CN1052040C - 热稳定性改进的纤维或薄膜及其制法和该纤维制成的织物 - Google Patents

热稳定性改进的纤维或薄膜及其制法和该纤维制成的织物 Download PDF

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CN1052040C
CN1052040C CN93121332A CN93121332A CN1052040C CN 1052040 C CN1052040 C CN 1052040C CN 93121332 A CN93121332 A CN 93121332A CN 93121332 A CN93121332 A CN 93121332A CN 1052040 C CN1052040 C CN 1052040C
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R·V·卡索斯基
李圭昇
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Abstract

通过用六氯化钨浸渍芳族聚酰胺和聚苯并咪唑纤维和薄膜而获得改进了的耐火性能。

Description

芳族聚酰胺纤维类，例如，聚间苯二甲酰间苯二胺(MPD-I)纤维和聚对苯二甲酰对苯二胺(PPD-T)纤维被熟知为耐热纤维。聚苯并咪唑(PBI)纤维是另一种用于耐火的纤维。这些纤维用作消防队员的服装，用作可以置身于火焰和高温场合的工人的工作服，以及许多其他的应用。芳族聚酰胺和PBI纤维的热稳定性归因于其刚性链环结构和在链间的强氢键。要再提供耐火性，在有机纤维骨架内是困难的。
图1和2是热解重叠分析法曲线，表示出一种对比物(图1)和一种本发明的产品(图2)的重量损失。
本发明提供的改进了耐火性的芳族聚酰胺和聚苯并咪唑纤维和薄膜含有至少0.1％，而优选0.1-10％重量的钨(以混合氧化钨的形式)。该混合氧化物是在六氯化钨(WCl6)遇到水时生成的。由本发明还可领悟到的是制备该改进的纤维和薄膜的一种方法。
本发明的纤维和薄膜可以用两种一般方法中的任一种来制备。在较优选的方法中，将WCl6引入将被拉丝、浇注或用其他的方法成型的聚合物(芳族聚酰胺或PBI)的溶液中。如果聚合物溶液的溶剂是有机溶剂和可溶解WCl6，可以这么做。如果不是这样的情形，可使在有机溶剂中的(WCl6)溶液渗透入予成型的聚合物的纤维或薄膜内。(WCl6)在N-甲基吡咯烷酮(NMP)，二甲基乙酰胺(DMAc)和若干其他有机溶剂中是可溶的和稳定的。在该领域的技术人员可以容易地选择合适的溶剂。
下面的实施例1-2说明一种制备改进了耐火性芳族聚酰胺纤维的方法。在这些实施例中，WCl6直接加入到拉丝浓液中，因为WCl6可溶于浓液的溶剂中。拉丝浓液被挤出从而纤维暴露在水中。水把存在于刚挤出来的纤维中的WCl6转变成混合的钨氧化物(WOx)此处X是每个钨原子的平均氧原子数。
实施例4代表了另外一种从芳族聚酰胺制备改进了耐火性的薄膜的方法，该芳族聚酰胺不溶于适合溶解WCl6的溶剂中。在这个实施例中，已成型的PPD-T薄膜(含有硫酸)用WCl6在一种有机溶剂中的溶液处理。有机溶剂从薄膜中提取出硫酸而把WCl6透入薄膜内。在用水处理该薄膜之后，WCl6即转变成混合氧化物。如果需要，已成型的PPD-T薄膜可以先用水溶液冲洗以去除硫酸，然后再将该水润湿的薄膜用溶于一种有机溶剂中的WCl6溶液处理，以便把WCl6渗透入薄膜中而转变成混合钨氧化物。无论怎样，应该相信，薄膜或纤维用WCl6浸渍并与水接触以在薄膜或纤维中生成所要的混合钨氧化物。要使用的WCl6的用量应足够提供为改进耐火性所需的钨。
即使是少量钨的存在也可以改进芳族聚酰胺纤维或薄膜的耐火性。PBI纤维和薄膜也可指望依同样的方式而改进。改进了的聚合纤维或薄膜有不是以所引入的WCl6而是以混合的钨氧化物的形式存在的钨，这是因为WCl6遇水而转变成混合的钨氧化物。
本发明的产品被以混合氧化物的形式存在的钨的百分含量限定。在纤维或薄膜中的任何含量的钨都是有益的，但优选至少为0.1％(重量)。含量超过约10％(重量)并不表现出更高的改进，因而不合算。限氧指数(L.O.I)用来作为耐火性能的尺度。
钨的含量用ASTM-C 1111-88所述的电感耦合等离子一原子发射光谱法测定。
下面的实施例用于说明本发明而不是用来限制本发明的。
实施例1
制备拉丝溶液
把经过滤的拉丝溶液(含20份的MPD-I聚间苯二甲酰间苯二胺，9份的氯化钙(C12，Cl2)和71份的二甲基乙酰胺(DMAc)加入到反应釜中，反应釜装备了搅拌器，氮气进/出口，温度计和一个附加开口。聚合物在DMAc/4％LiCl中的0.5％溶液在25℃时测得有1.60的特性粘度。溶液在氮气保持下搅拌加热至70℃。以每100份的抽丝溶液将1.5份的干燥的六氯化钨(WCl6)粉缓慢加入到溶液中并搅拌，直到所有的WCl6颗粒完全溶解。溶液的颜色变成浅蓝，这种溶液用于制备纤维。
纤维的制备
拉丝溶液加热至120-125℃并以0.57克/分/孔的流量从多孔喷丝头中挤出，每个孔直径为0.006英寸(150微米)，长0.012英寸(300微米)，加入加热了的纺丝室(spining cell)中。每个室有5个加热区，从顶部到底部为320、300、250、200和150℃，395℃的惰性气流，流量为约3.67磅/小时(1.67公斤/小时)。纤维汇聚在纺丝室底部的导丝器，用含有7-10％DMAc和5-7％CaCi的水溶液浸没。一旦纤维接触了浸没溶液，就从浅蓝色变成黑色。纤维以125码/分的速度绕在线轴上。湿绕卷放置在一塑料袋中以免变干。几小时后，纤维变成白色。
湿绕卷以30码/分(ypm)供入一个冲洗-拉伸(wash-draw)装置中，在一个10-槽装置所含有的水浴中抽提和拉伸。总拉伸速率是4.2X，各个水浴的浓度，温度和拉伸速率示于表1中
表1冲洗-拉伸机械装置
槽号        拉伸速率(X)     ％DMAc    CaCl2 温度，℃
 1                1.93        29        3     80
 2                1.92        29        3     80
 3                1.05        29        3     90
 4                1.06        5         1     90
 5                1.02        1         -     90
 6                1.01        -         -     90
 7                1.01        -         -     90
 8                1.00        -         -     90
 9                1.00        -         -     90
 10               1.00        -         -     90
抽提拉伸之后纤维在温度设定为150℃的干燥辊上干燥。纤维后处理之后绕到卷筒上。纤维的特性，如表2所示，加入了WCl6与上备相同的纤维但不加入WCl6到纺丝溶液中的结果，没有显著的变化。
表2-纤维的物理性能
纤维试样    钨含量    强度    伸长    模量
             (％)     (gpd)   (％)    (gpd)
对比物        0.0      5.34   22.65    128
 MPD-I/WOx    3.24     5.08   23.24    119
该纤维织成织物并以ASTMD2863-77测量其限氧指数(LOI)。结果归纳在表3中。
表3-织物试样的LOI
纤维    钨含量    限氧指数(LOI)
试样    (％)
对比物    0.00       30
PDI/WOx   3.24       43
实施例2
这个实施例表明了MPD-I纤维不同的钨含量(以混合的钨氧化物的形式)时对LOI的改善情形。使用在实施例1中描述的相同的工艺(除了WCl6量不同)制备纤维试样，然后把该纤维试样织成织物并测试。结果列于表4中。
表4-不同钨含量的MPD-I织物的LOI
纤维    钨含量    限氧指数(LOI)
试样    (％)
对比物   0.00        30
MPD-I/WOx 0.92       37
MPD-I/WOx 3.24       43
MPD-I/WOx 6.94       44
实施例3
这个实施例表明了含钨MPD-I纤维的热降解率，用热解质量分析法按ASTMD3850-84测量。结果示于表5和图1及2中。对比的纤维，在438和524℃之间，重量损失38.5％，而含有3.24％钨的MPD-I纤维在高得多的温度范围(452℃至589℃)重量损失仅22.1％，在800℃，对比纤维只保存了45％的重量，而含3.24％钨的MPD-I纤维却保存60％的重量。这表明，钨在氧存在的条件下不仅迟滞MOD-I聚合物的燃烧，并且也防止在惰性环境例如氮气氛围下聚合物的分解。
表5-纤维的热解重量分析数据纤维  钨含量     最高温度     降解        重量损失试样      (％)     (℃)    重量损失(％)  (800时℃)对比试样  0.00   438-523     38.5           40MPD-IWOx  3.24   425-589     22.1           55
实施例4
本实施例要说明PPD-T聚对苯二甲酰对苯二胺薄膜的制备，该膜含有用于提高耐火性的混合的钨氧化物。
通过把20份(重量)的PPD-T聚合物(特性粘度6)在约80℃在氮气氛围中溶解于80份(重量)的100％硫酸中而制得液晶PPD-T溶液。把这种溶液倒在一热(90℃)玻璃板上并用5密耳的刮片抹成薄膜。让这种薄膜在一干燥箱中冷却形成固体膜。把该膜放入含六氯化钨20％(重量比)的DMAc溶液中，在100℃加热1小时。薄膜从溶液中取出，放置在室温的水中过夜以去掉多余的硫酸。薄膜变蓝色，在水中放置2小时后变回到黄色。重新换水直到pH值接近7时为止。薄膜再放到一真空炉中干燥。除了不再加入WCl6之外，用同样的工艺制对比膜试样。各膜的LOI测试结果例于表6中。
表6 PPD-T膜的LOI
试样                LOI
PPD-T对比膜         28.5
PPD-T(含有WOx)      35.0

Claims (8)

1.改进了热稳定性的纤维或薄膜，包括芳族聚酰胺和聚苯并咪唑中的一种聚合物，含有至少0.1％重量的以混合的钨氧化物形式的钨，以聚合物的重量为基数计。
2.按照权利要求1的纤维或薄膜，含有0.1至10％的混合的氧化物形式的钨。
3.按照权利要求1的纤维或薄膜，其中，芳族聚酰胺聚合物是聚间苯二甲酰间苯二胺。
4.按照权利要求1的纤维或薄膜，其中，混合的钨氧化物通过把六氯化钨暴露水中而形成。
5.制备权利要求1所述的芳族聚酰胺或聚苯并咪唑纤维或薄膜的方法，包括：用在二甲基乙酰胺有机溶剂中的六氯化钨溶液浸泡芳族聚酰胺或聚苯并咪唑的纤维或薄膜，溶液量应足够提供至少0.1％重量的钨，用水溶液处理浸泡过的纤维或薄膜以抽提溶剂并把钨的六氯化物转变成混合的钨氧化物。
6.制备权利要求1所述的芳族聚酰胺或聚苯并咪唑纤维或薄膜的方法，包括：把六氯化钨溶解于聚合物在二甲基乙酰胺有机溶剂中的溶液中，把该溶液制成纤维或薄膜，用水溶液处理该纤维或薄膜以抽提有机溶剂，并把六氯化钨转变成混合的钨氧化物。
7.按照权利要求6的方法，其中所述的芳族聚酰胺为聚对苯二甲酰间苯二胺。
8.一种织物，由权利要求1的纤维制成。
CN93121332A 1992-11-10 1993-11-10 热稳定性改进的纤维或薄膜及其制法和该纤维制成的织物 Expired - Fee Related CN1052040C (zh)

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