CN101426825A - 官能化聚乙烯基酯用于增加bmc/smc模制品的表面张力的用途 - Google Patents
官能化聚乙烯基酯用于增加bmc/smc模制品的表面张力的用途 Download PDFInfo
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Abstract
本发明涉及官能化固体聚乙烯基酯树脂在不饱和聚酯树脂组合物中作为添加剂用于改进由其得到的模制品的表面张力的用途。
Description
技术领域
本发明涉及官能化聚乙烯基酯用于增加BMC/SMC模制品的表面张力的用途。
背景技术
片状塑料部件的制造通常使用不饱和聚酯树脂组合物(UP树脂)。这些聚酯树脂是二羧酸或二羧酸酐与多元醇的反应产物。这些聚酯树脂组合物也包含具有烯属不饱和基团的单体,通常为苯乙烯。将苯乙烯加入到聚酯树脂组合物中,以便溶解聚酯,并确保聚酯组合物是可流动材料。纤维材料,例如玻璃纤维、碳纤维或相应的纤维垫,也存在于该聚酯树脂组合物中,以便增强使用聚酯树脂组合物得到的塑料部件。
加工这些聚酯树脂组合物(纤维增强塑料复合材料=FPR复合材料)的问题是:当聚酯树脂在升高温度下固化时体积收缩。因此,为了在聚酯树脂硬化期间减少体积收缩,向该树脂中加入称作低轮廓添加剂的材料。低轮廓添加剂降低了硬化期间的收缩,消除了内应力,减少了微裂纹,并且促进了与制造误差的相容。低轮廓添加剂是热塑性材料,例如聚苯乙烯、聚甲基丙烯酸甲酯以及尤其是聚乙酸乙烯酯。也使用具有高达1重量%的羧基官能共聚单体的聚乙酸乙烯酯。当羧基官能共聚单体单元的浓度高时,收缩降低是不令人满意的。
由FRP复合材料制造热固性模制品的方法是BMC技术(整体模塑料)和SMC技术(片状模塑料)。在BMC方法中,模塑料的组分、苯乙烯类聚酯树脂溶液、低轮廓添加剂、交联催化剂、填料、脱模剂以及任选的其他添加材料被混合,形成糊状物,然后混合玻璃纤维,然后暴露在压力下并加热,制得模制品。举例而言,此技术用于制备汽车前灯的反射物。在SMC方法中,通过类似于BMC的方法,由苯乙烯类聚酯树脂溶液、低轮廓添加剂、交联催化剂、填料、脱模剂以及任选的其他添加材料制备糊状物,并且将该糊状物涂覆到聚酰胺薄膜上。然后将玻璃纤维分散在此层上,最后涂覆另一层该糊状物。此片状夹层结构然后从薄膜上剥离出去,切割成小段,并暴露在压力和加热下压成模制品。通过此技术制造的模制品的实例是汽车的后挡板。
EP 501176 A1和DE 102004031968公开了,通过添加含有酸基团的热塑性乙烯基聚合物可促进可固化聚酯树脂模制品组合物的增稠。
然而,在许多情况下,需要油漆所得模制品。这里的缺点是,使用所述技术得到的模制品的表面仅具有低表面张力,结果是油漆层的粘着力不足。因此迄今为止,于油漆之前,表面张力在通过火焰处理或等离子体处理的额外操作下来增加。
发明内容
因此,本发明的目标是改性FRP复合材料,使得他们可给出具有增加表面张力的模制品。
本发明提供了官能化固体聚乙烯基酯树脂在不饱和聚酯树脂组合物中作为添加剂的用途,用于改进由其得到的模制品的表面张力。
用于官能化固体聚乙烯基酯树脂的适合乙烯基酯单体是具有1—18个碳原子的非支化或支化的羧酸。优选的乙烯基酯是乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、新戊酸乙烯酯和具有5—13个碳原子的α-支化的一羧酸的乙烯基酯,实例是VeoVa9R或VeoVa10R(Shell公司的商标),或者上述乙烯基酯单体的混合物。乙酸乙烯酯是特别优选的。
具有官能团的合适共聚单体是具有羧酸基团、磺酸基团或膦酸基团的共聚单体。优选烯属不饱和一羧酸和二羧酸、乙烯基磺酸酯和乙烯基膦酸酯。特别优选丙烯酸、甲基丙烯酸、富马酸和巴豆酸。在固体聚乙烯基酯中具有官能团的共聚单体单元的比例优选大于1重量%且不高于10重量%,特别优选3—10重量%,每种情况下都以固体聚乙烯基酯树脂的总重量计。
最优选基于乙酸乙烯酯的固体树脂,其含有上述量的丙烯酸共聚单体单元或巴豆酸共聚单体单元。
该官能化固体聚乙烯基酯树脂是通过本体、悬浮或优选溶液聚合方法来制备的。适合溶剂的实例是具有1—6个碳原子的一元脂族醇,优选甲醇、乙醇、丙醇、异丙醇。特别优选乙醇和异丙醇。反应通常在回流条件下进行,通常聚合温度为40—140℃,以便利用蒸发冷却来除去反应热。这可在大气压或在轻微超大气压下进行。
所用引发剂包括有机过氧化物或偶氮化合物。适合引发剂的实例是二酰基过氧化物如二月桂酰基过氧化物、过氧酯如过氧新戊酸叔丁酯或2-乙基过氧己酸叔丁酯、或过氧二碳酸酯如过氧二碳酸二乙酯。以单体计,引发剂的量通常为0.01—5.0重量%。引发剂可以作为初始装料使用,或者作为加料使用。这里已经证实:使用一定比例的所需量的引发剂作为初始装料并且在反应期间连续加入剩余的引发剂是成功的。
分子量可以以本领域技术人员已知的方式通过在分子量调节剂存在下聚合来调整。合适调节剂的实例是醇如乙醇或异丙醇、醛如乙醛或丙醛、或者含硅烷调节剂如巯基硅烷,所述巯基硅烷例如为3-巯基丙基三甲氧基硅烷。
分批法可用于制备聚合物,其中所有的聚合混合物的组分在反应器中用作初始装料,或者可以使用半分批法,其中单个或多个组分用作初始装料,而剩余组分用作加料,或者可以使用连续聚合方法,其中各组分在聚合反应期间用作加料。如果合适,加料可以是分开的(空间和时间上)
用于BMC(整体模塑料)技术和SMC技术的FRP复合材料的配制品是本领域技术人员已知的。用于BMC技术和SMC技术的不饱和聚酯树脂组合物的典型配制品包括60—70重量份的不饱和聚酯树脂(以在苯乙烯中50—75%浓度溶液的形式)、30—40重量份的低轮廓添加剂或聚甲基丙烯酸甲酯、0.5—2重量份引发剂如过苯甲酸叔丁酯、150—200重量份的填料如碳酸钙、25—30重量份的玻璃纤维、0.5—30重量份的脱模剂如硬脂酸锌,以及任选的其他添加材料,例如颜料、增稠剂、阻燃剂。配制品优选不包括增稠剂如碱金属化合物,例如元素周期表第一至第三主族的金属的氧化物或氢氧化物。
本发明用途中所用官能化聚乙烯基酯树脂的量为10—80重量%,优选50—80重量%,每种情况都基于配制品中低轮廓添加剂的重量。这里在苯乙烯溶液中使用此添加剂是有利的。
表面张力的改进是指表面张力的增加。在本发明的用途中,基于不饱和聚酯树脂组合物的模制品的表面张力应优选为≥35N/mm2,特别优选≥38N/mm2。表面张力通常使用DIN 53364的测试油墨或测试标记物来确定。
具体实施方式
以下实施例用于进一步说明本发明:
测试以下SMC配制品:
组分 | 本发明实施例1(pts.重量) | 比较例1(pts.重量) |
邻苯二甲酸UP树脂(65重量%于苯乙烯中) | 65.5 | 65.5 |
聚乙酸乙烯酯(40重量%于苯乙烯中) | 30.0 | 30.0 |
VAc-CA共聚物(40重量%于苯乙烯中) | 10.0 | |
苯乙烯 | 4.5 | 4.5 |
过苯甲酸叔丁酯 | 1.5 | 1.5 |
硬脂酸锌 | 4.0 | 4.0 |
碳黑颜料 | 10.0 | 10.0 |
碳酸钙 | 200.0 | 200.0 |
苯醌 | 0.3 | 0.3 |
加工添加剂(润湿剂、除气) | 7.9 | 7.9 |
氧化镁 | 2.5 | 2.5 |
玻璃纤维 | 90.0 | 90.0 |
VAc-CA共聚物=具有5重量%巴豆酸的乙酸乙烯酯—巴豆酸共聚物
配制品进行如下加工以给出SMC模制品:
除了氧化镁之外,配制品的组分在溶解器中混合以给出糊状物。等候5分钟后,在减低的旋转速率下通过搅拌加入氧化镁。使用1.5mm刮板施用糊状物至聚酰胺薄膜上。将玻璃纤维分散到糊状物层上。第二聚酰胺薄膜以相同的方式涂覆有糊状物,然后用于覆盖玻璃纤维层。这些层通过滚动杆来压实。在3天的储存时间后,将复合材料压制为模制品。
如此得到的模制品的表面用标准标记物测试以显示表面张力。
使用比较例1的组合物得到模制品的表面的表面张力为34N/mm2。低于35N/mm2,颜料粘合力不令人满意。
使用本发明实施例1的组合物得到的模制品的表面的表面张力为38N/mm2。
Claims (6)
1.官能化固体聚乙烯基酯树脂在不饱和聚酯树脂组合物中作为添加剂用于改进由其得到的模制品的表面张力的用途。
2.权利要求1的用途,其中使用羧基官能化固体聚乙酸乙烯酯树脂,该树脂具有衍生自烯属单不饱和一羧酸或二羧酸的共聚单体单元。
3.权利要求1或2的用途,其中以所述官能化固体聚乙烯基酯树脂的总重量计,在所述官能化固体聚乙烯基酯树脂中共聚单体单元的比例为大于1重量%且不高于10重量%。
4.权利要求1—3之一的用途,其中所述配制品包括60—70重量%的不饱和聚酯树脂(以在苯乙烯中浓度为50—75重量%的溶液的形式)、30—40重量份的低轮廓添加剂(以在苯乙烯中浓度为30—50重量%的溶液的形式)、0.5—2重量份的引发剂、150—200重量份的填料、25—30重量份的玻璃纤维、0.5—3重量份的脱模剂以及任选的其他添加材料。
5.权利要求4的用途,其中以所述配制品中低轮廓添加剂的重量计,10—80重量%由官能化固体聚乙烯基酯树脂代替。
6.权利要求4的羧基官能化固体聚乙酸乙烯酯树脂的用途,其中以所述配制品中低轮廓添加剂的重量计,50—80重量%由官能化固体聚乙烯基酯树脂代替。
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DE102006019676A DE102006019676A1 (de) | 2006-04-27 | 2006-04-27 | Verwendung von funktionalisierten Polyvinylestern zur Erhöhung der Oberflächenspannung von BMC/SMC-Formteilen |
DE102006019676.7 | 2006-04-27 |
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CN101426825A true CN101426825A (zh) | 2009-05-06 |
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CNA200780014435XA Pending CN101426825A (zh) | 2006-04-27 | 2007-04-19 | 官能化聚乙烯基酯用于增加bmc/smc模制品的表面张力的用途 |
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US (1) | US20090105406A1 (zh) |
EP (1) | EP2010582A1 (zh) |
JP (1) | JP2009534510A (zh) |
CN (1) | CN101426825A (zh) |
DE (1) | DE102006019676A1 (zh) |
TW (1) | TW200740919A (zh) |
WO (1) | WO2007125045A1 (zh) |
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US4288571A (en) * | 1971-01-18 | 1981-09-08 | Union Carbide Corporation | Polyester compositions |
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 |
US5162401A (en) * | 1989-10-30 | 1992-11-10 | Owens-Corning Fiberglas Corporation | Unsaturated polyester resin compositions containing compatible compounds |
IT1246629B (it) * | 1991-01-21 | 1994-11-24 | Gd Spa | Metodo per il controllo e la correzione della ventilazione in sigarette provviste di perforazioni. |
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 |
DE102004031968A1 (de) * | 2004-07-01 | 2006-01-19 | Wacker Polymer Systems Gmbh & Co. Kg | Mit Säuregruppen funktionalisierte Polyvinylacetat-Festharze |
-
2006
- 2006-04-27 DE DE102006019676A patent/DE102006019676A1/de not_active Ceased
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2007
- 2007-04-19 US US12/297,772 patent/US20090105406A1/en not_active Abandoned
- 2007-04-19 JP JP2009507041A patent/JP2009534510A/ja not_active Withdrawn
- 2007-04-19 EP EP07728313A patent/EP2010582A1/de not_active Withdrawn
- 2007-04-19 CN CNA200780014435XA patent/CN101426825A/zh active Pending
- 2007-04-19 WO PCT/EP2007/053854 patent/WO2007125045A1/de active Application Filing
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EP2010582A1 (de) | 2009-01-07 |
JP2009534510A (ja) | 2009-09-24 |
WO2007125045A1 (de) | 2007-11-08 |
DE102006019676A1 (de) | 2007-11-08 |
US20090105406A1 (en) | 2009-04-23 |
TW200740919A (en) | 2007-11-01 |
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