CN102186925A - 用于生产基于脂肪族聚酯的可生物降解模制品以及可在水中再分散的聚合物粉末的混合物 - Google Patents
用于生产基于脂肪族聚酯的可生物降解模制品以及可在水中再分散的聚合物粉末的混合物 Download PDFInfo
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Abstract
本发明的目的是用于生产可生物降解模制品的混合物,所述混合物基于一种或多种脂肪族聚酯,其特征在于,所述混合物还包含一种或多种可在水中再分散的聚合物粉末。
Description
本发明涉及用于生产基于脂肪族聚酯的可生物降解模制品和水可再分散的聚合物粉末的混合物,还涉及用所述混合物生产可生物降解模制品的方法,以及涉及其用途。
脂肪族聚酯如聚乳酸被用于生产可生物降解模制品,被用作例如食品工业的包装薄膜。然而,聚乳酸也可以被纺成纤维,并因而用作枕头填料、地毯纤维、和化妆品擦拭布。问题是脂肪族聚酯的脆性。
WO 96/31561 A1描述了在脂肪族聚酯被用于生产可生物降解模制品时得到的不令人满意的材料性质。因此提出基于淀粉的混合物,其另外还包含至少一种其它生物聚合物,实例为芳香族聚酯、聚酯酰胺。在WO 98/40434 A1中提出了聚乳酸与淀粉、增塑剂、和热塑性聚合物如聚乙烯醇或乙烯-乙烯醇共聚物的混合物。WO 2005/059031提出通过添加可交联抗冲改性剂改善基于聚乳酸的模制品的性质。提出的抗冲改性剂是乙烯-(甲基)丙烯酸酯共聚物,其包含具有环氧基团的(甲基)丙烯酸酯单元。US 2008/0188597 A1描述了用于生产可生物降解模制品的混合物,其包含脂肪族聚酯作为可生物降解组分,更特别的是聚乳酸。为了改善机械强度,所述脂肪族聚酯与具有≥80℃的相当高的Tg的热塑性塑料例如聚苯乙烯或PMMA混合。为了改善阻燃性,添加有机磷酸。WO 2006/074815 A1提出通过在与脂肪族-芳香族聚酯的混合物中用脂肪族聚酯如聚乳酸,更特别的,还用环氧化物交联剂,如环氧官能聚合物或双酚A环氧化物,改善终产品的性质并且避免在进行热塑性加工之前进行昂贵和不方便的聚乳酸预干燥。US 5,726,220提出由聚乳酸与乙烯-乙酸乙烯酯共聚物的混合物生产可生物降解模制品。
影响聚乳酸与其它弹性更好的聚酯和/或热塑性塑料混合的问题是单个组分的不令人满意的混溶性。
因此,本发明的目的是提供基于脂肪族聚酯,更特别的是基于聚乳酸的组合物,其显著特征不仅在于良好的加工性能,而且在于改善的机械性能。
已经令人惊奇地发现,水可再分散的聚合物粉末具有优越的与脂肪族聚酯的混溶性,并还与聚乳酸和其它生物聚酯(脂肪族聚酯、脂肪族-芳香族聚酯)的混合物相容,还改善了基于生物聚酯的模制品的机械性能。
本发明提供用于生产基于一种或多种脂肪族聚酯的可生物降解模制品的混合物,其特征在于所述混合物还包含一种或多种水可再分散的聚合物粉末。
适合的脂肪族聚酯例如为聚乳酸(PLA)、聚羟基脂肪酸(聚羟基链烷酸酯),如聚3-羟基丁酸(PHB)、C2-C6亚烷基的聚亚烷基琥珀酸酯或聚亚烷基己二酸酯,如聚琥珀酸丁二酯或聚己二酸丁二酯。优选聚乳酸。在此聚乳酸指L-乳酸、D-乳酸或L和D-乳酸的外消旋混合物的均聚物。聚乳酸还指共聚物,其除了乳酸单元外还包含其它共聚单体单元。实例为具有羟基丁酸、己内酯和/或乙醇酸单元的乳酸共聚物。在这种情况下,共聚单体单元的分数<50mol%,优选<10mol%。
所述脂肪族聚酯可以通过已知的聚合方法制备,如缩聚或开环聚合,或通过已知的微生物学方法(Ullmann’s Encyclopedia of Industrial Chemistry,第7版,在线版本,DOI 10.1002/14356007)。商业上可得到的聚乳酸例如为NatureWorksR PLA。商业上可得到的聚羟基丁酸为BiomerR聚酯。
已经发现,水可再分散的聚合物粉末也可以使聚乳酸与其它脂肪族聚酯或脂肪族-芳香族聚酯混合。因此,本发明的混合物优选不仅包括聚乳酸与水可再分散的聚合物粉末的混合物,而且包括聚乳酸与其它脂肪族聚酯和水可再分散的聚合物粉末的混合物组合物,和聚乳酸与脂肪族-芳香族聚酯、任选的除了聚乳酸外的脂肪族聚酯和水可再分散的聚合物粉末的混合物。适合的脂肪族-芳香族聚酯例如为WO 2006/074815 A1中描述的半芳香族聚酯。商业上可得到的一个这样的产品为EastarBioR。除了所述生物聚酯外,混合物还可以包含生物聚合物如淀粉、蛋白质或纤维素酯。优选混合物不含任何淀粉。
水可再分散的聚合物粉末是可通过在保护胶体存在下干燥相应的基础聚合物的水分散体而得到的粉末组合物。基于所述制备方法,分散体中高度分散的树脂涂覆了足够量的水溶性保护胶体。在干燥的过程中,保护胶体的作用类似外套,防止颗粒粘合在一起。一旦在水中再分散,保护胶体再次溶解在水中,得到原始聚合物颗粒的水分散体(Schulze J.in TIZ,No.9,1985)。
适合的聚合物为基于一种或多种选自乙烯酯、(甲基)丙烯酸酯、乙烯基芳香化合物、烯烃、1,3-二烯、和卤代乙烯、以及任选可与其共聚合的其它单体的单体。
适合的乙烯酯是具有1-15个碳原子的羧酸的乙烯酯,优选为乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、乙酸1-甲基乙烯酯、新戊酸乙烯酯、和具有9-11个碳原子的α-支化单羧酸的乙烯酯,例如VeoVa9R或VeoVa10R(Resolution公司的商标名),特别优选为乙酸乙烯酯。
选自丙烯酸酯或甲基丙烯酸酯的适合的单体为具有1-15个碳原子的未支化或支化醇的酯。优选的甲基丙烯酸酯或丙烯酸酯为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、和丙烯酸2-乙基己酯。特别优选丙烯酸甲基、甲基丙烯酸甲基、丙烯酸正丁酯、丙烯酸叔丁酯、和丙烯酸2-乙基己酯。
优选的乙烯基芳香化合物为苯乙烯、甲基苯乙烯、和乙烯基甲苯。优选的卤代乙烯是氯乙烯。优选的烯烃为乙烯、丙烯,以及优选的二烯为1,3-丁二烯和异戊二烯。
任选的是,基于单体混合物的总重量,可以额外共聚合0.1-5wt%的辅助单体。优选使用0.5-2.5wt%的辅助单体。辅助单体的实例为烯键式不饱和单羧酸和二羧酸,优选丙烯酸、甲基丙烯酸、富马酸、和马来酸;烯键式不饱和羧酸酰胺和腈,优选丙烯酰胺和丙烯腈;富马酸和马来酸的单酯和二酯,如二乙酯和二异丙酯,以及马来酐;烯键式不饱和磺酸和/或其盐,优选乙烯基磺酸、2-丙烯酰胺-2-甲基丙烷磺酸。其它实例为预交联共聚单体,如聚烯键式不饱和共聚单体,实例为邻苯二甲酸二烯丙酯、己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰尿酸三烯丙酯,或者后交联共聚单体,实例为丙烯酰胺基乙醇酸(AGA)、甲基丙烯酰胺基乙醇酸甲酯(MAGMA)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺、N-羟甲基烯丙基氨基甲酸酯,N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、和N-羟甲基烯丙基氨基甲酸酯的烷基醚如异丁氧基醚或酯。环氧官能共聚单体也是适合的,例如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯。其它实例为硅官能性共聚单体,如丙烯酰氧基丙基三(烷氧基)-和甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷,其中作为烷氧基,可以有例如乙氧基和乙氧基丙二醇醚基团。还可以提及具有羟基或CO基团的单体,实例为甲基丙烯酸和丙烯酸羟基烷基酯,如羟乙基、羟丙基或羟丁基丙烯酸酯或甲基丙烯酸酯,以及化合物如双丙酮丙烯酰胺和乙酰基乙酰氧基乙基丙烯酸酯或甲基丙烯酸酯。
选择单体,以及选择共聚单体的重量分数,从而使玻璃转化温度Tg通常≤120℃,优选为-40℃~+80℃,更优选为-20℃~+50℃。聚合物的玻璃转化温度Tg可以用已知的方式通过差示扫描量热法(DSC)测定。也可以事先通过Fox方程近似计算Tg。依据Fox T.G.,Bull.Am.Physics Soc.1,3,123页(1956),以下是正确的:1/Tg=x1/Tg1+x2/Tg2+...+xn/Tgn,其中xn代表单体n的质量分数(wt%/100),而Tgn是单体n的均聚物的玻璃转化温度,以开尔文计。对于均聚物的Tg值,在Polymer handbook,第2版,J.Wiley & Sons,New York(1975)中列出。
优选的均聚物或共聚物包含一种或多种选自乙酸乙烯酯、具有9-11个碳原子的α-支化单羧酸的乙烯酯、氯乙烯、乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、和苯乙烯的单体。特别优选乙酸乙烯酯和乙烯的共聚物;乙酸乙烯酯、乙烯、和具有9-11个碳原子的α-支化单羧酸的乙烯酯的共聚物;丙烯酸正丁酯和丙烯酸2-乙基己酯和/或甲基丙烯酸甲酯的共聚物;苯乙烯和一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、和丙烯酸2-乙基己酯的单体的共聚物;乙酸乙烯酯与一种或多种选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯的单体和任选的乙烯的共聚物;1,3-丁二烯与苯乙烯和/或甲基丙烯酸甲酯以及任选的其它丙烯酸酯的共聚物;所述混合物还可以任选地包含一种或多种上述辅助单体。
通过乳液聚合法或悬浮液聚合法,在保护胶体存在下制备聚合物,优选通过乳液聚合法,其中聚合温度通常为20℃-100℃,优选60℃-90℃,并且在共聚合气体共聚单体如乙烯的情况下,也可以在超大气压下操作,通常在5-100巴下操作。用水溶性和/或单体可溶性引发剂或氧化还原引发剂组合引发聚合,两种引发剂通常分别用于乳液聚合或悬浮液聚合。水溶性引发剂的实例为过硫酸钠、过氧化氢、和偶氮二异丁腈。单体可溶性引发剂的实例为过氧化二碳酸联十六烷酯、过氧化二碳酸二环己酯、和过氧化二苯甲酰。基于单体的总重量,所述引发剂通常用量为0.01-0.5wt%。所用的氧化还原引发剂是所述引发剂与还原剂的组合。适合的还原剂例如为亚硫酸钠、羟甲亚磺酸钠、和抗坏血酸。基于单体的总重量,还原剂的量优选为0.01-0.5wt%。
为了控制分子量,可以在聚合期间使用调节物质。如果使用调节剂,基于要聚合的单体,其典型的用量为0.01-5.0wt%,并单独添加或作为与反应组分的预混合物添加。所述物质的实例为正十二烷基硫醇、叔十二烷基硫醇、巯基丙酸、巯基丙酸甲酯、异丙醇、和乙醛。优选不使用任何调节物质。
为了稳定聚合批料,使用保护胶体,任选与乳化剂的组合。适合的保护胶体是部分水解或完全水解的聚乙烯醇;聚乙烯吡咯烷酮;聚乙烯醇缩醛;水溶性多糖,如淀粉(直链淀粉或支链淀粉)或糊精或环糊精、纤维素和其羧甲基、甲基、羟乙基、和羟丙基衍生物;蛋白质,如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶;木质素磺酸盐;合成聚合物,如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯磺酸、和其水溶性共聚物;三聚氰胺-甲醛磺酸酯、萘-甲醛磺酸酯、苯乙烯-马来酸共聚物和乙烯醚-马来酸共聚物。优选部分水解或完全水解的聚乙烯醇。特别优选部分水解的聚乙烯醇,其水解度为80-95mol%,并且在4%浓度的水溶液中的粘度为1-30mPas(法,20℃,DIN 53015)。
当聚合结束后,可以用已知的方法,通过后聚合去除残余的单体,例如通过由氧化还原催化剂引发的后聚合。也可以通过蒸馏去除挥发性残余单体,优选在减压下,并任选在批料中通入或在批料上方通入惰性夹带气体,如空气、氮气或蒸汽。以这种方式可以得到的水分散体的固含量为30-75wt%,优选50-60wt%。
为了制备水可再分散聚合物粉末组合物,任选在添加其它保护胶体作为干燥助剂后,通过例如流化床干燥、冷冻干燥或喷雾干燥对分散体进行干燥。优选喷雾干燥分散体。在这种情况下,喷雾干燥在常规喷雾干燥体系中进行,其中雾化可以通过单流体、双流体或多流体喷嘴或者用转盘产生。根据体系、树脂Tg、和期望的干燥程度,选择的出口温度通常为45℃-120℃,优选60℃-90℃。通过固含量调节要雾化的进料的粘度,以得到<500mPas(在20转和23℃下的Brookfield粘度),优选<250mPas。要雾化的分散体的固含量>35%,优选>40%。
通常而言,基于分散体中的聚合物成分,干燥助剂的总用量为0.5-30wt%。换句话说,在进行干燥之前,基于聚合物分数,保护胶体的总量为至少1wt%-30wt%;基于聚合物分数,优选用量为5-20wt%。
在雾化阶段,基于基础聚合物,至多1.5wt%的量的防沫剂被证明在许多情况下是有利的。为了通过改善结块稳定性延长保存期,特别是对于具有低玻璃转化温度的粉末,基于聚合物成分的总重量,可以给得到的粉末加入优选1-30wt%的防结块剂。防结块剂的实例为碳酸钙和碳酸镁、滑石、石膏、硅石、高岭土如偏高岭土、和硅酸盐,粒径优选为10nm-10μm。
最优选再分散粉末组合物包含乙酸乙烯酯均聚物;或乙酸乙烯酯与乙烯的共聚物;或乙酸乙烯酯、乙烯、和具有9-11个碳原子的α-支化单羧酸的乙烯酯的共聚物作为成膜聚合物和部分水解的聚乙烯醇作为保护胶体。
使用具有-20℃~+20℃的相对低的Tg的水可再分散聚合物粉末如基于乙酸乙烯酯和乙烯的共聚物的那些,与具有+30℃~+60℃的相对高的Tg的水可再分散聚合物粉末如基于乙酸乙烯酯均聚物的那些的混合物通常是特别有利的。相对低的Tg的聚合物粉末使模制品的弹性最优化,同时相对高的Tg的聚合物粉末使模制品的强度最优化。
可再分散聚合物粉末也可以与传统的不可再分散热塑性塑料混合使用。传统的热塑性塑料的实例为聚乙烯、聚丙烯、PVC、ABS、以及固体聚乙酸乙烯酯树脂。这些热塑性塑料在与可再分散聚合物粉末的混合物中的重量分数优选不应该超过70wt%。可再分散聚合物还可以任选与交联剂混合使用。其实例为环氧化物交联剂,如Epicote,或异氰酸酯交联剂。
在用于生产可生物降解的模制品的混合物中,水可再分散聚合物粉末的分数为1-95wt%,优选2-50wt%,更优选5-40wt%,每种情况下均基于生物聚酯、以及任选存在的生物聚合物、和再分散粉末、以及任选存在的热塑性塑料的总重量。
如果期望的话,还可以在混合物中存在其它在塑料的热塑加工中惯用的添加剂。其实例为染料、颜料、稳定剂、增塑剂、润滑剂、和阻燃剂。通常而言,所述添加剂的量高达20wt%,优选为1-10wt%,在每种情况下均基于用于生产可生物降解模制品的混合物的总重量。
优选还使用填料。适合的填料是无机和有机填料。无机填料的实例为白云石、白垩、和细石英粉。优选的有机填料例如木屑,尤其是植物或动物纤维材料,如棉花、黄麻、木材、亚麻、剑麻、大麻、椰子或皮革纤维。还可以使用人造纤维,如聚酯或聚丙烯纤维。填料通常以5∶95-100∶0的聚合物∶填料重量比使用,聚合物组分由生物聚酯组分、任选存在的生物聚合物组分、可再分散聚合物粉末组分、和任选存在的热塑性塑料组分构成。
为了生产模制品,将脂肪族聚酯和水可再分散聚合物粉末,以及任选的其它添加剂,在例如粉末混合器或热混合器中彼此混合,并通过典型的成型技术加工形成模制品。术语“模制品”指成型方法的产品,如压塑成型、造粒、粒化、和热塑成型技术。热塑成型方法的实例为注射成型、注射吹塑、薄膜吹塑、压延、和挤出方法。加工优选通过具有相应的脱挥处理区域的挤出,以及注射成型来进行。加工温度通常为60℃-200℃,优选90℃-160℃。优选在高压下操作,优选在10-600bar abs下。模制品也可以通过粒化过程生产。
令人惊奇的是,已经发现,通过在热塑加工中使用水可再分散聚合物粉末,无需对生物聚酯和任选的生物聚合物进行预干燥,因为在加工过程中释放的水蒸气被水可再分散聚合物粉末束缚。因此模制品的生产通过依据本发明的方法变得相当容易。
本发明的方法的产品适于用作可生物降解模制品。对于用作可堆肥包装材料,例如薄膜、泡沫填充材料、容器如袋、瓶、罐、管、和泡罩包装。对于用于可堆肥餐饮用品,如可堆肥餐具、刀叉、饮品容器、和饮用吸管。在园艺和景观美化中,本发明方法的产品可以用作可堆肥产品,如覆盖薄膜,并用作花盆和生长盆。在医药领域作为可堆肥产品的应用是作为胶囊材料和药丸材料、外科缝合材料、和可吸收植入物。在露营领域作为可堆肥产品的一种应用是用于生产可堆肥帐篷桩。
本发明的混合物可以显著扩展脂肪族聚酯的应用范围。聚乳酸(PLA)通常是难于与市场上可得到的更具弹性的生物聚酯如部分芳基聚酯或聚羟基丁酸一起加工的。通过添加水可再分散聚合物粉末,PLA与其它生物聚酯的相容性可以得到改善。
以下实施例用于进一步说明本发明:
为了测试,使用下列成分:
可再分散聚合物粉末1(RDP 1):
VinnexR 2510:基于用部分水解的聚乙烯醇稳定的Tg为43℃的乙酸乙烯酯均聚物的水可再分散聚合物粉末。
可再分散聚合物粉末2(RDP 2):
VinnexR 2504:基于用部分水解的聚乙烯醇稳定的Tg为-4℃的乙酸乙烯酯-乙烯共聚物的水可再分散聚合物粉末。
生物聚合物1(Bio1):
NatureWorksR PLA聚合物2002D:产自NatureWorks的聚乳酸。
生物聚合物2(Bio2):
EastarRBio:产自Novamont的脂肪族-芳香族共聚酯。
润滑剂(LB):
用表1和表2中列出的通式,在表中所报道的轧制温度下,生产轧板,并在表中报道的温度下取出,进行压塑以形成厚度符合标准要求的板。
熔融行为(薄膜)用肉眼评价。依据DIN 53479测定密度。依据DIN 53505测定Shore D硬度。
所用的混合物的粘度用高毛细管粘度测定法(喷嘴:30×2)在100s-1的剪切速率以及150℃(Visco1)和170℃(Visco2)的温度下测量。依据DIN EN ISO 527,用拉伸测试测定机械强度,测量破裂时的拉伸应力(TSF)。
依据DIN EN ISO 306,用1019g的重量,作为维卡软化点A测定模制品的硬度。为了评价冲击韧性(IT),依据DIN EN ISO 179-1eU测量断裂类型。
表1
表2
可见,可再分散粉末可以非常容易地混入PLA中:尽管在熔融物中,PLA和生物聚酯的粉末不产生均一的轧板(甚至添加非常少量的弹性生物聚酯就相当大地增加了不均匀性,其仅通过强力剪切动作即破坏),然而任何期望的RD粉末与PLA的混合物总是产生均匀的轧板(对比实施例2和对比实施例3的薄膜与实施例1-6相比)。PLA与RDP的模制品的机械性能显著优于PLA/生物聚酯混合物(对比实施例2与实施例1的TSF与IT对比,以及对比实施例2和实施例2的TSF与IT对比)。所述混合物的最终性能通过选择RD粉末来控制(实施例5与实施例6的TSF对比)。
可再分散聚合物粉末可以用比生物聚酯(生物聚合物)大得多的量与PLA混合。这证明了可再分散聚合物粉末与PLA的显著相容性。拉伸应力TSF可以保持高水平,而在高水平的生物聚酯的情况下,拉伸应力消失或不再可测(实施例3和4与对比实施例3对比,以及实施例5或6与对比实施例4对比)。
Claims (11)
1.用于生产可生物降解模制品的混合物,所述混合物基于一种或多种脂肪族聚酯,其特征在于,所述混合物还包含一种或多种水可再分散聚合物粉末。
2.权利要求1的混合物,其特征在于,所述脂肪族聚酯包括选自聚乳酸、聚羟基脂肪酸、C2-C6亚烷基的聚亚烷基琥珀酸酯和聚亚烷基己二酸酯中的一种或多种。
3.权利要求1或2的混合物,其特征在于,所述混合物包含聚乳酸和水可再分散聚合物粉末;或聚乳酸和至少一种其它脂肪族聚酯、以及水可再分散聚合物粉末;聚乳酸和至少一种脂肪族-芳香族聚酯、和任选存在的至少一种除聚乳酸之外的其它脂肪族聚酯、以及水可再分散聚合物粉末。
4.权利要求1-3之一的混合物,其特征在于,所述混合物还包含至少一种选自淀粉、蛋白质和纤维素酯的生物聚合物。
5.权利要求1-4之一的混合物,特征在于,所述水可再分散聚合物粉末包括一种或多种基于乙酸乙烯酯的均聚物、乙酸乙烯酯与乙烯的共聚物、乙酸乙烯酯、乙烯和具有9-11个碳原子的α-支化单羧酸的乙烯酯的共聚物的物质,以及每种情况下作为保护胶体的部分水解的聚乙烯醇。
6.权利要求1-5之一的混合物,特征在于,所述水可再分散聚合物粉末包括具有-20℃~+20℃的较低的Tg的水可再分散聚合物粉末与具有+30℃~+60℃的较高的Tg的水可再分散聚合物粉末的混合物。
7.用权利要求1-6之一的混合物生产可生物降解模制品的方法,所述方法是将所述脂肪族聚酯和水可再分散聚合物粉末、以及任选存在的其它添加剂彼此混合,并通过热塑成型技术加工成模制品。
8.权利要求7的生产可生物降解模制品的方法,其中还另外使用在塑料的热塑加工中惯用的添加剂。
9.权利要求7或8的生产可生物降解模制品的方法,其中还另外使用无机填料或有机填料。
10.权利要求7-9的方法产品作为可生物降解模制品的用途。
11.权利要求10的用途,其是作为可堆肥包装材料、可堆肥餐饮用品、园艺和景观美化中的可堆肥产品、医药领域中的可堆肥产品、露营领域中的可堆肥产品的用途。
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PCT/EP2009/063403 WO2010043648A1 (de) | 2008-10-16 | 2009-10-14 | Mischungen zur herstellung von biologisch abbaubaren formkörpern auf basis von aliphatischen polyestern und in wasser redispergierbaren polymerpulvern |
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CN (2) | CN104974488A (zh) |
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Cited By (8)
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CN104169237A (zh) * | 2012-03-13 | 2014-11-26 | 瓦克化学股份公司 | 无机材料在制备复合材料中的用途 |
CN104169237B (zh) * | 2012-03-13 | 2018-02-16 | 瓦克化学股份公司 | 无机材料在制备复合材料中的用途 |
CN107109041A (zh) * | 2014-12-22 | 2017-08-29 | 3M创新有限公司 | 包含聚乳酸聚合物、聚乙酸乙烯酯聚合物和增塑剂的组合物和膜 |
CN107109041B (zh) * | 2014-12-22 | 2020-10-16 | 3M创新有限公司 | 包含聚乳酸聚合物、聚乙酸乙烯酯聚合物和增塑剂的组合物和膜 |
CN108779370A (zh) * | 2015-12-22 | 2018-11-09 | 3M创新有限公司 | 包含含聚乳酸的包装材料的包装的预粘合剂组合物、粘合剂和制品 |
CN108779370B (zh) * | 2015-12-22 | 2021-02-12 | 3M创新有限公司 | 包含含聚乳酸的包装材料的包装的预粘合剂组合物、粘合剂和制品 |
CN109312147A (zh) * | 2016-06-21 | 2019-02-05 | 3M创新有限公司 | 包括半结晶聚乳酸基膜的图形制品 |
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JP5124687B2 (ja) | 2013-01-23 |
AU2009305379B2 (en) | 2012-10-11 |
US8202947B2 (en) | 2012-06-19 |
US20110207858A1 (en) | 2011-08-25 |
CA2736208A1 (en) | 2010-04-22 |
CA2736208C (en) | 2013-10-08 |
KR20110058873A (ko) | 2011-06-01 |
JP2012505942A (ja) | 2012-03-08 |
AU2009305379A1 (en) | 2010-04-22 |
KR101258191B1 (ko) | 2013-04-25 |
BRPI0920120A2 (pt) | 2015-12-22 |
DE102008042893A1 (de) | 2010-04-29 |
EP2334734A1 (de) | 2011-06-22 |
WO2010043648A1 (de) | 2010-04-22 |
BRPI0920120B1 (pt) | 2019-02-05 |
EP2334734B1 (de) | 2012-09-05 |
CN104974488A (zh) | 2015-10-14 |
ES2394557T3 (es) | 2013-02-01 |
MY150590A (en) | 2014-01-30 |
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