CN100471878C - 酸基官能化的固体聚乙酸乙烯酯树脂作为低轮廓添加剂的用途 - Google Patents
酸基官能化的固体聚乙酸乙烯酯树脂作为低轮廓添加剂的用途 Download PDFInfo
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Abstract
本发明涉及由酸基官能化的聚乙酸乙烯酯固体树脂,所述反应的特征在于:除了羧基-官能共聚单体单元以外,该聚乙酸乙烯酯固体树脂还包括末端羧基。
Description
本发明涉及酸基官能化的固体聚乙酸乙烯酯树脂用作低轮廓添加剂的用途。
薄片状塑胶零件的生产经常使用不饱和聚酯树脂(UP树脂),该不饱和聚酯树脂是通过玻璃纤维或碳纤维进行补强。为了减低聚酯树脂固化期间的收缩,将称作低轮廓添加剂(low-profile additive)的材料加入到这种树脂中。该低轮廓添加剂可减低固化期间收缩、消除内应力、减少大裂痕的形成,且可使其易于符合制造可耐度。该低轮廓添加剂是热塑性的,例如聚苯乙烯、聚甲基丙烯酸甲酯,尤其聚乙酸乙烯酯,且这些添加剂中常含有羧基-官能共聚单体单元。当使用低轮廓添加剂时,理想的是苯乙烯中的良好溶解度,且该苯乙烯溶液的初始粘度较低及快速的稠化效果以达到稳定的最后水平。与初始粘度及稠化效果相关,常规的低轮廓添加剂(例如以具有羧基-官能共聚单体单元的聚乙酸乙烯酯为主要成分的)仍然不够满意。
EP 0831153 A1公开了羧基-官能化乙酸乙烯酯聚合物用于处理皮革的用途。巴西专利BR 8700832公开了丙烯酸和乙烯醚的共聚物用作抑制沉淀物形成的涂布剂,该共聚物具有末端羧基。JP-A51-63425公开了由环氧-官能苯乙烯-甲基丙烯酸甲酯聚合物和具有末端羧基的乙酸乙烯酯改性的聚酯树脂组合物。
所以本发明的目的是提供用作低轮廓添加剂的使关于上述性质轮廓(profile)最佳的固体聚乙酸乙烯基酯树脂。
本发明提供酸基-官能化的固体聚乙酸乙烯酯树脂作为低轮廓添加剂的用途,其特征在于除了羧基-官能共聚单体单元以外,该固体聚乙酸乙烯酯树脂还含有末端羧基。
优选地,酸基官能化的固体树脂在c)0.1至5重量%的一种或多种、具有2至6个碳原子的氢硫基烷基羧酸存在的情况下,经由下列各组分的聚合而制得:
a)85至99.8重量%的乙酸乙烯酯,及
b)0.1至10重量%的一种或多种烯键式不饱和一元羧酸,
重量%的总和为100重量%。
乙酸乙烯酯的使用量优选为90至99重量%。
合适的烯键式不饱和一元羧酸是丙烯酸、甲基丙烯酸、巴豆酸。烯键式不饱和酸的优选聚合比例为0.2至5重量%,以组分a)到c)的总重量计。
氢硫基烷基羧酸用以引进末端羧基。其中优选氢硫基乙酸及氢硫基丙酸。使用氢硫基烷基羧酸的优选比例为0.2至1重量%,以组分a)到c)的总重量计。
用酸基官能化的固体聚乙酸乙烯酯树脂的重均分子量Mw为10000至500000。
由酸基官能化的固体聚乙酸乙烯酯树脂通过整体、悬浮或优选溶液的聚合法制得。适当溶剂的实例是具有1至6个碳原子的一元脂肪族醇,优选甲醇、乙醇、丙醇、异丙醇。更优选乙醇及异丙醇。为了利用蒸发性冷却作用以消除反应热,通常在回流情况下及40℃至140℃的聚合温度下进行反应。该反应可在大气压力下或略低于超大气压力下进行。所用引发剂包括有机过氧化物或偶氮化合物。适当化合物的实例是二酰基过氧化物(如二月桂酰过氧化物)、过氧酯(如过氧新戊酸叔丁酯或过氧-2-乙烯基己酸叔丁酯)或过氧二碳酸酯(如过氧二碳酸二乙酯)。引发剂的使用量通常为0.01至5.0重量%,以单体计。该引发剂可形成初始装填或其它进给方式。此处经证实的一种成功方法中,所需引发剂的一部分形成初始装填,其余部分则在反应期间继续进给。
可以使用分批法制造该聚合物,其中聚合混合物的所有组分在反应器内形成初始装填,也可以使用半分批法,其中一种或多种组分形成初始装填,而其余部分形成进料,或可以使用连续聚合法,其中在聚合作用进行期间使组分形成进料。如适用,可以以(空间及时间地)分离该进料。至少一些氢硫基烷基羧酸部分优选在聚合作用进行期间形成进料。一旦放热反应终止,优选通过蒸馏作用将剩余的自由单体及溶剂移除。为达到极低的挥发性化合物含量,将内部温度升至100℃至160℃,然后施以真空。
为了用作低轮廓添加剂,以公知方式将酸基官能化的固体聚乙酸乙烯酯树脂溶解在苯乙烯中,如适用,连同其他添加剂一起使用,例如填料、增稠剂、引发剂及加工助剂。
聚合物链中的共聚合的羧基与链端处的末端羧基的结合可产生在苯乙烯中的树脂溶液,当该树脂溶液与填料混合时可显示出低初始粘度和快速的稠化效果,经过短短一天时间即达到稳定的最终水平。
使用下列实施例对本发明作进一步说明:
实施例1:
在4升反应器内,使350克甲醇、540克乙酸乙烯酯及3.5克巴豆酸形成初始装填,以150转/分钟,在温和沸腾情况下,将33克15%浓度的过新戊酸二叔丁酯的甲醇溶液加入到该混合物中,历时4小时。30分钟之后,将由1220克乙酸乙烯酯、14克氢硫基丙酸和9克巴豆酸所组成的混合物陆续加入,历时3.5小时。一旦进料终止,在该沸点温度下使反应继续进行2小时,然后通过蒸馏作用将溶剂及残留的单体移除。
实施例2:
在4升反应器内,使140克甲醇、540克乙酸乙烯酯及3.5克巴豆酸形成初始装填,以150转/分钟,在温和沸腾的情况下,将33克15%浓度的过新戊酸二叔丁酯的甲醇溶液加入到该混合物,历时4小时。30分钟后,将由1220克乙酸乙烯酯、14克氢硫基丙酸及9克巴豆酸所组成的混合物陆续加入,历时3.5小时。一旦进料终止,在该沸点温度下使该反应继续进行2小时,然后通过蒸馏作用将溶剂及残留的单体移除。
对比实施例3:
在4升反应器内,使350克甲醇、540克乙酸乙烯酯及3.5克氢硫基丙酸形成初始装填,以150转/分钟,在温和沸腾的情况下,将33克15%浓度的过新戊酸二叔丁酯的甲醇溶液加入到该混合物中,历时4小时。30分钟后,将由1220克乙酸乙烯酯、21克氢硫基丙酸所组成的混合物陆续加入,历时3.5小时。一旦进料终止,在该沸点温度下使该反应继续进行2小时,然后通过蒸馏作用将溶剂及残留的单体移除。
对比实施例4:
在4升反应器内,使210克甲醇、540克乙酸乙烯酯形成初始装填,以150转/分钟,在温和沸腾的情况下,将33克15%浓度的过新戊酸二叔丁酯的甲醇溶液加入到该混合物中,历时4小时。30分钟之后,将由1220克乙酸乙烯酯、14克氢硫基丙酸所组成的混合物陆续加入,历时3.5小时。一旦进料终止,在该沸点温度下使该反应继续进行2小时,然后通过蒸馏作用将溶剂及残留的单体移除。
对比实施例5:
程序与对比实施例4类似,但不同的是不加入氢硫基丙酸。
对比实施例6:
在4升反应器内,使350克甲醇、540克乙酸乙烯酯及3.5克巴豆酸形成初始装填,以150转/分钟,在温和沸腾的情况下,将33克15%浓度的过新戊酸二叔丁酯的甲醇溶液加入到该混合物中,历时4小时。30分钟之后,将由1220克乙酸乙烯酯及14克氢硫基丙酸所组成的混合物陆续加入,历时3.5小时。一旦进料终止,在该沸点温度下使该反应继续进行2小时,然后通过蒸馏作用将溶剂及残留的单体移除。
利用下列程序测试稠化效果:
在每一情况中,对由120克40%浓度的该固体树脂的苯乙烯溶液、180克碳酸钙填料(Omyacarb5GU)及3克氧化镁(Luvakol MK-35)所组成的组成物进行如下测试:在附有螺纹塞的250毫升玻璃容器内,使120克固体树脂溶液形成初始装填,在27℃的温度下,利用相对较高速(约800至1200转/分钟)的叶片型搅拌器搅拌的情况下,分批将180克碳酸钙混入。然后,在2000转/分钟的情况下搅拌1分钟来将3克氧化镁混入,立即测定温度及粘度(Helipath)。3小时后,1天后及7天后重复测定该粘度。所得结果如表内所示。
表:
实施例1 | 实施例2 | 对比实施例3 | 对比实施例4 | 对比实施例5 | 对比实施例6 | |
巴豆酸(重量%) | 0.7 | 0.7 | 0.0 | 0.0 | 0.0 | 1.0 |
MPA(重量%) | 0.8 | 0.8 | 1.4 | 0.8 | 0.0 | 0.0 |
重均分子量(Mw) | 76000 | 85000 | 40000 | 85000 | 130000 | 84000 |
粘度(Pas)0小时 | 11 | 12 | 3 | 12 | 147 | 32 |
粘度(Pas)3小时 | 14800 | 12900 | 7 | 29 | 153 | 706 |
粘度(Pas)1天 | 33000 | 25500 | 10 | 39 | 154 | 24800 |
粘度(Pas)7天 | 33000 | 25000 | 10 | 45 | 182 | 33000 |
测试结果显示:不仅链内而且终端处均含有羧基的固体树脂具有低初始粘度(0小时)、快速稠化(3小时),及1天后的稳定粘度等所需的性能分布(本发明实施例1/2)。
如果仅仅末端处出现羧基,虽然可得到低的初始粘度,但无法稠化(对比实施例3/4)。
如果没有末端羧基,稠化作用显著延后(对比实施例6)。
如果完全没有羧基,结果是:初始粘度高且粘度随后不提高(对比实施例7)。
Claims (4)
1.酸基官能化的固体聚乙酸乙烯酯树脂作为低轮廓添加剂的用途,其特征在于除羧基-官能共聚单体单元以外,该固体聚乙酸乙烯酯树脂还含有末端羧基。
2.根据权利要求1所述的用途,其固体聚乙酸乙烯酯树脂是在c)0.1至5重量%的一种或多种、具有2至6个碳原子的氢硫基烷基羧酸存在的情况下,经由下列组分的聚合而制得的:
a)85至99.8重量%的乙酸乙烯酯,和
b)0.1至10重量%的一种或多种烯键式不饱和一元羧酸,
其中,重量%的总和为100重量%。
3.根据权利要求1或2所述的用途,其特征在于使得自丙烯酸、甲基丙烯酸、巴豆酸的一种或多种烯键式不饱和一元羧酸进行共聚。
4.根据权利要求1或2所述的用途,其特征在于聚合作用是在氢硫基乙酸和/或氢硫基丙酸存在的情况下进行的。
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DE102004031968A DE102004031968A1 (de) | 2004-07-01 | 2004-07-01 | Mit Säuregruppen funktionalisierte Polyvinylacetat-Festharze |
DE102004031968.5 | 2004-07-01 |
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US (1) | US20070265394A1 (zh) |
EP (1) | EP1763541B1 (zh) |
JP (1) | JP2008504417A (zh) |
CN (1) | CN100471878C (zh) |
AT (1) | ATE380201T1 (zh) |
BR (1) | BRPI0512840A (zh) |
DE (2) | DE102004031968A1 (zh) |
RU (1) | RU2385326C2 (zh) |
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WO (1) | WO2006002833A1 (zh) |
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DE102006012200A1 (de) * | 2006-03-16 | 2007-09-27 | Wacker Polymer Systems Gmbh & Co. Kg | Verwendung von Polyvinylacetalen als Low-Profile-Additiv |
DE102006019676A1 (de) * | 2006-04-27 | 2007-11-08 | Wacker Polymer Systems Gmbh & Co. Kg | Verwendung von funktionalisierten Polyvinylestern zur Erhöhung der Oberflächenspannung von BMC/SMC-Formteilen |
WO2007134988A1 (de) * | 2006-05-24 | 2007-11-29 | Wacker Polymer Systems Gmbh & Co. Kg | Verwendung von silanfunktionellen polyvinylestern als low-profile-additiv |
WO2013119769A1 (en) * | 2012-02-07 | 2013-08-15 | Saudi Arabian Oil Company | SULFUR MODIFIED POLYVINYL ACETATE (PVAc) |
CN104910352A (zh) * | 2015-05-26 | 2015-09-16 | 常州华科聚合物股份有限公司 | 一种模具用乙烯基酯树脂及其制备方法 |
CN105566859A (zh) * | 2015-12-04 | 2016-05-11 | 常州百思通复合材料有限公司 | 一种smc/bmc增稠方法 |
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US3718714A (en) * | 1970-09-16 | 1973-02-27 | Union Carbide Corp | Unsaturated polyester compositions |
US4032494A (en) * | 1976-03-03 | 1977-06-28 | Union Carbide Corporation | Liquid siloxanes as additives for curable polyester moulding compositions containing vinyl acetate polymer and unsaturated monomer |
US4555534A (en) * | 1981-03-26 | 1985-11-26 | Union Carbide Corporation | Uniformly pigmented, low shrinking polyester molding compositions |
BR8700832A (pt) * | 1987-02-23 | 1987-08-18 | Aquatec Quimica Sa | Polimero sintetico anti-precipitante de sais de zinco e ferro em aguas de caldeiras e torres de resfriamento,processo de preparacao |
EP0319203A3 (en) * | 1987-11-30 | 1990-08-29 | MITSUI TOATSU CHEMICALS, Inc. | Improvements in materials for the manufacture of fiber-reinforced thermosetting resin mouldings |
US5202366A (en) * | 1988-07-20 | 1993-04-13 | Union Carbide Chemicals & Plastics Technology Corporation | Crosslinkable polyester compositions with improved properties |
US5266646A (en) * | 1989-05-15 | 1993-11-30 | Rohm And Haas Company | Multi-stage polymer particles having a hydrophobically-modified, ionically-soluble stage |
FR2661682B1 (fr) * | 1990-05-04 | 1993-12-10 | Norsolor | Nouvelles compositions resineuses a base de resines polyesters non saturees et de nouveaux additifs anti-retrait. |
DE4106341A1 (de) * | 1991-02-28 | 1992-09-03 | Basf Ag | Eingedickte haertbare formmasse aus ungesaettigten polyesterharzen |
JPH05163425A (ja) * | 1991-12-17 | 1993-06-29 | Mitsui Toatsu Chem Inc | 不飽和ポリエステル樹脂組成物 |
US5820633A (en) * | 1996-09-20 | 1998-10-13 | Lesko; Patricia Marie | Method of treating leather with improved retaining agents |
US7009003B2 (en) * | 2002-09-30 | 2006-03-07 | Rohm And Haas Company | Plastic composition |
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- 2005-06-28 TW TW094121729A patent/TWI322155B/zh not_active IP Right Cessation
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TW200617029A (en) | 2006-06-01 |
DE102004031968A1 (de) | 2006-01-19 |
WO2006002833A1 (de) | 2006-01-12 |
EP1763541A1 (de) | 2007-03-21 |
CN1972965A (zh) | 2007-05-30 |
RU2007103715A (ru) | 2008-08-10 |
ATE380201T1 (de) | 2007-12-15 |
BRPI0512840A (pt) | 2008-04-08 |
EP1763541B1 (de) | 2007-12-05 |
JP2008504417A (ja) | 2008-02-14 |
RU2385326C2 (ru) | 2010-03-27 |
TWI322155B (en) | 2010-03-21 |
DE502005002173D1 (de) | 2008-01-17 |
US20070265394A1 (en) | 2007-11-15 |
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