CN101432323A - 羧基官能的聚乙酸乙烯酯用于制备bmc模制品的用途 - Google Patents
羧基官能的聚乙酸乙烯酯用于制备bmc模制品的用途 Download PDFInfo
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Abstract
本发明涉及羧基官能的聚乙酸乙烯酯固体树脂作为不含增稠剂的配制品中的添加剂用于制备BMC模制品的用途。
Description
技术领域
本发明涉及羧基官能的聚乙酸乙烯酯固体树脂用于制备BMC模制品的用途。
背景技术
在制造片状塑料部件时，经常使用不饱和聚酯树脂组合物(UP树脂)。该聚酯树脂是二羧酸或二羧酸酐与多元醇的反应产物。此类聚酯树脂组合物还包含具有烯键式不饱和基团的单体，通常是苯乙烯。将苯乙烯添加至聚酯树脂组合物，以溶解聚酯树脂并确保聚酯组合物是可流动的组合物。聚酯树脂组合物还包含纤维材料，例如玻璃纤维、碳纤维或相应的纤维垫，以用聚酯树脂组合物增强所得的塑料部件。
在加工该聚酯树脂组合物(纤维增强的塑料组合物＝FRP复合材料)中的问题是，聚酯树脂热硬化期间的体积收缩。因此为了减少聚酯树脂硬化期间的收缩，将所谓的“低收缩添加剂(Low-Profile-Additiven)”加入其中。低收缩添加剂降低硬化期间的收缩，减轻内应力，减少微裂纹的形成，并且能够更容易符合制造公差。低收缩添加剂为热塑性塑料，例如聚苯乙烯、聚甲基丙烯酸甲酯，尤其是聚乙酸乙烯酯。还使用具有最高1重量％的羧基官能的共聚单体单元的聚乙酸乙烯酯。在更高含量的羧基官能的共聚单体单元的情况下，收缩减少并不令人满意。
由FRP复合材料制备热固性模制品的两种方法是BMC技术(整体模塑料)和SMC技术(片状模塑料)。在SMC法中，将由苯乙烯聚酯树脂溶液、低收缩添加剂、交联催化剂、填料、脱模剂以及任选使用的其他添加剂制备的糊状组合物施加在聚酰胺薄膜上。随后将玻璃纤维分散在该层上，最后施加另一层糊状组合物。然后，将该片状夹层物从薄膜剥离，切成块，并加压和加热而压制成模制品。
在BMC法中，将化合物组分、苯乙烯聚酯树脂溶液、低收缩添加剂、交联催化剂、填料、脱模剂以及任选使用的其他添加剂混合成为糊状组合物，然后混入玻璃纤维，随后加压和加热而制成模制品。
对于BMC法，非官能的聚乙酸乙烯酯固体树脂通常用作低收缩添加剂。此处的缺点是，使该配制品更便宜的填料的添加受限于苯乙烯聚乙酸乙烯酯溶液的相对更高的特性粘度。对于SMC法，EP 501 176 A1公开了通过添加包含酸性基团的热塑性乙烯基聚合物而可以促进可硬化的聚酯树脂模制组合物的增稠。DE-A 21 04 575也描述了在具有增稠剂的配制品中使用乙酸乙烯酯丙烯酸共聚物。
发明内容
因此，本发明的目的在于发现一种能够将更大量的填料混入用于BMC法的模制组合物的配制品中的方法。
令人惊奇地发现，在相同分子量的情况下，用羧基官能的聚乙酸乙烯酯固体树脂获得具有明显更小的特性粘度的苯乙烯溶液，这能够混入更大量的填料。
本发明涉及羧基官能的聚乙酸乙烯酯固体树脂作为配制品中的添加剂用于制备BMC模制品的用途，该配制品不含模制组合物的增稠剂。
合适的用于制备羧基官能的聚乙酸乙烯酯固体树脂的具有羧基的共聚单体是单重烯键式不饱和的单羧酸和二羧酸。优选为丙烯酸、甲基丙烯酸、富马酸、巴豆酸。特别优选为巴豆酸。均基于聚乙酸乙烯酯固体树脂的总重量，聚乙酸乙烯酯固体树脂中具有羧基的共聚单体单元的比例为0.5至10重量％，优选为大于1重量％直至10重量％，特别优选为3至10重量％。
以已知的方式根据本体聚合法、悬浮聚合法或优选的溶液聚合法制备羧基官能的聚乙酸乙烯酯固体树脂。合适的溶剂例如是具有1至6个碳原子的脂肪族一元醇，优选为甲醇、乙醇、丙醇、异丙醇。特别优选为乙醇和异丙醇。通常在回流条件下通常在40℃至140℃的聚合温度下进行反应，以利用汽化冷却排出反应热。这可以在大气压或者轻微的超压下进行。
使用有机过氧化物或偶氮化合物作为引发剂。合适的化合物例如是过氧化二酰，如过氧化二月桂酰；过氧化酯，如过氧化新戊酸叔丁酯或过氧化2-乙基己酸叔丁酯；或过氧化二碳酸酯，如过氧化二碳酸二乙酯。引发剂的量通常为基于单体的0.01至5.0重量％。引发剂可以预先装入，也可按计量加入。在此已被证明为成功的方法中，预先装入一部分所需量的引发剂，并在反应期间连续地按计量加入剩余部分。
可以本领域技术人员已知的方式通过在存在分子量调节剂的情况下进行聚合而调节分子量。合适的调节剂例如是醇，如乙醇或异丙醇；醛，如乙醛或丙醛；或含有硅烷的调节剂，例如巯基硅烷，如3-巯基丙基三甲氧基硅烷。
为了制备聚合物，可以根据分批法加以实施，其中将聚合批料的所有组分均预装入反应器中；或者根据半分批法加以实施，其中预先装入单独的组分或多种组分，并按计量加入剩余部分；或者连续地进行聚合，其中在聚合期间按计量加入组分。需要时可以(空间和时间上)分离的方式按计量加入。
用于BMC技术(整体模塑料)的FRP复合材料的配制品是本领域技术人员已知的。用于BMC技术的模制组合物的不饱和聚酯树脂组合物的典型的配制品含有60至70重量份的不饱和聚酯树脂(作为苯乙烯中的浓度为50至75％的溶液)、30至40重量份的低收缩添加剂(作为苯乙烯中的浓度为30至50％的溶液)如聚乙酸乙烯酯或聚甲基丙烯酸甲酯、0.5至2重量份的引发剂如过氧化苯甲酸叔丁酯、150至200重量份的填料如碳酸钙、25至30重量份的玻璃纤维、0.5至3重量份的脱模剂如硬脂酸锌，以及任选存在的其他添加剂，如颜料、阻燃添加剂。该配制品不含增稠剂，例如碱性金属化合物，如元素周期表第I至III主族的金属的氧化物或氢氧化物。
在根据本发明的用途中，低收缩添加剂，优选基于聚乙酸乙烯酯或聚甲基丙烯酸甲酯，完全或部分地被羧基官能的聚乙酸乙烯酯代替。均基于配制品中低收缩添加剂的重量，羧基化的聚乙酸乙烯酯固体树脂的使用量通常为10至100重量％，优选为50至80重量％。在此，针对性地使用在苯乙烯溶液中的该添加剂。
附图说明
图1所示为测量结果。
具体实施方式
以下实施例用于进一步阐述本发明：
对于各种不同的固体树脂，测定包含及不含填料的苯乙烯中的固体树脂溶液的粘度：
共聚物1：
具有5重量％巴豆酸单元且具有Mw＝67500重均分子量的聚乙酸乙烯酯固体树脂。
均聚物1：
具有Mw＝69000重均分子量的聚乙酸乙烯酯固体树脂。
均聚物2：
具有Mw＝116600重均分子量的聚乙酸乙烯酯固体树脂。
共聚物2：
具有5重量％巴豆酸单元且具有Mw＝116750重均分子量的聚乙酸乙烯酯固体树脂。
共聚物3：
具有5重量％巴豆酸单元且具有Mw＝137000重均分子量的聚乙酸乙烯酯固体树脂。
在每种情况下均制备所列聚合物在苯乙烯中的浓度为40重量％的溶液，均在23℃下利用Brookfield测量仪测定溶液的粘度。测量结果在下表和附图中表示为V in ST(苯乙烯中的粘度)，以mPas计。
随后均将200重量份苯乙烯聚合物溶液与300重量份碳酸钙(Omyacarb 5GU)混合，均在23℃下利用Brookfield测量仪测定分散体的粘度。测量结果在下表和附图中表示为V in ST+F(含有填料的苯乙烯中的粘度)，以mPas计。
表和附图表明，将填料混入均聚物中使粘度剧烈地升高，而在可比较的分子量的共聚物的情况下，在添加填料时粘度非常平缓地升高。
| 共聚物1 | 均聚物1 | 均聚物2 | 共聚物2 | 共聚物3 | |
| V in ST[mPas] | 1030 | 1230 | 2310 | 3090 | 3700 |
| V in ST+F[mPas] | 9850 | 67400 | 71200 | 19000 | 32200 |
Claims (6)
1、羧基官能的聚乙酸乙烯酯固体树脂作为不含增稠剂的配制品中的添加剂用于制备BMC模制品的用途。
2、根据权利要求1的用途，其中所用的羧基官能的聚乙酸乙烯酯固体树脂具有衍生自单重烯键式不饱和的单羧酸或二羧酸的共聚单体单元。
3、根据权利要求1或2的用途，其中基于聚乙酸乙烯酯固体树脂的总重量，聚乙酸乙烯酯固体树脂中具有羧基的共聚单体单元的比例为0.5至10重量％。
4、根据权利要求1至3之一的用途，其中所述配制品含有60至70重量份的不饱和聚酯树脂(作为苯乙烯中的浓度为50至75％的溶液)、30至40重量份的低收缩添加剂(作为苯乙烯中的浓度为30至50％的溶液)、0.5至2重量份的引发剂、150至200重量份的填料、25至30重量份的玻璃纤维、0.5至3重量份的脱模剂、以及任选存在的其他添加剂。
5、根据权利要求4的用途，其中基于配制品中低收缩添加剂的重量，10至100重量％被羧基官能的聚乙酸乙烯酯固体树脂代替。
6、根据权利要求4的用途，其中基于配制品中低收缩添加剂的重量，50至80重量％被羧基官能的聚乙酸乙烯酯固体树脂代替。
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| Application Number | Priority Date | Filing Date | Title |
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| DE102006019686A DE102006019686A1 (de) | 2006-04-27 | 2006-04-27 | Verwendung von carboxylfunktionellen Polyvinylacetaten zur Herstellung von BMC-Formteilen |
| DE102006019686.4 | 2006-04-27 |
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| CN101432323A true CN101432323A (zh) | 2009-05-13 |
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| US (1) | US20090182090A1 (zh) |
| EP (1) | EP2010581A1 (zh) |
| JP (1) | JP2009534508A (zh) |
| CN (1) | CN101432323A (zh) |
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| CN107603095A (zh) * | 2017-09-18 | 2018-01-19 | 张家港九力新材料科技有限公司 | 一种可常温使用的低收缩剂及其制备方法 |
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| DE102007047837A1 (de) | 2007-11-21 | 2009-05-28 | Wacker Chemie Ag | Herstellung von Lösungen von Vinylpolymeren in reaktiven Monomeren |
| DE102007055692A1 (de) * | 2007-12-03 | 2009-06-04 | Wacker Chemie Ag | Radikalisch vernetzbare Polymerisat-Zusammensetzungen enthaltend Epoxy-funktionelle Copolymere |
| DE102008054482A1 (de) | 2008-12-10 | 2010-06-17 | Wacker Chemie Ag | Pfropfcopolymere und deren Verwendung als Low-Profile-Additive |
| DE102009001498A1 (de) | 2009-03-11 | 2010-09-16 | Wacker Chemie Ag | Verwendung von Vinylester-Copolymeren als Low-Profile-Additive (LPA) |
| DE102009001818A1 (de) | 2009-03-24 | 2010-09-30 | Wacker Chemie Ag | Verwendung von Schutzkolloid-stabilisierten Polymerisaten als Low-Profile-Additive (LPA) |
| DE102010028952A1 (de) | 2010-05-12 | 2011-11-17 | Wacker Chemie Ag | Low-Profile-Additive auf Basis nachwachsender Rohstoffe |
| DE102012200735A1 (de) | 2012-01-19 | 2013-07-25 | Wacker Chemie Ag | Verwendung von funktionalisierten Polymerisaten als Low-Profile-Additive (LPA) |
| MX2019010427A (es) | 2017-03-03 | 2019-10-15 | Wacker Chemie Ag | Uso de copolimeros de vinilacetato como aditivos para reducir el grado de contraccion en sistemas de curado en frio. |
| WO2020228953A1 (de) | 2019-05-15 | 2020-11-19 | Wacker Chemie Ag | Verwendung von vinylacetat-copolymeren als low-profile-additiv |
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| US4626570A (en) * | 1984-06-29 | 1986-12-02 | Union Carbide Corporation | Low shrinking thermosetting polyester resin compositions and a process for the preparation thereof |
| DE3617514A1 (de) * | 1986-05-24 | 1987-11-26 | Bayer Ag | Verfahren zur herstellung schrumpfarmer formkoerper auf polyesterbasis |
| DE4106341A1 (de) * | 1991-02-28 | 1992-09-03 | Basf Ag | Eingedickte haertbare formmasse aus ungesaettigten polyesterharzen |
| DE19532872A1 (de) * | 1995-09-06 | 1997-03-13 | Menzolit Fibron Gmbh | Eingefärbte Dekor-Partikel in glasfaserverstärkten Duroplasten |
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- 2007-04-18 WO PCT/EP2007/053746 patent/WO2007125035A1/de active Application Filing
- 2007-04-18 CN CNA2007800149851A patent/CN101432323A/zh active Pending
- 2007-04-18 US US12/297,767 patent/US20090182090A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107603095A (zh) * | 2017-09-18 | 2018-01-19 | 张家港九力新材料科技有限公司 | 一种可常温使用的低收缩剂及其制备方法 |
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| US20090182090A1 (en) | 2009-07-16 |
| WO2007125035A1 (de) | 2007-11-08 |
| JP2009534508A (ja) | 2009-09-24 |
| EP2010581A1 (de) | 2009-01-07 |
| DE102006019686A1 (de) | 2007-10-31 |
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