CN1389604A - 芳香族聚砜酰胺纤维的制造方法 - Google Patents
芳香族聚砜酰胺纤维的制造方法 Download PDFInfo
- Publication number
- CN1389604A CN1389604A CN 02136060 CN02136060A CN1389604A CN 1389604 A CN1389604 A CN 1389604A CN 02136060 CN02136060 CN 02136060 CN 02136060 A CN02136060 A CN 02136060A CN 1389604 A CN1389604 A CN 1389604A
- Authority
- CN
- China
- Prior art keywords
- manufacture method
- diamino
- bath
- dds
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 125000003118 aryl group Chemical group 0.000 title claims description 13
- 150000001408 amides Chemical class 0.000 title description 3
- 229920002492 poly(sulfone) Polymers 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 230000015271 coagulation Effects 0.000 claims abstract description 7
- 238000005345 coagulation Methods 0.000 claims abstract description 7
- 238000004804 winding Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- 238000009987 spinning Methods 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 12
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000002166 wet spinning Methods 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000009736 wetting Methods 0.000 abstract 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000001110 calcium chloride Substances 0.000 abstract 1
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 1
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 150000003457 sulfones Chemical class 0.000 description 14
- 229920002994 synthetic fiber Polymers 0.000 description 14
- 229920000784 Nomex Polymers 0.000 description 11
- 239000004763 nomex Substances 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002783 friction material Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VUTBELPREDJDDH-UHFFFAOYSA-N 4-amino-5-hydroxymethyl-2-methylpyrimidine Chemical compound CC1=NC=C(CO)C(N)=N1 VUTBELPREDJDDH-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical group ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 terephthalamide amine Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
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％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02136060XA CN1176256C (zh) | 2002-07-16 | 2002-07-16 | 芳香族聚砜酰胺纤维的制造方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02136060XA CN1176256C (zh) | 2002-07-16 | 2002-07-16 | 芳香族聚砜酰胺纤维的制造方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1389604A true CN1389604A (zh) | 2003-01-08 |
| CN1176256C CN1176256C (zh) | 2004-11-17 |
Family
ID=4748483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02136060XA Expired - Lifetime CN1176256C (zh) | 2002-07-16 | 2002-07-16 | 芳香族聚砜酰胺纤维的制造方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1176256C (zh) |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345886C (zh) * | 2004-04-14 | 2007-10-31 | 邢哲 | 一种提高间位芳香族聚酰胺聚合体阻燃性的方法 |
| WO2009026481A1 (en) * | 2007-08-22 | 2009-02-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026478A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Spun staple yarns made from blends of rigid-rod fibers and fibers derived from diamino diphenyl sulfone and fabrics and garments made therefrom and methods for making same |
| WO2009026476A1 (en) | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and high modulus fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026480A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone, low thermal shrinkage fibers, flame resistant fibers, and antitstatic fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026479A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and textile fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026489A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Fibers comprising copolymers containing structures derived from 4.4' diamino diphenyl sulfone and a plurality of acid monomers and methods of making same |
| WO2009026482A1 (en) * | 2007-08-22 | 2009-02-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and polyoxadiazole fibers and fabrics and garments made therefrom and methods for making same |
| WO2009086226A2 (en) * | 2007-12-21 | 2009-07-09 | E. I. Du Pont De Nemours And Company | Papers containing floc derived from diamino diphenyl sulfone |
| EP1975285A3 (en) * | 2007-03-26 | 2009-10-07 | Shanghai Tanlon Fiber Co., Ltd. | A method for producing omni-meta aromatic polysulfonamide fiber |
| US7819936B2 (en) | 2007-08-22 | 2010-10-26 | E.I. Du Pont De Nemours And Company | Filter felts and bag filters comprising blends of fibers derived from diamino diphenyl sulfone and heat resistant fibers |
| CN101892611A (zh) * | 2010-08-18 | 2010-11-24 | 骏源特种纸（上海）有限公司 | 芳砜纶绝缘纸的加工工艺 |
| US7955692B2 (en) | 2007-08-22 | 2011-06-07 | E. I. Du Pont De Nemours And Company | Protective garment comprising fibers comprising copolymers containing structures derived from a plurality of amine monomers including 4,4′ diamino diphenyl sulfone |
| CN101718002B (zh) * | 2009-10-21 | 2011-06-08 | 南通信一服饰有限公司 | 一种超细芳砜纶纤维的制备方法 |
| CN101255616B (zh) * | 2007-03-02 | 2011-08-10 | 上海特安纶纤维有限公司 | 芳香族聚砜酰胺纤维的制造方法 |
| CN102337600A (zh) * | 2011-07-27 | 2012-02-01 | 东华大学 | 一种聚芳砜酰胺初生纤维的热拉伸方法 |
| US8114251B2 (en) | 2007-12-21 | 2012-02-14 | E.I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| US8118975B2 (en) | 2007-12-21 | 2012-02-21 | E. I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| CN102358958A (zh) * | 2011-07-27 | 2012-02-22 | 东华大学 | 一种聚芳砜酰胺纤维的制备方法 |
| US8133827B2 (en) | 2007-08-22 | 2012-03-13 | E.I. Du Pont De Nemours And Company | Fibers comprising copolymers containing structures derived from 4,4 diamino diphenyl sulfone and a plurality of acid monomers and methods of making same |
| CN102131965B (zh) * | 2008-08-27 | 2012-09-05 | 欧瑞康纺织有限及两合公司 | 用于熔纺、拉伸和卷绕复丝的方法以及用于实施该方法的装置 |
| CN102698611A (zh) * | 2012-06-27 | 2012-10-03 | 上海大学 | 湿法纺丝法制备聚砜酰胺中空纤维分离膜的方法 |
| CN104040041A (zh) * | 2012-01-11 | 2014-09-10 | 纳幕尔杜邦公司 | 用于制备衍生自具有低残余硫的芳族聚酰胺共聚物纤维的纱线的方法 |
| CN104372435A (zh) * | 2014-11-18 | 2015-02-25 | 上海大学 | 含ppta链段的芳香族聚砜酰胺共聚物纤维及其制造方法 |
| CN104562434A (zh) * | 2015-01-04 | 2015-04-29 | 上海特安纶纤维有限公司 | 芳砜纶永久阻燃隔热保暖絮片及其制备方法 |
| WO2015149063A1 (en) | 2014-03-28 | 2015-10-01 | E. I. Du Pont De Nemours And Company | Fiber-reinforced composite laminate and articles made therefrom |
| CN106519220A (zh) * | 2015-09-11 | 2017-03-22 | 中国科学院上海有机化学研究所 | 一种聚砜芳酰胺纤维、待纺丝浆液及其制造方法 |
| WO2017105995A1 (en) | 2015-12-14 | 2017-06-22 | E I Du Pont De Nemours And Company | Thermoplastic composite laminate and articles manufactured therefrom |
| CN107725649A (zh) * | 2017-09-30 | 2018-02-23 | 江阴市蒋氏汽摩部件有限公司 | 一种耐摩擦的刹车片及其制备方法 |
| CN115704116A (zh) * | 2021-08-04 | 2023-02-17 | 中蓝晨光化工有限公司 | 一种芳香族聚砜酰胺纤维的制造方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235552B (zh) * | 2008-02-29 | 2010-06-09 | 上海大学 | 无规共聚聚砜酰胺纺丝液及其制备方法 |
-
2002
- 2002-07-16 CN CNB02136060XA patent/CN1176256C/zh not_active Expired - Lifetime
Cited By (60)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345886C (zh) * | 2004-04-14 | 2007-10-31 | 邢哲 | 一种提高间位芳香族聚酰胺聚合体阻燃性的方法 |
| CN101255616B (zh) * | 2007-03-02 | 2011-08-10 | 上海特安纶纤维有限公司 | 芳香族聚砜酰胺纤维的制造方法 |
| EP1975285A3 (en) * | 2007-03-26 | 2009-10-07 | Shanghai Tanlon Fiber Co., Ltd. | A method for producing omni-meta aromatic polysulfonamide fiber |
| US7700190B2 (en) | 2007-08-22 | 2010-04-20 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and textile fibers and fabrics and garments made therefrom and methods for making same |
| US7749601B2 (en) | 2007-08-22 | 2010-07-06 | E. I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone, low thermal shrinkage fibers, flame resistant fibers, and antistatic fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026479A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and textile fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026489A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Fibers comprising copolymers containing structures derived from 4.4' diamino diphenyl sulfone and a plurality of acid monomers and methods of making same |
| WO2009026482A1 (en) * | 2007-08-22 | 2009-02-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and polyoxadiazole fibers and fabrics and garments made therefrom and methods for making same |
| US7537831B2 (en) | 2007-08-22 | 2009-05-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
| US7537830B2 (en) | 2007-08-22 | 2009-05-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone, low thermal shrinkage fibers, flame resistant fibers, and antistatic fibers and fabrics and garments made therefrom and methods for making same |
| CN101784323B (zh) * | 2007-08-22 | 2016-04-13 | 纳幕尔杜邦公司 | 包括得自二氨基二苯砜的纤维和耐热纤维的共混物的过滤毡和袋式过滤器 |
| KR101563374B1 (ko) * | 2007-08-22 | 2015-10-26 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 다이아미노다이페닐 설폰으로부터 유도된 섬유 및 내열성 섬유의 블렌드를 포함하는 필터 펠트 및 백 필터 |
| WO2009026476A1 (en) | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and high modulus fibers and fabrics and garments made therefrom and methods for making same |
| US7618707B2 (en) | 2007-08-22 | 2009-11-17 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026478A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Spun staple yarns made from blends of rigid-rod fibers and fibers derived from diamino diphenyl sulfone and fabrics and garments made therefrom and methods for making same |
| US7700191B2 (en) | 2007-08-22 | 2010-04-20 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and high modulus fibers and fabrics and garments made therefrom and methods for making same |
| WO2009026480A1 (en) * | 2007-08-22 | 2009-02-26 | E. I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone, low thermal shrinkage fibers, flame resistant fibers, and antitstatic fibers and fabrics and garments made therefrom and methods for making same |
| CN104726983A (zh) * | 2007-08-22 | 2015-06-24 | 纳幕尔杜邦公司 | 阻燃短纤纱和由其制得的织物和衣服以及它们的制备方法 |
| US7819936B2 (en) | 2007-08-22 | 2010-10-26 | E.I. Du Pont De Nemours And Company | Filter felts and bag filters comprising blends of fibers derived from diamino diphenyl sulfone and heat resistant fibers |
| CN101784708B (zh) * | 2007-08-22 | 2012-07-18 | 纳幕尔杜邦公司 | 由刚棒纤维和得自二氨基二苯砜的纤维的共混物制成的短纤纱和由其制得的织物和衣服以及它们的制备方法 |
| JP2010537074A (ja) * | 2007-08-22 | 2010-12-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ジアミノジフェニルスルホンから誘導された繊維とモダクリル繊維とのブレンドから製造された難燃性紡績スフ糸、それから製造された布及び衣類並びにそれらの製造方法 |
| JP2010537071A (ja) * | 2007-08-22 | 2010-12-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 剛性ロッド繊維とジアミノジフェニルスルホンから誘導された繊維とのブレンドから製造された紡績スフ糸、それらから製造された布及び衣類並びにそれらの製造方法 |
| JP2010537070A (ja) * | 2007-08-22 | 2010-12-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ジアミノジフェニルスルホンから誘導された繊維と高弾性率繊維とのブレンドから製造された難燃性紡績スフ糸、それらから製造された布及び衣類並びにそれらの製造方法 |
| JP2010537072A (ja) * | 2007-08-22 | 2010-12-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ジアミノジフェニルスルホンから誘導された繊維と織物繊維とのブレンドから製造された難燃性紡績スフ糸ならびにそれらから製造された布および衣類ならびにそれらの製造方法 |
| JP2010537075A (ja) * | 2007-08-22 | 2010-12-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | ジアミノジフェニルスルホンから誘導された繊維とポリオキサジアゾール繊維とのブレンドから製造された難燃性紡績スフ糸、それらから製造された布及び衣類並びにそれらの製造方法 |
| US7955692B2 (en) | 2007-08-22 | 2011-06-07 | E. I. Du Pont De Nemours And Company | Protective garment comprising fibers comprising copolymers containing structures derived from a plurality of amine monomers including 4,4′ diamino diphenyl sulfone |
| US8166743B2 (en) | 2007-08-22 | 2012-05-01 | E.I. Du Pont De Nemours And Company | Spun staple yarns made from blends of rigid-rod fibers and fibers derived from diamino diphenyl sulfone and fabrics and garments made therefrom and methods for making same |
| WO2009026481A1 (en) * | 2007-08-22 | 2009-02-26 | E.I. Du Pont De Nemours And Company | Flame resistant spun staple yarns made from blends of fibers derived from diamino diphenyl sulfone and modacrylic fibers and fabrics and garments made therefrom and methods for making same |
| CN101784713B (zh) * | 2007-08-22 | 2012-03-21 | 纳幕尔杜邦公司 | 由得自二氨基二苯砜的纤维和聚噁二唑纤维的共混物制成的阻燃短纤纱和由其制得的织物和服装以及它们的制备方法 |
| US8133827B2 (en) | 2007-08-22 | 2012-03-13 | E.I. Du Pont De Nemours And Company | Fibers comprising copolymers containing structures derived from 4,4 diamino diphenyl sulfone and a plurality of acid monomers and methods of making same |
| US8118975B2 (en) | 2007-12-21 | 2012-02-21 | E. I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| CN101952509B (zh) * | 2007-12-21 | 2014-01-08 | 纳幕尔杜邦公司 | 含有衍生自二氨基二苯砜的絮状物的纸材 |
| US8114251B2 (en) | 2007-12-21 | 2012-02-14 | E.I. Du Pont De Nemours And Company | Papers containing fibrids derived from diamino diphenyl sulfone |
| WO2009086226A2 (en) * | 2007-12-21 | 2009-07-09 | E. I. Du Pont De Nemours And Company | Papers containing floc derived from diamino diphenyl sulfone |
| WO2009086226A3 (en) * | 2007-12-21 | 2009-08-27 | E. I. Du Pont De Nemours And Company | Papers containing floc derived from diamino diphenyl sulfone |
| US7803247B2 (en) | 2007-12-21 | 2010-09-28 | E.I. Du Pont De Nemours And Company | Papers containing floc derived from diamino diphenyl sulfone |
| CN101952510B (zh) * | 2007-12-21 | 2013-01-02 | 纳幕尔杜邦公司 | 包含衍生自二氨基二苯砜的纤条体的纸材 |
| CN101952511B (zh) * | 2007-12-21 | 2013-03-13 | 纳幕尔杜邦公司 | 包含衍生自二氨基二苯砜的纤条体的纸材 |
| CN102131965B (zh) * | 2008-08-27 | 2012-09-05 | 欧瑞康纺织有限及两合公司 | 用于熔纺、拉伸和卷绕复丝的方法以及用于实施该方法的装置 |
| CN101718002B (zh) * | 2009-10-21 | 2011-06-08 | 南通信一服饰有限公司 | 一种超细芳砜纶纤维的制备方法 |
| CN101892611B (zh) * | 2010-08-18 | 2015-05-20 | 骏源新材料（上海）有限公司 | 芳砜纶绝缘纸的加工工艺 |
| CN101892611A (zh) * | 2010-08-18 | 2010-11-24 | 骏源特种纸（上海）有限公司 | 芳砜纶绝缘纸的加工工艺 |
| CN102358958B (zh) * | 2011-07-27 | 2013-10-30 | 东华大学 | 一种聚芳砜酰胺纤维的制备方法 |
| CN102337600B (zh) * | 2011-07-27 | 2013-08-07 | 东华大学 | 一种聚芳砜酰胺初生纤维的热拉伸方法 |
| CN102358958A (zh) * | 2011-07-27 | 2012-02-22 | 东华大学 | 一种聚芳砜酰胺纤维的制备方法 |
| CN102337600A (zh) * | 2011-07-27 | 2012-02-01 | 东华大学 | 一种聚芳砜酰胺初生纤维的热拉伸方法 |
| CN104040041A (zh) * | 2012-01-11 | 2014-09-10 | 纳幕尔杜邦公司 | 用于制备衍生自具有低残余硫的芳族聚酰胺共聚物纤维的纱线的方法 |
| CN104040041B (zh) * | 2012-01-11 | 2017-06-13 | 纳幕尔杜邦公司 | 用于制备衍生自具有低残余硫的芳族聚酰胺共聚物纤维的纱线的方法 |
| CN102698611A (zh) * | 2012-06-27 | 2012-10-03 | 上海大学 | 湿法纺丝法制备聚砜酰胺中空纤维分离膜的方法 |
| WO2015149063A1 (en) | 2014-03-28 | 2015-10-01 | E. I. Du Pont De Nemours And Company | Fiber-reinforced composite laminate and articles made therefrom |
| CN104372435A (zh) * | 2014-11-18 | 2015-02-25 | 上海大学 | 含ppta链段的芳香族聚砜酰胺共聚物纤维及其制造方法 |
| CN104562434A (zh) * | 2015-01-04 | 2015-04-29 | 上海特安纶纤维有限公司 | 芳砜纶永久阻燃隔热保暖絮片及其制备方法 |
| CN104562434B (zh) * | 2015-01-04 | 2017-02-22 | 上海特安纶纤维有限公司 | 芳砜纶永久阻燃隔热保暖絮片及其制备方法 |
| CN106519220A (zh) * | 2015-09-11 | 2017-03-22 | 中国科学院上海有机化学研究所 | 一种聚砜芳酰胺纤维、待纺丝浆液及其制造方法 |
| CN106519220B (zh) * | 2015-09-11 | 2020-08-07 | 中国科学院上海有机化学研究所 | 一种聚砜芳酰胺纤维、待纺丝浆液及其制造方法 |
| WO2017105995A1 (en) | 2015-12-14 | 2017-06-22 | E I Du Pont De Nemours And Company | Thermoplastic composite laminate and articles manufactured therefrom |
| US10946631B2 (en) | 2015-12-14 | 2021-03-16 | Dupont Safety & Construction, Inc. | Thermoplastic composite laminate and articles manufactured therefrom |
| CN107725649A (zh) * | 2017-09-30 | 2018-02-23 | 江阴市蒋氏汽摩部件有限公司 | 一种耐摩擦的刹车片及其制备方法 |
| CN115704116A (zh) * | 2021-08-04 | 2023-02-17 | 中蓝晨光化工有限公司 | 一种芳香族聚砜酰胺纤维的制造方法 |
| CN115704116B (zh) * | 2021-08-04 | 2024-05-28 | 中蓝晨光化工有限公司 | 一种芳香族聚砜酰胺纤维的制造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1176256C (zh) | 2004-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1176256C (zh) | 芳香族聚砜酰胺纤维的制造方法 | |
| CA2369681C (en) | Meta-type wholly aromatic polyamide filaments and process for producing same | |
| CN107313126B (zh) | 一种通过高速纺丝生产石墨烯改性锦纶6纤维的方法 | |
| JP4820379B2 (ja) | 高温加工性に優れたメタ型全芳香族ポリアミド繊維及びその製造方法 | |
| WO2014069853A1 (en) | Aramid fiber product with excellent conductivity and method of manufacturing the same | |
| CN102822398A (zh) | 间位型全芳香族聚酰胺纤维 | |
| EP0007631B1 (en) | Wholly aromatic polyamide composition and filaments or fibres thereof | |
| JP3937050B2 (ja) | メタ型全芳香族ポリアミド繊維の製造法及びそれによって得られる繊維 | |
| CA1282923C (en) | High strength polymetaphenylene isophthalamide fiber and process for producing the same | |
| JP3995532B2 (ja) | 緻密なメタ型全芳香族ポリアミド繊維の製造法 | |
| CN110804767B (zh) | 一种芳纶1313纤维及其制备方法和应用 | |
| US3839529A (en) | Preparation of polyamide-imide filaments | |
| JPH0874121A (ja) | メタ型芳香族ポリアミド繊維の製造法 | |
| JP3847515B2 (ja) | 緻密なメタ型芳香族ポリアミド繊維の製造法 | |
| JP2010126826A (ja) | 防刃衣料用布帛 | |
| CN113355764A (zh) | 一种一步法制备有色间位芳纶纤维的方法 | |
| CN114016187A (zh) | 一种阻燃防电弧复合面料及其制备方法、应用 | |
| Bajaj et al. | Some recent advances in the production of acrylic fibres for specific end uses | |
| JPH04257315A (ja) | 難燃性高耐熱性ポリイミド繊維およびその製法 | |
| JP2001348726A (ja) | 緻密なポリメタフェニレンイソフタルアミド系繊維の製造法 | |
| JP2008063698A (ja) | 無機微粒子含有芳香族ポリアミド繊維 | |
| JP2003342832A (ja) | 熱収縮安定性に優れたメタ型全芳香族ポリアミド繊維の製造法 | |
| JP4773887B2 (ja) | 防刃衣料用布帛 | |
| JP3929342B2 (ja) | 緻密なメタ型全芳香族ポリアミド繊維の製造方法 | |
| JP2013112919A (ja) | パラ型全芳香族ポリアミド繊維 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGTEX ( GROUP ) CO., LTD. Free format text: FORMER OWNER: SHANGHAI TEXTILE HOLDING ( GROUP ) CO.,LTD.; SHANGHAI CITY SPINNING SCIENCE INSTITUTE; SHANGHAI SYNTHETIC FIBRE INST. Effective date: 20070518 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070518 Address after: 200336 Shanghai textile (Group) Co., Ltd., 1488 Hongqiao Road, Shanghai Patentee after: Shanghai textile (Group) Co.,Ltd. Address before: 200336 No. 1488, Hongqiao Road, Shanghai Co-patentee before: SHANGHAI TEXTILE Research Institute Patentee before: Shanghai Textile Holding (Group) Corp. Co-patentee before: Shanghai Synthetic Fiber Research Institute |
|
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI TANLON FIBRE CO., LTD. Effective date: 20130507 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20130507 Address after: 200336 No. 1488, Hongqiao Road, Shanghai Patentee after: Shanghai textile (Group) Co.,Ltd. Patentee after: SHANGHAI TANLON FIBER Co.,Ltd. Address before: 200336 Shanghai textile (Group) Co., Ltd., 1488 Hongqiao Road, Shanghai Patentee before: Shanghai textile (Group) Co.,Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20041117 |
|
| CX01 | Expiry of patent term |