CN102971357B - 增加聚酯分子量的方法 - Google Patents
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Abstract
本发明涉及一种通过在挤出机中将100份聚酯与i)0.01-5份四羧酸二酐和ii)0.01-5份含有环氧基且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物加热至160-350°C而增加聚酯分子量的方法。
Description
发明内容
本发明涉及一种经由在挤出机中将100份聚酯与i)0.01-5份四羧酸二酐和ii)0.01-5份含有环氧基且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物加热至160-350°C而增加聚酯分子量的方法。
WO03/066704描述了一种作为聚酯如聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二醇酯(PBT)用合适增链剂的含有环氧基且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物(组分ii)。聚酯回收对用于增加分子量的方法的速度和效率有严格的要求。向再循环物仅添加上述组分ii)不总能满足分子量增加的要求。此外，该方法有时太慢而不经济。
EP748364描述了四羧酸二酐和位阻羟基苯基烷基膦酸酯在增加聚酯或聚酯混合物的分子量中的用途。再次，该方法的效率可进一步改善。
令人惊奇地，现已发现组分ii)的效率可以通过添加四羧酸二酐(组分i)而显著提高。特别地，已证明遵守下述添加顺序是有利的：首先添加组分i)，且直接在其后或延时(5-600s)后添加组分ii)。
术语聚酯主要指聚酯如聚对苯二甲酸乙二醇酯(PET)和聚对苯二甲酸丁二醇酯(PBT)或所述聚酯与其他聚合物的混合物，其中实例为PBT/PA、PBT/PS、PBT/ASA、PBT/ABS、PBT/PC、PET/PC、PET/ABS、PBT/PET/PC、PBT/PC/ABS；该术语也包括半芳族或脂族聚酯。特别优选PET、再循环PET和再循环PBT。在此，有效的分子量增加特别重要从而可以保留起始聚合物的工作特性。
原则上，也可使用基于脂族和芳族二羧酸以及基于脂族二羟基化合物的聚酯，其中这些已知为半芳族聚酯，或使用衍生于脂肪二羧酸和脂族二醇的脂族聚酯。所述聚合物的共同特征为它们根据DIN EN13432可降解。当然也可使用多种这些聚酯的混合物。
本发明中术语半芳族聚酯还指聚酯衍生物如聚醚酯、聚酯酰胺或聚醚酯酰胺。合适的半芳族聚酯尤其为线性未增链聚酯(WO92/09654)。优选增链和/或支链半芳族聚酯。后者可由WO96/15173-15176或WO98/12242已知，明确参考该文献。同样可使用不同的半芳族聚酯的混合物。令人感兴趣的更多最近的开发方案基于可再生原材料(见WO-A2006/097353、WO-A2006/097354和EP08165372.7)。术语半芳族聚酯尤其是指产品如(BASF SE)和Bio，(Novamont)。
术语脂族聚酯指衍生于脂族C2-C12链烷二醇和脂族C4-C36链烷二羧酸的聚酯，其中实例为聚琥珀酸丁二醇酯(PBS)，聚己二酸丁二醇酯(PBA)，聚琥珀酸己二酸丁二醇酯(PBSA)，聚琥珀酸癸二酸丁二醇酯(PBSSe)，聚癸二酸己二酸丁二醇酯(PBSeA)和聚癸二酸丁二醇酯(PBSe)，或相应的聚酯酰胺。脂族聚酯由Showa Highpolymers以商标和由Mitsubishi以商标销售。更多最近的开发方案描述于EP08165370.1。
术语脂族聚酯还包括脂环族聚酯，特别是纤维素酯如乙酸纤维素、乙酸丁酸纤维素或丁酸纤维素。
该方法还可使用基于羟基羧酸的聚酯。例如可使用聚乳酸、聚己酸内酯或聚羟基链烷酸酯如3-PHB、4-PHB或PHB(V)。
优选聚酯在分子量增加前的摩尔质量(Mn)通常为100-100000g/mol，特别为900-75000g/mol，优选为1000-50000g/mol，其中其熔点为60-300°C，优选为80-150°C。
术语四羧酸二酐(组分i)特别指1,2,4,5-苯四酸酐、3,3’,4,4’-联苯四甲酸二酐、3,3’,4,4’-二苯甲酮四甲酸二酐和3,3’,4,4’-二苯醚四甲酸二酐。特别优选1,2,4,5-苯四酸酐。
对于每100份聚酯，四羧酸二酐的添加量为0.01-5份，优选为0.02-1份，特别优选为0.05-0.5份。
含有环氧基且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物(组分ii)特别包括下述结构特征。带有环氧基的单元优选为(甲基)丙烯酸缩水甘油酯。已证明有利的共聚物的甲基丙烯酸缩水甘油酯含量占该共聚物的大于20重量%，特别优选大于30重量%，特别优选大于50重量%。在这些聚合物中优选环氧当量(EEW)为150-3000g/当量，特别优选为200-500g/当量。聚合物的平均分子量(重均)MW优选为2000-25000，特别为3000-8000。聚合物的平均分子量(数均)Mn优选为400-6000，特别为1000-4000。多分散性(Q)通常为1.5-5。含有环氧基的上述类型的共聚物例如由BA SF Resins B.V以ADR销售。特别合适的增链剂为ADR4368、如申请号为EP08166596.0中所述的长链丙烯酸酯和来自Shell的E10。
含有环氧基的上述类型的共聚物的用量基于100份聚酯为0.01-5份，优选为0.1-2份，特别优选为0.2-1份。
如果合适，本发明方法可通过使用其他添加剂而更高效。
在添加组分i)和ii)后，进一步添加除酸剂也可能是有利的。已证明特别成功的除酸剂为选自双唑啉、聚唑啉、碳二亚胺、聚碳化二亚胺、二己内酰胺、聚己内酰胺、二嗪和聚嗪的化合物，其中这些更详细地描述于WO2010/012695中。就所述组分而言，明确参考WO2010/012695的第7页15行至第8页24行。
聚合物混合物还可以包含常见添加剂。这里发现经由添加含有环氧基的共聚物对生物聚合物熔体的稳定性没有影响。常见添加剂的实例为成核剂如滑石、白垩、炭黑、石墨、硬脂酸钙或硬脂酸锌、聚右旋乳酸、N,N’-亚乙基二-12-羟基硬脂酰胺、聚羟基乙酸、润滑剂和防粘连剂、蜡、抗静电剂，其他增容剂如硅烷、马来酸酐、富马酸酐、异氰酸酯、二酰氯、抗雾化剂、UV稳定剂或染料，填料如玻璃纤维，淀粉-用增塑剂如甘油或山梨醇增塑的或未增塑的-淀粉衍生物、谷物、纤维素衍生物、滑石、白垩、炭黑和石墨。
测试方法
特性粘度通过使用M-II micro Ubbelohde装置于25°C下在1:1的苯酚/邻二氯苯中根据DIN EN ISO1628测量。特性粘度以cm3/g计。
毛细管常数： 0.09185
测量温度[°C]： 5
溶剂： 苯酚/邻二氯苯1:1(PODB)
溶剂流动时间[s]： 28.54
Hagenbach溶剂校正[s]: 0.01
浓度： 0.5g聚合物/100mL溶剂
基于ISO6721-10，通过使用Rheometric Scientific的SR2剪切应力受控的板对板(platte-platte)旋转流变仪确定作为时间函数的样品熔体粘度。板的直径为25mm且各板之间的距离为1mm。剪切应力设定为100Pa，测量时间为30min，且预热时间为5min。相应的测量温度如所述。
样品的熔体流动指数(熔体体积率=MVR)根据ISO1133确定。
所用材料：
聚酯：
a)商标为FBX7011(BASF SE)的半芳族聚酯
b)RT51聚对苯二甲酸乙二醇酯(来自Kosa)
c)使用0.2kg原钛酸四丁酯作为催化剂使120kg1,4-丁二醇，91.3kg对苯
二甲酸二甲酯和0.2kg甘油进行酯交换，其中加热并通过蒸发除去甲醇，
并然后混合77.5kg己二酸。首先通过在常压下蒸馏而除去水，然后在
至多250°C下进行缩聚反应1.5h，最终真空度<10毫巴，然后使聚合物
制成线料。脂族-芳族聚酯的酸值为1.2且其特性粘度为84。
组分i)：
i-1)来自Aldrich的苯均四酸二酐。
组分ii)：
ii-1)来自BASF Resins B.V的ADR4368。
实验在DSM Xplore15Micro-compounder2005中进行。在测量过程中，记录聚合物熔体作用于基板的力(以牛顿计)。该力与熔体的粘度成比例，因此熔体粘度的变化可直接在线观测并记录。
本发明实施例1：
使20g聚酯a)在240°C下熔融。在添加0.2g组分i-1后没有观测到粘度上升。在30s后，将0.2g组分ii-1计量加入混合物中。在组分ii-1添加后观测到粘度显著上升，在约4min内从2600N上升至6000N。反应混合物在整个实验过程中维持在240°C下。
本发明实施例2：
使20g聚酯c)在240°C下熔融。在添加0.2g组分i-1后没有观测到粘度上升。在3min后，将0.2g组分ii-1计量加入混合物中。在组分ii-1添加后观测到粘度显著上升，在约4min内从200N上升至1300N。
本发明实施例3：
使20g聚酯c)在240°C下熔融。在添加0.2g组分i-1后没有观测到粘度上升。在3min后，将0.4g组分ii-1计量加入混合物中。在组分ii-1添加后观测到粘度显著上升，在约4min内从200N上升至3500N。
对比例4：
使20g聚酯a)在240°C下熔融。在添加0.2g组分i-1后，在15min内观测到粘度下降。
对比例5：
使20g聚酯a)在240°C下熔融。在1min后添加0.2g组分ii-1。在15min内熔体粘度显示仅由3600N至4000N的缓慢上升。
本发明实施例6：
使20g聚酯b)在280°C下熔融。在添加0.06g组分i-1后没有观测到粘度上升。在30s后，将0.1g组分ii-1计量加入混合物中。在组分ii-1添加后观测到粘度显著上升，在约4min内从1800N上升至5400N。
对比例7：
使20g聚酯b)在280°C下熔融。在添加0.06g组分i-1后，在15min内观测到粘度下降。
对比例8：
使20g聚酯a)在240°C下融化。在1min后添加0.1g组分ii-1。在15min内熔体粘度显示仅由1800N至2300N的缓慢上升。
对比例4和7清楚地证实仅添加苯均四酸二酐(组分i)导致分子量的减小而不是增加。在对比例5和8中，仅添加组分ii)最多引起小的分子量增加。本发明实施例显示组合添加组分i)和ii)引起迅速和有效的分子量增加。
Claims (6)
1.一种增加聚酯分子量的方法，其中在挤出机中将100份聚酯与i)0.01-5份四羧酸二酐和ii)0.01-5份含有环氧基且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物加热至160-350℃，所述四羧酸二酐为1,2,4,5-苯四酸酐、3,3’,4,4’-联苯四甲酸二酐、3,3’,4,4’-二苯甲酮四甲酸二酐和3,3’,4,4’-二苯醚四甲酸二酐，所述共聚物具有的环氧当量为150-3000g/当量，平均分子量MW为2000-25000，平均分子量Mn为400-6000且多分散性为1.5-5，组分ii)的添加在组分i)的添加后进行。
2.根据权利要求1的方法，其中首先添加组分i)，且直接在其后或延时5-600s后添加组分ii)。
3.根据权利要求1的方法，其中所述聚酯为聚对苯二甲酸乙二醇酯。
4.根据权利要求1的方法，其中所述聚酯为脂族聚酯或脂族-芳族聚酯或所述聚酯的聚合物混合物。
5.根据权利要求1的方法，其中所述四羧酸二酐为1,2,4,5-苯四酸酐。
6.根据权利要求1的方法，其中所述含有环氧基的共聚物包含作为环氧单元的丙烯酸缩水甘油酯或甲基丙烯酸缩水甘油酯。
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| PCT/EP2011/062189 WO2012019868A2 (de) | 2010-07-19 | 2011-07-18 | Verfahren zur erhöhung des molekulargewichts von polyestern |
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| TW460525B (en) | 1994-02-28 | 2001-10-21 | Ciba Sc Holding Ag | A process for increasing the molecular weight of polyesters with a tetracarboxylic acid dianhydride and a sterically hindered hydroxy-phenylalkylphonic acid ester or half-ester |
| DE4440858A1 (de) | 1994-11-15 | 1996-05-23 | Basf Ag | Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper |
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| DE19638488A1 (de) | 1996-09-20 | 1998-03-26 | Basf Ag | Biologisch abbaubare Polyester |
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| CN101098932B (zh) * | 2005-01-12 | 2011-08-17 | 巴斯福股份公司 | 可生物降解聚酯混合物 |
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