CN1389604A - 芳香族聚砜酰胺纤维的制造方法 - Google Patents
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Abstract
化学纤维制造业中芳香族聚砜酰胺纤维的制造方法,包括纺丝浆液制备、湿法纺丝、后处理三个步骤。浆液制备过程为:将4,4’－二氨基二苯砜和3,3’－二氨基二苯砜溶解于二甲基乙酰胺中,冷却至－20～－5℃后加入与二氨基二苯砜等摩尔的对苯二甲酰氯,制成聚合体含量为10%～20%的纺丝浆液。制备中产生的氯化氢用无机碱中和。湿法纺丝的凝固浴组成和拉伸浴组成为二甲基乙酰胺、CaCl2和水;拉伸浴30～100℃条件下拉伸1～3倍,50～70℃水洗,200～250℃干燥,250～450℃热管拉伸1～2倍,阳离子型油剂上油并卷绕成形。优点为工艺合理,符合环保要求,纤维质量指标高。
Description
①技术领域
本发明涉及化学纤维制造业中一种耐高温合纤-芳香族聚砜酰胺纤维的制造方法。
②背景技术
芳香族聚砜酰胺纤维商品名芳砜纶，是一种以产业用为主的耐热纤维。耐热纤维通常是指可以在180℃以上长期使用，或在更高温度下可瞬间使用的纤维。耐热纤维代表品种有芳香族聚酰胺纤维、芳香族聚砜酰胺纤维、芳香族聚酰胺酰亚胺纤维、芳香族聚酰亚胺纤维、聚苯硫醚纤维、聚醚醚酮纤维、嘧胺纤维等。目前以美国DuPont公司的芳香族聚酰胺纤维Nomex最具代表性。Nomex的聚合体原料为间苯二甲酰氯和间苯二胺。
Nomex和芳砜纶相比，有以下不足。(1)耐热性和热稳定性较低。Nomex在250℃和300℃的强力保持率分别为60％～65％和40％～45％，在350℃遭破坏；而芳砜纶在250℃和300℃时的强力保持率达70％和50％，350℃仍保持38％的强力。Nomex在250℃和300℃热空气中处理100h后强力保持率为78％和60％；芳砜纶则为90％和80％。(2)高温下尺寸稳定性差，其沸水收缩率为3％，在300℃热空气中的收缩率达8％；而芳砜纶在上述两种条件下的收缩率则分别为0.5％1％和2％。(3)阻燃性低于芳砜纶。Nomex的LOI值为28，而芳砜纶则为33。
芳砜纶生产方法的公开报导不多，目前我们发现报导较多的只有前苏联的相关文献。
前苏联公开报导的芳砜纶的制造方法主要有以下两篇。(1)前苏联《化学纤维》杂志(1966，1，22～25题为《聚砜酰胺纤维的溶液纺丝成形过程》)的文章中提到芳香族聚砜酰胺纤维的制备。
原料：芳族聚砜酰胺
用实验室微型装置制备。
工艺：聚合溶剂为二甲基甲酰胺(DMF)；
溶液浓度22％；
凝固浴温度20±1℃；
纺丝速度1.0m/mm；
喷丝板孔数×孔径100×0.08mm；
喷丝头拉伸20％；
纺出新丝在凝固浴逗留时间30s；
凝固浴采用水、一元醇、二元醇和三元醇，以及它们与二甲基甲酰
胺的混合物。(2)前苏联《化学纤维》杂志(1971，6，38～40题为《以芳香族聚砜酰胺为基的纤维的制取》)文章中提到芳香族聚砜酰胺纤维的制备：采用低温缩聚方法制备聚合物，聚合溶剂采用二甲基乙酰胺(DMAc)，纺丝液聚合物的含量为15％，通过湿法纺丝制备纤维，纺丝凝固浴采用二甲基甲酰胺和5％LiCl。
未发现有关工业化生产芳砜纶的报导。
③发明内容
本发明的目的是建立一种工艺合理、生产过程符合环保要求、能制取高质量产品的芳香族聚砜酰胺纤维的制造方法。
本发明提出的芳香族聚砜酰胺纤维的制造方法包括纺丝浆液制备、湿法纺丝、后处理三个步骤，即以对苯二甲酰氯和二氨基二苯砜(4，4’-二氨基二苯砜及3，3’-二氨基二苯砜)为原料，使它们在极性酰胺溶剂-二甲基乙酰胺中进行缩聚反应，并加入无机碱中和副产物氯化氢，制成聚合体含量为10％～20％的纺丝浆液，将制得的浆液进行湿法纺丝，随之水洗、干燥、热拉伸制成芳香族聚砜酰胺纤维。
纺丝浆液制备过程的特征如下：将4，4’-二氨基二苯砜(4，4’-DDS)50％～95％和3，3’-二氨基二苯砜(3，3’-DDS)5％～50％(均为质量百分比)，溶解于二甲基乙酰胺(DMAc)中，冷却至-20～5℃，再加入与二氨基二苯砜等摩尔的对苯二甲酰氯(TPC)，制成聚合体含量为10％～20％的纺丝浆液。加入TPC时，应控制加入速度，使反应温度不超过50℃。聚合反应中会产生副产物氯化氢，可加入与二氨基二苯砜等摩尔的无机碱将氯化氢中和，生成中性的无机盐和水。上述无机碱为氢氧化钙或氧化钙，加入的时间是：在TPC全部加完继续反应0.5～1h后。
湿法纺丝和后处理过程如下。在传统湿法纺丝设备上将上述纺丝浆液经计量泵计量、过滤器过滤、从喷丝头喷入凝固浴槽。凝固浴组成为：DMAc40％～70％，CaCl20～10％，加水至100％(均为质量百分比)。凝固成丝后进入拉伸浴槽，拉伸浴组成为：DMAc40％～60％，CaCl20％～10％，加水至100％(均为质量百分比)；在拉伸浴中30～100℃条件下拉伸1～3倍；随后在50～70℃条件下水洗，并在200～250℃条件下干燥处理，再经250～450℃的热管拉伸1～2倍，最后用阳离子型油剂上油并卷绕成形，上油率为0.2％～0.8％。
本发明的优点是工艺相对合理，可利用现有纺丝设备，生产中产生的氯化氢及时被中和，符合环保要求，制得的芳砜纶纤维许多质量优于Nomex。
④具体实施方式
取3，3’-DDS 7.542kg，4，4’-DDS 22.624kg，放入装有375L DMAc的聚合釜中，搅拌至完全溶解。溶解后用冷冻水将釜内溶液冷却至-5℃，缓慢加入TPC24.664kg，加入时使釜内温度不超过50℃。TPC加完后撤去冷冻水，继续反应0.5h，再加入6.813kgCaO，以中和缩聚反应中生成的副产物HCl，搅拌使HCl和CaO完全中和生成CaCl2和水。CaCl2不必析出，它可溶解于DMAc中，并能改善聚合体的溶解性能，得到聚二氨基二苯砜对苯二甲酰胺含量为13％的纺丝浆液。
在传统湿法纺丝设备上纺丝。将上述浆液真空脱泡，并升温至70℃，经计量泵计量，过滤器过滤后，浆液由孔径为0.07mm、孔数为1000孔的喷丝头挤出，进入凝固浴。凝固浴组成为：DMAc60％，CaCl23％，H2037％(均为质量百分比)；凝固浴温度为10～15℃，丝条以3m/min的速度引出。然后丝条在90℃塑化拉伸浴中拉伸2.5倍。塑化拉伸浴的组成为：DMAc40％，CaCl22％，H2O58％(均为质量百分比)。然后在60℃下水洗，250℃条件下干燥，再用400℃热管拉伸1.1倍。最后用阳离子型油剂上油，上油率0.5％，随后卷绕成形。
制得芳砜纶纤维主要性能与Nomex的性能对比见下表。
| 指标名称 | 单位 | 芳砜纶 | Nomex |
| 密度 | g/cm3 | 1.42 | 1.38 |
| 断裂强度 | cN/dtex | 2.8～3.0 | 5.0 |
| 伸长 | ％ | 20-25 | 15-17 |
| 抗拉模量 | kg/mm2 | 760 | 1680-1850 |
| 回潮率(RH65％20℃) | ％ | 6.28 | 4.5-5.0 |
| 软化温度 | ℃ | 367 | 370 |
| 熔点 | ℃ | 不熔 | 不熔 |
| 起始分解温度 | ℃ | 422 | 415 |
| 高温强度保持率 | 200℃ | ％ | 83 | 90 | |
| 250℃ | ％ | 70 | 70 | ||
| 300℃ | ％ | 50 | 40 | ||
| 350℃ | ％ | 38 | - | ||
| 在热空气中的强度保持率 | 200℃ 100h | ％ | 90 | 78 | |
| 250℃ 100h | ％ | 80 | 50-60 | ||
| 300℃ 50h | ％ | 55 | - | ||
| 350℃ 50h | ％ | 15 | - | ||
| 热收缩率 | 沸水 | ％ | 0.5-1.0 | 3.0 | |
| 300℃空气 | ％ | 2.0 | 8.0 | ||
| LOI值 | ％ | 33 | 28 | ||
| 燃烧性能 | 难燃，具自熄性 | 难燃，具自熄性 | |||
| 电绝缘性能 | 体积电阻系数 | Ω·cm | 2.6×1016 | ||
| 介电常数 | 1.79 | ||||
| 电压击穿强度 | kV/mm | 15-22 | 20 | ||
| 耐辐射性能(丙种射线)1×107red | 无明显变化 | 无明显变化 | |||
| 耐化学性能 | 良好 | 良好 | |||
芳砜纶用途广泛，凡用Nomex纤维的领域均可用芳砜纶取代，某些耐热性和阻燃性要求更高而Nomex无法满足的领域也可用芳砜纶。
主要用途：
1.防护制品：宇航服、飞行通风服、特种军服、军用篷布、消防服、消防战斗服、炉前工作服、电焊工作服、森林工作服、均压服、防辐射工作服、化学防护服、高压屏蔽服、宾馆用纺织品及救生通道、防火帘、儿童睡衣及床上用品等。
2.过滤材料：烟道除尘过滤袋、化工滤布、稀有金属回收袋、热气体过滤软管等。
3.电绝缘材料：电极绝缘材料、变压器绝缘材料、防电晕绝缘板、绝缘无纺布、絮片和毡、印刷电路板等。
4.蜂窝结构材料：飞机夹层材料、赛艇夹层材料、隔音隔热和自熄材料、护墙材料、复合材料等。
5.代石棉制品：摩擦材料、垫片盘根等密封材料。
其它工业织物：耐热输送带、造纸和印染用衬布和毛毯、缆绳、熨烫台布装饰材料、体育用品、扬声器、复印机清洁毡、涂层织物等。
Claims (10)
1.芳香族聚砜酰胺纤维的制造方法，包括纺丝浆液制备、湿法纺丝、后处理三个步骤，其特征在于将4，4’-二氨基二苯砜(4，4’-DDS)50％～95％和3，3’-二氨基二苯砜(3，3’-DDS)5％～50％(均为质量百分比)，溶解于二甲基乙酰胺(DMAc)中，冷却至-20～-5℃，再加入与二氨基二苯砜等摩尔的对苯二甲酰氯(TPC)，制成聚合体含量为10％～20％的纺丝浆液。
2.如权利要求1所述的制造方法，其特征在于加入TPC的速度应控制在使反应温度不超过50℃。
3.如权利要求1或2所述的制造方法，其特征在于在TPC加完并继续反应0.5～1h后加入与二氨基二苯砜等摩尔的无机碱。
4.如权利要求3所述的制造方法，其特征在于所述无机碱为氢氧化钙和氧化钙。
5.如权利要求1所述的制造方法，将所述制成的纺丝浆液经计量、过滤、从喷丝头喷入凝固浴槽，其特征在于凝固浴组成为DMAc40％～70％，CaCl20％～10％，加水至100％(均为质量百分比)。
6.如权利要求5所述的制造方法，经凝固成丝后丝束进入拉伸浴槽，其特征在于所述拉伸浴的组成为DMAc40％～60％，CaCl20％～10％，加水至100％(均为质量百分比)。
7.如权利要求6所述的制造方法，其特征在于在所述拉伸浴的温度为30～100℃条件下拉伸1～3倍。
8.如权利要求7所述的制造方法，其特征在于拉伸1～3倍后的丝束在50～70℃条件下水洗，并在200～250℃条件下干燥，再经250～450℃热管拉伸1～2倍。
9.如权利要求8所述的制造方法，其特征在于热管拉伸1～2倍后丝束用阳离子型油剂上油并卷绕成形。
10.如权利要求9所述的制造方法，其特征在于阳离子型油剂的上油率为0.2％～0.8％。
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