CN101563393B - 形状记忆型聚酰胺以及使用其制备形状记忆型聚酰胺织物的方法 - Google Patents

形状记忆型聚酰胺以及使用其制备形状记忆型聚酰胺织物的方法 Download PDF

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CN101563393B
CN101563393B CN200780047322XA CN200780047322A CN101563393B CN 101563393 B CN101563393 B CN 101563393B CN 200780047322X A CN200780047322X A CN 200780047322XA CN 200780047322 A CN200780047322 A CN 200780047322A CN 101563393 B CN101563393 B CN 101563393B
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金昌佑
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Xiaoxing Tianxi (zhu)
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Abstract

本发明公开了一种形状记忆型聚酰胺，其是在由ε-己内酰胺或者由己二胺和己二酸聚合生成聚酰胺时，通过添加多元羧酸和多元胺而制备得到的，并且其具有芳香组分，所述芳香组分是通过所述多元羧酸和多元胺中的一种或多种而引入的，并且所述芳香组分的总量为聚酰胺的原料的量的0.4摩尔％至10摩尔％。此外，提供一种使用该形状记忆型聚酰胺来制备形状记忆型聚酰胺织物的方法。使用该形状记忆型聚酰胺制备的聚酰胺织物是一种高功能的织物，其不易起皱，并且即使在起皱时也易于恢复原状，因此这种聚酰胺织物可以用作各种服装的材料。

Description

形状记忆型聚酰胺以及使用其制备形状记忆型聚酰胺织物的方法
技术领域
本发明涉及一种形状记忆型聚酰胺以及使用该形状记忆型聚酰胺制备形状记忆型聚酰胺织物的方法。更具体而言，本发明涉及一种形状记忆型聚酰胺以及使用该聚酰胺制备形状记忆型聚酰胺织物的方法，所述形状记忆型聚酰胺的特征在于：该聚酰胺在其主链上包含预定的芳香组分部分，因而在后加工中显示出形状记忆性能。
背景技术
通常，其强度、耐磨性和可染性均优于其它合成纤维的聚酰胺纤维已被有效地用于多个领域。然而，使用聚酰胺织物制造的服装是不利的，因为它容易起皱，并且在洗涤之后或在穿旧时不能充分地恢复原状。服装的起皱受到包括聚合物的分子形状、捻数、布料的密度和厚度在内的多种结构因素、以及包括温度和湿度在内的外部环境的影响。
为了防止聚酰胺织物因这样的各种因素而导致的起皱，可使用如下方法：树脂加工方法，包括酸或碱处理或者防缩处理；化学处理方法，包括老化处理或退火处理；以及物理方法，包括混合纺纱。但是，酸或碱处理会不利地给布料带来严重损害，而且，与较少起皱的纤维进行混合纺纱处理并不会得到充分的抗皱效果。
因此，目前人们正尝试研发形状记忆型纤维，该纤维在洗涤之后不发生变形或起皱，并且在穿着期间不易起皱。形状记忆型纤维的特征在于，其不易起皱，并且易于恢复原状。因此，即使形状记忆型纤维发生了起皱，也可以用手将其铺平，从而易于使其恢复原状，并且该形状记忆型纤维在熨烫或洗涤时表现出高的耐久性。
关于形状记忆型布料，日本未审查专利公开No.昭61-252353公开了一种无纺布，其由形状记忆型树脂纤维和形状记忆型树脂粘合剂构成。然而，由于此类无纺布是通过用粘合剂将短纤维粘结在一起而形成的，因此其较厚且不均匀，并且由于使用了粘合剂，因而容易导致生产成本较高。此外，作为形状记忆型纤维，已经研发出了形状记忆型聚酯或形状记忆型聚对苯二甲酸乙二酯纤维，但是尚未研发出形状记忆型聚酰胺纤维或形状记忆型聚酰胺织物。因此，亟需开发具有形状记忆性能以及聚酰胺纤维优点的高功能性聚酰胺织物。
发明内容
技术问题
因此，针对相关技术中产生的上述问题，设计了本发明，本发明提供一种形状记忆型聚酰胺，其表现出形状记忆性能，因而能够被加工成不易起皱并具有高恢复力的织物。
此外，本发明提供一种使用具有被引入其分子链中的芳香族化合物的共聚酰胺来制备形状记忆型聚酰胺织物的方法。
此外，本发明提供一种按照本发明的方法制备的形状记忆型聚酰胺织物，以及使用该形状记忆型聚酰胺织物制备的服装。
技术方案
根据本发明，可以通过在使用ε-己内酰胺或者己二胺和己二酸作为其原料聚合生成聚酰胺时，添加多元羧酸和多元胺来制备所述形状记忆型聚酰胺，并且该形状记忆型聚酰胺可以具有由多元羧酸和多元胺中的一种或多种而引入的芳香组分，并且该芳香组分的总量为聚酰胺原料的量的0.4摩尔％至10摩尔％。
根据本发明，制备形状记忆型聚酰胺织物的方法可以包括：在聚合生成聚酰胺时添加多元羧酸和多元胺，由此合成得到具有芳香组分的共聚酰胺，所述芳香组分的总量为聚酰胺原料的量的0.4摩尔％至10摩尔％；将共聚酰胺进行纺织或编织，由此制备机织织物或针织织物；以及将机织织物或针织织物在下述条件(1)下进行热处理，然后在下述条件(2)下进行染色。
Tg+40℃≤Tx≤Tm-20℃  (1)
Tg≤Td≤Tx            (2)
其中Tg为半芳香族共聚酰胺的玻璃化转变温度，Tx为热处理温度，Tm为共聚酰胺的熔点，并且Td为染色温度。
根据本发明，可以使用本发明的方法制备形状记忆型聚酰胺织物，并且可以使用该形状记忆型聚酰胺织物制造服装。
最佳实施方式
下文中将对本发明进行详尽的描述。
根据本发明，在由ε-己内酰胺或者己二胺和己二酸聚合生成聚酰胺时，通过添加多元羧酸和多元胺来制备所述形状记忆型聚酰胺，并且该形状记忆型聚酰胺具有由多元羧酸和多元胺中的一种或多种而引入的芳香组分，所述芳香组分的总量为聚酰胺原料的量的0.4摩尔％至10摩尔％。
本发明的形状记忆型聚酰胺实现形状记忆性能的原理尚未明确建立，但可以推测如下。通常，由于强的氢键结合力，聚酰胺纤维具有规则的排列，因此不具有弹性。而本发明的聚酰胺具有芳基，因此可以降低链的扭曲和由此导致的主链间的相互作用，因此表现出形状记忆性能。
聚酰胺纤维的具体例子包括(但不限于)：尼龙6、尼龙66、以及尼龙6/66共聚物。尼龙6由ε-己内酰胺聚合而成，并且尼龙66由己二胺和己二酸聚合而成。
在本发明中，所述芳香组分优选为含有磺酸基团的芳香组分。具体而言，当在芳香组分中存在磺酸基团时，通过基于磺酸基团的强离子键的物理网络，能够有利地表现出形状记忆性能。
可以通过芳香族多元羧酸和脂肪族多元胺的组合、脂肪族多元羧酸和芳香族多元胺的组合、或者芳香族多元羧酸和芳香族多元胺的组合来引入芳香组分。
本发明中可用的多元羧酸的例子包括(但不限于)：己二酸、癸二酸、十二烷二酸、对苯二甲酸、间苯二甲酸；3，5-二羧基苯磺酸或其钠、钾、锂的磺酸盐；以及它们的混合物。
多元胺化合物可以选自乙二胺、丁二胺、己二胺、辛二胺、癸二胺、十一烷二胺、十二烷二胺、对苯二胺、间苯二胺、对二甲苯二胺、间二甲苯二胺，以及它们的混合物。
此外，本发明涉及一种制备形状记忆型聚酰胺织物的方法。本发明的制备形状记忆型聚酰胺织物的方法包括：将芳基引入聚酰胺的分子链中，由此合成半芳香族共聚酰胺，将该共聚酰胺预聚物进行熔融纺丝以制备纱线，然后对该纱线进行本发明的处理以赋予其形状记忆性能。
具体而言，为了制备本发明的形状记忆型聚酰胺织物，首先，在聚合生成聚酰胺时添加多元羧酸和多元胺，由此合成具有芳香组分的共聚酰胺预聚物，该芳香组分的总量为聚酰胺原料的量的0.4摩尔％至10摩尔％。如上所述，用于尼龙6的原料包括ε-己内酰胺，用于尼龙66的原料包括己二酸和己二胺。随后，将如此获得的共聚酰胺预聚物进行通常的熔融纺丝以获得纱线，然后将该纱线进行机织或针织，由此制备机织织物或针织织物。最后，将所述机织织物或针织织物在下述条件(1)下进行热处理以使其热定形，然后在下述条件(2)下进行染色，由此制备本发明的形状记忆型聚酰胺织物：
Tg+40℃≤Tx≤Tm-20℃  (1)
Tg≤Td≤Tx            (2)
其中Tg为共聚酰胺预聚物的玻璃化转变温度，Tx为热处理温度，Tm为共聚酰胺预聚物的熔点，并且Td为染色温度。
在本发明中，当由ε-己内酰胺或己二胺和己二酸来合成共聚酰胺预聚物时，加入芳香族化合物，使得芳香族化合物的量为聚酰胺原料的量的0.4摩尔％至10摩尔％。当芳香族化合物的量低于0.4摩尔％时，最终获得的布料不会表现出充分的形状记忆性能。另一方面，当芳香族化合物的量超过10摩尔％时，聚合程度会急剧下降，或者会使聚酰胺织物丧失其独特的性能。
本发明中使用的芳香族化合物可以选自芳香族多元羧酸和脂肪族多元胺的组合、脂肪族多元羧酸和芳香族多元胺的组合、以及芳香族多元羧酸和芳香族多元胺的组合。在任何情况下，为了合成共聚酰胺预聚物，芳香族化合物的总量必须等于或低于聚酰胺原料的量的10摩尔％。
本发明中可用的多元羧酸可以包括(但不限于)选自下列物质中的一种或多种：己二酸、癸二酸、十二烷二酸、对苯二甲酸、间苯二甲酸；3，5-二羧基苯磺酸或其钠、钾、锂的磺酸盐；以及它们的混合物。
本发明中可用的多元胺化合物可以包括(但不限于)选自下列物质中的一种或多种：乙二胺、丁二胺、己二胺、辛二胺、癸二胺、十一烷二胺、十二烷二胺、对苯二胺、间苯二胺、对二甲苯二胺、以及间二甲苯二胺。
当根据本发明合成共聚酰胺预聚物时，可以添加消光剂(例如二氧化钛)以实现不同的光泽度。此外，可以添加镁化合物、铜化合物、锰化合物、或锌化合物以赋予预定的功能。
将共聚酰胺预聚物(其聚酰胺链中引入有芳香组分)进行通常的熔融纺丝以制备纱线，然后将该纱线进行机织或针织，由此获得机织织物或针织织物，之后将该机织织物或针织织物在下述条件(1)下进行干式热处理或湿式热处理以使其热定形，然后在下述条件(2)下在低于热处理温度的温度下进行染色，由此赋予机织织物或针织织物以形状记忆性能：
Tg+40℃≤Tx≤Tm-20℃  (1)
Tg≤Td≤Tx            (2)
其中Tg为共聚酰胺预聚物的玻璃化转变温度，Tx为热处理温度，Tm为共聚酰胺预聚物的熔点，并且Td为染色温度。
在本发明中，在热处理温度低于聚酰胺材料的Tg+40℃的情况下，机织织物或针织织物的热定形性能会劣化。另一方面，若热处理温度高于所述材料的Tm-20℃，则材料会不利地发生部分熔融。
染色温度优选低于热处理温度。若染色温度低于聚酰胺材料的玻璃化转变温度(Tg)，则染色会变得不均匀。另一方面，如果染色温度高于聚酰胺材料的熔点(Tx)，会不利地使形状记忆性能丧失。
由本发明的方法制备的形状记忆型聚酰胺织物可以用作各种服装的材料。此外，本发明的聚酰胺织物可以用作各种服装的织物，这些服装包括：内衣服装(例如紧身胸衣、束腰紧身衣、连体服装等)、运动服装(例如高尔夫服装、登山服等)、短袜、长袜、男装、女装等等；除服装之外，本发明的聚酰胺织物还可以用于其它的需要形状记忆性能的领域中。
本发明的实施方式
根据下面的实施例，可以更好地理解本发明，所述实施例用于阐述本发明，但不应理解为对本发明的限制。
例子
实施例1～5和比较例1～2
将用于尼龙6的ε-己内酰胺以及作为引发剂的水置于配备有搅拌器的混合器中，添加下表1中所示类型和数量的多元羧酸和多元胺，然后在250℃～300℃下进行聚合反应。将由此获得的产物放到水浴中使其固化，之后将聚合物带子(polymer lace)切片、挤出、并干燥，由此获得最终切片性能为硫酸相对粘度约2.6的共聚酰胺切片。
将水含量为0.05重量份或更低的共聚酰胺切片进行熔融纺丝。例如，使用具有68个直径为0.25mm的孔的SUS-316纺丝头，在纺丝温度为265℃的条件下，用气流速度为0.5m/min的20℃的冷空气流对挤出的线状聚酰胺进行冷却，加入纺丝油剂，然后进行拉伸，拉伸比通过4500m/min的纺丝速度进行控制，由此制得强度为5.2g/d并且伸长率为45％的70d/68f聚酰胺纱线。
将制得的纱线进行机织或针织以获得机织织物或针织织物，之后将该机织织物或针织织物在170℃下进行蒸汽热处理，然后在100℃下染色，由此制备所需的织物。用肉眼评价实施例1～5和比较例1～2中制得的织物的形状记忆性能。结果如下表1所示。
表1
Figure GSB00000538116100071
备注：AA：己二酸
TPA：对苯二甲酸
IPA：间苯二甲酸
t-IPA：1，3，5-三羧酸
SiPA：间苯二甲酸-5-磺酸单钠盐
HMD：己二胺
MXD：间二甲苯二胺
[形状记忆性能和形状恢复力的评价]
通过用肉眼评价制得的织物在起皱时是否保持原状来确定形状记忆性能，并且通过用肉眼评价起皱后的织物在铺平时恢复至原状的程度来确定形状恢复力。
◎：出色，○：良好，△：中等，×：无效果
实施例6～10和比较例3～4
与实施例1～5类似，将用于尼龙66的己二酸和己二胺置于配备有搅拌器的混合器中，添加下表2中所示类型和数量的多元羧酸和多元胺，然后在270℃～350℃下进行聚合反应。之后，将由此获得的产物放到水浴中使其固化，之后将聚合物带子(polymer lace)切片、挤出、并干燥，由此获得最终切片性能为硫酸相对粘度约2.6的共聚酰胺切片。
将水含量为0.05重量份或更低的共聚酰胺切片进行熔融纺丝。例如，使用具有68个直径为0.25mm的孔的SUS-316纺丝头，在纺丝温度为295℃的条件下，用气流速度为0.5m/min的20℃的冷空气流对挤出的线状聚酰胺进行冷却，加入纺丝油剂，然后进行拉伸，拉伸比通过4500m/min的纺丝速度进行控制，由此制得强度为5.8g/d并且伸长率为43％的70d/68f聚酰胺纱线。
将制得的纱线进行机织或针织以获得机织织物或针织织物，之后将该机织织物或针织织物在210℃下进行蒸汽热处理，然后在100℃下染色，由此制备所需的织物。用肉眼评价实施例6～10和比较例3～4中制得的织物的形状记忆性能。结果如下表2所示。
表2
可以看到，随着间位芳香族化合物的加入，尼龙6和尼龙66表现出彼此相同的形状记忆性能。特别是，在共聚酰胺预聚物含有磺酸基团的情况下，形状记忆的效果最佳。
工业实用性
根据本发明，形状记忆型聚酰胺织物具有较好的形状记忆性能和形状恢复力，显示出较小的收缩变形，洗涤后不起皱，并且在穿着期间表现出的起皱或变形程度较低。
尽管本发明已公开的优选实施方式是为了进行阐述本发明，然而本领域技术人员应理解的是，在不背离所附的权利要求书中所公开的本发明的范围和精神的情况下，可进行各种变形、添加和替换。

Claims (13)

1.一种形状记忆型聚酰胺，其是在由ε-己内酰胺或者由己二胺和己二酸作为原料聚合生成聚酰胺时，通过添加多元羧酸和多元胺而制备得到的，并且其具有芳香组分，所述芳香组分是通过所述多元羧酸和所述多元胺中的一种或多种而引入的，并且所述芳香组分的总量为所述聚酰胺的原料的量的0.4摩尔％至10摩尔％。
2.根据权利要求1所述的形状记忆型聚酰胺，其中所述聚酰胺为尼龙6、尼龙66、或者尼龙6/66共聚物。
3.根据权利要求1所述的形状记忆型聚酰胺，其中所述芳香组分为含有磺酸基团的芳香组分。
4.根据权利要求1所述的形状记忆型聚酰胺，其中所述芳香组分通过芳香族多元羧酸和脂肪族多元胺的组合、脂肪族多元羧酸和芳香族多元胺的组合、或者芳香族多元羧酸和芳香族多元胺的组合而引入。
5.根据权利要求1所述的形状记忆型聚酰胺，其中所述多元羧酸选自由下列物质组成的组：己二酸、癸二酸、十二烷二酸、对苯二甲酸、间苯二甲酸；3，5-二羧基苯磺酸或其钠、钾、锂的磺酸盐；以及它们的混合物。
6.根据权利要求1所述的形状记忆型聚酰胺，其中所述多元胺选自由下列物质组成的组：乙二胺、丁二胺、己二胺、辛二胺、癸二胺、十一烷二胺、十二烷二胺、对苯二胺、间苯二胺、对二甲苯二胺、间二甲苯二胺，以及它们的混合物。
7.一种制备形状记忆型聚酰胺织物的方法，包括：
在聚合生成聚酰胺时添加多元羧酸和多元胺，由此合成具有芳香组分的共聚酰胺预聚物，所述芳香组分的总量为聚酰胺的原料的量的0.4摩尔％至10摩尔％；
将所述共聚酰胺预聚物进行机织或针织，由此制备机织织物或针织织物；以及
将所述机织织物或针织织物在下述条件(1)下进行热处理，然后在下述条件(2)下进行染色：
Tg+40℃≤Tx≤Tm-20℃  (1)
Tg≤Td≤Tx            (2)
其中Tg为共聚酰胺预聚物的玻璃化转变温度，Tx为热处理温度，Tm为共聚酰胺预聚物的熔点，并且Td为染色温度。
8.根据权利要求7所述的方法，其中所述聚酰胺为尼龙6、尼龙66、或者尼龙6/66共聚物。
9.根据权利要求8所述的方法，其中所述共聚酰胺预聚物具有芳香族多元羧酸和脂肪族多元胺的组合、脂肪族多元羧酸和芳香族多元胺的组合、或者芳香族多元羧酸和芳香族多元胺的组合。
10.根据权利要求7所述的方法，其中所述多元羧酸选自由下列物质组成的组：己二酸、癸二酸、十二烷二酸、对苯二甲酸、间苯二甲酸；3，5-二羧基苯磺酸或其钠、钾、锂的磺酸盐；以及它们的混合物。
11.根据权利要求7所述的方法，其中所述多元胺选自由下列物质组成的组：乙二胺、丁二胺、己二胺、辛二胺、癸二胺、十一烷二胺、十二烷二胺、对苯二胺、间苯二胺、对二甲苯二胺、间二甲苯二胺，以及它们的混合物。
12.由权利要求7至11中任一项所述的方法制备的形状记忆型聚酰胺织物。
13.使用权利要求12所述的形状记忆型聚酰胺织物制备的形状记忆型服装。
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CN107438677A (zh) * 2015-02-23 2017-12-05 帝斯曼知识产权资产管理有限公司 高强度聚酰胺纱线
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CN108148200A (zh) * 2016-12-02 2018-06-12 上海杰事杰新材料(集团)股份有限公司 水溶性聚酰胺树脂及其制备方法
CN110004513B (zh) * 2019-04-12 2021-05-07 太原理工大学 一种智能变形丙纶纤维及其制备方法
CN110092907B (zh) * 2019-05-29 2020-05-26 四川大学 含硫醚耐高温形状记忆型聚酰胺树脂及其制备方法和应用
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1624021A (zh) * 2003-05-20 2005-06-08 三菱瓦斯化学株式会社 聚酰胺的制备方法
CN1777631A (zh) * 2003-02-27 2006-05-24 史蒂文·W·福克斯 芳酰胺聚合物体系及其制备方法

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898200A (en) * 1972-09-06 1975-08-05 Allied Chem Cationic dyeable polyamide of improved physical properties
US3828009A (en) * 1972-09-06 1974-08-06 Allied Chem Cationic dyeable polyamide of improved physical properties
JPS57130A (en) * 1980-05-30 1982-01-05 Unitika Ltd Melt-moldable copolyamide having aromatic amide unit
US4579762A (en) 1984-12-24 1986-04-01 Monsanto Company Stain resistant carpet with impervious backing
JPS63235524A (ja) * 1987-03-19 1988-09-30 Mitsubishi Kasei Corp ポリアミドモノフイラメント
JP2597906B2 (ja) * 1989-04-11 1997-04-09 三菱化学株式会社 ポリアミド細物モノフィラメントよりなる釣り糸
JP2726564B2 (ja) * 1990-11-20 1998-03-11 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ２−メチルペンタメチレンジアミンのアミド単位を含有する三元ポリアミドおよび多元ポリアミド、ならびにこれから製造した製品
CA2066876C (en) * 1991-06-06 1999-12-14 Matthew B. Hoyt Acid-dye resistant polyamide products and process for preparation
KR930011332B1 (ko) * 1991-12-09 1993-11-30 주식회사 코오롱 강도 및 탄성이용률이 우수한 폴리아미드 필라멘트사의 제조방법
JPH05247778A (ja) * 1992-02-27 1993-09-24 Unitika Ltd 形状記憶織編物
KR100225738B1 (ko) * 1992-05-06 1999-10-15 전원중 고수축성 폴리아미드섬유의 제조방법
US5637653A (en) * 1995-05-02 1997-06-10 Dainippon Ink And Chemicals, Incorporated Polymer blend materials composed of an aromatic polyamide and a soluble polyamide
JP3474992B2 (ja) * 1995-11-22 2003-12-08 市川毛織株式会社 形状記憶性を有するニードルフェルト
EP0811718A4 (en) * 1995-12-18 1998-10-07 Toray Industries WOVEN OR KNITTED ARTICLES AND THEIR PRODUCTION METHOD
US5698658A (en) * 1996-05-31 1997-12-16 E. I. Du Pont De Nemours And Company Linear very high molecular weight polyamides and process for producing them
KR100220220B1 (ko) * 1996-12-28 1999-10-01 전 원 중 고속방사에 적합한 개질 폴리아미드-6의 제조방법
JP2000053762A (ja) * 1998-08-11 2000-02-22 Toray Ind Inc 共重合ポリアミド、その製造方法、及びその用途
JP2001200054A (ja) * 2000-01-19 2001-07-24 Toray Ind Inc ナイロン６共重合体の製造方法および繊維
FR2812879B1 (fr) * 2000-08-09 2002-10-25 Rhodia Eng Plastics Srl Copolyamides et compositions a base de ces copolyamides
JP2004250556A (ja) * 2003-02-19 2004-09-09 Mitsubishi Engineering Plastics Corp ポリアミドモノフィラメントからなる漁網
DE10321789A1 (de) * 2003-05-14 2004-12-09 Basf Ag Polyamide
KR100624150B1 (ko) * 2003-10-15 2006-09-18 주식회사 코오롱 잠재권축성 폴리아미드 섬유
KR101408636B1 (ko) * 2005-03-18 2014-06-17 가부시키가이샤 구라레 반방향족 폴리아미드 수지
KR100937086B1 (ko) * 2006-12-20 2010-01-15 주식회사 효성 형상기억성 폴리아미드 및 그를 이용한 형상기억성폴리아미드 원단의 제조방법

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1777631A (zh) * 2003-02-27 2006-05-24 史蒂文·W·福克斯 芳酰胺聚合物体系及其制备方法
CN1624021A (zh) * 2003-05-20 2005-06-08 三菱瓦斯化学株式会社 聚酰胺的制备方法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JP平2-268630A 1990.11.02
JP特开2004-250556A 2004.09.09
金和等.（E/VAC)-g-MAH/PA6共混物的热致形状记忆功能.《工程塑料应用》.2005,第33卷(第2期),12-15. *
金和等.MAH改性PE/PA6共混体系的热致形状记忆功能.《工程塑料应用》.2004,第32卷(第2期),11-13. *

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