CN104628982B - 一种碱木质素基水性聚氨酯的制备方法 - Google Patents

一种碱木质素基水性聚氨酯的制备方法 Download PDF

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CN104628982B
CN104628982B CN201510079976.7A CN201510079976A CN104628982B CN 104628982 B CN104628982 B CN 104628982B CN 201510079976 A CN201510079976 A CN 201510079976A CN 104628982 B CN104628982 B CN 104628982B
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任龙芳
贺齐齐
王学川
强涛涛
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Shaanxi University of Science and Technology
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Abstract

本发明为一种碱木质素基水性聚氨酯的制备方法，其制备是选用二异氰酸酯、聚醚多元醇、碱木质素、扩链剂和中和剂等为原料，在采用预聚体分散法合成水性聚氨酯乳液的过程中添加碱木质素，进而制备一系列不同碱木质素含量的碱木质素基水性聚氨酯；该方法把碱木质素引入到水性聚氨酯体系中，是减少多元醇用量、提高水性聚氨酯材料性能和赋予制品生物降解性能的理想方法之一。

Description

一种碱木质素基水性聚氨酯的制备方法
技术领域
本发明属于天然高分子材料领域，也属于环境友好生态材料领域，涉及一种碱木质素基水性聚氨酯的制备方法。
技术背景
木质素(lignin)简称木素，是植物界中仅次于纤维素第二丰富的天然芳香族高分子，工业木质素来源于造纸黑液，因而具有价廉、可再生、环境友好等优点。木质素结构的复杂性、来源的多元性和提取过程的多样性造成开发利用的难度和工业化的阻碍，因而研究和开发木质素高分子材料面临着巨大的机遇和挑战。目前，随着社会的飞速发展,石油资源日趋枯竭,各种来自石油的高分子单体受到限制,严重影响了聚氨酯工业的原料来源,并时刻影响着聚氨酯工业的发展。因此产量巨大、可再生的环境友好型生物原料越来越得到人们的重视与青睐。碱木质素就是一种来源丰富、价格低廉的可再生植物资源，所以碱木质素的充分合理性利用，对缓解当前人类所面临的能源和环境危机都具有十分重要的现实意义和战略意义。
而水性聚氨酯由于主链或侧链亲水基团的引入使得所形成的涂膜往往具有较高的表面能，通过成盐的方法虽然使得聚氨酯可以分散在水相中，但是正由于这些基团的存在使得水性聚氨酯耐水性、耐溶剂性、耐化学品性及机械强度等性能较差。为克服上述缺点，近年来采用不同方法对水性聚氨酯进行改性研究已成为水性聚氨酯研究的热点，国内外许多科研工作者进行了大量深入全面的研究。
发明内容
为了克服上述现有技术的缺点，本发明的目的在于提供一种碱木质素基水性聚氨酯的制备方法，所得产物的机械强度较高，制备工艺简单且成本低廉。
为了实现上述目的，本发明采用的技术方案如下：
一种碱木质素基水性聚氨酯的制备方法，包括以下步骤：
步骤一：制备精制碱木质素；
步骤二：将二异氰酸酯、聚醚多元醇和精制碱木质素加入到三口烧瓶中，在60～90℃下搅拌反应1～5h，然后降温至50～70℃，再加入DMPA亲水扩链剂和丙酮，反应1～4h，降温至20～50℃出料，得水性聚氨酯预聚体；
步骤三：将所得水性聚氨酯预聚体用中和剂中和后，加水进行高速乳化，减压蒸馏脱去溶剂后即得水性聚氨酯乳液。
所述精制碱木质素的制备方法为：将粗碱木质素的水溶液用质量浓度5％～10％的NaOH溶液调节pH至13～14，使碱木质素充分溶解，过滤除去不溶物，然后用质量浓度12％的盐酸于60℃下调节pH至2～3，过滤，反复用蒸馏水洗涤沉淀至中性，真空干燥即得。
所述步骤二中，聚醚多元醇与二异氰酸酯的摩尔比为1:(2～4)，精制碱木质素的加入量为精制碱木质素和聚醚多元醇质量之和的0.5％～3.0％，DMPA亲水扩链剂的加入量为二异氰酸酯、聚醚多元醇和精制碱木质素总质量的2.0％～5.0％，丙酮的加入量为10～80mL。
所述步骤二中，精制碱木质素以丙酮溶解后再与二异氰酸酯和聚醚多元醇混合，溶解所用的丙酮的量为20mL。
所述步骤二中，搅拌反应前加入催化剂，催化剂的加入量为二异氰酸酯、聚醚多元醇和精制碱木质素总质量的0.05％～0.2％。
所述催化剂为二月桂酸二丁基锡(简写为DBTDL)。
所述二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)或二苯基甲烷-4,4‵-二异氰酸酯(MDI)。
所述聚醚多元醇为聚丙二醇(PPG)、聚四氢呋喃醚二醇(PTMG)或聚乙二醇(PEG)，数均分子量均为2000。
所述中和剂为三乙胺、氢氧化钠或氢氧化钾，加入量与DMPA的摩尔比为1:1。
与现有技术相比，本发明通过在水性聚氨酯乳液的合成过程中添加碱木质素，其乳液固化后形成的膜材料的力学性能显著提高。本发明中的木质素是碱木质素，是造纸工业的副产品，成本低廉、来源丰富。水性聚氨酯是一种环保型材料，本发明将工业上的废弃物木质素与环保型水性聚氨酯结合既得到了性能改善的材料，而且提高了木质素的应用价值，同时其生产成本低廉且具有可生物降解、环保的特点，而且本发明工艺简单，具有较高的技术含量。该发明所得到的碱木质素改性水性聚氨酯的机械强度有明显的提高，可用作膜、涂料等材料。
附图说明
图1为以IPDI为例，碱木质素基水性聚氨酯的合成路线图。
具体实施方式
下面结合实施例对本发明做进一步详细说明。
实施例一
一种碱木质素基水性聚氨酯的制备方法，产品的合成路线图如图1所示，包括以下步骤：
步骤一：将粗碱木质素的水溶液用质量浓度6％的NaOH溶液调节pH至13～14，使碱木质素充分溶解。过滤除去不溶物，然后用质量浓度12％的盐酸于60℃下调pH至2左右，过滤，反复用蒸馏水洗涤沉淀至中性，真空干燥即得到精制碱木质素。
步骤二：将17.2g异佛尔酮二异氰酸酯(IPDI)、50.0g聚丙二醇(PPG2000)、0.26g精制碱木质素(用丙酮溶解)和0.05g二月桂酸二丁基锡加入到三口烧瓶中，在85℃下搅拌反应3h，然后降温至65℃，再加入2.46g DMPA和30mL的丙酮，反应3h，降温至40℃出料，得水性聚氨酯预聚体。
步骤三：将步骤二得到的预聚体用与DMPA摩尔比为1:1的三乙胺(TEA)中和后，加水进行高速乳化，减压蒸馏脱去溶剂后即得改性水性聚氨酯乳液。
性能验证：将乳液均匀倒在聚四氟乙烯板上，在室温下放置一段时间，然后放入烘箱中，在60℃下干燥48h后，冲压成标准哑铃试片。采用XWW-20B电子万能试验机，按GB/T1040-92测定胶膜的拉伸强度和断裂伸长率。结果表明：其拉伸强度由27.6MPa增加到36.3MPa，断裂伸长率由456.4％增加到457.2％，机械强度明显提高。
实施例二
一种碱木质素基水性聚氨酯的制备方法，包括以下步骤：
步骤一：将粗碱木质素的水溶液用质量浓度6％的NaOH溶液调节pH至13～14,使碱木质素充分溶解。过滤除去不溶物，然后用质量浓度12％的盐酸于60℃下调pH至2左右，过滤，反复用蒸馏水洗涤沉淀至中性，真空干燥即得到精制碱木质素。
步骤二：将12.5g甲苯二异氰酸酯(TDI)、45.0g聚四氢呋喃醚二醇(PTMG2000)、0.25g精制碱木质素(用丙酮溶解)和0.05g二月桂酸二丁基锡加入到三口烧瓶中，在85℃下搅拌反应4h，然后降温至60℃，再加入1.74g DMPA和40mL的丙酮，反应2h，降温至35℃出料，得水性聚氨酯预聚体。
步骤三：将步骤二得到的预聚体加入到NaOH水溶液当中，高速剪切搅拌，进行中和乳化，减压蒸馏脱去溶剂后即得改性水性聚氨酯乳液。其中NaOH与DMPA摩尔比为1:1。
性能验证：将乳液均匀倒在聚四氟乙烯板上，在室温下放置一段时间，然后放入烘箱中，在60℃下干燥48h后，冲压成标准哑铃试片。采用XWW-20B电子万能试验机，按GB/T1040-92测定胶膜的拉伸强度和断裂伸长率。结果表明：其拉伸强度由11.2MPa增加到12.7MPa，断裂伸长率变化不大，机械强度略有提高。
实施例三
一种碱木质素基水性聚氨酯的制备方法，包括以下步骤：
步骤一：将粗碱木质素的水溶液用质量浓度6％的NaOH溶液调节pH至13～14,使碱木质素充分溶解。过滤除去不溶物，然后用质量浓度12％的盐酸于60℃下调pH至2左右，过滤，反复用蒸馏水洗涤沉淀至中性，真空干燥即得到精制碱木质素。
步骤二：将13.75g二苯基甲烷-4,4‵-二异氰酸酯(MDI)、47.6g聚乙二醇(PEG2000)、0.28g精制碱木质素(用丙酮溶解)和0.05g二月桂酸二丁基锡加入到三口烧瓶中，，在85℃下搅拌反应5h，然后降温至65℃，再加入2.24g DMPA和35mL的丙酮，反应1.5h，降温至30℃出料，得水性聚氨酯预聚体。
步骤三：将步骤二得到的预聚体加入到KOH水溶液当中，高速剪切搅拌，进行中和乳化，减压蒸馏脱去溶剂后即得改性水性聚氨酯乳液。其中KOH与DMPA摩尔比为1:1。
性能验证：将乳液均匀倒在聚四氟乙烯板上，在室温下放置一段时间，然后放入烘箱中，在60℃下干燥48h后，冲压成标准哑铃试片。采用XWW-20B电子万能试验机，按GB/T1040-92测定胶膜的拉伸强度和断裂伸长率。结果表明：其拉伸强度由30.8MPa增加到38.6MPa，断裂伸长率由433.6％增加到443.5％，机械强度明显提高。

Claims (8)

1.一种碱木质素基水性聚氨酯的制备方法，其特征在于，包括以下步骤：
步骤一：制备精制碱木质素：将粗碱木质素的水溶液用质量浓度5％～10％的NaOH溶液调节pH至13～14，使碱木质素充分溶解，过滤除去不溶物，然后用质量浓度12％的盐酸于60℃下调节pH至2～3，过滤，反复用蒸馏水洗涤沉淀至中性，真空干燥即得；
步骤二：将二异氰酸酯、聚醚多元醇和精制碱木质素加入到三口烧瓶中，聚醚多元醇与二异氰酸酯的摩尔比为1:(2～4)，在60～90℃下搅拌反应1～5h，然后降温至50～70℃，以二异氰酸酯、聚醚多元醇和精制碱木质素总质量为基准，再加入DMPA亲水扩链剂2.0％～5.0％和10～80mL丙酮，反应1～4h，降温至20～50℃出料，得水性聚氨酯预聚体；
步骤三：将所得水性聚氨酯预聚体用中和剂中和后，加水进行高速乳化，减压蒸馏脱去溶剂后即得水性聚氨酯乳液。
2.根据权利要求1所述的一种碱木质素基水性聚氨酯的制备方法，其特征在于：所述步骤二中，精制碱木质素的加入量为精制碱木质素和聚醚多元醇质量之和的0.5％～3.0％。
3.根据权利要求1所述的一种碱木质素基水性聚氨酯的制备方法，其特征在于：所述步骤二中，精制碱木质素以丙酮溶解后再与二异氰酸酯和聚醚多元醇混合，溶解所用的丙酮的量为20mL。
4.根据权利要求1所述的一种碱木质素基水性聚氨酯的制备方法，其特征在于：所述步骤二中，搅拌反应前加入催化剂，催化剂的加入量为二异氰酸酯、聚醚多元醇和精制碱木质素总质量的0.05％～0.2％。
5.根据权利要求4所述的一种碱木质素基水性聚氨酯的制备方法，其特征在于：所述催化剂为二月桂酸二丁基锡(DBTDL)。
6.根据权利要求1所述的一种碱木质素基水性聚氨酯的制备方法，其特征在于：所述二异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)或二苯基甲烷-4,4‵-二异氰酸酯。
7.根据权利要求1所述的一种碱木质素基水性聚氨酯的制备方法，其特征在于：所述聚醚多元醇为聚丙二醇(PPG)、聚四氢呋喃醚二醇(PTMG)或聚乙二醇(PEG)，数均分子量均为2000。
8.根据权利要求1所述的一种碱木质素基水性聚氨酯的制备方法，其特征在于：所述中和剂为三乙胺、氢氧化钠或氢氧化钾，加入量与DMPA的摩尔比为1:1。
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