CN113322536A - 聚（对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑）纤维制备方法 - Google Patents
聚（对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑）纤维制备方法 Download PDFInfo
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- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明涉及一种新型的高性能聚(对苯二甲酸‑2‑(己‑5‑烯基)‑琥珀酸基‑1,4‑苯并二咪唑)纤维制备方法。步骤1、中间体DADNP的合成及纯化步骤，2、单体TAP·H3PO4·H2O合成及纯化，步骤3、新型PIPD纤维合成。本发明提供一种聚(对苯二甲酸‑2‑(己‑5‑烯基)‑琥珀酸基‑1,4‑苯并二咪唑)纤维制备方法。该纤维合成方法简便、价格低廉、高强度、高模量、耐高温和抗拉伸、用途广泛。
Description
技术领域
本发明属于高分子材料制备领域，具体涉及一种新型的高性能聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法。
背景技术
高性能纤维是航空、航天、交通运输、工业生产、农林、海洋水产、能源、环境保护、通信、医疗卫生、体育器材等相关领域的重要材料。随着科技的不断发展，航天、航空电子通讯以及军事等尖端工业部门对纤维复合材料提出了更高的要求。高性能合成纤维具有普通纤维无法比拟的力学性能、热性能和耐化学稳定性能，其主要品种有对位芳纶(聚对苯二甲酰对苯二胺)、全芳香族聚酯、超高分子量的高强聚乙烯纤维及聚苯并双咪唑等。
近年来，在众多的高性能纤维中聚苯并唑类纤维得到前所未有快速发展，“纤维之王”PBO纤维就是典型的代表，与其较为优异的模量与抗张性能相比较，其抗压性能差强人意。荷兰AkzoNobel公司设计并合成了一种剪切模量极强的聚[2,5-二羟基-1,4-苯撑吡啶并二咪唑](PIPD纤维)，为全芳杂环高分子聚合物，其化学结构如下式：
该纤维径向即大分子之间存在特殊的氢键网络结构,所以PIPD纤维不仅具有类似PBO纤维的优异的抗张性能,而且还显示出优于PBO纤维的压缩性能,其压缩强度达到1.7GPa。PIPD纤维与PBO纤维的分子结构相比最大的区别在于恶唑环系上的-O-被-NH-单元取代，苯撑环系上增加了两个极性-OH基团。
市场上这些芳香族高性能纤维大分子链都具有刚性，具有高的模量和强度，具有十分突出的机械性能，但因为其内部分子链相互仅存在着弱的范德华力，当纤维受到剪切力或是压缩作用后，由于相互作用力较弱，分子链相互产生相对的滑动从而造成了纤维材料的抗压缩性能表现差，同时界面粘接性能以及耐扭曲性能较差。
目前PIPD纤维的优秀的综合性能已经引发了国内外的极大关注，而在国外方面则已经达到了中试的地步，有了批量级别产品的出现，虽未很大规模地应用，但国外对PIPD纤维的纺丝工艺并未开放。国内对PIPD纤维的研究在实验室阶段，优化单体合成路线得到稳定的高纯度单体，特别地，优化聚合工艺以及完善PIPD纤维制备纺丝工艺也至关重要。开展PIPD的研究，对其实现我国PIPD纤维大量商业化生产尤为急迫和重要。
现急需一种价格低廉、高强度、耐高温、抗拉伸、抗压缩和模量可控等综合性优越的高性能纤维。
发明内容
本发明的目的是要提供一种成本低、高强度、耐高温、抗压缩、抗拉伸、模量可控的聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法。
本发明的技术方案
一种聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法，
步骤1、中间体DADNP的合成及纯化
将2,6-二氨基吡啶(DAP)、甲苯混合加热，加热至DAP全溶，加入一定量的活性炭，回流1h，趁热滤除活性炭，滤液自然冷却后DAP结晶析出，过滤，真空干燥，得到白色鳞片状结晶DAP，另取20％的发烟硫酸，冰盐浴冷却至0℃以下，快速搅拌下分批缓慢加入提纯后的DAP，搅拌4h，随后缓慢滴加发烟硝酸，反应3h，将反应生成物缓慢加到冰水中，形成黄色的浑浊液，多次水洗，抽滤，真空干燥24h，得到浅黄色的DADNP粗品，将DADNP粗品加入到二甲基亚砜中，加热至完全溶解，搅拌条件下加入去离子水，底部出现浅黄色固体，静置24h，抽滤，水洗三次，50℃下真空干燥24h，得到浅黄色DADNP固体；
步骤2、单体TAP·H3PO4·H2O合成及纯化
将纯化后的DADNP和H3PO3、H3PO4，体系内通N2保护，设定水浴温度80℃进行还原反应，反应8h后混合物全部溶解，生成橙黄色溶液，在N2保护下将反应液导入装有四氢呋喃和H3PO4的玻璃容器中，密封，放置冷却24h，橙黄色溶液底部析出浅黄色针状结晶，N2保护下抽滤，水洗三次，真空干燥，得到浅黄色晶体状TAP·H3PO4·H2O，将TAP·H3PO4·H2O加入到H3PO4和四氢呋喃混合液中，加入SnCl2，加热至全溶，溶液呈橙黄色，用N2排除体系内空气，密封静置24h，底部析出结晶。N2保护下抽滤，水洗三次，真空干燥，得到浅黄色晶体状TAP·H3PO4·H2O；
步骤3、新型PIPD纤维合成
将H3PO4和P2O5，搅拌均匀，体系内通N2保护，随后加入TAP·H3PO4·H2O，对苯二甲酸，2-(己-5-烯基)-琥珀酸和锡粉，油浴开始加热，温度每升高10℃加入P2O5，升温过程中加入P2O5，体系中多聚磷酸浓度达到85％。P2O5全部加完后，升高体系温度至140℃，在140-160℃时高速搅拌下反应10h，体系粘度升高，颜色加深，补加P2O5，升温至180℃继续反应8h，反应结束，冷却，将聚合物再次浸入水中，除去残留的H3PO4，真空干燥除水，得到聚合物，最后通过液晶相浓溶液干喷湿纺法得到新型PIPD纤维。
本发明的有益效果:
1、本发明提供一种聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法。在合成过程中加入的对苯二甲酸和2-(己-5-烯基)-琥珀酸两种酸价格低廉，合成的纤维在很大程度上降低了成本，从而促进市场销售量。
2、本反应与现有技术相比，采用常压法制备PIPD单体和纤维，反应条件温和，操作安全简单、得到的产品纯度高，适用于工业化生产。
3、本高性能纤维在合成的过程中加入了第三单体2-(己-5-烯基)-琥珀酸，当
2-(己-5-烯基)-琥珀酸加入量为0时，即为传统的PIPD纤维，可以根据环境所需，调节2-(己-5-烯基)-琥珀酸的用量来制备出不同模量的高性能纤维。
4、在合成过程中本发明将2-(己-5-烯基)-琥珀酸作为第三单体引入到高性能纤维，其具有较多的纵向化学键，由传统的氢键改变为化学键，增加了高性能纤维的抗拉伸性能；并且其具有双键，在反应过程中可以发生聚合，这样使纤维结构由链状结构变成网状结构，较大程度上增加了高性能纤维的各项性能。
5、聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维改变自身的缺陷，不但拥有顺向单体聚合，而且还有横向烯烃聚合提高聚合物的耐压模量，这样侧底改进了纤维之王PIPD的抗压强度不够的问题可广泛地应用在航空航天、通讯、军工类产品等行业。
6、本纤维的抗压强度为1.9GPa(较传统PIPD纤维提高1O％)，抗拉强度5.6GPa(较传统PIPD纤维提高12％)。
具体实施方案
下面结合具体实施例对本发明做出进一步的说明，这些实施例并非是对本发明的限定，依照本领域现有的技术，本发明的实施方式并不限于此，凡依照本发明公开内容所做出的本领域的等同替换，均属本发明的保护内容。
步骤1、中间体2,6-二氨基-3,5-二硝基吡啶(DADNP)的合成及纯化
在三口烧瓶中加入2,6-二氨基吡啶(DAP)15g，甲苯120ml，加热至DAP全溶，加入一定量的活性炭，回流1h，趁热滤除活性炭，滤液自然冷却后DAP结晶析出，过滤，真空干燥，得到白色鳞片状结晶DAP。在三口烧瓶中加入50ml20％的发烟硫酸，冰盐浴冷却至0℃以下，快速搅拌下分批缓慢加入10g提纯后的DAP，加药速度控制在1g/12min，搅拌4h。随后缓慢滴加8.5ml发烟硝酸，反应3h。将反应生成物缓慢加到冰水中，形成黄色的浑浊液，多次水洗，抽滤，真空干燥24h，得到浅黄色的DADNP粗品。将20gDADNP粗品加入到180ml二甲基亚砜中，加热至完全溶解，搅拌条件下加入150ml去离子水，底部出现浅黄色固体，静置24h，抽滤，水洗三次，50℃下真空干燥24h，得到浅黄色DADNP固体。
步骤2、单体2,3,5,6-四氨基吡啶磷酸盐(TAP·H3PO4·H2O)合成及纯化
在三口烧瓶中加入6g纯化后的DADNP，7.5gH3PO3和150mlH3PO4，体系内通N2保护，设定水浴温度80℃进行还原反应，反应8h后混合物全部溶解，生成橙黄色溶液，在N2保护下将反应液导入装有150ml四氢呋喃和50mlH3PO4的玻璃容器中，密封，放置冷却24h，橙黄色溶液底部析出浅黄色针状结晶。N2保护下抽滤，水洗三次，真空干燥，得到浅黄色晶体状TAP·H3PO4·H2O。将8g TAP·H3PO4·H2O加入到100mlH3PO4和100ml四氢呋喃混合液中，加入1.5gSnCl2，加热至全溶，溶液呈橙黄色，用N2排除体系内空气，密封静置24h，底部析出结晶。N2保护下抽滤，水洗三次，真空干燥，得到浅黄色晶体状TAP·H3PO4·H2O。
步骤3、新型PIPD纤维合成
在四口烧瓶中加入100mlH3PO4和80gP2O5，搅拌均匀，体系内通N2保护，随后加入19gTAP·H3PO4·H2O，13.4g对苯二甲酸，3.6g2-(己-5-烯基)-琥珀酸和2g锡粉，油浴开始加热，温度每升高10℃加入20gP2O5，升温过程中加入140gP2O5，体系中多聚磷酸浓度达到85％。P2O5全部加完后，升高体系温度至140℃，在140-160℃时高速搅拌下反应10h，体系粘度升高，颜色加深，补加20gP2O5，升温至180℃继续反应8h，反应结束，冷却，将聚合物再次浸入水中，除去残留的H3PO4，干燥除水，得到聚合物。最后通过液晶相浓溶液干喷湿纺法得到新型PIPD纤维。
合成路线如下：
本发明涉及一种高分子聚合物，具体地说采用第三单体聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法。聚[2,5-二羟基-1,4-苯撑吡啶并二咪唑](PIPD)纤维(商品名M5),是由阿克苏·诺贝尔研究所(AkzoNobel)Sikkema研究团队开发的一种新型刚棒状聚合物。PIPD分子链上存在大量的—OH和—NH—,容易在分子间和分子内形成强烈的氢键。因此PIPD纤维不仅具有优异的拉伸性能,而且其压缩强度为目前所有聚合物之首。PIPD纤维的拉伸强度和拉伸模量分别为5GPa和330GPa,其压缩强度接近碳纤维,高达1.7GPa,其剪切模量约为6GPa。PIPD纤维成功解决了PBO纤维抗压缩性能低、黏结性能差的缺点,具有良好的发展前景。本发明主要对聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维的中间体和单体进行优化，探索最佳的合成工艺，在合成过程中本发明将2-(己-5-烯基)-琥珀酸作为第三单体引入到高性能纤维，其具有较多的纵向化学键，由传统的氢键改变为化学键，增加了高性能纤维的抗拉伸性能；并且其具有双键，在反应过程中可以发生聚合，这样使纤维结构由链状结构变成网状结构，较大程度上增加了高性能纤维的各项性能。从而为我国PIPD高性能纤维工业化和规模化生产打下良好的基础。
本申请纤维与现有纤维技术参数对比：
Claims (4)
1.一种聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法，其特征在于：
步骤1、中间体DADNP的合成及纯化
将2,6-二氨基吡啶(DAP)、甲苯混合加热，加热至DAP全溶，加入一定量的活性炭，回流1h，趁热滤除活性炭，滤液自然冷却后DAP结晶析出，过滤，真空干燥，得到白色鳞片状结晶DAP，另取20％的发烟硫酸，冰盐浴冷却至0℃以下，快速搅拌下分批缓慢加入提纯后的DAP，搅拌4h，随后缓慢滴加发烟硝酸，反应3h，将反应生成物缓慢加到冰水中，形成黄色的浑浊液，多次水洗，抽滤，真空干燥24h，得到浅黄色的DADNP粗品，将DADNP粗品加入到二甲基亚砜中，加热至完全溶解，搅拌条件下加入去离子水，底部出现浅黄色固体，静置24h，抽滤，水洗三次，50℃下真空干燥24h，得到浅黄色DADNP固体；
步骤2、单体TAP·H3PO4·H2O合成及纯化
将纯化后的DADNP和H3PO3、H3PO4，体系内通N2保护，设定水浴温度80℃进行还原反应，反应8h后混合物全部溶解，生成橙黄色溶液，在N2保护下将反应液导入装有四氢呋喃和H3PO4的玻璃容器中，密封，放置冷却24h，橙黄色溶液底部析出浅黄色针状结晶，N2保护下抽滤，水洗三次，真空干燥，得到浅黄色晶体状TAP·H3PO4·H2O，将TAP·H3PO4·H2O加入到H3PO4和四氢呋喃混合液中，加入SnCl2，加热至全溶，溶液呈橙黄色，用N2排除体系内空气，密封静置24h，底部析出结晶。N2保护下抽滤，水洗三次，真空干燥，得到浅黄色晶体状TAP·H3PO4·H2O；
步骤3、新型PIPD纤维合成
将H3PO4和P2O5，搅拌均匀，体系内通N2保护，随后加入TAP·H3PO4·H2O，对苯二甲酸，2-(己-5-烯基)-琥珀酸和锡粉，油浴开始加热，温度每升高10℃加入P2O5，升温过程中加入P2O5，体系中多聚磷酸浓度达到85％。P2O5全部加完后，升高体系温度至140℃，在140-160℃时高速搅拌下反应10h，体系粘度升高，颜色加深，补加P2O5，升温至180℃继续反应8h，反应结束，冷却，将聚合物再次浸入水中，除去残留的H3PO4，真空干燥除水，得到聚合物，最后通过液晶相浓溶液干喷湿纺法得到新型PIPD纤维。
2.根据权利要求1所述的一种聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法，其特征在于：
步骤1中2,6-二氨基吡啶(DAP)、甲苯、发烟硫酸、提纯后的DAP、发烟硝酸、DADNP粗品、二甲基亚砜、去离子水的用量比为15g：120ml:50ml:10g:8.5ml:20g:180ml：150ml；
快速搅拌下分批缓慢加入提纯后的DAP，加药速度控制在1g/12min。
3.根据权利要求1所述的一种聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法，其特征在于：
步骤2中的DADNP、H3PO3、H3PO4、四氢呋喃、H3PO4、TAP·H3PO4·H2O、H3PO4、四氢呋喃、SnCl2的用量比为6g：7.5g：150ml:150ml:50ml:8g:100ml:100ml:1.5g。
4.根据权利要求1所述的一种聚(对苯二甲酸-2-(己-5-烯基)-琥珀酸基-1,4-苯并二咪唑)纤维制备方法，其特征在于：
步骤3中H3PO4、、TAP·H3PO4·H2O、对苯二甲酸、2-(己-5-烯基)-琥珀酸、锡粉、P2O5、用量比为100ml：19g：13.4g：3.6g：2g：24g。
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