), and is characterized in that steps (4) and subsequent steps are performed continuously.
（１）メタクリル酸メチル単独またはメタクリル酸メチ
ルを主成分とする単量体混合物および重合助剤を重合反
応域に供給し、単量体の２０〜５０重１％を重合体に転
化する
（２）減圧下に前記重合反応物から未反応単量体を脱気
して、その重合体含有率を多くとも６５％まで高めると
ともに、重合反応物の温度を５０℃以下とする
（３）前記の脱気された重合反応物に重合開始側照ひに
必要に応じて他の添加剤を加えて混合する（４）前記（
３）の重合反応物をダイスより押し出して板状に賦型す
る
（５）前記の板状に賦型された重合反応物を６０−１０
０℃の温水浴中で実質的に重合を完結させる本発明の方
法で用いられる単量体は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成分とする単量体混合物である
。単量体混合物の場合メタクリル酸メチルはｅ、ｏ−Ｍ
里％以上であることが好ましい。メタクリル酸メチルと
ともに使用される単量体としてはメタクリル酸メチル、
メック１ノル酸プロピル、メタクリル酸メチル、メタク
リル酸／クロヘキ、／ル、メタクリル酸−２−エチルへ
牛／ル、メック１ノル酸ベンンル等のメタクリル酸エス
テル、アクリル酸メチル、アクリル酸エチル、アクリル
酸ブチル、アクリル酸シクロヘキンル
アクリル酸−２−エチルヘキンル、アクｌ）ル酸ヘンシ
ル等のアクリル酸エステル、スチレン、α−メテルスチ
レン等が挙げられる。(1) Methyl methacrylate alone or a monomer mixture containing methyl methacrylate as a main component and a polymerization aid are supplied to the polymerization reaction zone, and 20 to 50% by weight of the monomers are converted into a polymer (2 ) Degassing unreacted monomers from the polymerization reaction product under reduced pressure to increase the polymer content to at most 65%, and lowering the temperature of the polymerization reaction product to 50°C or less. (3) The above-mentioned Add other additives to the degassed polymerization reaction product as needed on the polymerization initiation side and mix (4)
3) Extrude the polymerization reaction product from a die and shape it into a plate shape.
The monomer used in the method of the present invention, in which the polymerization is substantially completed in a hot water bath at 0°C, is methyl methacrylate alone or a monomer mixture containing methyl methacrylate as a main component. In the case of a monomer mixture, methyl methacrylate is e, o-M
It is preferable that it is more than 1%. Monomers used with methyl methacrylate include methyl methacrylate,
Methacrylic acid esters such as MEC propyl 1-nolate, methyl methacrylate, methacrylic acid/chlorohexyl, 2-ethyl methacrylate, MEC 1-norate benyl, methyl acrylate, ethyl acrylate, acrylic acid Examples include acrylic acid esters such as butyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, and hensyl acrylate, styrene, α-methelstyrene, and the like.
上記の単量体の重合助剤としては、ラジカル重合開始剤
、例えばジ−イソプロピルバーオキ／シカ−ボネート、
ｔｅｒｔ−ブチルネオデカノエート、ｔｅｒｔ−プチル
バーオキンビパレート、ラウロイルパーオキづイド、ベ
ンゾイルパーオキサイド、ｔｅｒｔ−プチルバーオキン
イソブ口ビルカーボ不一ト、ｔｅｒｔ−ブチルパーオキ
シベンゾエート、ジクミルパーオキサイド、ジーｔｅｒ
ｔ−ブチルパーオキサイド等の有機過酸化物、２．２−
一アゾビス（２４−ジメチルバレロニトリル）、２．２
−−アゾビスイソブチロニトリル、１−１−アゾビス（
１／クロへ牛サンカルボニトリル）、２．２−−アゾビ
ス（２４４−トリメチルペンタン）等のアゾ化合物が挙
げられる。Examples of polymerization aids for the above monomers include radical polymerization initiators, such as di-isopropyl peroxy/carbonate,
tert-butyl neodecanoate, tert-butyl peroxybenzoate, lauroyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, dicumyl peroxide oxide, jeter
Organic peroxides such as t-butyl peroxide, 2.2-
monoazobis(24-dimethylvaleronitrile), 2.2
--Azobisisobutyronitrile, 1-1-azobis(
Examples include azo compounds such as 2,2-azobis(244-trimethylpentane) and 2,2-azobis(244-trimethylpentane).
この他に必要に応じて分子量調節剤を使用することかで
きる。具体的にはアルキル基または置換アルキル基を有
する第１級、第２級、第３級メルカプタン、たとえばｎ
−ブチノじメルカプタン、１ｓｏ−ブチルメルカプタン
、ｎ−オクチルメルカフタノ、ｎ−ドテンルメル力ブタ
ン、５ｅＣ−ブチルメルカプタン、５ｅｃ−ドデ／ルメ
ルカブタン、ｔｅｒｔブチルメルカプタンが挙げられる
。In addition to this, a molecular weight regulator may be used if necessary. Specifically, primary, secondary, and tertiary mercaptans having an alkyl group or a substituted alkyl group, such as n
-butynodimercaptan, 1so-butylmercaptan, n-octylmercaptano, n-dotenelumercaptan, 5eC-butylmercaptan, 5ec-dode/lumercaptan, and tertbutylmercaptan.
更に必要に応じて各種の添加剤、例えば酸化安定剤、可
塑剤、染料、顔料、剥離剤等を添加してもよい。Furthermore, various additives such as oxidation stabilizers, plasticizers, dyes, pigments, release agents, etc. may be added as necessary.
重合開始剤の使用量に特に制限はなく、重合温度や目的
とする重合体転化率によって適宜決定されるが、通常単
量体混合物に対して０．０１〜０５重量％である。The amount of the polymerization initiator to be used is not particularly limited and is appropriately determined depending on the polymerization temperature and the desired polymer conversion rate, but is usually 0.01 to 05% by weight based on the monomer mixture.
本発明の製造方法は、まず（１）の工程で前記重合助剤
を含む単量体または単量体混合物を重合反応域に供給し
て重合せしめる。重合反応は撹拌槽型反応器、パイプ状
反応器等の通常使用される反応器によって達成されるが
、反応液の停滞をなくすことが好ましい。重合反応温度
は６０〜１８０ ’Ｃ好ましくは７０−１７０’Ｃであ
る。この重合反応域で単量体の２０〜５０Ｍｆｉ％、好
ましくは２５〜４５重量％を重合体に転化する。重合体
転化率が２０重量％未満では、次に行う（２）の工程て
Ｍ呑体含有璽を高める操作か困難となる。一方、重合体
転化率かｓｏ：！回％を超えると、（２）の工程で１ｊ
われる、減圧下に重合反応物から未反応単量体を脱気し
てその蒸発潜熱により重合反応物の温度を５０’Ｃ以下
とすると同時にその重合体含有率を多くとも６５重里％
まで高めるという操作が困難となる。In the production method of the present invention, first, in step (1), a monomer or a monomer mixture containing the polymerization aid is supplied to a polymerization reaction zone and polymerized. The polymerization reaction is achieved in a commonly used reactor such as a stirred tank reactor or a pipe reactor, but it is preferable to eliminate stagnation of the reaction solution. The polymerization reaction temperature is 60-180'C, preferably 70-170'C. In this polymerization reaction zone, 20-50 Mfi% of monomer is converted to polymer, preferably 25-45% by weight. If the polymer conversion rate is less than 20% by weight, it becomes difficult to perform the next step (2) to increase the M-containing plate. On the other hand, the polymer conversion rate is so:! If it exceeds 1j% in step (2),
At the same time, the temperature of the polymerization reaction product is reduced to 50'C or less by degassing unreacted monomers from the polymerization reaction product under reduced pressure and using the latent heat of vaporization, and at the same time, the polymer content is reduced to at most 65%.
It becomes difficult to raise the temperature to a certain level.
次に（２）の工程では、重合反応終了後の重合反応物か
ら、減圧下に未反応単量体を脱気してその４合体含有量
を多くとも６５重量％まで高めるとともにその温度を５
０ ’Ｃ以下とする。未反応単ｍ体を脱気する方法とし
ては、重合反応物を必要ならば加熱昇温して減圧雰囲気
に導入し、未反応単量体を所定量、瞬時的に蒸発脱気す
る。これによって重合反応物の重合体含有率を多くとも
６５重１％才で高めると同時に単量体が蒸発する際の蒸
発潜熱により重合反応物の温度を５０″Ｃ以下とする。Next, in the step (2), unreacted monomers are degassed from the polymerization reaction product after the polymerization reaction is completed under reduced pressure to increase the content of the 4-mers to at most 65% by weight, and the temperature is increased to 5%.
0'C or less. As a method for degassing unreacted monomers, the polymerization reaction product is heated to an elevated temperature if necessary and introduced into a reduced pressure atmosphere, and a predetermined amount of unreacted monomers are instantaneously evaporated and degassed. This increases the polymer content of the polymerization reaction product by at most 65 wt.
脱気後の重合反応物の重合体含有率は減圧雰囲気に真空
度および脱気前の重合体転化率によって決定される。ま
た、脱気後の重合反応物の温度は減圧雰囲気の真空度お
よび脱気前の重合反応物の温度によって決定される。脱
気後の重合反応物の重合体含有率が６５重量％を超える
と、次に（３）の工程で重合開始剤等を混合する場合、
均一な混合が困難となる。The polymer content of the polymerization reaction product after degassing is determined by the degree of vacuum in the reduced pressure atmosphere and the polymer conversion rate before degassing. Further, the temperature of the polymerization reaction product after degassing is determined by the degree of vacuum of the reduced pressure atmosphere and the temperature of the polymerization reaction product before degassing. If the polymer content of the polymerization reaction product after degassing exceeds 65% by weight, when mixing a polymerization initiator etc. in the next step (3),
Uniform mixing becomes difficult.
また、脱気後の重合反応物の温度が５０ ’Ｃを超える
と重合開始剤を添加後、ダイスより押し出されるまでに
重合反応が進行し、重合反応物移送系が閉塞する場合が
ある。Furthermore, if the temperature of the polymerization reaction product after degassing exceeds 50'C, the polymerization reaction will proceed after the addition of the polymerization initiator until it is extruded from the die, and the polymerization reaction product transfer system may become clogged.
また、ダイスより重合反応物を均一な厚みに押し出して
板状に賦型するためには、脱気後の重合反応物の重合体
含有率は少なくとも４０重↑％であることが好ましい。Further, in order to extrude the polymerization reaction product from a die to a uniform thickness and shaping it into a plate shape, it is preferable that the polymer content of the polymerization reaction product after degassing is at least 40% by weight.
未反応単量体を脱気する装置例としてはキャヂンブ等の
取り出し装置を備えたヂホラタイザーまたは脱気用ベン
ト付きスクリュー押出機等がある。Examples of devices for degassing unreacted monomers include a diholatizer equipped with a removal device such as a cavern, a screw extruder equipped with a degassing vent, and the like.
次に（３〉の工程では、上記の脱気された重合反応物に
重合開始剤並びに必要に応じて他の添加剤を加えて混合
する。ここで使用する重合開始剤並びに添加剤は、前記
のラジカル重合開始剤、酸化安定剤、可Ｖ剤、染料、顔
料、剥離剤等である。これらの重合開始剤等は、少量の
単量体または重合体を低含有率で含む７０ノブに混合し
て添加することが好ましい。重合反応物と重合開始剤等
の混合はスタティックミキサー インラインミキサー等
を利用することができる。未反応単量体の脱気にベント
付きスクリュー押出機を使用する場合は先端部に重合開
始剤を添加してスクリューにより混合する。Next, in step (3), a polymerization initiator and other additives are added and mixed as necessary to the degassed polymerization reaction product.The polymerization initiator and additives used here are the same as those described above. radical polymerization initiators, oxidation stabilizers, UV stabilizers, dyes, pigments, release agents, etc.These polymerization initiators are mixed into 70 knobs containing a small amount of monomer or polymer at a low content. It is preferable to add the polymerization reactant and the polymerization initiator etc. using a static mixer, in-line mixer, etc. When using a vented screw extruder for degassing unreacted monomers, A polymerization initiator is added to the tip and mixed using a screw.
重合開始剤等を添加混合した重合反応物は（４）の工程
により、ダイスより押し出して板状に賦型する。ダイス
は重合反応物が移送中に重合が進行し固化するのを防止
するために５０℃以下に保持することが好ましい。In step (4), the polymerization reaction product to which a polymerization initiator and the like have been added and mixed is extruded from a die and shaped into a plate shape. The die is preferably maintained at a temperature of 50° C. or lower to prevent the polymerization reaction product from proceeding with polymerization and solidifying during transportation.
最後に、（５ンの工程では、板状ｌこ賦型した重合反応
物は６０〜１００″Ｃの温水浴中にて実質的に重合を完
結せしめる。実質的な重合の完結は少なくとも重合体含
有率が９ｏ％、好ましくは９７Ｍ＠％以上きすることに
より達成される。温水浴への板状重合反応物の浸漬時間
は温水浴の温度および含有する重合開始剤にもよるが、
通常３〜６０分である。温水浴は必要ならば複数個の温
度レベルの異なるものを使用することもできる゛。Finally, in the 5th step, the polymerization reaction product shaped into a plate is placed in a hot water bath at 60 to 100"C to substantially complete the polymerization. This is achieved by increasing the content to 90%, preferably 97M@% or more.The immersion time of the plate-shaped polymerization reactant in the hot water bath depends on the temperature of the hot water bath and the polymerization initiator contained.
Usually it takes 3 to 60 minutes. Hot water baths with different temperature levels can be used if necessary.
実質的に重合を完結した板状重合物は、残存する未反応
単量体を更に減少せしめるために、更に１１０〜１５０
℃に加熱してもよい。表面仕上げを必要とする場合は、
表面をクロムメツキ等で加工した複数の加熱ローラーに
接触せしめると同時にローラー間で挟んで厚みのより一
層の均一化を図る。In order to further reduce the remaining unreacted monomers, the plate-like polymer which has substantially completed polymerization is further treated with 110 to 150
It may be heated to ℃. If surface finishing is required,
It is brought into contact with a plurality of heating rollers whose surfaces are processed with chrome plating, etc., and at the same time is sandwiched between the rollers to further equalize the thickness.
なお、（４）から（５）の工程は、連続的に行われるこ
とが好ましい。Note that it is preferable that steps (4) to (5) are performed continuously.
以下本発明を第１図によって説明する。The present invention will be explained below with reference to FIG.
メタクリル酸メチルを主成分とする単量体混合物および
重合開始剤を含む重合助剤をポンプｌによって重合槽２
に供給する。重合槽２は熱媒ジャケットおよび重合原料
を実質的に均一に混合するための攪拌機３を有する。単
量体を所定量まで重合した後、ギヤポンプ４により重合
反応物を脱気器５へ送る。脱気器５は減圧雰囲気とする
ための真空ライン１８および脱気された重合反応物を移
送するためのギヤポンプ６を備えている。単量体を所定
量脱気した後、重合反応物をギヤポンプ６で混合器８へ
送る。重合開始剤および必要な添加剤はポンプ７によっ
て添加し、混合器８て重合反応物と混合する。混合器８
はスタティックミキサーを内蔵している。重合開始剤お
よび必要な添加剤を混合した重合反応物は、ダイス９よ
り押し出して所定厚みの板状に賦型した後、温水浴１１
．１２へ送る。温水浴１１．１２は板状重合物１０をガ
イドするためのローラー１３、温水を所定温度に維持す
るためのヒーター１６およびｍ 水ｍ 環ポンプ１５を
備えている。温水浴にて実質的に重合を完結した板状重
合物は引き取りニップローラー１７にて一定速度で引き
取る。A monomer mixture containing methyl methacrylate as a main component and a polymerization aid containing a polymerization initiator are pumped into polymerization tank 2 using a pump l.
supply to. The polymerization tank 2 has a heat medium jacket and a stirrer 3 for substantially uniformly mixing the polymerization raw materials. After the monomer has been polymerized to a predetermined amount, the polymerization reaction product is sent to a deaerator 5 by a gear pump 4. The deaerator 5 is equipped with a vacuum line 18 for creating a reduced pressure atmosphere and a gear pump 6 for transferring the degassed polymerization reaction product. After degassing a predetermined amount of monomer, the polymerization reaction product is sent to a mixer 8 by a gear pump 6. The polymerization initiator and necessary additives are added by pump 7 and mixed with the polymerization reactants in mixer 8. mixer 8
has a built-in static mixer. The polymerization reaction product mixed with a polymerization initiator and necessary additives is extruded from a die 9 and shaped into a plate of a predetermined thickness, and then heated in a hot water bath 11.
．． Send to 12. The hot water bath 11.12 is equipped with a roller 13 for guiding the plate-shaped polymer 10, a heater 16 for maintaining the hot water at a predetermined temperature, and a ring pump 15. The plate-like polymer material, which has substantially completed polymerization in the hot water bath, is taken off at a constant speed by a take-off nip roller 17.
［実施例］ 以下、実施例により本発明をさらに詳細に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
００６重量％のジーイソプロビルパーオキンジカーホ不
−トを余有するメタクリル酸メチルをｌＯＲ／ｈの速度
てポンプにより重合槽に供給し、重合槽の内液を充分に
均一に攪拌し、温度を１２０℃に維持して重合を行った
。重合槽内の重合反応物の重合体転化率は３４％であっ
た。この重合反応物をギヤポンプにより脱気器に送った
。脱気器内は−６９０ｍｍＨｇの減圧状態に維持した。Example 1 Methyl methacrylate containing 0.006% by weight of diisoprobyl peroxyene dicarbonate was supplied to a polymerization tank at a rate of 1OR/h, and the liquid in the polymerization tank was thoroughly and uniformly stirred. The polymerization was carried out while maintaining the temperature at 120°C. The polymer conversion rate of the polymerization reactant in the polymerization tank was 34%. This polymerization reaction product was sent to a deaerator by a gear pump. The inside of the deaerator was maintained at a reduced pressure of -690 mmHg.
脱気後の重合反応物の重合体含有率は５１％、温度は３
９℃てあった。The polymer content of the polymerization reaction product after degassing was 51%, and the temperature was 3.
It was 9 degrees Celsius.
脱気後、重合反応物を脱気器下部に設けたギヤポンプに
より取り出し、これに重合開始剤を含有するメタクリル
酸メチルのンロノブを０．７ Ｒ／ｈの速度で添加した
。メタクリル酸メチル／ロノフの重合体含有率は２２％
であり、これには／−イソブロピルバーオキンジカーホ
不−ト２重量％、ｔ−プチルパーオキンイソブチレート
２重量％の重合開始剤が含まれており、室温に維持した
。After degassing, the polymerization reaction product was taken out by a gear pump provided at the bottom of the deaerator, and methyl methacrylate nitrogen containing a polymerization initiator was added thereto at a rate of 0.7 R/h. Methyl methacrylate/Lonoff polymer content is 22%
It contained a polymerization initiator of 2% by weight of /-isopropyl peroquine dicarbonate and 2% by weight of t-butylperoquine isobutyrate and was maintained at room temperature.
メタクリル酸メチルシロップ添加後の重合反応物は、ス
タティックミキサーを内蔵した混合器を通した後、ダイ
スより幅５００ ｍｍ、厚み３ｍｍの板状に押し出し、
それぞれ７０℃および９５℃の温水浴を通した。それぞ
れの温水浴での浸漬時間は７分および１５分であった。The polymerization reaction product after addition of methyl methacrylate syrup was passed through a mixer equipped with a static mixer, and then extruded from a die into a plate shape with a width of 500 mm and a thickness of 3 mm.
Passed through hot water baths at 70°C and 95°C, respectively. Immersion times in each hot water bath were 7 and 15 minutes.
板状重合物は二ノフローラにて温水浴より引き取った。The plate-shaped polymer was taken out from the hot water bath at Ninoflora.
この板状重合物の重合体含有率は９８９％であり、板厚
３±０ 、１ ｍｍの厚み均一性に優れた外観良好なも
のであった。The polymer content of this plate-shaped polymer was 989%, and the plate thickness was 3±0 and 1 mm, with excellent thickness uniformity and good appearance.
実施例２
０．０９重！ｔ％のジーイソブロピルパーオキンジカー
ボ不一ト、０．０８重量％を含有するメタクリル酸メチ
ルを実施例】と同様にして重合した。重合槽内の重合反
応物の重合体転化率は４０％であった。この重合反応物
を実施例１と同様にして脱気器にて脱気し、重合体含有
率５９％、温度３３℃の重合反応物とし、以下実施例１
と同様にして板状重合物を得た。Example 2 0.09 weight! Methyl methacrylate containing 0.08% by weight of t% of diisopropylperoquine dicarbohydrate was polymerized in the same manner as in Example. The polymer conversion rate of the polymerization reaction product in the polymerization tank was 40%. This polymerization reaction product was degassed using a deaerator in the same manner as in Example 1 to obtain a polymerization reaction product with a polymer content of 59% and a temperature of 33°C.
A plate-shaped polymer was obtained in the same manner as above.
この板状重合物の重合体含有率は９８５％であり実施例
１と同様の厚み均一性に優れた外観良好なものであった
。The polymer content of this plate-shaped polymer was 985%, and the same as in Example 1, it had excellent thickness uniformity and good appearance.
実施例３
０．０５重重％の／−ローフロピルバーオキフジ力一才
不一トを含有するメタクリル酸メチルとアクリル酸メチ
ル（重量比９５５）の単量体混合物を実施例１と同様に
して重合した。重合槽内の重合反応物の重合体転化率は
２８％であった。Example 3 A monomer mixture of methyl methacrylate and methyl acrylate (weight ratio 955) containing 0.05% by weight of /-low-flow pill bar Okifuji was prepared in the same manner as in Example 1. and polymerized. The polymer conversion rate of the polymerization reactant in the polymerization tank was 28%.
この重合反応物を実施例１と同様にして脱気器にて脱気
し、重合体含有率４８％、温度３１’Ｃの重合反応物さ
し、以下実施例１と同様にして板状重合物とした。但し
、温水浴の温度はそれぞれ６５℃および８０℃とした。This polymerization reaction product was degassed using a deaerator in the same manner as in Example 1, and the polymerization reaction product with a polymer content of 48% and a temperature of 31'C was then subjected to plate-shaped polymerization in the same manner as in Example 1. It became a thing. However, the temperatures of the hot water baths were 65°C and 80°C, respectively.
この板状重合物を更に１２５℃の熱風中で３分間加熱し
た後、冷却したところ、重合体含有率９９６％であり、
実施例１と同様の厚み均一性に優れた外観良好なもので
あった０
［発明の効果コ
本発明の方法は、簡単かつ安価な装置でメタクリル酸メ
チル板状重合物を製造する経済的に極めて有利な方法を
提供するとともに、従来のメタクリル酸メチル板状重合
物の品質を改良するものであり、工業上優れた効果を奏
する。When this plate-shaped polymer was further heated in hot air at 125°C for 3 minutes and then cooled, the polymer content was 996%.
[Effects of the Invention] The method of the present invention is an economical method for producing methyl methacrylate platelet polymers using simple and inexpensive equipment. This method not only provides an extremely advantageous method, but also improves the quality of conventional methyl methacrylate plate polymers, and has excellent industrial effects.
第１図は、本発明の実施に使用される装置例であり、１
． ７． １５はポンプ、２は重合槽、３は攪拌機、４
，６はギヤポンプ、５は脱気器、８は混合器、９はダイ
ス、１０は板状重合物、１１゜１２は温水槽、１３．１
７はローラ、１４は温水循環ライン、１６はヒーター
１８は真空ラインを示す。
ＩＩ Ｃ０８Ｌ
３３：１２
幸町２０番１号
三菱レイヨン株式会社中央FIG. 1 shows an example of an apparatus used to carry out the present invention.
．． 7. 15 is a pump, 2 is a polymerization tank, 3 is a stirrer, 4
, 6 is a gear pump, 5 is a deaerator, 8 is a mixer, 9 is a die, 10 is a plate-shaped polymer, 11° 12 is a hot water tank, 13.1
7 is a roller, 14 is a hot water circulation line, 16 is a heater
18 indicates a vacuum line. II C08L 33:12 Saiwai-cho 20-1 Mitsubishi Rayon Co., Ltd. Chuo
Claims (1)
降の工程を連続的に行うことを特徴とする板状重合物の
製造方法。 （１）メタクリル酸メチル単独またはメタクリル酸メチ
ルを主成分とする単量体混合物および重合助剤を重合反
応域に供給し、単量体の２０〜５０重量％を重合体に転
化する （２）減圧下に前記重合反応物から未反応単量体を脱気
して、その重合体含有率を多くとも６５％まで高めると
ともに、重合反応物の温度を５０℃以下とする （３）前記の脱気された重合反応物に重合開始剤並びに
必要に応じて他の添加剤を加えて混合する （４）前記（３）の重合反応物をダイスより押し出して
板状に賦型する （５）前記の板状に賦型された重合反応物を６０〜１０
０℃の温水浴中で実質的に重合を完結させる[Scope of Claims] A method for producing a plate-like polymer comprising the following steps (1) to (5), and characterized in that steps (4) and subsequent steps are performed continuously. (1) Methyl methacrylate alone or a monomer mixture containing methyl methacrylate as a main component and a polymerization aid are supplied to the polymerization reaction zone, and 20 to 50% by weight of the monomers are converted into a polymer (2) (3) Degassing the unreacted monomer from the polymerization reaction product under reduced pressure to increase the polymer content to at most 65%, and lowering the temperature of the polymerization reaction product to 50°C or less. Adding and mixing a polymerization initiator and other additives as necessary to the vaporized polymerization reaction product (4) Extruding the polymerization reaction product from (3) above through a die and shaping it into a plate shape (5) Forming the above polymerization reaction product into a plate shape The polymerization reaction product shaped into a plate shape of 60 to 10
Substantially complete the polymerization in a 0°C hot water bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27122690A JPH04146903A (en) | 1990-10-09 | 1990-10-09 | Production of sheetlike polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27122690A JPH04146903A (en) | 1990-10-09 | 1990-10-09 | Production of sheetlike polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04146903A true JPH04146903A (en) | 1992-05-20 |
Family
ID=17497109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27122690A Pending JPH04146903A (en) | 1990-10-09 | 1990-10-09 | Production of sheetlike polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04146903A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5530080A (en) * | 1993-12-01 | 1996-06-25 | Roehm Gmbh Chemische Fabrik | Polymethacrylate molding compound with high heat deflection temperature and stability against thermal degradation |
| CN108690154A (en) * | 2017-04-10 | 2018-10-23 | 江俊慧 | Acrylic plate manufacturing method and its use fixture |
-
1990
- 1990-10-09 JP JP27122690A patent/JPH04146903A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5530080A (en) * | 1993-12-01 | 1996-06-25 | Roehm Gmbh Chemische Fabrik | Polymethacrylate molding compound with high heat deflection temperature and stability against thermal degradation |
| CN108690154A (en) * | 2017-04-10 | 2018-10-23 | 江俊慧 | Acrylic plate manufacturing method and its use fixture |
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