CN114042437A - 一种胺基弱碱性阴离子交换纤维制备工艺 - Google Patents
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Abstract
本发明公开了一种胺基弱碱性阴离子交换纤维制备工艺，属于高分子材料技术领域。本发明以聚丙烯腈纤维为原料纤维，通过其与有机胺化合物饱和蒸汽发生气固反应，将胺基接枝到聚丙烯腈纤维中，制备得到胺基弱碱性阴离子交换纤维，其交换容量和性能与传统液固反应制备的胺基纤维相当。该制备工艺具有操作简便、反应均匀等优点，且出料过程无需离心回收改性剂，克服了传统液固反应制备工艺搅拌困难、反应不均匀、出料困难、有机胺化合物消耗量大、废水量大等不足。
Description
技术领域
本发明涉及一种纤维材料制备工艺，尤其涉及一种胺基弱碱性阴离子交换纤维材料制备工艺，属于高分子材料技术领域。
背景技术
纺织纤维供应充足、品种繁多、价格适宜，是获取新材料的良好原料来源。对常见的纺织纤维(合成纤维和天然纤维)进行功能化或者进行预接枝能够使其具有进一步功能化的条件,比如聚丙烯纤维辐射接枝或溶液化学反应接枝苯乙烯和二乙烯基苯，是聚丙烯纤维功能化的首选路线，国内外已有数十年的研究，工艺成熟，且相关产品已商品化。功能化后的纤维既保持纤维原有的特点和优点，又具有各种特殊的性能和用途，这一领域的研究近年来日益受到人们的关注。化学改性是对纤维进行功能化的重要手段，通过纤维所带有的活性化学基团与某种分子或离子发生化学反应，使纤维具有新的表面化学特性，从而具有抗静电、吸水保湿、吸附分离、抗菌除臭、净化水和空气等新功能。其中，接枝胺基功能基团的纤维不但具有弱碱性阴离子交换纤维的重金属吸附、酸性气体吸附等吸附分离特性，而且具有优异的抗菌除臭性能，且基于胺基弱碱性阴离子交换纤维的这些特性，其已在相关领域进行了产业化。胺基弱碱性阴离子交换纤维可采用不同的纤维作为原料，通过不同的处理方法和过程得以实现，有以下的相关文献报道：
文献“电子束辐射接枝制备弱碱性胺基阴离子交换纤维”(河南科技，2018，643(6)：133-135)：通过电子束辐射聚烯烃纤维湿法非织布，接枝氯甲基苯乙烯制备苯乙烯无纺布，然后进一步与胺化试剂二乙烯三胺反应，制备得到一种弱碱性胺基阴离子交换纤维；文献“胺基键合蔗渣纤维素的制备及其对Cu(Ⅱ)和Cr(Ⅵ)的吸附研究”(硕士论文，广西民族大学，2016)：以蔗渣为原料，在传统碱法提纯纤维素基础上，加入无水亚硫酸钠得到纯度更高的纤维素，用高碘酸钠选择性氧化纤维素，得到双醛纤维素，双醛纤维素再与三乙烯四胺发生希夫碱反应，制备三乙烯四胺基纤维素；文献“胺基接枝纤维的制备及其对铜离子吸附的应用研究”(化工技术与开发，2013，42(11)：16-21)：以漂白蔗渣浆纤维素为基体，二乙烯三胺为单体，硝酸铈铵为引发剂，制备胺基接枝纤维；文献“制备胺基离子交换纤维的反应条件优化研究”(功能材料，2012，43(06)：779-782)：以聚丙烯接枝苯乙烯纤维为原料,采用乙酰化及胺基化两步法反应,制备多胺基离子交换纤维；文献“弱碱性多胺基纤维的制备及结构性能研究”(高科技纤维与应用，2010，35(03)：31-35)：以工业化生产的普通商品级腈纶为基体，采用先交联后胺化的两步法，以水合肼为交联剂，二乙烯三胺为胺化试剂制备弱碱性多胺基纤维；文献“新型脱硫吸附剂胺基棉纤维的合成研究”(环境工程，2008，(02)：16-20+2)：以棉纤维为基体材料，通过氯甲基化和胺化两步反应合成胺基棉纤维；专利“一种胺基螯合竹纤维的重金属离子吸附剂的制备方法”(CN111375387A)公开了一种胺基螯合竹纤维的重金属离子吸附剂的制备方法，包括竹子的预处理、制备竹纤维素粉、将竹纤维素粉进行氯化、将氯化纤维素进行胺化反应；专利“一种PAN-PEI胺基螯合纤维及其制备方法”(CN 108212124 A)通过聚丙烯腈(PAN)纤维的水解反应，得到PAN-COOH水解纤维，PEI上的胺基与PAN-COOH水解纤维上的羧基接枝反应生成酰胺键，制备得到PAN-PEI胺基螯合纤维。
上述文献报道中，改性制备胺基功能纤维大多以聚丙烯腈纤维、聚烯烃纤维、纤维素纤维为原料，通过辐照、引发聚合、酰胺化、直接胺化等手段制备得到胺基纤维，但其均在溶液中进行，主步骤为液固反应。目前以聚丙烯腈纤维为原料纤维，通过气固反应直接胺化引入胺基，制备得到胺基弱碱性阴离子交换纤维材料，则尚未见于报道。
发明内容
本发明的目的在于提供一种气固反应制备胺基弱碱性阴离子交换纤维新工艺，克服传统液固反应制备工艺搅拌困难、反应不均匀、出料困难、有机胺化合物消耗量大、废水量大等不足。
为实现本发明目的，本发明以聚丙烯腈纤维为原料纤维，通过有机胺化合物饱和蒸汽与聚丙烯腈纤维之间发生反应制备得到胺基弱碱性阴离子交换纤维。
本发明提供的制备工艺具体过程为：将聚丙烯腈纤维用蒸馏水洗涤，烘干待用；将洗涤烘干后的聚丙烯腈纤维置于有机胺化合物饱和蒸汽中，首先在60-90℃溶胀，然后将温度升至110-180℃反应，反应完成后，冷却降温，取出纤维，洗涤至洗出液中性，烘干，即得胺基弱碱性阴离子交换纤维。
所述有机胺化合物为乙二胺、二乙烯三胺、三乙烯四胺、多乙烯多胺中的一种或多种。
本发明整个制备过程采用的是气固两相反应，由于气相的高扩散性，使得纤维反应比较均匀；所用聚丙烯腈纤维中丙烯腈质量百分含量大于90％，所制得的胺基弱碱性阴离子交换纤维与现有液固反应法制备得到的纤维性能相当，其碱性交换容量为4.0-8.0mmol·g-1。可用于重金属吸附、酸性废气净化和抗菌等。
本发明的有益效果在于：(1)本发明采用气固反应法制备胺基弱碱性阴离子交换纤维，由于气相的高扩散性，使得纤维反应比较均匀。具有操作简便、反应均匀、出料过程无需离心回收改性剂等优点。(2)克服了液固反应制备工艺搅拌困难、反应不均匀、出料困难、有机胺化合物消耗量大、废水量大等不足，具有更好的经济效益和环境效益。
附图说明
图1为原料聚丙烯腈纤维、液固反应制备的胺基纤维与本发明制备工艺所合成纤维的红外光谱图。图中a为聚丙烯腈纤维的红外光谱，b为液固反应合成的胺基纤维的红外光谱，c为本发明制备工艺合成的胺基纤维的红外光谱。
图中腈纶原纤维的各红外吸收峰可标记为：2928cm-1和2870cm-1(CH3，CH2基团中对称和不对称γC–H)，1450cm-1(δs C-H)，1357cm-1(δs CH2)，2242cm-1(γCN)，1730cm-1(γC＝O)，其中γ代表伸缩振动，δs代表剪切振动。本发明以及液固反应制备的胺基纤维，2242cm-1处的γCN吸收峰均大幅度减弱，这说明接枝反应主要发生在腈纶纤维的-CN基团上，本发明工艺与常规液固反应机理相同；3000-3700cm-1范围内均出现了一个较宽的吸收峰，这是由于-NH-和-NH2中N-H吸收峰以及-OH吸收峰的叠加引起的；1730cm-1处的羰基吸收峰均消失，说明随着反应的进行，第二单体丙烯酸酯中的酯基发生了水解；本发明工艺与液固反应制备的胺基纤维相比主要区别为，本发明所制纤维在1667cm-1和1639cm-1处出现了两个吸收峰，而液固反应只有1629cm-1一个吸收峰，这主要是由于本发明所用工艺为气固反应，反应体系碱度较弱，且水含量少，制备得到的胺基纤维中保留了较多的C＝N基团，这使其与C＝O的伸缩振动吸收峰同时显示了出来，而液固反应制备的纤维由于反应体系水含量较多且碱性较强，反应生成的C＝N发生了水解，使纤维中C＝O含量大幅度增加，其吸收峰将C＝N的吸收峰进行了覆盖。因此，本发明制备得到的纤维为胺基弱碱性阴离子交换纤维，且其与常规液固反应所制备得到的纤维结构基本相同，C＝O和C＝N基团含量方面存在的微弱区别不影响纤维的整体性能。
图2为采用本发明工艺制得的胺基弱碱性阴离子交换纤维对二氧化硫的动态吸附性能曲线。
具体实施方式
为更好地对本发明进行详细说明，举实施例如下：所用聚丙烯腈纤维中丙烯腈含量大于90％，所用原料均为市售品。
实施例1：
将聚丙烯腈纤维用蒸馏水洗涤2-3次，烘干待用；将洗涤烘干后的聚丙烯腈纤维与三乙烯四胺溶液共同置于密闭容器中(二者不接触)，首先将密闭容器加热至90℃并恒温2h，使纤维溶胀，然后将温度升至180℃反应12h，反应完成后，冷却降温至60℃以下，取出纤维，洗涤至洗出液中性，60℃烘干，即得胺基弱碱性阴离子交换纤维。测得所得纤维的交换容量为8.0mmol/g。
实施例2：
将聚丙烯腈纤维用蒸馏水洗涤2-3次，烘干待用；将洗涤烘干后的聚丙烯腈纤维与乙二胺溶液共同置于密闭容器中(二者不接触)，首先将密闭容器加热至60℃并恒温6h，使纤维溶胀，然后将温度升至110℃反应2h，反应完成后，冷却降温至60℃以下，取出纤维，洗涤至洗出液中性，60℃烘干，即得胺基弱碱性阴离子交换纤维。测得所得纤维的交换容量为4.0mmol/g。
实施例3：
将聚丙烯腈纤维用蒸馏水洗涤2-3次，烘干待用；将洗涤烘干后的聚丙烯腈纤维置于两颈烧瓶中，首先将烧瓶加热至80℃并从烧瓶的一侧入口连续通入80℃下乙二胺饱和蒸汽，烧瓶的另一侧出口连接乙二胺饱和蒸汽发生瓶，恒温12h，使纤维溶胀，然后将烧瓶温度和乙二胺蒸汽发生瓶温度均升至110℃反应6h，反应完成后，冷却降温至60℃以下，取出纤维，洗涤至洗出液中性，60℃烘干，即得胺基弱碱性阴离子交换纤维。测得所得纤维的交换容量为5.6mmol/g。
实施例4：
将聚丙烯腈纤维用蒸馏水洗涤2-3次，烘干待用；将洗涤烘干后的聚丙烯腈纤维与二乙烯三胺溶液共同置于密闭容器中(二者不接触)，首先将密闭容器加热至80℃并恒温12h，使纤维溶胀，然后将温度升至160℃反应6h，反应完成后，冷却降温至60℃以下，取出纤维，洗涤至洗出液中性，60℃烘干，即得胺基弱碱性阴离子交换纤维。测得所得纤维的交换容量为6.5mmol/g。
应用例1：
称取实施例4中所制备的胺基弱碱性阴离子交换纤维1.0g，装入直径1cm的吸附柱中，以1.0L/min向吸附柱中连续通入浓度为102.3ppm的二氧化硫气体，检测出口二氧化硫浓度为0ppm，其吸附穿透曲线如图2所示，计算得到其二氧化硫吸附容量为111mg/g干纤维。
应用例2：
称取实施例4中所制备的胺基弱碱性阴离子交换纤维0.1005g，放入50mL浓度为45.6mg·L-1的Cu(II)水溶液中，于25℃恒温振荡吸附15h，溶液中Cu(II)检不出(火焰原子吸收光谱仪测试)，此时纤维对Cu(II)的吸附量为22.7mg·g-1干纤维，纤维对Cu(II)的吸附去除率为100％。
Claims (3)
1.一种胺基弱碱性阴离子交换纤维制备工艺，其特征在于，采用气固两相反应，通过如下工艺实现：将聚丙烯腈纤维用蒸馏水洗涤，烘干待用；将洗涤烘干后的聚丙烯腈纤维置于有机胺化合物饱和蒸汽中，首先在60-90℃溶胀，然后将温度升至110-180℃反应，反应完成后，冷却降温，取出纤维，洗涤至洗出液中性，烘干，即得胺基弱碱性阴离子交换纤维；
所述有机胺化合物为乙二胺、二乙烯三胺、三乙烯四胺、多乙烯多胺中的一种或多种。
2.如权利要求1所述的胺基弱碱性阴离子交换纤维制备工艺，其特征在于，聚丙烯腈纤维中丙烯腈质量百分含量大于90%。
3.如权利要求1或2所述的胺基弱碱性阴离子交换纤维制备工艺，其特征在于，所述有机胺化合物饱和蒸汽通过将有机胺化合物与聚丙烯腈纤维共同置于密闭容器中加热或通过将有机胺化合物单独加热制得蒸汽，持续导入放有聚丙烯腈纤维的容器中，将出口蒸汽进行收集冷凝回收。
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