CN105330810A - 一种凹凸棒土改性木质素型聚氨酯材料的制备方法 - Google Patents

一种凹凸棒土改性木质素型聚氨酯材料的制备方法 Download PDF

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CN105330810A
CN105330810A CN201510852273.3A CN201510852273A CN105330810A CN 105330810 A CN105330810 A CN 105330810A CN 201510852273 A CN201510852273 A CN 201510852273A CN 105330810 A CN105330810 A CN 105330810A
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attapulgite
xylogen
polyurethane material
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CN105330810B (zh
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曹云峰
刘祝兰
皮成忠
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Nanjing Forestry University
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Abstract

本发明涉及一种凹凸棒土改性木质素型聚氨酯材料的制备方法，属于木质复合材料领域。目的是为了提供一种工艺简单、生产成本低、工业化容易实施的新型聚氨酯材料的制备方法。将木质素分散溶解于有机溶剂中，并与多元醇和凹凸棒土复配得到复配多元醇，再将复配多元醇与异氰酸酯、扩链剂和催化剂混合反应得到凹凸棒土改性木质素型聚氨酯材料。本发明所用的凹凸棒土和木质素以共混或共聚的方式复配至聚氨酯材料中，其中凹凸棒土可以微米填充和纳米增强两种方式改善聚氨酯材料性能；木质素可替代部分多元醇作为反应主体与异氰酸酯发生共聚反应，从而改善聚氨酯材料的力学性能。

Description

一种凹凸棒土改性木质素型聚氨酯材料的制备方法
技术领域
本发明属于环保新材料领域，特别涉及一种凹凸棒土改性木质素型聚氨酯材料的制备方法。
背景技术
聚氨酯是一种新兴的有机高分子材料，被誉为“第五大塑料”，因其卓越的性能而被广泛应用于国民经济众多领域。聚氨酯树脂制成的产品有泡沫塑料、弹性体、涂料、胶粘剂、纤维、合成皮革以及铺面材料等品种。产品应用领域涉及轻工、化工、电子、纺织、医疗、建筑、建材、汽车、国防、航天、航空等，产品与品种逐年递增，在材料工业中占有相当重要的地位。因此，各国都竞相发展聚氨酯树脂工业。
聚氨酯是聚氨基甲酸酯(Polyurethane)的简称，通常是由二元或多元异氰酸酯与含有两个或多个活泼氢化合物通过逐步聚合反应聚合成为高分子链的主链上含有重复的氨基甲酸酯结构单元的高分子化合物。除了生成氨基甲酸酯基团外，还生成脲、缩二醛等基团。所以，从广泛意义上说，聚氨酯是异氰酸酯的加成产物。
常用的异氰酸酯有甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)和多次甲基多苯基异氰酸酯(PAPI)等。所用的多元醇品种也很多，主要有聚醚及聚酯两大类，不下数十种。生产过程中可根据所需产品性能的需要选择不同的多元醇或异氰酸酯。但是目前生产聚酯、聚醚多元醇的原料均是来自毒性和腐蚀性较强的石油化工产品，如苯酐、苯二甲酸是从萘、二甲苯等芳香族石油或者煤化工产品氧化得到。然而，随着社会的进步和发展，作为世界经济发展重要支柱的石油资源日益枯竭，各种来自石油的高分子单体也受到严重困扰，从而限制了聚氨酯工业原材料的来源，时刻影响着聚氨酯工业的发展；所制成的聚氨酯不易生物降解，也将对环境造成很大污染；且随着人们生活水平的提高，对聚氨酯材料性能提出了更高的要求。因此，为改善聚氨酯综合性能以适应市场需求、降低生产成本、减少环境污染等，开发和寻找新的替代资源生产聚氨酯材料及改性聚氨酯材料已成为聚氨酯发展的一个主要方向。
木质素是广泛存在于植物体中的一种天然高聚物，是自然界非常丰富的可再生资源，储量仅次于纤维素和甲壳素，而且每年都以6×1014t的速度再生，价格便宜，又具有分散性、生物可降解性、无毒耐候等诸多优点。而且，木质素及其改性产品中含有活性羟基，可以被看作是一种多元醇，可代替聚醚多元醇与异氰酸酯发生亲核加成反应制备聚氨酯材料，这不但可以提高资源的利用率，而且可以减少聚氨酯工业对石油产品的依赖性。同时，木质素作为一种活性填料添加到聚氨酯体系中，起到交联剂和填充剂的作用，与聚氨酯具有良好的相容性，容易制成均相材料。
关于木质素用于聚氨酯材料合成的研究已有报道，如专利CN103183801A，利用CIMV小麦秸秆木质素和聚醚多元醇混合，制备聚氨酯薄膜。专利CN103215005A为解决聚氨酯密封胶容易受紫外光老化的技术问题，将含有木质素的预聚体、催化剂、潜固化剂、增塑剂和填料在80℃的条件下搅拌1小时，即得到含木质素的聚氨酯密封胶。专利CN1651478将高沸醇木质素或其衍生物溶于有机溶剂，再与多元醇或多元醇的溶液混合均匀，然后再加入一定量的多异氰酸酯、改性添加剂或填料，加热反应制备聚氨酯。专利CN101696261A将秸秆生产燃料乙醇的残渣中用氢氧化钠抽提分离出木质素，并用环氧化物改性，再溶解于多元醇，最后与异氰酸酯等原料复配，得到聚氨酯材料。但是木质素是网状结构的刚性分子，参入量太大会降低聚氨酯的柔韧性，同时木质素的玻璃化温度较高，大量引入会使聚氨酯的黏流温度和玻璃化温度增高，所以木质素在聚氨酯材料中的使用量受限。
近年来，随着纳米技术的飞速发展，纳米改性为各类材料的功能化和高性能化提供了崭新的手段和途径。由于纳米粒子具有表面效应、小尺寸效应、量子尺寸效应和宏观量子隧道效应等特殊性质，将其键入水性聚氨酯(WPU)分子链上，使得聚氨酯的成膜、耐水和耐磨指标均达到或者超过溶剂型PU的国家标准，所以纳米改性WPU成为目前PU改性的热点。
凹凸棒土是一种层链状过渡结构的、以含水富镁铝硅酸盐为主的天然粘土矿物。根据X衍射分析提出凹凸棒土的理想晶体结构层状晶体结构模式和经典化学式Mg5(Si4O10)2(H2O)·4H2O得到公认。凹凸棒晶体形态为棒状或者纤维状，单晶直径大多是10-100nm，长度为0.1-1μm，所以具有很大的长径比，属于一维纳米粒子，具有滑感、质轻、吸水性强、遇水不膨胀、遇水时具有黏性和可塑性等特性。由于其本身的特殊结构，可广泛应用于建材、采矿、化肥、食品、农药、印染、环保等领域，素有“千面用土”之称。专利CN102127827A采用超声和/或强力机械搅拌以及研磨等措施，使纳米凹凸棒土在低聚二元醇和反应控制剂a的混合液中分散形成稳定均匀的交替，然后分别加入二异氰酸酯、扩链剂、反应控制剂b，嵌段共聚制备聚氨酯弹性纤维。专利CN103665293利用纤维素类生物质液化得到的植物多元醇与凹凸棒土进行复配植物多元醇，将改性凹凸棒土与异氰酸酯进行复配得到异氰酸酯；将植物多元醇或复配植物多元醇、泡沫稳定剂、发泡剂、催化剂混合均匀得到粘稠混合物；在搅拌状态下，将异氰酸酯或复配异氰酸酯快速加入粘稠混合物中，制备具有阻燃功能的硬质聚氨酯泡沫保温材料。凹凸棒土可显著提高聚氨酯膜的耐热稳定性、柔韧性、拉伸强度及耐水性，并改善聚氨酯材料的吸水速率及透水汽速率。
以上专利都是关于单独使用木质素或者凹凸棒土改性聚氨酯材料。虽然在聚氨酯乳液中单独添加木质素可改善产品力学性能，但是木质素是刚性分子，木质素的大量引入会使聚氨酯柔韧性和伸长率降低。若在聚氨酯乳液中单独添加凹凸棒土，虽可提高产品的力学性能，但是凹凸棒土比表面积较大，分散性较差，在使用过程中很容易出现聚集，导致聚氨酯产品中某一部位出现应力集中，从而影响产品质量。
发明内容
为了克服背景技术的不足，本发明提供了一种凹凸棒土改性木质素型聚氨酯材料的制备方法。主要解决了现有方法单独使用木质素或者凹凸棒土改性聚氨酯材料会降低聚氨酯柔韧性和伸长率等问题。利用凹凸棒土改善单独复配木质素所引起的聚氨酯柔韧性和伸长率降低，同时木质素的存在可提高乳液和凹凸棒土在乳液中的分散性及稳定性，两者相互配合，控制聚氨酯乳液流变性能和加工性能，全面提高产品的拉伸强度和柔韧性等，大大降低聚氨酯的生产成本。
本发明所采用的技术方案是：一种凹凸棒土改性木质素型聚氨酯材料的制备方法，包括以下步骤：
(1)称取干燥的木质素溶解于有机溶剂中，向其中加入多元醇搅拌混合均匀，再与酸处理凹凸棒土进行复配得到复配多元醇；
(2)将复配多元醇、催化剂、扩链剂混合均匀得到混合溶液；
(3)向混合溶液中加入异氰酸酯，反应完全后所得树脂加入含有NaOH的去离子水乳化，所制备好的乳液铺展在聚四氟乙烯板上，经干燥得到凹凸棒土改性木质素型聚氨酯产品。
本发明提供的工艺方法中，步骤(1)中所述的木质素可以为碱木质素、酸木质素、醇解木质素、酶解木质素和木质素磺酸盐中的一种，木质素添加量占多元醇总量的5％～50％。
本发明提供的工艺方法中，步骤(1)中所述的酸处理凹凸棒土的添加量占多元醇和木质素总量的1％～40％；
本发明提供的工艺方法中，步骤(1)中所述的有机溶剂可以为二甲基甲酰胺、甲苯、丙酮、丁酮和环己酮中的一种。
本发明提供的工艺方法中，步骤(1)中所述的多元醇可以为聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己二酸乙二醇酯二醇、聚己二酸-1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇、聚己内酯二醇和聚碳酸酯二醇中的一种。
本发明提供的工艺方法中，步骤(1)中所述的酸处理凹凸棒土由以下方法制备得到：称取50g原本凹凸棒土，加入250ml含有25ml盐酸的蒸馏水，于60℃下恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土。
本发明提供的工艺方法中，步骤(2)中所述的催化剂可以为三乙烯二胺、二丁基锡二月桂酸酯和辛酸亚锡中的一种；其中，催化剂用量占多元醇和木质素总量的1％～4％。
本发明提供的工艺方法中，步骤(2)中所述的扩链剂可以为乙二醇、一缩二乙二醇、1，2-丙二醇、一缩二丙二醇、1，4-丁二醇、1，6-己二醇、三羟甲基丙烷和蓖麻油中的一种；其中，扩链剂用量占多元醇和木质素总量的8％～12％。
本发明提供的工艺方法中，步骤(3)中所述的异氰酸酯为甲苯二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯和多苯基多亚甲基多异氰酸酯中的至少一种；
本发明提供的工艺方法中，步骤(3)中所述的异氰酸根与复配多元醇中醇羟基摩尔比为3.0∶1～1∶1.5。本发明具有如下优点：
(1)本发明中所使用的木质素可提高凹凸棒土、多元醇和异氰酸酯体系的分散性及稳定性，破坏凹凸棒土在使用过程中的聚集现象，避免聚氨酯产品出现应力集中；而凹凸棒土可缓解因添加木质素而造成的聚氨酯柔韧性和伸长率降低问题。两者相互配合，取长补短，共同改善聚氨酯产品的力学性能。
(2)木质素价格便宜，具有生物可降解和无毒耐候等诸多优点，代替部分多元醇用于聚氨酯材料不但可以提高资源的利用率，而且还可以减少聚氨酯工业对石油产品的依赖性。
(3)本发明得到的凹凸棒土改性木质素型聚氨酯材料的制备方法具有工艺简单、生产成本低、不需要特殊设备、工业化实施容易等特点。下面结合附图对本发明作进一步说明。
附图说明
图1凹凸棒土的扫描电镜图和结构图，a电镜图，b结构图
图2凹凸棒土改性的木质素型聚氨酯材料的扫描电镜图
具体实施方式
下面将结合本发明实施例中的附图，技术工艺步骤，具体实施条件和材料，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
(1)酸处理凹凸棒土的制备：称取50g原本凹凸棒土，加入250ml含有25ml盐酸的蒸馏水，于50℃恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土HAT。
(2)称取6g干燥的醇解木质素溶解于100ml二甲基甲酰胺(DMF)中，然后加入100g聚乙二醇PEG1000在60℃下搅拌30min，使其充分混合均匀。然后加入2gHAT，复配得到多元醇。
(3)复配多元醇与1.5g二丁基锡二月桂酸酯、2.2g三乙烯二胺、10.6g三羟甲基丙烷混合均匀，得到混合溶液。
(4)在步骤(3)混合溶液中加入一定量甲苯二异氰酸酯，调整异氰酸酯指数(n(-N℃O)∶n(-OH))为1∶1.5，在90℃下密闭搅拌反应30min，反应完全后所得树脂加入含有NaOH的去离子水，乳化30min。所制备好的乳液铺展在水平放置的聚四氟乙烯板上，室温下静置24h，然后在80℃下熟化6h，再40℃真空干燥，从而得到干燥的聚氨酯膜。所得凹凸棒土改性木质素型聚氨酯膜的拉伸应力为23.8MPa，断裂伸长率为995％。
实施例2
(1)酸处理凹凸棒土的制备：称取50g原本凹凸棒土，加入250ml含有25ml盐酸的蒸馏水，于60℃恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土HAT。
(2)称取15g干燥的碱木质素溶解于100ml甲苯中，然后加入100g聚己内酯二醇在60℃下搅拌30min，使其充分混合均匀。然后加入6gHAT，复配得到复配多元醇。
(3)复配多元醇与1.6g辛酸亚锡、2.4g三乙烯二胺、11.5g一缩二丙二醇混合均匀，得到混合溶液。
(4)在(3)中混合溶液中加入一定量二苯基甲烷二异氰酸酯，调整异氰酸酯指数(n(-NCO)∶n(-OH))为2∶1，在70℃下密闭搅拌反应60min，反应完全后所得树脂加入含有NaOH的去离子水，乳化30min。所制备好的乳液铺展在水平放置的聚四氟乙烯板上，室温下静置24h，然后在80℃下熟化6h，再40℃真空干燥，从而得到干燥的聚氨酯膜。所得凹凸棒土改性木质素型聚氨酯膜的拉伸应力为48.6MPa，断裂伸长率为1641％。
实施例3
(1)酸处理凹凸棒土的制备：称取50g原本凹凸棒土，加入250ml含有25ml盐酸的蒸馏水，于60℃恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土HAT。
(2)称取15g干燥的酸木质素溶解于100ml丙酮中，然后加入100g聚己二酸乙二醇酯二醇在60℃下搅拌30min，使其充分混合均匀。然后加入30gHAT，分散后得到复配多元醇。
(3)复配多元醇与1.6g辛酸亚锡、2.4g三乙烯二胺、11.5g蓖麻油混合均匀，得到混合溶液。
(4)在(3)中混合溶液中加入一定量苯二亚甲基二异氰酸酯，调整异氰酸酯指数(n(-NCO)∶n(-OH))为2∶1，在90℃下密闭搅拌反应30min，反应完全后所得树脂加入含有NaOH的去离子水，乳化30min。所制备好的乳液铺展在水平放置的聚四氟乙烯板上，室温下静置24h，然后在80℃下熟化6h，再40℃真空干燥，从而得到干燥的聚氨酯膜。所得凹凸棒土改性木质素型聚氨酯膜的拉伸应力为50.4MPa，断裂伸长率为1951％。
实施例4
(1)酸处理凹凸棒土的制备：称取50g原本凹凸棒土，加入250ml含有25ml盐酸的蒸馏水，于60℃恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土HAT。
(2)称取30g干燥的木质素磺酸盐溶解于100ml丁酮中，然后加入100g聚己二酸乙二醇酯二醇在60℃下搅拌30min，使其充分混合均匀。然后加入30gHAT，分散后得到复配多元醇。
(3)复配多元醇与4.5g三乙烯二胺、13g1，4-丁二醇混合均匀，得到混合溶液。
(4)在(3)中混合溶液中加入一定量六亚甲基二异氰酸酯，调整异氰酸酯指数(n(-NCO)∶n(-OH))为2∶1，在90℃下密闭搅拌反应30min，反应完全后所得树脂加入含有NaOH的去离子水，乳化30min。所制备好的乳液铺展在水平放置的聚四氟乙烯板上，室温下静置24h，然后在80℃下熟化6h，再40℃真空干燥，从而得到干燥的聚氨酯膜。所得凹凸棒土改性木质素型聚氨酯膜的拉伸应力为53.9MPa，断裂伸长率为1803％。
实施例5
(1)酸处理凹凸棒土的制备：称取50g原本凹凸棒土，加入250ml含有25ml盐酸的蒸馏水，于60℃恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土HAT。
(2)称取50g干燥的酶解木质素溶解于100ml环己酮中，然后加入100g聚四氢呋喃二醇在60℃下搅拌30min，使其充分混合均匀。然后加入40gHAT，分散后得到复配多元醇。
(3)复配多元醇与2.1g二丁基锡二月桂酸酯、3.2g三乙烯二胺、15g1，2-丙二醇混合均匀，得到混合溶液。
(4)在(3)中混合溶液中加入一定量多苯基多亚甲基多异氰酸酯，调整异氰酸酯指数(n(-NCO)∶n(-OH))为3∶1，在60℃下密闭搅拌反应180min，反应完全后所得树脂加入含有NaOH的去离子水，乳化30min。所制备好的乳液铺展在水平放置的聚四氟乙烯板上，室温下静置24h，然后在80℃下熟化6h，再40℃真空干燥，从而得到干燥的聚氨酯膜。所得凹凸棒土改性木质素型聚氨酯膜的拉伸应力为48.2MPa，断裂伸长率为1478％。
实施例6
(1)酸处理凹凸棒土的制备：称取50g原本凹凸棒土，加入250ml含有25ml盐酸的蒸馏水，于60℃恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土HAT。
(2)称取20g干燥的碱木质素溶解于100ml丁酮中，然后加入100g聚丙二醇在60℃下搅拌30min，使其充分混合均匀。然后加入30gHAT，分散后得到复配多元醇。
(3)复配多元醇与1.8g二丁基锡二月桂酸酯、3.5g三乙烯二胺、17g三羟基丙烷混合均匀，得到混合溶液。
(4)在(3)中混合溶液中加入一定量多苯基多亚甲基多异氰酸酯，调整异氰酸酯指数(n(-NCO)∶n(-OH))为2∶1，在60℃下密闭搅拌反应180min，反应完全后所得树脂加入含有NaOH的去离子水，乳化30min。所制备好的乳液铺展在水平放置的聚四氟乙烯板上，室温下静置24h，然后在80℃下熟化6h，再40℃真空干燥，从而得到干燥的聚氨酯膜。所得凹凸棒土改性木质素型聚氨酯膜的拉伸应力为49.9MPa，断裂伸长率为1538％。
由上述实施例可见，本方法所制备的凹凸棒土改性木质素型聚氨酯材料具有优异的力学性能。
各位技术人员须知：虽然本发明已按照上述具体实施方式做了描述，但是本发明的发明思想并不仅限于此发明，任何运用本发明思想的改装，都将纳入本专利专利权保护范围内。

Claims (10)

1.一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于包含以下具体步骤：
(1)称取干燥的木质素溶解于有机溶剂中，向其中加入多元醇搅拌混合均匀，再与酸处理凹凸棒土进行复配得到复配多元醇；
(2)将复配多元醇、催化剂、扩链剂混合均匀得到混合溶液；
(3)向混合溶液中加入异氰酸酯，反应完全后所得树脂加入含有NaOH的去离子水乳化，所制备好的乳液铺展在聚四氟乙烯板上，经干燥得到凹凸棒土改性木质素型聚氨酯产品。
2.根据权利要求1所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(1)中所述的木质素可以为碱木质素、酸木质素、醇解木质素、酶解木质素和木质素磺酸盐中的一种，木质素添加量占多元醇总量的5％～50％。
3.根据权利要求1所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(1)中所述的酸处理凹凸棒土的添加量占多元醇和木质素总量的1％～40％。
4.根据权利要求1所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(1)中所述的有机溶剂可以为二甲基甲酰胺、甲苯、丙酮、丁酮和环己酮中的一种。
5.根据权利要求1所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(1)中所述的多元醇可以为聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己二酸乙二醇酯二醇、聚己二酸-1，4-丁二醇酯二醇、聚己二酸己二醇酯二醇、聚己内酯二醇和聚碳酸酯二醇中的一种。
6.根据权利要求1所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(1)中所述的酸处理凹凸棒土由以下方法制备得到：称取50g原本凹凸棒土，加入250m1含有25ml盐酸的蒸馏水，于60℃下恒温搅拌3h后过滤、洗涤并干燥后研磨成粉末，得到酸处理凹凸棒土。
7.根据权利要求1中所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(2)中所述的催化剂可以为三乙烯二胺、二丁基锡二月桂酸酯和辛酸亚锡中的一种；其中，催化剂用量占多元醇和木质素总量的1％～4％。
8.根据权利要求1中所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(2)中所述的扩链剂可以为乙二醇、一缩二乙二醇、1，2-丙二醇、一缩二丙二醇、1，4-丁二醇、1，6-己二醇、三羟甲基丙烷和蓖麻油中的一种；其中，扩链剂用量占多元醇和木质素总量的8％～12％。
9.根据权利要求1中所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(3)中所述的异氰酸酯为甲苯二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯和多苯基多亚甲基多异氰酸酯中的至少一种。
10.根据权利要求1中所述的一种凹凸棒土改性木质素型聚氨酯材料的制备方法，其特征在于：步骤(3)中所述的异氰酸根与复配多元醇中醇羟基摩尔比为3.0∶1～1∶1.5。
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