CN102165013B - 可生物降解的聚合物混合物 - Google Patents
可生物降解的聚合物混合物 Download PDFInfo
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- CN102165013B CN102165013B CN2009801384383A CN200980138438A CN102165013B CN 102165013 B CN102165013 B CN 102165013B CN 2009801384383 A CN2009801384383 A CN 2009801384383A CN 200980138438 A CN200980138438 A CN 200980138438A CN 102165013 B CN102165013 B CN 102165013B
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Abstract
本发明涉及可生物降解的聚合物混合物,包含i)基于组分i至ii的总重量计40至95重量%的至少一种基于脂族或脂族和芳族二羧酸与脂族二羟基化合物的聚酯;ii)基于所述组分i至ii的总重量计5至60重量%的聚碳酸亚烷基二酯,特别是聚碳酸亚丙酯;iii)基于所述组分i至iii的总重量计0至60重量%的至少一种选自聚乳酸、聚己内酯和聚羟基链烷酸酯的可生物降解的均聚酯或共聚酯,和/或无机或有机填料;iv)基于所述组分i至ii的总重量计0至10重量%基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的含环氧基共聚物,和v)0至15重量%的选自润滑剂、防结块剂、抗静电剂、UV吸收剂、UV稳定剂、热稳定剂、染料、颜料、着色剂、增塑剂、肥料和活性作物保护成分的添加剂。本发明还涉及生产可生物降解的聚合物混合物的方法,涉及可生物降解的聚合物混合物在生产模制品、膜或纤维的用途以及包含可生物降解的聚合物混合物的模制品、膜或纤维。
Description
本发明涉及可生物降解的聚合物混合物,其包含
i)基于组分i至ii的总重量计,40重量%至95重量%的至少一种基于脂族二羧酸或脂族和芳族二羧酸和脂族二羟基化合物的聚酯;
ii)基于所述组分i至ii的总重量计,5重量%至60重量%的聚碳酸亚烷基酯,特别是聚碳酸亚丙酯;
iii)基于所述组分i至iii的总重量计,0重量%至60重量%的至少一种选自由聚乳酸、聚己内酯和聚羟基链烷酸酯组成的组中的可生物降解的均聚酯或共聚酯,和/或无机或有机填料;
iv)基于所述组分i至ii的总重量计,0重量%至10重量%的基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的含环氧基共聚物,和
v)0重量%至15重量%的选自由润滑剂、防结块剂、抗静电剂、UV吸收剂、UV稳定剂、热稳定剂、染料、颜料、着色剂、增塑剂、肥料和活性作物保护成分组成的组中的添加剂。
本发明进一步涉及生成可生物降解的聚合物混合物的方法,涉及可生物降解的聚合物混合物在生产模制品、膜或纤维中的用途以及包含可生物降解的聚合物混合物的模制品、膜或纤维。
包含i)20重量%至5重量%的基于脂族和芳族二羧酸和脂族二羟基化合物的聚酯,ii)20重量%至80重量%的聚碳酸亚丙酯和iii)60重量%至15重量%的聚交酯的可生物降解混合物已知于WO2007/125039。在这些聚合物混合物中,一直是聚碳酸亚丙酯、或聚碳酸亚丙酯和聚乳酸的混合物构成连续相。包含这些混合物的膜在其机械性能方面并非总是令人满意的。
实际上,往往很难经由混合物实现所需的性质组合。混合物的性质并不是由单个组分的性质的加和而得到。而且,诸如韧度和劲度的性质的变化趋势经常为相反方向。而且,对于一些聚合物混合物,至少部分损失各组分的性质如透明度和阻隔效应。
本发明的一个目的是提供具有良好阻隔性质和良好机械性质如高拉伸强度和抗穿刺性的可生物降解混合物。
我们已经发现,该目的通过在开篇处定义的可生物降解的聚合物混合物实现,其将在以下内容中更加具体地进行描述。本发明的聚合物混合物具体而言通过包含较高比例的组分i而不同于现有技术的聚合物混合物。优选在聚合物混合物中形成连续相的组分i。
原则上,基于脂族和芳族二羧酸和脂族二羟基化合物的聚酯——已知为部分芳族聚酯——和由脂族二羧酸和脂族二醇形成的脂族聚酯,均可作为组分i用于生成本发明的可生物降解聚酯混合物。这些聚酯都具有它们满足DIN EN 13432可生物降解性的特性。应该理解到,两种或多种这种聚酯的混合物也适用于用作组分i。
部分芳族聚酯(组分i)应该为了本发明的目的也包含聚酯衍生物如聚醚酯,聚酯酰胺或聚醚酯酰胺。有用的部分芳族聚酯包括直链非链增长聚酯(WO 92/09654)。优选链增长和/或支化的部分芳族聚酯。后者已知于上述参考文献WO 96/15173至15176、21689至21692、25446、25448或WO 98/12242,其各自明确通过引证的方式纳入本文。不同部分芳族聚酯的混合物是同样有用的。有意思的最近的开发是基于可再生原料的(参见WO-A 2006/097353、WO-A 2006/097354和EP 08165372.7)。部分芳族聚酯应该理解为特别是指诸如Ecoflex(BASF SE)和EastarBio、Origo-Bi(Novamont)的产品。
尤其优选的部分芳族聚酯包括包含以下物质作为基本组分的聚酯:
A)由以下物质构成的酸组分
a1)30mol%至99mol%的至少一种脂族二羧酸或其成酯衍生物或其混合物,
a2)1mol%至70mol%的至少一种芳族二羧酸或其成酯衍生物或其混合物,和
a3)0至5mol%的磺化化合物,
B)由至少一种C2至C12烷二醇或其混合物构成的二醇组分
和,如果需要,还有选自以下的一种或多种组分
C)一种选自以下的组分
c1)至少一种包含醚官能团并具有结构式I的二羟基化合物
HO-[(CH2)n-O]m-H (I)
其中n表示2、3或4,m表示2至250的整数,
c2)至少一种结构式IIa或IIb的羟基羧酸
其中p表示1至1500的整数,r表示1至4的整数,G表示选自由亚苯基、邻羟基亚苯基、-(CH2)q-(其中q为1至5的整数)、-C(R)H-和-C(R)HCH2(其中R表示甲基或乙基)组成的组中的基团,
c3)至少一种氨基-C2至C12烷醇或至少一种氨基-C5至C10环烷醇或其混合物,
c4)至少一种二氨基-C1至C8烷烃,
c5)至少一种通式III的2,2′-二噁唑啉
其中R1表示单键、(CH2)z亚烷基(其中z=2、3或4)、或亚苯基基团,
c6)至少一种选自由以下化合物组成的组中的氨基羧酸:天然氨基酸、可通过具有4至6个碳原子的二羧酸和具有4至10个碳原子的二胺缩聚获得的聚酰胺、结构式IVa和IVb的化合物,和包含重复单元V的聚噁唑啉
其中s表示1至1500的整数,t表示1至4的整数且T表示选自由亚苯基、-(CH2)u-(其中u表示1至12的整数)、-C(R2)H-和-C(R2)HCH2(其中R2表示甲基或乙基)组成的组中的基团,
其中R3表示氢、C1-C6烷基、C5-C8环烷基、未被取代的苯基、被C1-C4烷基取代最高达3次的苯基,或四氢呋喃基,
或c1)至c6)的混合物
和
D)一种选自以下物质的组分:
d1)具有至少三个能够成酯的基团的化合物,
d2)二异氰酸酯或聚异氰酸酯,
d3)二环氧化物或聚环氧化物
或d1)至d3)的混合物。
在一个优选实施方案中部分芳族聚酯的酸组分A包含30mol%至70mol%,尤其是40mol%至60mol%的a1和30mol%至70mol%,尤其是40mol%至60mol%的a2。
作为脂族酸及其对应衍生物a1,一般可设想具有2至18个碳原子,优选4至10个碳原子的物质。它们可为支链的也可以是直链的。然而一般而言,也可使用具有更大数量的碳原子,例如最高达30个碳原子的二羧酸。
合适的实例有草酸、丙二酸、琥珀酸、戊二酸、2-甲基戊二酸,3-甲基戊二酸、α-酮基戊二酸、己二酸、庚二酸、壬二酸、癸二酸、十三烷二酸、富马酸、2,2-二甲基戊二酸、辛二酸、二甘醇酸、草酰乙酸、谷氨酸、天冬氨酸、衣康酸和马来酸。二羧酸或其成酯衍生物可单个使用或以其两种或多种的混合物的形式使用。
优选使用琥珀酸、己二酸、壬二酸、癸二酸、十三烷二酸或其各自的成酯衍生物或其混合物。特别优选使用琥珀酸、己二酸或癸二酸或其各自的成酯衍生物或其混合物。尤其优选使用己二酸或其成酯衍生物,如其烷基酯或其混合物。癸二酸,或癸二酸与己二酸的混合物优选用作脂族二羧酸而生成具有“硬”或“脆”的组分ii)如聚羟基丁酸酯或特别是聚交酯的聚合物混合物。琥珀酸或琥珀酸与己二酸的混合物优选用作脂族二羧酸而生产具有“硬”或“韧”的组分ii)如聚羟基丁酸酯-共-戊酸酯的聚合物混合物。
琥珀酸、壬二酸、癸二酸和十三烷二酸也具有可作为可再生原料而获得的优点。
芳族二羧酸或其成酯衍生物a2可单个使用或以其两种或多种的混合物的形式使用。特别优选使用对苯二甲酸或其成酯衍生物如对苯二甲酸二甲酯。
一般而言,二醇B选自具有2至12个碳原子,优选4至6个碳原子的支链或直链烷二醇,或具有5至10个碳原子的环烷二醇。
有用的烷二醇的实例是乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇、1,5-戊二醇、2,4-二甲基-2-乙基己-1,3-二醇、2,2-二甲基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、2-乙基-2-异丁基-1,3-丙二醇、2,2,4-三甲基-1,6-己二醇,特别是乙二醇、1,3-丙二醇、1,4-丁二醇和2,2-二甲基-1,3-丙二醇(新戊二醇);环戊二醇、1,4-环己二醇、1,2-环己烷二甲醇、1,3-环己烷二甲醇、1,4-环己烷二甲醇或2,2,4,4-四甲基-1,3-环丁二醇。特别优选1,4-丁二醇,特别是与己二酸组合作为组分a1),和1,3-丙二醇,特别是与癸二酸组合作为组分a1)。1,3-丙二醇另外也具有可作为可再生原料获得的优点。也可使用不同烷二醇的混合物。
根据是否需要酸或OH端基过量,组分A或组分B可过量使用。在一个优选的实施方案中,所用组分的A∶B摩尔比可处于0.4∶1至1.5∶1的范围,优选0.6∶1至1.1∶1的范围。
优选的部分芳族聚酯的特征在于分子量(Mn)在1000至100 000,特别是9000至75 000g/mol的范围,优选10 000至50 000g/mol的范围并且熔点处于60至170℃的范围,优选80至150℃的范围。
所提及的部分芳族聚酯可具有任何所需比例的羟基和/或羧基端基。所提及的部分芳族聚酯也可进行端基改性。例如,OH端基可通过与邻苯二甲酸、邻苯二甲酸酐、偏苯三酸、偏苯三酸酐、均苯四酸或均苯四酸酐反应而进行酸改性。
除了组分A和B之外,本发明聚酯混合物所基于的聚酯可包含另外的组分,如前述组分C和D。
脂族聚酯(组分i)包括包含衍生自脂族二醇和脂族二羧酸如聚琥珀酸丁二酯(PBS)、聚琥珀酸己二酸丁二酯(PBSA)、聚琥珀酸癸二酸丁二酯(PBSSe)、聚癸二酸丁二酯(PBSe)或对应的聚酯酰胺的单元的聚酯。脂族聚酯由Showa Highpolymers以名称Bionolle、由Mitsubishi以名称GSPla进行市售。更多近来的开发描述于EP08165370.1中。
脂族聚酯(组分i)进一步包括环脂族聚酯,特别是纤维素烷基酯如纤维素乙酸酯、纤维素乙酸酯丁酸酯或纤维素丁酸酯。
聚碳酸亚烷基二酯(组分ii)主要包括聚碳酸亚乙酯(参见EP-A1264860)(可通过环氧乙烷和二氧化碳共聚获得)和特别是聚碳酸亚丙酯(参见,例如WO 2007/125039PPC)(可通过环氧丙烷与二氧化碳共聚获得)。
聚碳酸亚烷基二酯链可不仅包含醚基团也包含碳酸酯基团。在聚合物中碳酸酯基团的比例取决于反应条件,如特别是所用的催化剂。在优选的聚碳酸亚烷基二酯中,超过85%并且优选超过90%的所有连接基团是碳酸酯基团。合适的锌和钴催化剂描述于US 4789727和US 7304172中。聚碳酸亚丙酯还可根据文献Soga et al.,PolymerJournal,1981,13,407-10类似地获得。聚合物也可购得,例如获自Empower Materials Inc.或Aldrich。
后处理中,特别重要的是催化剂要尽可能地定量除去。为此,一般的做法是用极性非质子溶剂如羧酸酯(特别是乙酸乙酯)、酮(特别是丙酮)和醚(特别是四氢呋喃)将反应混合物稀释至2至10倍的体积。随后,反应混合物与酸如乙酸和/或酸酐如乙酸酐掺混并在稍微升高的温度下搅拌几个小时。将有机相洗涤并分离。溶剂优选在减压下蒸出并将残余物干燥。
通过以上提及的以下方法制备的聚碳酸亚丙酯的分子量Mn一般处于70 000至90 000Da的范围。分子量Mw通常处于250 000至400000Da的范围。在聚合物中醚与碳酸酯基团的比率为5∶100至90∶100。为了改善性能特性,用MA、乙酸酐、二异氰酸酯或聚异氰酸酯、二噁唑啉或聚噁唑啉、或二噁嗪或聚噁嗪、或二环氧化物或聚环氧化物处理聚碳酸亚烷基二酯是有利的。分子量Mn在30 000至5000 000Da的范围,优选35 000至250 000Da并且更优选40 000至150 000Da的范围的聚碳酸亚丙酯可以按照这种方式获得。Mn低于25 000Da的聚碳酸亚丙酯一般具有的玻璃化转变温度低于25℃。另外,这些模塑材料具有低于400MPa的ISO 527-2/DIN 53455弹性模量和低于10MPa的断裂应力。这些低分子量聚碳酸亚丙酯对于大多数膜应用毫无用处。多分散性(重均(Mw)与数均(Mn)的比率)一般为1至80,优选2至10。所用的聚碳酸亚丙酯可包含最高达1%的氨基甲酸酯和脲基团。
对于聚碳酸亚烷基二酯有用的增链剂具体而言是MA、乙酸酐、二异氰酸酯或聚异氰酸酯、二噁唑啉或聚噁唑啉、二噁嗪或聚噁嗪、或二环氧化物或聚环氧化物。异氰酸酯的实例是甲苯2,4-二异氰酸酯、甲苯2,6-二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、萘1,5-二异氰酸酯或亚二甲苯基二异氰酸酯并且特别是1,6-己二异氰酸酯、异佛尔酮二异氰酸酯或亚甲基二(4-异氰酰基环己烷)。特别优选的脂族二异氰酸酯是异佛尔酮二异氰酸酯和特别是1,6-己二异氰酸酯。作为二噁唑啉,可以提及的有2,2’-二(2-噁唑啉)、二(2-噁唑啉基)甲烷、1,2-二(2-噁唑啉基)乙烷、1,3-二(2-噁唑啉基)丙烷或1,4-二(2-噁唑啉基)丁烷,特别是1,4-二(2-噁唑烷基啉基)苯、1,2-二(2-噁唑烷基啉基)苯或1,3-二(2-噁唑烷基啉基)苯。增链剂优选使用的量为基于聚合物的量计0.01重量%至5重量%,优选0.05重量%至2重量%,更优选0.08重量%至1重量%。
组分iii包含一种或多种选自由聚乳酸、聚己内酯和聚羟基链烷酸酯组成的组中的可生物降解的均聚酯或共聚酯,和/或无机或有机填料。优选的组分iii是聚乳酸(PLA)和聚羟基链烷酸酯,特别是聚羟基丁酸酯(PHB)和聚羟基丁酸酯-共-戊酸酯(PHBV),以及作为有机填料:天然的或塑化的淀粉,木粉或天然纤维如剑麻,纤维素,和/或无机填料如:白垩、石墨、石膏、导电性碳黑、氧化铁、氯化钙、白云石、高岭土、二氧化硅、碳酸钠、二氧化钛、硅酸盐、硅灰石、云母、蒙脱石,更特别是滑石、玻璃纤维和矿物纤维。
优选使用具有以下性能分布的聚乳酸(组分iii):
●在190℃和2.16kg下ISO 1133MVR熔体体积流速为0.5——优选2——至30特别是9mL/10min;
●熔点低于240℃;
●玻璃化转变点Tg高于55℃
●水含量低于1000ppm
●剩余单体含量(交酯)低于0.3%
●分子量大于80 000道尔顿。
聚羟基链烷酸酯主要是聚-4-羟基丁酸酯和聚-3-羟基丁酸酯,但还包括前述羟基丁酸酯与3-羟基戊酸酯或3-羟基己酸酯的共聚酯。具体而言,聚-3-羟基丁酸酯-共-4-羟基丁酸酯已知自Metabolix。它们以商标名Mirel进行销售。聚-3-羟基丁酸酯-共-3-羟基己酸酯已知自P&G或Kaneka。聚-3-羟基丁酸酯例如由PHB Industrial以商标名Biocycle、由Tianan以商标名Enmat进行销售。
聚羟基链烷酸酯的分子量Mw一般处于100 000至1 000 000的范围,优选300 000至600 000的范围。
一个优选的实施方案包括选择基于组分i至iii的总重量计1重量%至60重量%,优选5重量%至40重量%的选自由天然的或塑化的淀粉、天然纤维、木粉填料、粉碎软木、磨碎树皮、坚果壳、磨碎的压滤饼(植物油精炼)、饮料(如啤酒、酿造柠檬水(如Bionade)、白酒或清酒)发酵或蒸馏的干燥生产残余物组成的组中的有机填料和/或选自由白垩、石墨、石膏、导电性碳黑、氧化铁、氯化钙、白云石、高岭土、二氧化硅(石英)、碳酸钠、二氧化钛、硅酸盐、硅灰石、云母、蒙脱石、滑石、玻璃纤维和矿物纤维组成的组中的无机填料。
淀粉和直链淀粉可为天然的,如非热塑化的,或它们可为用增塑剂如甘油或山梨醇进行热塑化的(EP-A 539 541,EP-A 575 349,EP652 910)。
天然纤维的实例有纤维素纤维、麻纤维、剑麻、洋麻、黄麻、亚麻、蕉麻、椰壳纤维或Cordenka纤维。
优选的纤维填料是玻璃纤维、碳纤维、芳香聚酰胺纤维、钛酸钾纤维和天然纤维,其中E-玻璃的形式的玻璃纤维是特别优选的。这些可作为以市售形式的粗纱或尤其是作为切碎玻璃使用。这些纤维的直径一般处于3至30μm的范围,优选6至20μm的范围,更优选8至15μm的范围内。化合物中纤维的长度一般处于20μm至1000μm的范围,优选180至500μm的范围,更优选200至400μm的范围内。
组分iv具体包含基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的含环氧基的共聚物。含有环氧基团的单元优选是(甲基)丙烯酸缩水甘油酯。甲基丙烯酸缩水甘油酯含量大于该共聚物的20重量%,更优选大于30重量%,甚至更加优选大于50重量%的共聚物,将是特别有利的。在这些聚合物中环氧基当量(EEW)优选处于150至3000g/当量的范围,更优选200至500g/当量的范围。聚合物的重均分子量MW优选处于2000至250 00的范围、尤其是3000至8000的范围。该聚合物的数均分子量Mn优选处于400至6000的范围,特别是1000至4000的范围。多分散性(Q)一般为1.5至5。以上所提及类型的含环氧基共聚物可购得,例如以商标名JoncrylADR获自BASFResins B.V.。JoncrylADR 4368尤其适于用作增链剂。
组分iv)一般使用的量是基于组分i)至iii)的总重量计0重量%至10重量%,优选0.1重量%至5重量%,更优选0.5重量%至2重量%。
本发明的可生物降解聚酯混合物可含有其它本领域技术人员已知的对于本发明并不重要的其他添加剂(组分v)。实例有塑料技术中常规加入的物质如稳定剂;成核剂;中和剂;润滑和脱模剂如硬脂酸盐(特别是硬脂酸钙);增塑剂如例如柠檬酸酯(特别是乙酰柠檬酸三丁酯)、甘油酯如三乙酰基甘油或乙二醇衍生物;表面活性剂如聚山梨酸酯、棕榈酸酯或月桂酸酯;蜡如蜂蜡或蜂蜡酯;抗静电剂;UV吸收剂;UV稳定剂;热稳定剂;防雾剂;染料;颜色颜料或活性物质(例如作物保护剂如杀真菌剂、杀虫剂、杀生物剂、生长促进剂、信息激素和维生素)。有用的添加剂进一步包括含环氧基的(环氧化的)天然油或脂肪酸酯。天然油是指例如橄榄油、亚麻籽油、大豆油、棕榈仁油、花生油、椰子油、海藻油,鱼肝油或其混合物。特别优选环氧化的豆油(例如,获自Hobum,Hamburg的MerginatESBO,或获自Cognis,Düsseldorf的EdenolB 316)。添加剂的使用浓度为基于本发明的聚酯计0%至15重量%,特别是0.1重量%至2重量%。增塑剂可以以0.1重量%至10重量%存在于本发明的聚酯中。
常用的聚合物混合物包括:
本发明的可生物降解聚酯混合物通常包含40重量%至95重量%,优选40重量%至80重量%,更优选40重量%至60重量%的组分i和5重量%至60重量%,优选20重量%至60重量%,更优选40重量%至60重量%的组分ii,每一重量百分数都基于组分i至ii的总重量计并且加起来等于100重量%。
挤出的热塑性材料如膜的生产例如要求泡沫稳定性。现在发现,其中组分i构成优选的连续相或至少共连续相且组分ii嵌埋于这个相中的独立的区域内的混合物具有泡沫稳定性。为了组分i可形成连续相,混合物包括一般大于40重量%,优选大于50重量%的组分i,所有百分比都基于组分i和ii的总重量计。
通过注塑进行的模制品的生产例如可利用具有高含量的聚羟基丁酸酯(PHB)或尤其是聚乳酸(PLA)(组分iii)的聚酯混合物。一定程度上,聚乳酸尤其是还有聚羟基链烷酸酯与聚碳酸亚丙酯在宽范围内构成共连续相。
本发明聚合物混合物的优选实施方案包含:
基于组分i至ii的总重量计,20重量%至80重量%,更优选40重量%至60重量%的组分i;和
基于组分i至ii的总重量计,80重量%至20重量%,更优选60重量%至40重量%由以下物质组成的混合物:
-20重量%至80重量%的聚碳酸亚丙酯;和
-80重量%至20重量%的聚羟基链烷酸酯和特别是聚乳酸。
“可生物降解性”的特性对于本发明的目的而言,应该被理解为当任何一种材料或物质组合物具有等于至少90%的DIN EN 13432生物降解百分数时,其满足所述可生物降解性。
可生物降解性的一般效应是聚酯(共混物)在合适的可确定的时间段内发生分解。降解可以是通过酶作用、水解作用、氧化作用和/或通过电磁辐射作用,例如UV辐射而发生,并可主要是由于微生物如细菌、酵母、真菌和藻类的作用。可生物降解性可例如通过聚酯与堆肥混合并储存一定时间而进行定量。根据DIN EN 13432,例如,去除了CO2的空气流过堆肥期间的成熟堆肥并使这种成熟堆肥经受预定温度程序。此时可生物降解性定义为由样品释放的净CO2(在扣除由堆肥而不是样品释放的CO2之后)与样品可释放的CO2最大量(根据样品碳含量计算)的比率,以生物降解的百分数表示。刚刚堆肥处理几天后,可生物降解的聚酯/聚酯共混物通常示出明显的降解信号,如真菌生长、开裂和破洞。
确定生物可降解性的其它方法,例如描述于ASTM D 5338和ASTM D 6400-4中。
由各组分生产本发明的可生物降解的聚合物混合物可通过以下已知的方法(EP 792 309和US 5,883,199)进行。例如,所有的混合组分可在一个操作步骤中在常规混合设备,如捏合机或挤出机中在升高的温度,例如120至250℃下混合并发生反应。
例如,所有组分i、ii和iii可在一个操作步骤中在常规混合设备,例如捏合机或挤出机中在升高的温度,例如120至250℃下混合并反应。
另外,组分i和ii首先混合并随后与组分iii和iv的混合物进行掺混/反应是有利的。
类似地,将会发现,在由组分i至iii构成的三元混合物的情况下,组分ii和iii进行预混并与组分i——如果合适组分iv和如果合适组分v——的混合物进行掺混是有利的。
为此,在第一步骤中,1重量%至50重量%,优选5重量%至35重量%的组分iv与50重量%至99重量%,优选65重量%至95重量%的组分i在110至145℃——优选120至140℃——下混合而获得支化剂母料。在该温度下,获得均匀的掺混物,而不出现显著的分子量升高。由此获得的支化剂母料可毫无困难地在室温下储存。在第二步骤中,所需的组合物可通过向组分ii和iii以及如果合适的另外的组分i中加入支化剂母料而获得。这个混合步骤在150至250℃,优选在160至190℃下实施。
本发明的可生物降解聚酯混合物尤其适用于生产模制品、膜或纤维。生产可通过以下本领域内技术人员已知的方法进行实施。
具有改善的降解速率的可生物降解聚酯混合物的应用的一个具体领域涉及在膜、尤其是农用覆盖薄膜的生产中的用途。这种覆盖膜应用于农耕区域以保护幼苗并主要促进幼苗生长。在收获之后,这些覆盖膜残留在土壤上或——对于可生物降解的覆盖膜——犁于土壤之下。这些覆盖膜在来年播种开始之前必须发生大部分生物降解。
本发明的聚合物混合物非常适用于泡沫体应用(参见EP07102477.2和EP 07102497.0;“foam extrusion-principles andpractice”,Shau-Tarng Lee,376页,CRC出版社,2000;“thermoplasticfoam extrusion”,James Thorne,Carl Hanser,2006)。获得以下优点:
●半透明、高度透光的发泡材料
●手感柔软—即使是以共挤出的形式
●DIN EN 13432的可生物降解性
●所需的触觉
●适用于食品包装
●高UV抗性
●低密度
●良好的隔音性
●良好的阻隔性质
泡沫体适用作肉、鱼、水果、蔬菜、海味、快餐食品的托盘、容器;作为具有敏感表面的产品如消费品、汽车、电器、高保真设备、电话、手机的保护外层;包装材料、插入物和清洁海绵。
本发明的聚合物混合物可加工处理成低密度的泡沫层或者其它珠状泡沫。密度显著低于150g/L的泡沫体例如用59重量%的脂族-芳族聚酯(EcoflexFBX 7011)和40重量%的聚碳酸亚丙酯(参见实施例1)的二元混合物是可实现的。纯聚碳酸亚丙酯可类似地进行发泡,但是具有较高的密度。在发泡之前向聚合物混合物中加入0.02重量%至5重量%,优选0.1重量%至2重量%的成核剂是有利的。有用的成核剂特别包括滑石、白垩,碳黑或其它矿物填料。有用的发泡剂特别包括物理发泡剂如氮气、丁烷、戊烷,特别是二氧化碳。在发泡期间,发泡剂一般受压最高达400大气压。发泡作用不仅能够在挤出过程中发生而且也能在注塑过程中发生。类似地,在膜上原位发泡将是有利的。发泡温度一般处于30至240℃,优选40至100℃的范围。泡沫体具有均匀的微孔结构并一般包括封闭的和开放的孔。封闭孔的含量可通过加入组分vi)如Joncryl ADR 4368而显著地增加。对于声波吸收,提高开放孔结构的比例是有利的。
本发明的聚合物混合物非常适用于透明的刚性的或半刚性包装、元件、容器等,这些公开于文献:“Polymer Extrusion“,ChrisRauwendaal,Carl Hanser,1986;“Thermoforming“,James Thorne,Carl Hanser,1986;“Einführung indie Kunststoffverarbeitung”,Walter Michaeli,Carl Hanser,2006;“Handbuch Spritzgieβen“,Friedrich Johannaber,W.Michaeli,Carl Hanser,2004;“BlowMolding Handbook“,Dominik V.Rosato et al.,Carl Hanser,2004;“Kunststoff Maschinenführer”,Friedrich Johannaber,Carl Hanser,2004中。引述于本文中的尤其是杯、壶、盖、盘、托盘、餐饮业、快餐业中的饮料吸管。奶制品的透明包装,香肠和肉、奶酪、鱼、水果和蔬菜、药片和药品的透明的半刚性包装。
本发明的聚合物混合物非常易于进一步加工成管式膜、拉伸包装膜(stretch wrapping film)、可剥离膜(peelable film)和收缩包装膜(shrink wrapping film)。本文中可能的应用是底折袋、侧缝袋、握孔手提袋、收缩标签或背心式手提袋。
收缩包装膜具有的收缩率在收缩包装膜的挤出方向上超过40%,优选超过50%,更优选超过60%。在垂直方向上,收缩包装膜具有小于40%,优选小于25%,更优选小于15%的相对较低的收缩值。收缩值涉及到膜在收缩管中被加热到超过其玻璃化转变温度至少10℃,优选至少30℃。特别优选将膜加热至低于膜材料熔化温度至少50℃(优选至少30℃)从而使膜也可随着其收缩而熔合。
收缩包装膜或收缩标签目前经常用于将可打印信息赋予瓶子或其它容器。其实例是全身套(full body sleeve)、收缩套(shrink sleeve)、促销包(promotion pack)、安全外罩等,这描述于例如文献“Kunststoff-Folien Herstellung-Eigenschaften-Anwendung“,Joachim Nentwig,Carl Hanser,2001”中。
该过程将本发明的混合物转化成以下产品例如:卫生应用的膜:例如尿布背板、女性护理产品、水果和蔬菜袋、报纸包裹薄膜、手提袋、购物袋、堆肥袋、垃圾袋、可剥离封膜——透明或不透明、可熔封膜——透明或不透明,肠衣、沙拉膜、水果和蔬菜、肉类和鱼类的保鲜膜(拉伸包装膜)、包装托盘的拉伸膜包装膜、网薄膜、点心包装薄膜、糖果柄和穆兹利棒,乳品包装(酸奶,奶油等)、水果和蔬菜的可剥离盖膜、烟熏香肠和奶酪的半刚性包装。
本发明的可生物降解聚酯混合物提供加工成抗穿刺膜而不存在泡沫稳定性问题的可生物降解聚合物混合物。
包装技术的全面综述将能在文献“Food Packaging Technology”,Richard Coles,Derek McDowell,Mark Blackwell Publishing,CNCPress,2003和“Wursthüllen Kunstdarm-Herstellung-Eigenschaften-Anwendung”,Gerhard Effenberger,HolzmannVerlag,1991中找到。由本发明的混合物可获得的产品实例是保护性气体包装、透明隔离膜、能够烹饪和灭菌的膜,以及无金属隔离膜。
本发明的混合物具有可生物降解膜的优异的氧和香味阻隔性质而因此注定用于以下这些物质的包装:肉、家禽肉、肉制品、加工肉食、小香肠、烟熏腊肠、海鲜、鱼、蟹肉、奶酪、奶酪制品、甜点,例如具有肉、鱼、家禽肉、番茄馅、面团和面包涂酱的馅饼;面包、蛋糕、其它烘烤食品;水果、水果汁、蔬菜、番茄酱、沙拉;宠物食物;药品;咖啡、类咖啡制品;牛奶或可可粉、咖啡奶精、婴儿食品;干燥食品;果酱和果冻、面包涂酱、巧克力奶油涂酱;速食套餐。其它信息参见文献“Food Processing Handbook”,James G.Brennan,Wiley-VCH,2005。
该混合物也适用作卫生产品的结构材料如牙刷、梳子,棉签,口红或刷子,以园林浇灌管形式的挤出软管,二或三维工艺制品等。
由于其具有所需的触感性质,本发明的混合物可用于鞋类,例如作为鞋底或镶嵌件,作为雪地靴的镶嵌件,作为护膝、垫肩片、胸罩填料或其它运动用品、化妆品或医疗制品。
混合物也可通过例如纺纱形成纤维,并用于衣服、床单或毯子的生产。
混合物也非常易于进一步可加工成木塑料复合物(WPC)。
WPC(也已知作为木(-纤维)聚合物复合物)是可热塑性加工的建筑复合材料,其由不同比例的木材、塑料和添加剂组成并经由热塑成型加工方法,例如挤出、注塑、旋转成型、压制成型或热成型进行加工。超过20%的纤维含量则被分类作为生物质。
木塑料复合物优于木材基材料的优点在于,木材塑料复合物的自由、3维可成形性和其较高的耐湿性。相比于全塑料材料,WPC提供了较高的劲度和明显较低的热膨胀系数。
WPC最重要的市场是甲板,其中生物质目前占有约6%的市场份额——特别是作为热带木材的替代品。未来20%的市场份额被认为是可能的。在家具工业中的应用(家具轮廓,地板条)已经显著增长,其中尤其可获得几种WPC椅子和架子系统。
欧洲汽车工业每年使用大约50 000t的WPC作为门内饰和包裹架(后来包括在装饰中)。由生物基WPC生产的热塑性注塑制品迄今仅在德国作为“生态产品(niche products)”(Wikipedia)提供。
使用木粉和天然纤维可进一步提高PPC(Tg 25至35℃)及其混合物的耐热性,因此新的使用领域可向PPC敞开。
PPC与淀粉、天然纤维和木粉的聚合物混合物已经描述于文献Polym Rev.2008,192-219中。一般而言,杨氏模量随着填料含量升高而增加,同时甚至在低填充水平下断裂伸长也显著降低。
实施例:
有关性能的测定:
部分芳族聚酯的分子量Mn如下测定:
将每种15mg的部分芳族聚酯溶解于10mL的六氟异丙醇(HEIP)中。在每一情况下,将125μL的该溶液通过凝胶渗透色谱(GPC)进行分析。测量过程在室温下进行。HFIP+0.05重量%三氟乙酸钾用于洗脱。洗脱速率为0.5mL/min。使用如下的柱组合(所有柱子来自Showa Denko Ltd.):ShodexHFIP-800P(直径8mm,长度5cm),ShodexHFIP-803(直径8mm,长度30cm),ShodexHFIP-803(直径8mm,长度30cm)。部分芳族聚酯通过RI检测器(差示折光)进行检测。分子量为Mn=505至Mn=2 740 000的窄分布聚甲基丙烯酸甲酯标准物用于标定。在该区间之外的洗脱范围通过外推法测定。
渗透测定
水蒸汽
在载气方法中,自由样品膜(无支撑材料)在这种情况下安装于每侧具有空腔的气密性池中5cm2面积内。在大气压下,载气(N2)通入经过样品的一侧而测定经过样品另一侧的气体(N2+水蒸汽)。扩散穿过样品的测定气体被载气吸收并带到选择性传感器。对于水蒸汽测定仪使用IR传感器。因此水蒸汽浓度可作为时间的函数而被测定。
测量过程在23℃下根据ASTM F-1249进行。仪器调节约半小时。穿过样品的透过率在设置为85%的相对湿度下尽可能精确地测定,在设置的相对湿度下产生的小实验误差随后在以下假设下进行数学校正:透过率与所测量范围内的相对湿度线性相关。
测量仪器运行时间为一天。
氧
在载气方法中,自由样品膜(无支撑材料)在这种情况下安装于每侧具有空腔的气密性池中5cm2面积内。在大气压下,载气(95%N2和5%H2)通入经过样品的一侧而测定气体(100%干燥O2)经过样品另一侧。扩散穿过样品的测定气体被载气吸收并带到选择性传感器。因此氧浓度可作为时间的函数而被测定。
对于氧测定仪使用电化学检测器。测量过程在23℃下进行。仪器根据ASTM D-3985操作。仪器调节花费大约半个小时。
对于所有测量的仪器运行时间为一天。
数据处理
对于两种测定方法,样品的透过率[g/m2/d]标准化至样品的平均厚度,在5个不同地方测量,从而得出渗透率[g.m/m2/d/bar]。数据和结果在以下表中给出。
所用材料:
组分i:
组分ii:
ii-1:聚碳酸亚丙酯
a.催化剂制备
首先向配备搅拌器、热浴和脱水器的1L四颈烧瓶中装入35g粉碎的氧化锌的250mL的无水甲苯溶液。在加入53g戊二酸之后,将混合物加热至55℃2小时并搅拌。此后,加热至沸腾,将反应产生的水在回流下共沸蒸出直至水停止通过。将甲苯蒸出而残余物在高真空下于80℃进行干燥。
b.聚合
首先将12g戊二酸锌装入反应器。使用配备机械搅拌器的3.5L高压釜。在反应器密封之后,反复通入氮气。随后,向反应器中于室温下(23℃)加入620g甲苯并注入6bar的CO2。然后,向反应器中注入310g环氧丙烷,接着加热至80℃。此后,在80℃下向反应器中注入足量的CO2以达到40bar的CO2压力。反应器在80℃维持4h,在此期间并未加入另外的CO2。然后冷却至室温。
c.后处理
将反应器与大气连通并将反应器内容物倾倒进1L用基于聚合物的量计65重量%的浓乙酸和基于乙酸计2重量%的乙酸酐酸化的乙酸乙酯中。之后在40℃下搅拌2h。随后将有机相用1L水洗涤3次。从有机相中除去溶剂并将聚合物残余物在减压下干燥。
d.分析
为了测定不想要的副产物(在聚合物骨架中环状碳酸亚丙酯和聚醚部分)的比例,在Bruker的AMX 300光谱仪上记录1H NMR谱。相对于碳酸酯总量,聚醚部分为4.2%,环状碳酸酯部分为约2.0%。
聚合物的分子量(Mn和Mw)也进行了测量:
Mn 52 000g/mol,Mw 910 000g/mol
组分iii:
组分iv:
其它组分:
添加剂:芥酸酰胺(Cognis GmbH,D-Düsseldorf),亚乙基双硬脂酰胺,碳酸钙(Omya BLS,OMYA GmbH,D-Cologne)
所用的母料为:
v-1:具有以下组分的FBA-SL1批料:
●73%的组分i-1,
●20%的组分iv-1,
●7%的芥酸酰胺(Cognis GmbH,D-Düsseldorf)
v-2:具有以下组分的SL1批料:
●90%的组分i-1,
●10%的芥酸酰胺(Cognis GmbH,D-Dusseldorf)
v-3:具有以下组分的AB 1批料:
●40%的组分i-1,
●60%的碳酸钙(Omya BLS,OMYA GmbH,D-Cologne)
复合
组分i-1和iii-1在热循环空气橱中于60℃下预干燥至残余水分含量低于800ppm。考虑到较低的Tg,将组分ii-1储存并于低于30℃的温度下预干燥。
组分i-1、ii-1和iii-1和v-1都在60℃下预干燥至低于800ppm的残余水分含量。这些组分与干冰预混以防止温度升高至超过30℃。
随后在来自Coperion,D-Stuttgart的ZSK 25上以300L/min和190℃的熔体温度下生产复合物。产量为10kg/h。挤出物在水浴中冷却至约15℃并用线材造粒机(strand pelletizer)造粒。
膜生产
在管式膜范围上生产膜。挤出机(直径45mm,长度25D)用槽进料区和具有剪切和混合部分的三区螺杆进行工作。进料区在最大产量下用冷水冷却至低于10℃。选择区域温度以使熔体温度为180至190℃。模头温度处于熔体温度范围内。模头直径为75mm,狭缝尺寸为1.2mm。旋转速度和所选的10kg/h的生产量为300L/min。3.5∶1的膨胀率为膜管产生一个宽度412mm的平台。引出速度对于30μm厚度的膜为2.7m/min。
在仅仅V1进行的情况下,组分在膜生产之前干燥混合以产生干燥的共混物。其它产品不经过预处理而加工成膜。上述实施例提供了膜F1、F2、F3、F4、F-V1、F-V2和F-V3。
膜F1和F-V1的对照(参见表1)
相比于F-V1(MD=轴向;CD=横向),F1膜的机械参数如下所示通过本发明组分ii-1的添加分数而得以改善:
劲度、屈服应力和抗穿刺性的优异增加仅仅导致在CD方向上的断裂伸长的非常小的降低。拉伸强度在MD方向上稍微升高而在CD方向上仅非常小地下降。
氧和水蒸汽的渗透率值对于相同的膜厚分别降至原始值的1/6和1/3。
膜的透明度(浊度值)改进超过50%。
收缩率值在两个方向上都显著增加。
这些结果是令人惊讶的,因为组分ii-1在组分i中以精细分散体存在并且未形成连续相。
膜F4和F-V2的对照(参见表1)
F1膜在组成上不同于F-V2对照膜,因为13%的组分i-1用组分ii-1代替。性质变化情况如下:
本发明的F4膜相比于F-V2显示出在劲度和强度的显著升高。断裂伸长正如对于较硬的膜F4所预期的那样发生了降低并且抗穿刺性降低。
改善的透明度表明了相对于F-V2的结构变化。透射电镜照片表明当前组分ii-1形成了相干相(coherent phase)。
木塑料复合物(WPC)
实施例
在轧制机上生产共混物
将轧制机的辊加热至180℃,实施例1和2的PPC、Ecoflex和聚交酯或聚合物混合物与木粉混合至少20min直至形成均匀的薄板:
选择以下掺混物作为实施例:
实施例5:50g实施例1化合物和50g云杉木粉
实施例6:50g实施例2化合物和50g云杉木粉
在所有的这些情况下获得的轧制板是坚硬的、非粘性的。将薄板切成更小的片(±50至100mm2)并压制成不同形状用于随后的分析。
1.Vicat(ISO 306):成型成大小1cm2厚度4mm的圆盘。
2.HDT(ISO 75-1,-2):成型成尺寸7×10×4mm的条。
3.E模量(拉伸测试):生产出尺寸为60×60×1mm的压制成型板材并随后用模具切成长度5cm的肩杆(shoulder bar)。
所获得的模制成型制品是坚硬的、非粘性的。
2.在挤出机上生产共混物
用DSM Mini Extruder随着收缩而生产PPC、Ecoflex、PLA和木粉的聚合物混合物。这通常用11g聚合物并在180℃下混合3至5min完成。聚合物熔体被注塑成为肩杆模制品并随后容易地脱模。所获得的肩杆是坚硬的、非粘性的。
3.耐热性
Vicat(ISO 360)[℃] | HDT ISO 75-1,-2[℃] | |
组分ii-1 | <23 | 不可测定 |
实施例1 | 63.9 | 36.6 |
实施例2 | 50 | 40.5 |
实施例5 | 99.1 | 71.6 |
实施例6 | 107.4 | 86.3 |
云杉木粉的加入提高了肩杆的耐热性。例如,对于实施例1,加入50%的云杉木粉提高了测得的耐热性,HDT ISO 75-1,-2的热挠曲温度从35℃升高至71.6℃。通过加入10%的PLA(实施例2)热挠曲温度可升高至86.3℃。
肩杆的机械性能
加入木粉显著提高了材料的劲度。例如,加入50%的云杉木粉,实施例1中的E模量提高了1400MPa。加入10%的PLA,劲度仍进一步提高(2400MPa)。
相反,加入天然填料断裂伸长显著降低。
Claims (18)
1.一种可生物降解的聚合物混合物,包含
i)基于组分i至ii的总重量计,40重量%至95重量%的至少一种基于脂族和芳族二羧酸与脂族二羟基化合物的聚酯;
ii)基于所述组分i至ii的总重量计,5重量%至60重量%的聚碳酸亚烷基二酯;
iii)基于所述组分i至iii的总重量计,0重量%至60重量%的选自由聚乳酸、聚己内酯和聚羟基链烷酸酯组成的组中的至少一种可生物降解的均聚酯或共聚酯,和/或无机或有机填料;
iv)基于所述组分i至ii的总重量计,0重量%至10重量%的基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的含环氧基共聚物,和
v)0重量%至15重量%的添加剂,
其中所述组分i包括:
A)酸组分,由以下物质组成
a1)30mol%至99mol%的至少一种脂族二羧酸或其成酯衍生物或其混合物,
a2)1至70mol%的至少一种芳族二羧酸或其成酯衍生物或其混合物,和
a3)0至5mol%的磺化化合物,
所述组分a1)至a3)的摩尔百分数总计最高达100%,和
B)由至少一种C2至C12烷二醇或其混合物构成的二醇组分以及,如果需要,还有选自以下组分的一种或多种组分
C)一种选自以下物质的组分
c1)至少一种包含醚官能团并具有所述结构式I的二羟基化合物
HO-[(CH2)n-O]m-H (I)
其中n表示2、3或4,m表示2至250的整数,
c2)至少一种结构式IIa或IIb的羟基羧酸
其中p表示1至1500的整数,r表示1至4的整数,并且G表示选自由亚苯基、α-羟基亚苯基、-(CH2)q-——其中q为1至5的整数、-C(R)H-和-C(R)HCH2——其中R表示甲基或乙基——组成的组中的基团,
c3)至少一种氨基-C2至C12烷醇或至少一种氨基-C5至C10环烷醇或其混合物,
c4)至少一种二氨基-C1至C8烷烃,
c5)至少一种结构通式III的2,2'-二噁唑啉
其中R1表示单键、(CH2)z亚烷基——其中z=2、3或4——或亚苯基基团,
c6)至少一种选自由天然氨基酸、通过具有4至6个碳原子的二羧酸和具有4至10个碳原子的二胺缩聚可获得的聚酰胺、结构式IVa和IVb的化合物组成的组中的氨基羧酸
其中s表示1至1500的整数,t表示1至4的整数并且T表示选自由亚苯基、-(CH2)u-——其中u表示1至12的整数、-C(R2)H-和-C(R2)HCH2——其中R2表示甲基或乙基——组成的组中的基团,
和包含重复单元V的聚噁唑啉
其中R3表示氢、C1–C6烷基、C5–C8环烷基、未被取代苯基、用C1-C4烷基取代最高达3次的苯基,或四氢呋喃基,
或c1)至c6)的混合物
和
D)选自由以下物质组成的组中的组分:
d1)具有至少三个能够成酯的基团的化合物,
d2)二异氰酸酯或聚异氰酸酯,
d3)二环氧化物或聚环氧化物
或d1)至d3)的混合物。
2.权利要求1的可生物降解的聚合物混合物,其中所述组分ii的聚碳酸亚烷基二酯是聚碳酸亚丙酯。
3.权利要求1的可生物降解聚合物混合物,其中在所述组分i)中:
·所述脂族二羧酸(组分a1))包括琥珀酸、己二酸或癸二酸、其成酯衍生物或其混合物;
·所述芳族二羧酸(组分a2))包括对苯二甲酸或其成酯衍生物,和
·所述二醇组分(组分B)包括1,4-丁二醇或1,3-丙二醇。
4.权利要求1至3的可生物降解聚合物混合物,其中所述组分iii为聚乳酸和/或选自由淀粉、木粉和天然纤维组成的组中的有机填料。
5.权利要求1的可生物降解聚合物混合物,其中在所述组分iv中的所述含环氧基的共聚物含有缩水甘油醚基团。
6.权利要求1的可生物降解聚合物混合物,包含
40重量%至80重量%的所述组分i和
60重量%至20重量%的所述组分ii,
所有百分比都基于所述组分i至ii的总重量计。
7.权利要求6的可生物降解聚合物混合物,包含
基于所述组分i至ii的总重量计,40重量%至60重量%的所述组分i;
基于所述组分i至ii的总重量计,60重量%至40重量%由以下物质组成的混合物:
-20重量%至80重量%的聚碳酸亚丙酯;和
-80重量%至20重量%的聚乳酸或聚羟基链烷酸酯。
8.权利要求6或7的可生物降解聚合物混合物,其中所述组分i形成连续或共连续相。
9.权利要求6或7的可生物降解聚合物混合物,其中所述组分ii或所述组分ii和iii形成连续或共连续相。
10.权利要求1的可生物降解聚合物混合物,包含基于所述组分i至ii的总重量计0.1重量%至5重量%的所述组分iv。
11.用于生产权利要求1至10的可生物降解的聚合物混合物的方法,其包括将所述组分i、ii和iii在一步操作中进行混合并进行反应。
12.用于生产权利要求1至10的可生物降解的聚合物混合物的方法,其包括将所述组分i、ii在一步操作中进行混合并随后与所述组分iii和iv混合和反应。
13.权利要求1至10的可生物降解聚合物混合物在生产模制品、膜或纤维中的用途。
14.包含权利要求1至10的可生物降解的聚合物混合物的模制品、膜或纤维。
15.包含权利要求1至10的可生物降解的聚合物混合物的收缩包装膜。
16.包含权利要求1至10的可生物降解的聚合物混合物的可剥离膜。
17.包含权利要求1至10的可生物降解的聚合物混合物的拉伸包装膜。
18.包含权利要求1至10的可生物降解的聚合物混合物的泡沫层或珠状泡沫。
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PCT/EP2009/062202 WO2010034689A1 (de) | 2008-09-29 | 2009-09-21 | Biologisch abbaubare polymermischung |
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EP (1) | EP2331634B1 (zh) |
JP (2) | JP2012504166A (zh) |
KR (1) | KR20110081235A (zh) |
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WO2010034689A1 (de) | 2010-04-01 |
EP2331634A1 (de) | 2011-06-15 |
JP6080931B2 (ja) | 2017-02-15 |
US20150094416A1 (en) | 2015-04-02 |
CN102165013A (zh) | 2011-08-24 |
JP2012504166A (ja) | 2012-02-16 |
US9206311B2 (en) | 2015-12-08 |
US8937135B2 (en) | 2015-01-20 |
KR20110081235A (ko) | 2011-07-13 |
US20110178196A1 (en) | 2011-07-21 |
AU2009295999A1 (en) | 2010-04-01 |
EP2331634B1 (de) | 2016-12-14 |
AU2009295999B2 (en) | 2013-12-19 |
JP2016033220A (ja) | 2016-03-10 |
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