CN1856515B - 通过热聚合而由无残余引发剂的预聚物生产无色的、经透明或不透明着色的plexiglas*块料 - Google Patents

通过热聚合而由无残余引发剂的预聚物生产无色的、经透明或不透明着色的plexiglas*块料 Download PDF

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CN1856515B
CN1856515B CN2004800272886A CN200480027288A CN1856515B CN 1856515 B CN1856515 B CN 1856515B CN 2004800272886 A CN2004800272886 A CN 2004800272886A CN 200480027288 A CN200480027288 A CN 200480027288A CN 1856515 B CN1856515 B CN 1856515B
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slurry
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K·卡比斯
F·舍费尔
K-H·雅各布
B·克洛塞克
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

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Abstract

本发明公开一种生产厚度大于或等于200mm的聚甲基丙烯酸甲酯(PMMA)块料的方法。

Description

通过热聚合而由无残余引发剂的预聚物生产无色的、经透明或不透明着色的PLEXIGLAS块料
技术领域
本发明涉及一种新型的浇铸聚合方法，采用该方法可以生产厚度为最高至200mm或更厚的聚甲基丙烯酸酯块料。
技术背景
US专利1,942,531公开了在管式反应器中将氯乙烯或苯乙烯聚合的方法。聚合在约1％萜烯类物质的存在下进行。
DE 0 632 951(Dr.Otto
Figure G2004800272886D00012
)公开了一种在选自萜烯系的化合物(最高至约1％)的存在下将丙烯酸酯聚合以获得无气泡的产品的方法。采用该方法，通过在玻璃板之间使单体混合物聚合可以生产非碎裂性的玻璃。
Munzer等人(Angewandte Makromolekulare Chemie 11(1970)第27-40页)描述了具有两个非共轭双键的碳环六元环化合物对抑制Trommsdorff效应的影响。萜品油烯与MMA共聚并因此导致避免了Trommsdorff效应。
DE 29 41 959公开了一种通过首先生产预聚物，然后借助于阻聚剂(例如硫醚)破坏预聚物中的引发剂而将甲基丙烯酸甲酯进行自由基聚合的方法。借助于浆料，生产厚度最高至20mm的片材。
从制成的片材是已知的并且商购自
Figure G2004800272886D00014
GmbH & Co.KG。片材的厚度为1mm-20mm。
如果需要更厚的片材用于特定应用，例如鱼缸构造时，则这些较厚的片材必须通过将较薄的片材粘合来生产。这是并非不显著的成本。由于聚合方面的热问题，较厚的片材仅可很难地生产。热量散出要求长的聚合时间。
但是，即使生产具有迄今为止商业上常用的厚度的由
Figure G2004800272886D00021
构成的片材也有多个缺点。在水浴和空气聚合箱的组合内的热聚合是复杂的。必需的反应时间极长。在100mm厚块料的情况下，需要在27℃下30天。
目的
因此，本发明的目的是开发一种聚合方法并寻找配方，该配方允许通过经济的方法生产具有厚度为30-约500mm的由
Figure G2004800272886D00022
构成的块料。块料的长度和宽度为约6000mm(长度)和约3000mm(宽度)。
解决方案
现在已发现，在热聚合方法中，通过使用具有以下组成的由部分聚合的甲基丙烯酸甲酯组成的无残余引发剂的浆料，可以迄今未知的品质、产率和聚合时间生产厚的块料(厚的块料是厚度大于29mm的块料)：
a)10-40质量％的甲基丙烯酸甲酯
b)0.0-1.0质量％的交联剂
c)0.001-0.1质量％的可与化合物a)-b)共聚的另外的化合物(碳环化合物)
d)0.01-1质量％的常规脱模剂
e)90-60质量％的浆料
f)作为浆料生产用引发剂的过氧化二碳酸酯。
有用的交联剂包括以下化合物：二醇二甲基丙烯酸酯、甲基丙烯酸烯丙酯、TAC(氰脲酸三烯丙酯)。
有用的可共聚化合物包括萜烯和二聚的α-甲基苯乙烯。
所使用的浆料必须无引发剂。无引发剂是指在达到所需要的聚合度后以热方式(＞90℃)破坏用于生产浆料的引发剂，以便它们不再能够引发聚合。
所使用的引发剂是过氧化二碳酸酯，优选过氧化二碳酸双(4-叔丁基环己基)酯。
预聚的浆料由溶解在单体中的MMA聚合物组成，并且对其粘度进行调节，以便可在常规装置中对其进行操作，例如调节至1200mPa·s-50mPa·S。
本发明的混合物还包含调节聚合用的具有至少一个双键的碳环化合物，例如萜烯，例如γ-萜品烯，或二聚苯乙烯化合物，例如二聚α-甲基苯乙烯。基于聚合反应批料的总量，具有至少一个双键的碳环化合物的数量为50ppm-300ppm，优选80ppm-250ppm，且非常特别优选100ppm-200ppm。所谓“无残余引发剂”是指用于浆料聚合的引发剂的量低于0.001％。对于厚度为30mm的片材而言，碳环化合物的数量为约100ppm；对于厚度为100mm的片材而言，碳环化合物的数量为140ppm；且对于厚度为200mm的片材而言，碳环化合物的数量为250ppm。
残余引发剂的残余量确定为＜5ppm。术语“无残余引发剂”涉及用于聚合反应的引发剂。在聚合方面，副反应中形成甲基丙烯酸甲酯过氧化物(MMA-过氧化物)。所述MMA-过氧化物在高温下分解(半衰期＞100℃)并且不干扰随后在约25℃-40℃下的聚合。
实施例
通过进料聚合生产无残余引发剂的浆料
每批料需要760升的MMA。为了聚合，加入0.08％的过氧化二碳酸酯，优选过氧化二碳酸双(4-叔丁基环己基)酯。在良好的充分混合后，预先将一半溶液进料至蒸煮容器内。第二半保留在进料容器内。在自动操作中开始蒸煮过程。在此将溶液加热至73℃。加热阶段结束之后，温度升高至86℃。在此温度下自动开始以18-30l/min从进料容器将第二半甲基丙烯酸甲酯进料。温度在此应该不超过93℃。在进料结束之后，将内容物排出到冷却容器中。根据冷却条件而定，聚合物比例为10-30％。在6mm福特(Ford)杯内所测的粘度为30-60秒。根据DIN 53211确定粘度。
100mm块料的生产
按已知方法，将待聚合的溶液注入两个玻璃板之间，所述玻璃板采用塑料绳被保持一定距离。溶液由60-90％的无残余引发剂的浆料、10-40％的MMA和常规添加剂：引发剂、热稳定剂和UV稳定剂、γ-萜品烯(140ppm)和脱模剂。聚合在27℃下进行。约12天之后，在调温炉内进行最终聚合。在无浆料，即单独采用MMA的情况下，水浴中的聚合时间为约30天。在调温炉内的时间保持不变。

Claims (7)

1.一种生产厚度为30-100mm的塑料模制品的方法，其通过将由无残余引发剂的聚(甲基)丙烯酸甲酯浆料组成的混合物和由甲基丙烯酸甲酯和常规添加剂和烯属碳环化合物组成的混合物热聚合而进行，其特征在于无残余引发剂的聚(甲基)丙烯酸甲酯浆料具有以下性能：
-所使用的引发剂过氧化物的含量为＜5ppm，低于检测极限
-平均分子量Mw：240000-350000
-组成：70-90质量％的甲基丙烯酸甲酯，
10-30质量％的聚甲基丙烯酸甲酯
-用福特杯测量的粘度为30-60秒。
2.权利要求1的方法，其特征在于基于聚合反应用料的数量，使用用量为50-300ppm的碳环化合物。
3.权利要求1的方法，其特征在于所使用的碳环化合物是萜烯。
4.权利要求3的方法，其特征在于所使用的萜烯是γ-萜品烯。
5.由聚甲基丙烯酸甲酯构成的片材，其可按照权利要求1的方法获得。
6.权利要求5的由聚甲基丙烯酸甲酯构成的片材用于生产鱼缸的用途。
7.一种生产无残余引发剂的聚(甲基)丙烯酸甲酯浆料的方法，其特征在于将由100份甲基丙烯酸甲酯和0.05-0.1份过氧化二碳酸酯组成的混合物初始聚合直至转化率为10-30％，其中在达到所需要的聚合度后以热方式在＞90℃下破坏用于生产浆料的引发剂，以便它们不再能够引发聚合。
CN2004800272886A 2003-10-22 2004-09-15 通过热聚合而由无残余引发剂的预聚物生产无色的、经透明或不透明着色的plexiglas*块料 Expired - Fee Related CN1856515B (zh)

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DE10349544A DE10349544A1 (de) 2003-10-22 2003-10-22 Herstellung von farblosen, transparent oder gedeckt eingefärbten PLEXIGLAS-Blöcken aus restinitiatorfreiem Präpolymerisat durch thermische Polymerisation
DE10349544.4 2003-10-22
PCT/EP2004/010301 WO2005049666A1 (de) 2003-10-22 2004-09-15 Herstellung von farblosen, transparent oder gedeckt eingefärbten plexiglas®-blöcken aus retinitiatorfreiem präpolymerisat durch tehrmische polymerisation

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DE102009003225A1 (de) 2009-05-19 2010-11-25 Evonik Degussa Gmbh Transparente, witterungsbeständige Barrierefolie, Herstellung durch Lamination, Extrusionslamination oder Extrusionsbeschichtung
DE102009003223A1 (de) 2009-05-19 2010-12-09 Evonik Degussa Gmbh Transparente, witterungsbeständige Barrierefolie für die Einkapselung von Solarzellen III
DE102009003221A1 (de) 2009-05-19 2010-11-25 Evonik Degussa Gmbh Transparente, witterungsbeständige Barrierefolie für die Einkapselung von Solarzellen II

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CN1856515A (zh) 2006-11-01
ATE384084T1 (de) 2008-02-15
DE502004005978D1 (de) 2008-03-06
KR20080011714A (ko) 2008-02-05
ZA200603224B (en) 2007-01-31
DE10349544A1 (de) 2005-05-25
MXPA06003904A (es) 2007-06-07
EP1678217B1 (de) 2008-01-16
US20070027282A1 (en) 2007-02-01
KR20070000401A (ko) 2007-01-02
EP1678217A1 (de) 2006-07-12
KR100829770B1 (ko) 2008-05-19
AU2004291222A1 (en) 2005-06-02
WO2005049666A1 (de) 2005-06-02
CA2543064A1 (en) 2005-06-02

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