CN1590460A - 增加聚酰胺分子量的方法 - Google Patents
增加聚酰胺分子量的方法 Download PDFInfo
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- CN1590460A CN1590460A CNA2004100566576A CN200410056657A CN1590460A CN 1590460 A CN1590460 A CN 1590460A CN A2004100566576 A CNA2004100566576 A CN A2004100566576A CN 200410056657 A CN200410056657 A CN 200410056657A CN 1590460 A CN1590460 A CN 1590460A
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- Prior art keywords
- polymeric amide
- salt
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- weight
- acid
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- -1 phosphorus compound Chemical class 0.000 claims abstract description 19
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- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
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- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 10
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Abstract
使用具有至少两个碳酸酯单元的化合物缩合聚酰胺，以增加其分子量的方法，该方法包括使用作为其制备的结果而包括5－500ppm的酸性化合物形式的磷的聚酰胺，以及将0.001－10重量％的弱酸的盐加入到聚酰胺中，如此消除了磷化合物的抑制作用。
Description
技术领域
本发明涉及缩合聚酰胺以增加其分子量的方法，其中该聚酰胺包含由于其制备而带来的含磷催化剂。
背景技术
聚酰胺是其主链含有-CO-NH-基团的大分子。它们由各自含有两个相同的反应性基团，例如-NH2或-COOH的两种不同的双官能化单体单元获得，或由各自携带一个氨基和一个羧基或能够形成这些基团的单一双官能化单元获得。例如，聚酰胺通过二胺类与二羧酸类的缩聚反应，或氨基羧酸的缩聚反应，或通过内酰胺类的开环聚合来制备。
制备具有高熔体粘度的聚酰胺模塑组合物对于许多应用来说是必要的。其原因在于诸如强制使用特定加工方法。满足该需要的一种方法使用具有高分子量和因此高粘度的聚酰胺。这类聚酰胺通过两步法来生产。在该方法中，在压力反应器中首先制备比较低粘度的预聚物，如在Kunststoff-Handbuch，Band 3/4 Technische Thermoplaste，Polyamide；编辑：Becker，Braun；Carl Hanser Verlag，1998中所述。质子酸性含磷化合物，例如H3PO2，H3PO3或H3PO4有利地用作催化剂。适合作为催化剂的化合物的其它实例是有机膦酸或有机次膦酸，或它们的前体。这种催化剂的存在不仅导致了在低温下的改进月桂内酰胺裂解，还导致了更低的残留内酰胺含量，而且通过催化剂的存在改进了相应缩聚产物的颜色，以及总体上加速了缩聚反应。该催化化合物的效果当然还延伸到了不含月桂内酰胺，而含有其它单体的聚酰胺。然后通过剩余端基的反应，例如通过固相后缩合，或熔体反应将在该第一段反应中这样获得的前体的分子量升高所需最终值，这能够在直接连接于该反应的第一段的装置的装置中进行。然后能够将各种典型添加剂加入到所得高分子量聚酰胺中，实例是导电性添加剂，稳定剂，加工助剂，着色剂等。通常用于此的方法是本领域技术人员已知的配混技术。所得模塑组合物然后用于需要增高熔体粘度的应用，尤其挤出或共挤出，例如管材的挤出或共挤出，或吹塑，抽吸吹塑，3D吹塑，或热成型，例如薄膜的热成型。然而，不利的是，分子量增高到所需水平和模塑组合物的其它必要成分的引入在单独的连续步骤中进行，因此产生了附加的工艺成本。
如果有可能将所述两个步骤合并，使得分子量的增高和所需添加剂的引入在该方法的单一步骤中进行的话，将增加该方法的效率。此外，为了补偿经常由于热和剪切的作用而在熔体加工过程中发生的分子量降低，希望分子量高于其规定的值。挤出和吹塑需要具有高熔体粘度的高分子量材料。当考虑到具有高粘度熔体的模塑组合物的应用领域时，不得不考虑具有高粘度熔体的模塑组合物不仅能够加工成单层结构，而且还能够与具有低熔体粘度的模塑组合物一起加工成多层结构，它们的不充分的熔体粘度通过高粘度模塑组合物的高粘度来补偿。这样做的结果是：该整个复合材料变得能够以上述方式加工。该方法能够有利地用于由包括特定功能层和不能以任何其它方式获得的多层复合材料生产模制品。
WO 00/66650描述了具有至少两个碳酸酯单元的化合物用于缩合聚酰胺，以增高其分子量的用途。这里，性能能够进行可靠地和稳定地调节，进行缩合来增高其分子量的该材料能够反复加工，没有招致任何凝胶形成或不均匀性。以该原理为基础和目的用于调节聚酰胺的分子量的添加剂由Bruggemann KG公司以Bruggolen M1251的名称市售。主要应用是由PA6或PA66组成的再循环材料的粘度调节领域，再用于挤出用模塑组合物。添加剂Bruggolen M1251是在酸终端的PA6中的低粘度聚碳酸酯的母料，如Lexan 141。当聚碳酸酯与存在于所要缩合，以便增加其分子量的材料中的氨基端基反应时，导致了分子量增加。
该方法的效力以用于增加该材料的分子量的PA6和PA66的缩合为例在WO 00/66650中得到例证，相应缩聚物在某些情况下以纯形式使用，但在其它情况下还包括添加剂，例如玻璃纤维和褐煤酸酯。
然而，令人惊奇的是，已经发现，在WO 00/66650中所述的方法没有导致许多聚酰胺，例如PA12，以其为基础的共聚酰胺，PA11，或PA612，或脂环族聚酰胺的分子量的任何增高。为此而必须发生的氨基端基与添加剂的反应显然没有发生。因此，目的是发现可以使这些材料的分子量在单一步骤中在配混过程中简单和可靠地增高的改良方法，对于包括上述和类似聚酰胺的材料，如在WO 00/66650中所要求的方法没有成功地增加分子量。
令人惊奇的是，已经发现，当在聚酰胺的制备过程中使用质子含磷酸作为催化剂时，出现了所述问题，以及当添加盐形式的对应于弱酸的碱时，该问题被消除，所添加的材料有利地是弱酸的盐。
发明内容
本发明因此提供了使用具有至少两个碳酸酯单元的化合物缩合聚酰胺或聚酰胺模塑组合物，以增加其分子量的方法，其中聚酰胺或聚酰胺模塑组合物包括由于其制备而带来的5-500ppm，尤其至少20ppm的酸性化合物形式的磷，其中将0.001-10重量％的弱酸的盐加入到聚酰胺或聚酰胺模塑组合物中，以聚酰胺为基准计。
适于本发明目的的聚酰胺是以内酰胺，氨基羧酸、二胺和二羧酸为基础的结构。此外，它可以含有具有支化效应的单元，例如由三羧酸，三胺或聚乙烯亚胺衍生的那些。例如，在均聚物或共聚物形式的各种情况下，适合类型是PA6，PA46，PA66，PA610，PA66/6，PA6-T，PA66-T，以及尤其PA612，PA1012，PA11，PA12，或透明聚酰胺。例如，可以使用的透明聚酰胺是：
-由三甲基六亚甲基二胺和对苯二甲酸的异构体混合物获得的产物，
-由双(4-氨基环己基)甲烷和癸二酸或十二烷二酸获得的产物，
-由双(4-氨基-3-甲基环己基)甲烷和癸二酸或十二烷二酸获得的产物。
其它适合的材料是以内酰胺，氨基羧酸，二胺，二羧酸，聚醚二胺和/或聚醚二醇为基础的聚醚酰胺。
起始化合物优选具有大于5000，尤其大于8000的分子量Mn。这里优选的是具有至少一些氨基端基的那些聚酰胺。例如，至少30％，至少40％，至少50％，至少60％，至少70％，至少80％或至少90％的端基是氨基端基。
本发明方法使用具有至少两个碳酸酯单元的至少一种化合物，其定量比例为0.005-10重量％，按与所使用的聚酰胺的比率计算。该比率优选为0.01-5.0重量％，尤其优选0.05-3重量％。术语“碳酸酯”这里是指碳酸的酯，尤其碳酸与苯酚或与醇的酯。
具有至少两个碳酸酯单元的化合物可以是低分子量化合物，低聚或聚合物。它可以完全由碳酸酯单元组成，或它还可以具有其它单元。其它单元优选是低聚酰胺或聚酰胺单元，低聚酯或聚酯单元，低聚醚或聚醚单元，低聚醚酯酰胺或聚醚酯酰胺单元，或低聚酯酰胺或聚酯酰胺单元。这类化合物可以由已知的低聚或聚合方法，或经由聚合物类似反应来制备。
这里特地引入供参考的WO 00/66650给出了具有至少两个碳酸酯单元的适合化合物的详细描述。
在本发明中，聚酰胺必须包括活性缩聚催化剂形式的质子酸性含磷化合物，它们可以该物质的形式添加，或以在反应条件下形成活性催化剂的前体的形式添加，或以催化剂的下游产物的形式添加。磷含量根据DIN EN ISO 11885利用ICPOES(感应耦合等离子体发射光谱测定法)来测定，但还可以使用例如AAS(原子吸收光谱法)。应该指出的是，其它含磷组分还可以存在于模塑组合物中，例如作为稳定剂。在该情况下，使用差分法来测定由缩聚获得的磷。样品制备技术然后与所需的特地数据匹配。
成为本发明的弱酸盐的效力的基础的原因可能是它抑制了所存在的磷化合物的破坏作用。这里弱酸的pKa值为≥2.5。例如，适合的弱酸选自羧酸，如单羧酸，二羧酸，三羧酸，羟基羧酸，氨基羧酸，苯酚类，醇，和CH酸性化合物。
除了这些以外，弱无机酸的盐也是适合的，例如碳酸盐，碳酸氢盐，磷酸盐，磷酸氢盐，氢氧化物，亚硫酸盐，适合金属的实例是碱金属，碱土金属，主族III的金属，或副II族的金属。原则上，其它适合的阳离子是有机阳离子，如被有机基团完全或部分取代的铵离子。
还可以使用属于大分子结构的一部分的弱酸的盐，例如以Surlyn(DuPont)类的离聚物的形式，或以完全或部分皂化聚乙烯蜡氧化物的形式。
例如，可以列举下列盐：硬脂酸铝，硬脂酸钡，硬脂酸锂，硬脂酸镁，油酸钾，油酸钠，月桂酸钙，褐煤酸钙，褐煤酸钠，乙酸钾，硬脂酸锌，硬脂酸镁，氢氧化钙，氢氧化镁，苯酚钠三水合物，甲醇钠，碳酸钙，碳酸钠，碳酸氢钠，磷酸三钠和磷酸氢二钠。
通常有利的是，在配混方法之前或在配混方法过程中，将具有至少两个碳酸酯单元的化合物加入到聚酰胺中，以及通过彻底混合来引入该化合物。添加可以在配混方法之后，加工之前进行，但在该情况下，必须注意在加工过程中进行彻底混合。
弱酸盐添加的时机可以用来控制分子量增加的时机。例如，一旦缩聚完成，可以将该盐计量加入到初始熔体中，例如直接计量加入到缩聚反应器中，或计量加入到辅助挤出机中。另一方面，它还可以在配混方法之前施加于聚酰胺粒料中，例如高温混合机或转筒式干燥机中。在另一种方法中，该盐在聚酰胺的加工过程中直接添加，以获得模塑组合物，例如与其它添加剂一起。在这些情况下，分子量的增加在配混过程开始之前发生，或在配混过程中发生。另一方面，如果目的是在配混方法过程中引入填料或增强剂，或如果要进行与模塑组合物有关的熔体过滤，能够有利的是，延迟添加弱酸的盐，直到配混步骤结束，例如通过将它施加于已预先混入具有两个以上碳酸酯单元的适当添加剂的模塑组合物的粒料中，或通过以母料的形式添加它，获得了粒料混合物。当加工者加工这样处理的粒料或粒料混合物时，那么发生了分子量的所需增加，于是生产出了成品部件，例如管材。
弱酸的盐的优选用量是0.001-5重量％，它尤其优选以0.01-2.5重量％的量使用，以及该用量特别优选是0.05-1重量％，所有重量％以聚酰胺为基准计。
当制备聚酰胺模塑组合物时，本发明方法而且可以使用常用添加剂。它们的实例是着色剂，阻燃剂，稳定剂，填料，润滑剂，脱模剂，冲击改性剂，增塑剂，结晶促进剂，抗静电剂，润滑剂，加工助剂，以及通常与聚酰胺配混的其它聚合物。
这些添加剂的实例如下所示：
着色剂：二氧化钛，铅白，锌白，锌钡白，锑白，炭黑，氧化铁黑，锰黑，钴黑，锑黑，铬酸铅，铅丹，锌黄，锌绿，镉红，钴蓝，普鲁士蓝，群青，锰紫，镉黄，巴黎绿，钼桔红，钼铬红，铬橙，铬红，氧化铁红，氧化铬绿，锶铬黄，钼蓝，白垩，赭石，棕土，绿土，富铁煅黄土，石墨，或可溶性有机染料。
阻燃剂：三氧化二锑，六溴环十二烷，四氯或四溴双酚和卤化磷酸酯，硼酸酯，氯链烷烃，以及红磷，锡酸盐，蜜胺氰脲酸酯及其缩合产物，如蜜白胺，蜜勒胺，氰脲酰胺，蜜胺类化合物，如蜜胺焦磷酸盐和多磷酸盐，多磷酸铵，氢氧化铝，氢氧化钙，以及不含卤素的有机磷化合物，例如间苯二酚磷酸二苯酯或膦酸酯类。
稳定剂：金属盐，尤其铜盐和钼盐，以及铜配合物，亚磷酸酯，位阻酚类，仲胺类，UV吸收剂和HALS稳定剂。
填料：玻璃纤维，玻璃珠，磨碎玻璃纤维，硅藻土，滑石，高岭土，粘土，CaF2，氧化铝以及碳纤维。
润滑剂：MoS2，石蜡，脂肪醇类，以及脂肪酰胺类。
脱模剂和加工助剂：蜡类(褐煤酸酯)，褐煤酸蜡，褐煤酸酯蜡，聚硅氧烷，聚乙烯醇，SiO2，硅酸钙，以及全氟化聚醚类。
增塑剂：BBSA，POBO。
冲击改性剂：聚丁二烯，EPM，EPDM，HDPE。
抗静电剂：炭黑，碳纤维，石墨原纤维，多羟基醇，胺类，酰胺类，季铵盐类，脂肪酸酯类。
这些添加剂的用量可以是本领域技术人员已知的常量。
根据本发明获得的高分子聚酰胺或相应模塑组合物可以进一步通过任何现有技术的方法进一步加工成模制品或薄膜，例如通过注塑，挤出(例如获取管材)，共挤出(例如获取多层管或多层薄膜)，吹塑，抽吸吹塑，3D吹塑或热成型(例如薄膜热成型)。关于进一步细节，WO 00/66650特地在这里引入作参照。本发明还尤其提供了如权利要求9-12所要求的用途。
具体实施方式
以下通过实施例来举例说明本发明。
方法描述：
通过实验室捏合机(Haake Rheocord System 90)的进口颈部进给适当的基础聚合物与适当的添加剂。利用加热和摩擦热将实验材料升温至适当调节的熔融温度。一旦已达到该温度，将该实验材料在该温度下混合另外60秒钟。然后趁热从该实验室捏合机中排出该材料。
该材料用于以下分析：
根据DIN EN ISO 307的溶液粘度ηrel；
使用高氯酸，通过电位滴定法测定氨基端基；
使用KOH和酚酞作为指示剂，通过目测滴定法测定羧基端基。
结果在表1-3中示出。这里E是指本发明实施例和CE是指对比
实施例。
表1：不用磷催化剂制备的由聚酰胺起始的对比实施例
| 起始原料 | 参照物 | VB1 | 参照物 | VB2 |
| PA12 | 100 | 99.4 | 0 | 0 |
| PA66 | 0 | 0 | 100 | 99 |
| Brüggolen M1251 | 0 | 0.6 | 0 | 1.0 |
| 熔融温度[℃] | 240 | 240 | 290 | 290 |
| ηrel | 1.96 | 2.23 | 1.79 | 1.91 |
| NH2[毫当量/kg] | 66 | 40.6 | 34.3 | 16.3 |
| COOH[毫当量/kg] | 20 | 20 | 67 | 65 |
表2：使用次磷酸作为催化剂制备的PA12的情况下的BrüggolenM1251的活化(磷含量25ppm)
| 起始原料 | 参照物 | VB3 | B1 | B2 | B3 | B4 | B5 | B6 | VB4 | VB5 |
| PA12 | 100 | 99.4 | 99.3 | 99.3 | 99.3 | 99.3 | 99.3 | 99.3 | 99.3 | 99.3 |
| Brüggolen M1251 | 0 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| 硬脂酸铝 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| 硬脂酸钙 | 0 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0 | 0 |
| 硬脂酸锂 | 0 | 0 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0 |
| 油酸钠 | 0 | 0 | 0 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 |
| 月桂酸钙 | 0 | 0 | 0 | 0 | 0 | 0 | 0.1 | 0 | 0 | 0 |
| 褐煤酸钙 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.1 | 0 | 0 |
| 硬脂酸 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.1 | 0 |
| 脂肪酸酯 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.1 |
| 熔点[℃] | 240 | 240 | 240 | 240 | 240 | 240 | 240 | 240 | 240 | 240 |
| ηrel | 2.10 | 2.07 | 2.77 | 2.63 | 2.72 | 2.58 | 2.64 | 2.69 | 2.11 | 2.16 |
| NH2[毫当量/kg] | 51.9 | 52.7 | 22 | 24.7 | 23.8 | 26.6 | 29.5 | 27.7 | 40.7 | 43.5 |
| COOH[毫当量/kg] | 13 | 15 | 7 | 10 | 7 | 6 | 5 | 8 | 8 | 9 |
表3：在使用次磷酸作为催化剂(在各种情况下的磷含量为25ppm)制备的其它聚酰胺的情况下的Brüggolen M1251的活化
| 起始原料 | 参照物 | VB6 | B7 | 参照物 | VB7 | B8 |
| PA612 | 100 | 99.4 | 99.3 | 0 | 0 | 0 |
| PA PACM12 | 0 | 0 | 0 | 100 | 99.2 | 99.2 |
| Brüggolen M1251 | 0 | 0.6 | 0.6 | 0 | 0.8 | 0.8 |
| 硬脂酸钙 | 0 | 0 | 0.1 | 0 | 0 | 0.1 |
| 熔点[℃] | 260 | 260 | 260 | 280 | 280 | 280 |
| ηrel | 1.85 | 1.83 | 2.00 | 1.85 | 1.85 | 1.96 |
| NH2[毫当量/kg] | 96.8 | 97.3 | 79.8 | 40.2 | 41.7 | 18 |
| COOH[毫当量/kg] | 5 | 9 | 7 | 70 | 69 | 69 |
Claims (12)
1、使用基于聚酰胺计为0.005-10重量％的具有至少两个碳酸酯单元的化合物缩合聚酰胺或聚酰胺模塑组合物以增加其分子量的方法，该方法的特征在于：
a)聚酰胺因其制备而包含5-500ppm的酸性化合物形式的磷，和
b)将以聚酰胺为基准计为0.001-10重量％的弱酸盐加入到聚酰胺或聚酰胺模塑组合物中。
2、如权利要求1所要求的方法，其特征在于，聚酰胺包含至少20ppm的酸性化合物形式的磷。
3、如前述权利要求任一项所要求的方法，其特征在于，将0.001-5重量％的弱酸的盐加入到聚酰胺或聚酰胺模塑组合物中。
4、如前述权利要求的任一项所要求的方法，其特征在于，将0.01-2.5重量％的弱酸的盐加入到聚酰胺或聚酰胺模塑组合物中。
5、如前述权利要求的任一项所要求的方法，其特征在于，0.05-1重量％的弱酸的盐加入到聚酰胺或聚酰胺模塑组合物中。
6、如前述权利要求的任一项所要求的方法，其中弱酸具有≥2.5的pKa值。
7、如前述权利要求的任一项所要求的方法，其中弱酸的盐是碱金属盐，碱土金属盐，III主族金属的盐，II副族的金属的盐，或铵盐。
8、按前述权利要求的任一项而缩合以提高其分子量的聚酰胺或相应模塑组合物用于通过注塑、挤出、共挤出、吹塑、抽吸吹塑、3D吹塑或热成型来生产模制品或薄膜的用途。
9、如权利要求8所要求的用途，其特征在于，该模制品或薄膜具有单层结构，并由按权利要求1-7而缩合以提高其分子量的聚酰胺或相应模塑组合物组成。
10、如权利要求8所要求的用途，其特征在于，该模制品或薄膜是多层复合材料并包含作为层的按权利要求1-7而缩合以提高其分子量的聚酰胺或相应模塑组合物。
11、如权利要求8-10的任一项所要求的用途，其特征在于，该模制品是管材、长丝或容器。
12、如权利要求8-11的任一项所要求的用途，其中该模制品是冷却液导管、作为燃料管道系统一部分的加油颈，或是机动车辆用容器或油箱。
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-
2004
- 2004-06-21 DE DE502004005948T patent/DE502004005948D1/de not_active Expired - Lifetime
- 2004-06-21 AT AT04102825T patent/ATE384090T1/de not_active IP Right Cessation
- 2004-06-21 EP EP04102825A patent/EP1512710B1/de not_active Expired - Lifetime
- 2004-08-13 JP JP2004236149A patent/JP4582624B2/ja not_active Expired - Lifetime
- 2004-08-13 CN CNB2004100566576A patent/CN1331944C/zh not_active Expired - Lifetime
- 2004-08-13 KR KR1020040063892A patent/KR101117082B1/ko not_active IP Right Cessation
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837287B (zh) * | 2005-02-15 | 2010-05-26 | 德古萨公司 | 在熔体刚度增高条件下制备模塑件的方法 |
| CN1900163B (zh) * | 2005-07-04 | 2010-09-29 | 赢创德固赛有限责任公司 | 具有高熔体刚度的聚酰胺模塑物料用于与高熔点聚合物共挤出的用途 |
| CN103242649A (zh) * | 2012-02-06 | 2013-08-14 | 金发科技股份有限公司 | 一种用于挤出成型的玻纤增强尼龙材料及制备方法与应用 |
| CN103242649B (zh) * | 2012-02-06 | 2015-09-30 | 金发科技股份有限公司 | 一种用于挤出成型的玻纤增强尼龙材料及制备方法与应用 |
| CN114144473A (zh) * | 2019-07-11 | 2022-03-04 | 东丽株式会社 | 聚酰胺树脂组合物及将其成型而成的成型品 |
| CN114144473B (zh) * | 2019-07-11 | 2023-01-03 | 东丽株式会社 | 聚酰胺树脂组合物及将其成型而成的成型品 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050019057A (ko) | 2005-02-28 |
| CN1331944C (zh) | 2007-08-15 |
| ATE384090T1 (de) | 2008-02-15 |
| CA2477487C (en) | 2012-10-02 |
| EP1512710A3 (de) | 2005-12-28 |
| CA2477487A1 (en) | 2005-02-16 |
| EP1512710B1 (de) | 2008-01-16 |
| DE10337707A1 (de) | 2005-04-07 |
| US20050038201A1 (en) | 2005-02-17 |
| DE502004005948D1 (de) | 2008-03-06 |
| EP1512710A2 (de) | 2005-03-09 |
| JP2005060705A (ja) | 2005-03-10 |
| JP4582624B2 (ja) | 2010-11-17 |
| KR101117082B1 (ko) | 2012-02-22 |
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