CN107002297A - 用于使纤维热稳定化的方法以及以这种方式稳定的纤维 - Google Patents

用于使纤维热稳定化的方法以及以这种方式稳定的纤维 Download PDF

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CN107002297A
CN107002297A CN201580052684.2A CN201580052684A CN107002297A CN 107002297 A CN107002297 A CN 107002297A CN 201580052684 A CN201580052684 A CN 201580052684A CN 107002297 A CN107002297 A CN 107002297A
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fiber
solvent
mixture
melt
temperature
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马赛厄斯·哈恩
安特耶·莱斯克
马茨·克诺普
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Abstract

本发明涉及一种用于生产热稳定化的熔纺纤维的方法，其中通过熔融纺丝生产的聚丙烯腈(PAN)纤维或PAN纤维前体在另外含有用于PAN的溶剂的碱性水溶液中处理。同样，本发明涉及可根据该方法生产的纤维。

Description

用于使纤维热稳定化的方法以及以这种方式稳定的纤维
技术领域
本发明涉及一种用于生产热稳定化的熔纺纤维的方法，其中通过熔融纺丝生产的聚丙烯腈(PAN)纤维或PAN纤维前体在另外含有用于PAN的溶剂的碱性水溶液中处理。同样，本发明涉及可根据该方法生产的纤维。
背景技术
根据现有技术的状态，在产业用纤维领域越来越重要的碳纤维通过将单独制备的前体纤维热转化而生产。用于前体纤维的材料尤其是PAN(共)聚合物(丙烯酸类前体)以及沥青。在商业上目前仅仅通过湿纺或干纺丝方法生产丙烯酸类前体纤维。为此，将浓度≤20％的聚合物溶液在凝固浴或热蒸汽气氛中纺丝，溶剂从纤维中扩散出来。以这种方式，产生在质量上高价值的前体，然而，所述方法的成本相对高。该结果一方面是由于所需的溶剂和其处理，另一方面是因为溶液纺丝方法的相对低的产量。
由于腈基团的强的分子间和分子内相互作用，PAN的熔点320℃高于聚合物的分解温度。这意味着纯PAN的熔融纺丝是不可能的，聚合物没有表现为热塑性塑料，而是表现为热固性塑料。同时，通过熔融纺丝生产前体纤维的可能性将意味着在前体生产中的显著的成本节约，因为在熔融纺丝期间的生产量基本上更高，此外不需要导致购买和回收/处置成本的溶剂。
几十年来已经努力使PAN适于通过熔融纺丝进行加工。原则上，因此必须区分通过外部软化(聚合物与添加剂的混合)和内部软化(共聚)的方法。在两种情况下，腈基的相互作用因此受到干扰，使得在聚合物的分解温度以下进行熔化。
进一步加工以形成碳纤维的必要先决条件是随后通过氧化将纤维稳定化的可能性。该方法在高于200℃的温度下进行，导致形成环状结构，其首先能够进行随后的碳化。当然，这只有在纤维在稳定化温度下不熔化时才能成功-这代表了要解决的另外的问题，因为稳定化温度通常高于熔融纺丝期间的加工温度。
如已经提到的，熔纺PAN纤维对于实际氧化稳定化/碳化的预稳定化是在可熔融纺丝PAN前体的背景下需要解决的关键问题之一。稳定化通常在空气气氛下在200℃至300℃的温度范围内进行。显然，上述熔纺PAN前体纤维在这些条件下软化/熔化，因此将使稳定化和同时维持纤维性能不可能。这意味着纤维必须在纺丝后首先进入不可熔化状态。
在文献中显示目前为此目的的唯一可行的途径是通过UV或电子辐射交联成品纤维(Mukundan等人，Polymer 2006 47:4163-4171)，前者要求引入另外的光敏共聚用单体，例如通过引入的交联剂(三烯丙基异氰脲酸酯或类似物)实现聚合物对电子束的第二敏化作用。这些方法的缺点是明显的；除了实际上不存在的UV活性单体的商业可得性之外，还向纤维中引入进一步的缺陷，这对所得碳纤维的性质具有负面影响。
发明内容
由此开始，本发明的目的是优化熔纺丙烯酸类纤维的热稳定性，使得纺丝后的纤维以不可熔化的状态存在用于进一步加工。
该目的通过具有权利要求1的特征的方法以及通过具有权利要求14的特征的熔纺纤维实现。其它从属权利要求揭示了有利的发展。
根据本发明，提供了一种用于生产热稳定化的熔纺丙烯酸类纤维的方法，其中通过熔融纺丝制备的纤维或纤维前体用包含用于PAN的溶剂的混合物预稳定化，所述溶剂特别选自由二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、碳酸亚乙酯、碳酸亚丙酯、硫氰酸钠水溶液及它们的混合物和碱性水溶液组成的组。
令人惊讶的是，确定通过熔融纺丝生产的纤维可以通过用这种溶液处理而转化为不可熔化状态。
因此优选混合物包含0.1-60体积％的PAN溶剂和40-99.9体积％的碱性水溶液。
预稳定化优选在包含所述混合物的改性浴中在20至80℃，优选40至65℃的温度下在5秒至2分钟，优选10秒至60秒的停留时间内进行。
优选地，碱性水溶液包含3至15mol/l的至少一种碱金属或碱土金属氢氧化物，优选碱金属氢氧化物，特别优选氢氧化钾或氢氧化钠。
优选将在混合物中PAN溶剂和碱性水溶液的比例作为相应纤维的纤度(titre)的函数进行调节。
优选地，在预稳定化之后进行氧化稳定化。因此，氧化稳定化优选在200-350℃的温度下在含氧或含空气的气氛中进行。
根据本发明，纤维优选为碳纤维，所述纤维前体由聚丙烯腈的共聚物组成或基本上包含它。
因此优选的是，纤维前体可通过以下方法制备，其中
i.在至少一种引发剂的存在下进行95至80摩尔％的丙烯腈与至少一种选自以下的共聚用单体的共聚：
a)5至20摩尔％的至少一种通式I的丙烯酸烷氧基烷基酯
其中
R＝CnH2n+1，n＝1-8和m＝1-8，特别是n＝1-4和m＝1-4
b)0至10摩尔％的至少一种通式II的丙烯酸烷基酯
其中
R＝CnH2n+1和n＝1-18，
c)0至10摩尔％的至少一种通式III的乙烯基酯
其中
R＝CnH2n+1和n＝1-18，
和
ii.用在挤出机出口处具有至少一个适于纺丝的喷嘴的挤出机纺丝该共聚物以形成单丝或复丝。
该共聚物优选具有保持恒定或随着温度升高直至240℃，特别是至260℃而降低的熔体粘度。
进一步优选存在8-12mol％的a)中的共聚用单体和/或1-5mol％的b)中的共聚用单体和/或1-5mol％的c)中的共聚用单体。
因此，共聚反应可以优选通过沉淀聚合、乳液聚合和/或在溶剂中的聚合实现。
溶剂优选选自二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、碳酸亚乙酯、碳酸亚丙酯、硫氰酸钠水溶液及它们的混合物。
根据本发明，同样提供可根据前述方法生产的纤维。这尤其涉及碳纤维。
附图说明
旨在参照随后的实施例和附图更详细地解释根据本发明的主题，而不希望将所述主题限于这里所示的具体实施方案。
图1参照示意图示出了在根据本发明的处理之前标准不可熔化丙烯酸类纤维和可熔化丙烯酸前体的储能模量的温度依赖性。
图2参照图表示出了未处理纤维的储能模量的温度依赖性。
图3显示未处理纤维的IR光谱。
图4参照图表示出了根据本发明处理的纤维的储能模量的温度依赖性。
图5显示了根据本发明处理的纤维的IR光谱。
图6显示了由42根纤维制成的未处理复丝(在顶部)和根据本发明处理的复丝(在底部)的照片，所述纤维均在230℃下进行氧化稳定化。可以清楚地识别未处理的长丝发生熔化，而处理过的长丝熔化并且不粘结。
具体实施方式
用以下测试描述处理的效果：
1.纤维粘结：
将大约500mg纤维短截部分(short section)放置在铝箔之间并在负载重量约为100g的干燥柜中在各种温度下分别孵育10分钟。记录结果是铝箔开始被纤维粘结的温度。该温度对应于软化或熔化温度。
2.熔化台显微镜：
在熔化台显微镜下观察纤维的热行为。记录是否可以检测纤维熔化。
3.纤维的溶解度：
将大约500mg纤维短截部分储存在10ml MDSO中，并注意到纤维在多少时间后溶解。用该测试方法检测交联。
4.动态力学分析(DMA)：
作为温度的函数确定10cm长的纤维的储能模量。图2和图4描述了曲线的基本过程。未改性的PAN(不可熔化)显示随温度高达约140℃储能模量的损失，此后保持恒定的剩余储能模量，确保纤维的机械稳定性。未经处理的可熔化PAN显示直到约80℃有储能模量的损失，在此温度下，模量已降至0。在80℃以上，纤维柔软，使得其不再可机械加载并发生撕裂(见图1)。
实施例：
对比例
未处理的熔纺纤维
检查由具有10％丙烯酸甲氧基乙基酯和摩尔质量为15,000g/mol的PAN共聚物制成的单纤维纤度为0.82tex的未处理的熔纺纤维。
因此在粘结试验中显示出纤维从80℃开始粘结。在熔化台显微镜下，可以观察到在185℃下完全熔化。在溶解度试验期间，纤维在2分钟内完全溶解。在DMA期间，模量在直至100℃时下降至0(见图2)。
从IR光谱(图3)可以清楚地检测到1730cm-1处的酯基团，就像在2,240cm-1处的腈基团一样。不存在其他特征带。
实施例
根据本发明处理的熔纺纤维
检查由具有10％丙烯酸甲氧基乙基酯和摩尔质量为15,000g/mol的共聚物制成的单纤维纤度为0.82tex的根据本发明处理的熔纺纤维。为此，在比较例中描述的纤维放置在70℃下的组成为50％DMSO和50％4.5M KOH水溶液的改性浴中60秒。纤维变色为红棕色。随后将其中性洗涤并在50℃下真空干燥。
在粘结试验期间，显示纤维直到230℃的温度都不粘结。在熔化台显微镜下，观察到纤维直到250℃都不熔化，只有纤维的颜色由红色经红棕色变成黑色。溶解度测试的结果是纤维在24小时后完全保持。在DMA期间，模量一直到250℃都降低，但即使在该温度下仍然具有大于0的值(参见图4)。
从红外光谱(图5)可以看出，与图3中的红外光谱相比，其在1,730cm-1处的酯基的谱带强度明显降低，而腈基团的谱带强度恒定为2,240cm-1。此外，可以归因于形成了PAN导体结构的谱带出现在1570cm-1。

Claims (15)

1.一种使熔纺丙烯酸类纤维热稳定化的方法，其中用包含用于聚丙烯腈的溶剂和碱性水溶液的混合物预稳定化由熔融纺丝生产的丙烯酸纤维或纤维前体。
2.根据权利要求1所述的方法，其特征在于混合物包含0.1-60体积％的溶剂和40-99.9体积％的碱性水溶液。
3.根据前述权利要求中任一项所述的方法，其特征在于溶剂选自二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、碳酸亚乙酯、碳酸亚丙酯、硫氰酸钠水溶液及它们的混合物。
4.根据前述权利要求中任一项所述的方法，其特征在于预稳定化在包含所述混合物的改性浴中在20至80℃，优选40至65℃的温度下在5秒至2分钟，优选10秒至60秒的停留时间内进行。
5.根据前述权利要求中任一项所述的方法，其特征在于所述碱性水溶液包含3至15mol/l的至少一种碱金属盐或碱土金属盐，优选碱金属氢氧化物，特别优选氢氧化钾或氢氧化钠。
6.根据前述权利要求中任一项所述的方法，其特征在于，将混合物中的溶剂和碱性水溶液的比例作为纤度的函数进行调节。
7.根据前述权利要求中任一项所述的方法，其特征在于，在预稳定化后，在800至1700℃的温度下，在惰性气体，特别是氩气或氮气下进行氧化稳定化和碳化，用于生产碳纤维。
8.根据前述权利要求中任一项所述的方法，其特征在于氧化稳定化在200-350℃的温度下在含氧或含空气的气氛中进行。
9.根据前述权利要求中任一项所述的方法，其特征在于纤维前体可通过以下方法制备，其中
i.在至少一种引发剂的存在下进行95至80摩尔％的丙烯腈与至少一种选自以下的共聚用单体的共聚：
a)5至20摩尔％的至少一种通式I的丙烯酸烷氧基烷基酯
其中
R＝CnH2n+1，n＝1-8和m＝1-8，特别是n＝1-4和m＝1-4
b)0至10摩尔％的至少一种通式II的丙烯酸烷基酯
其中
R＝CnH2n+1和n＝1-18，
c)0至10摩尔％的至少一种通式III的乙烯基酯
其中
R＝CnH2n+1和n＝118，
和
ii.用在挤出机出口处具有至少一个适于纺丝的喷嘴的挤出机纺丝共聚物以形成单丝或复丝。
10.根据权利要求9所述的方法，其特征在于所述共聚物具有保持恒定或随着温度升高至240℃，特别是至260℃而降低的熔体粘度。
11.根据权利要求9或10中任一项所述的方法，其特征在于存在8-12mol％的a)中的共聚用单体和/或1-5mol％的b)中的共聚用单体和/或1-5mol％的c)中的共聚用单体。
12.根据权利要求9至11中任一项所述的方法，其特征在于共聚反应通过沉淀聚合、乳液聚合和/或在溶剂中的聚合进行。
13.根据前述权利要求中任一项所述的方法，其特征在于溶剂选自二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、碳酸亚乙酯、碳酸亚丙酯、硫氰酸钠水溶液及它们的混合物。
14.一种熔纺纤维，其根据前述权利要求中任一项所述的方法进行热稳定化。
15.根据权利要求14所述的纤维，其根据权利要求7的方法被进一步加工以形成碳纤维。
CN201580052684.2A 2014-09-29 2015-09-10 用于使纤维热稳定化的方法以及以这种方式稳定的纤维 Pending CN107002297A (zh)

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