CN107217335A - 一种提高酚醛纤维残碳率的处理方法 - Google Patents

一种提高酚醛纤维残碳率的处理方法 Download PDF

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CN107217335A
CN107217335A CN201610163183.8A CN201610163183A CN107217335A CN 107217335 A CN107217335 A CN 107217335A CN 201610163183 A CN201610163183 A CN 201610163183A CN 107217335 A CN107217335 A CN 107217335A
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颜笑宇
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Abstract

一种提高酚醛树脂基纤维炭化产炭值的制备方法是将酚醛树脂基固化纤维先经过真空浸渍、然后在Ｂ、Ｐ、Ｓ无机酸和有机硼酸脂的乙醇溶液中进一步高温处理，大大提高了纤维的耐热性能，制得一种炭化后具有高残碳值的酚醛树脂基纤维。本发明不影响固化纤维的基本性能，但可以较大地提高纤维的耐热性能。炭化处理后，纤维在８００℃（Ｎ↓［２］气氛下）的残碳率可以达到６３－７０％，１０００℃下的残碳率在６０％以上，纤维的热分解析出峰变得较为平缓。

Description

一种提高酚醛纤维残碳率的处理方法
技术领域
本发明属于一种酚醛树脂基纤维的制备方法，具体地说涉及一种提高酚醛树脂基纤维残碳率的制备方法。
背景技术
国内外，酚醛树脂纤维的制备主要是以甲醛和苯酚热塑性酚醛树 脂为原料，经熔融纺丝后在盐酸和甲醛体系中进行交联而制得的体型 结构纤维。目前，在高科技军工、航天和航空领域，酚醛树脂纤维 是一种极其重要的耐烧蚀、防热材料。随着高科技技术领域对耐烧蚀、 防热材料性能要求的提高，对酚醛纤维的性能，尤其是残碳率提出了 更高的要求。目前，酚醛基炭纤维的制备一般均是采用上述酸醛交联 固化后的纤维炭化制得，其缺点是纤维耐热性能差，高温下的残碳率 低，800℃的残炭率一般为55％-60％，1000℃下的残炭率只有50 -55％，限制了它的应用，不能适应更高的使用温度和更苛刻的使用 环境。
发明内容
本发明的目的是提供一种提高酚醛树脂基纤维残碳率的制备方法。
本发明先用甲醛水溶液和苯酚在草酸催化作用下聚合得的热塑 性酚醛树脂为原料，经过一系列过滤、水蒸气蒸溜、提纯、真空干燥 处理后制得可纺丝用酚醛树脂。经熔融纺丝制得的原生丝，于80-110 ℃在盐酸和甲醛水溶液固化体系中固化交联，得到酚醛树脂基固化纤 维。再将固化后的酚醛基纤维先在有机溶剂中经真空浸泡，后经B、 P、S无机酸和有机硼酸脂的乙醇有机溶液中浸渍，干燥除去溶剂后， 再经过常规的炭化处理。在保持其基本性能不变的条件下，处理后的 纤维的残碳率大大提高，800℃和1000℃下的残炭率都比未处理前提 高3-10％，得到一种高残碳率酚醛树脂基纤维。
本发明的制备方法包括如下步骤：
(1)先将固化的酚醛树脂纤维放入有机溶剂中，在常温、常压 下，浸泡3-6h，然后排出溶液，常温下，在40-50KPa真空中处理1-2h；
(2)将硼酸、磷酸、硫酸、硼酸丁酯、三乙醇胺硼酸酯和无水 乙醇按一定的比例配制浸渍处理液；
(3)常压下，先将真空处理后的纤维放入配好的浸渍处理液中， 在常温中浸渍处理1-2h，然后在110-140℃高温浸渍处理3-6h；
(4)经过浸渍处理后的纤维先用去离子水冲洗，再放入真空烘箱 中，于100-110℃、真空度30-50KPa下干燥处理；
(5)干燥处理后的纤维经炭化处理，得到高残碳率酚醛树脂基纤 维；
所述的浸渍处理液中各组分的质量比为：
硼酸∶磷酸∶硫酸∶硼酸丁酯∶三乙醇胺硼酸酯∶无水乙醇 ＝1-1.5∶1-1.5∶0.3-0.5∶0.01-0.02∶0.01-0.02∶80-95。
如上所述的有机溶剂为乙醇、甲醇或丙酮。
本发明的优点：
1)采用本方法处理后，纤维的残碳率比未处理的纤维提高5-10％， 大量热分解温度缓延30-50℃。
2)本处理方法不影响纤维的其它基本性能，产品炭收率高，成 本低，操作方便，可靠。
3)采用本方法处理后，纤维上硼和磷的元素百分比含量可以分 别达到：硼％＝0.20-3.0，磷％＝0.20-3.0。
具体实施方式
实施实例：
实施实例1：采用800℃下残碳率为58.2％，1000℃下残碳率为 54.3％的酚醛树脂基固化纤维。先将5g固化后的酚醛纤维在1500ml 无水乙醇的小型浸渍釜中浸泡3h，然后排出溶液，再抽真空至 40-50KPa真空中常温处理1h。称取10g硼酸、10g磷酸、3g硫酸、 0.2g硼酸丁酯、0.2g三乙醇胺硼酸酯溶于1000ml的乙醇中，用超声 波分散溶解均匀，然后吸入小型浸渍釜。常压下，将浸泡后的纤维浸 渍在配好的硼磷浸渍处理液中，在110℃处理6h。取出纤维在100℃， 真空度40KPa的真空烘箱中处理1h，最后用去离子水冲洗。纤维在 (N2气氛下)800℃炭化的残碳率可达到63.7％，1000℃残碳率60.3％。
实施实例2：同例1采用同样的酚醛树脂基固化纤维。同例1将 10g固化后的酚醛纤维浸泡处理。称取10g硼酸、15g磷酸、3g硫酸、 0.1g硼酸丁酯、0.2g三乙醇胺硼酸酯溶于1200ml的乙醇中，用超声 波分散溶解均匀，然后吸入小型浸渍釜。常压下，将浸泡后的纤维浸 渍在配好的硼磷浸渍处理液中，在130℃处理4h。取出纤维在110℃， 真空度30KPa的真空烘箱中处理1h，最后用去离子水冲洗。纤维在 (N2气氛下)800℃炭化的残碳率可达到67.2％，1000℃残碳率63.1％。
实施实例3：同例1采用同样的酚醛树脂基固化纤维。先将10g 固化后的酚醛纤维在1500ml甲醇有机溶剂的小型浸渍釜中浸泡5h， 然后排出溶液，纤维在真空度40-50KPa真空中常温处理1h。同例1 一样配制浸渍处理液。常压下，将浸泡后的纤维浸渍在配好的硼磷浸 渍处理液中，在120℃处理5h。取出纤维在110℃，真空度30KPa的 真空烘箱中处理1h，最后用去离子水冲洗。纤维在(N2气氛下)800℃ 炭化的残碳率可达到64.7％，1000℃残碳率61.5％。
实施实例4：同例1采用同样的酚醛树脂基固化纤维。先将10g 固化后的酚醛纤维在1500ml丙酮有机溶剂的小型浸渍釜中浸6h，然 后取出纤维在真空度40-50KPa真空中常温处理2h。称取15g硼酸、 10g磷酸、5g硫酸、0.2g硼酸丁酯、0.1g三乙醇胺硼酸酯溶于1500ml 的乙醇中，用超声波分散溶解均匀，然后吸入小型浸渍釜。常压下， 将浸泡后的纤维浸渍在配好的硼磷浸渍处理液中，在140℃处理3h。 取出纤维在110℃，真空度50KPa的真空烘箱中处理1h，最后用去离 子水冲洗。纤维在(N2气氛下)800℃炭化的残碳率可达到66.2％，1000 ℃残碳率62.3％。

Claims (2)

1.一种提高酚醛纤维残碳率的处理方法，其特征在于包括如下步骤： (1)先将固化的酚醛树脂纤维放入有机溶剂中，在常温、常压 下，浸泡3-6h，然后排出溶液，常温下，在40-50KPa真空中处理1-2h； (2)将硼酸、磷酸、硫酸、硼酸丁酯、三乙醇胺硼酸酯和无水 乙醇按一定的比例配制浸渍处理液； (3)常压下，先将真空处理后的纤维放入配好的浸渍处理液中， 在常温中浸渍处理1-2h，然后在110-140℃高温浸渍处理3-6h； (4)经过浸渍处理后的纤维先用去离子水冲洗，再放入真空烘箱 中，于100-110℃、真空度30-50KPa下干燥处理； (5)干燥处理后的纤维经炭化处理，得到高残碳率酚醛树脂基 纤维； 所述的浸渍处理液中各组分的质量比为： 硼酸∶磷酸∶硫酸∶硼酸丁酯∶三乙醇胺硼酸酯∶无水乙醇 ＝1-1.5∶1-1.5∶0.3-0.5∶0.01-0.02∶0.01-0.02∶80-95。
2. 如权利要求1所述的一种提高酚醛纤维残碳率的处理方法，其特 征在于所述的有机溶剂为乙醇、甲醇或丙酮。
CN201610163183.8A 2016-03-22 2016-03-22 一种提高酚醛纤维残碳率的处理方法 Pending CN107217335A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109679045A (zh) * 2018-12-27 2019-04-26 山东圣泉新材料股份有限公司 一种轮胎橡胶用新型绿色补强树脂及其组合物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109679045A (zh) * 2018-12-27 2019-04-26 山东圣泉新材料股份有限公司 一种轮胎橡胶用新型绿色补强树脂及其组合物

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WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170929