CN115386063B - 一种木质素基水性聚氨酯及其制备方法 - Google Patents
一种木质素基水性聚氨酯及其制备方法 Download PDFInfo
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- CN115386063B CN115386063B CN202211137496.8A CN202211137496A CN115386063B CN 115386063 B CN115386063 B CN 115386063B CN 202211137496 A CN202211137496 A CN 202211137496A CN 115386063 B CN115386063 B CN 115386063B
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- aqueous polyurethane
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3278—Hydroxyamines containing at least three hydroxy groups
- C08G18/3281—Hydroxyamines containing at least three hydroxy groups containing three hydroxy groups
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Abstract
本发明涉及生物质资源高附加值利用领域,具体公开了一种木质素基水性聚氨酯及其制备方法。所述木质素基水性聚氨酯由以下重量份数的原料组成:低聚物多元醇80‑120份,多元异氰酸酯70‑90份,扩链剂5‑20份,有机胺类化合物5‑20份,肟基化合物30‑80份,乳化剂1~5份,异氰酸改性木质素100‑120份,去离子水300‑800份。本发明通过对木质素进行改性异氰酸,将其作为聚氨酯的填料,增加了木质素与聚氨酯的化学键结合位点,提高了聚氨酯薄膜的力学性能。
Description
技术领域
本发明属于生物质资源高附加值利用和聚氨酯交叉技术领域,尤其是涉及一种木质素基水性聚氨酯及其制备方法。
背景技术
在涂料应用领域,生物基材料特别是植物油已经广泛地用于制备新型的绿色环保涂料。这是因为植物油具有无毒性、低挥发性、生物可降解性和原材料丰富易得等特点。19世纪以来,人们对植物油基聚合物开展了一系列的研究。如植物油中的甘油三酸酯经过甘油醇解后,得到单甘油酯用于制备醇酸树脂;干性油或脂肪酸首先经过马来酸酐化,然后与环氧预聚物进行酯交换反应,制备脂肪酸改性环氧涂料;大豆油经过环氧化处理后,再与丙烯酸酯结合,用于制备环氧化大豆油丙烯酸酯树脂;单甘油酯也是一种多元醇,可以与二异氰酸酯反应制备聚氨酯,用于制备水基聚氨酯的植物油有向日葵油、蓖麻油、菜籽油、大豆油等;桐油热交联聚合后直接形成可生物降解的涂层。
木质素是一类复杂的有机聚合物,其在维管植物和一些藻类的支持组织中形成重要的结构材料。木质素在细胞壁的形成中是特别重要的,特别是在木材和树皮中,因为它们赋予刚性并且不容易腐烂。在化学上,木质素是交叉链接的酚聚合物。木质素是由3种苯丙烷单元通过醚键和碳碳键相互连接形成的具有三维网状结构的生物高分子,含有丰富的芳环结构、脂肪族和芳香族羟基以及醌基等活性基团,是植物界中储量仅次于纤维素的第二大生物质资源。作为典型的生物质材料,木质素是芳香族化合物中少有的可再生资源之一。木质素作为植物界继纤维素之后第二大资源的生物质材料,全球每年产量约5000万吨,其中源自农业残留物的木质素约占10%~20%,源自森林生物质材料的木质素约占20%~30%,来源甚广且产量巨大。
由于木质素的分子结构中存在着芳香基、酚羟基、醇羟基、碳基共扼双键等活性基团,因此可以进行氧化、还原、水解、醇解、酸解甲氧基、羧基、光解、酞化、磺化、烷基化、卤化、硝化、缩聚或接枝共聚等许多化学反应。其中,又以氧化、酞化、磺化、缩聚和接枝共聚等反应性能在研究木质素的应用中显示着尤为重要的作用,同时也是扩大其应用的重要途径。在此过程中,磺化反应又是木质素应用的基础和前提,到目前为止,木质素的应用大都以木质素磺酸盐的形式加以利用。制浆造纸过程中会产生大量的黑液,黑夜中含有大量的木质素,对其进行分离回收并利用具有十分重要的实际应用价值。木质素以及它们的衍生物可以作为涂料的增强填料,也可用于涂料树脂的合成原料或是成膜物质。我国生物基资源利用的技术和研究远远落后于日美等发达国家。因此,研究新型的可再生和环保涂料对于我国涂料工业的发展具有深远和重要的意义。
中国专利【202111492704.1】公开了一种木质素改性的水性聚氨酯薄膜及其制备方法,水性聚氨酯薄膜包括低聚物多元醇、多元异氰酸酯、亲水性扩链剂、肟基化合物、多元胺化合物、酸类化合物、有机溶剂和木质素。该发明将木质素以水相原位填加的方式引入到合成的聚氨酯乳液中,实现了木质素在水性聚氨酯体系中的原位纳米分散效果,加热固化得到水性聚氨酯薄膜,极大地提高了力学性能,并有效保留了自修复功能,提高了材料的循环使用性能。但是该发明仅仅将木质素作为填料进行使用,没有形成结合力更强的化学键,因此所制备的聚氨酯薄膜强度性能存在较大的提升空间。
中国专利【202010334761.6】公开了一种高阻燃性的改性木质素基聚氨酯涂层,尤其是反应型阻燃剂改性木质素的制备方法,包括如下步骤:(1)向1,4-二氧六环溶剂中加入碱木质素,超声分散均匀后加入催化剂4-二甲氨基吡啶,使用自动注射器缓慢滴加二苯基次膦酰氯,加热至80-100℃,反应15-20h,除去溶剂,洗涤并干燥,制备得到磷化木质素;(2)向N,N-二甲基甲酰胺溶剂中加入磷化木质素,超声分散均匀后加入1,5-二异氰酸萘、四氯三氧化二磷和催化剂吡啶,加热至100-120℃,反应12-18h,过滤、洗涤并干燥,制备得到异氰酸酯接枝的多磷化改性木质素。该发明的改性过程比较复杂,使用大量的有毒害作用的有机物,生产过程可能有大量的污染物产生,不利于大规模化的生产。
因此,本发明提出了对木质素先进行微纳化处理,然后对木质素进行异氰酸改性,最后制成基于木质素的聚氨酯。该过程简单,采用水作溶剂,反应过程比较绿色环保,具有规模化生产的潜力。
发明内容
本发明的目的是提供一种木质素基水性聚氨酯及其制备方法,特别是木质素为原料生产的生物基水性聚氨酯。
具体技术方案如下:
一种木质素基水性聚氨酯,由以下重量份数的原料组成:低聚物多元醇80-120份,多元异氰酸酯70-90份,扩链剂5-20份,有机胺类化合物5-20份,肟基化合物30-80份,乳化剂1-5份,异氰酸改性木质素100-120份,异氰酸改性木质素100-120份,去离子水300-800份,所述多元异氰酸酯为六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、多亚甲基多苯基多氰酸酯中的至少一种。所述异氰酸改性木质素的制备步骤包括:
(1)木质素的微纳化处理:将200-300份木质素分散在500-600份的聚乙烯醇中,在80-100℃下恒温处理1-3小时,过滤除去滤液将滤渣依次经过榨油机和胶体磨进行粉碎处理后,再将滤渣分散于400-600份甲乙酮中,以400-500W的功率超声处理1-3小时,得到微纳木质素在甲乙酮中的分散液;
(2)木质素的异氰酸改性:将步骤(1)得到的微纳木质素甲乙酮分散液加入多功能反应釜中,并依次加入300-450份的多元异氰酸酯和1-3份的二月桂酸二丁基锡,然后将混合物加热至80-100℃并反应24小时,反应后混合物冷却至25℃,将200-500份的正己烷在搅拌速度为1000-2000转/分钟的搅拌下将其加入混合物中,连续搅拌0.5-1小时,最后,过滤混合物,用正己烷洗涤至少三次,并在50-80℃下干燥10-12小时,得到干燥的异氰酸改性木质素。
所述步骤(2)中的多元异氰酸酯为六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯的至少一种。
在一些实施例中,所述木质素基聚氨酯包括以下重量份的各组分:低聚物多元醇90-120份,多元异氰酸酯70-90份,扩链剂5-20份,有机胺类化合物10-20份,肟基化合物40-80份,乳化剂1-5份,异氰酸改性木质素100-120份,去离子水300-800份。
在其中一些实施例中,所述低聚物多元醇为聚四氢呋喃醚二醇、聚丙二醇、聚己二酸已二醇酯、聚碳酸酯二醇、聚己二酸丁二醇酯、聚己内酯二醇中的至少一种。
在其中一些实施例中,所述扩链剂为乙二醇、丙二醇、1,4-丁二醇,一缩二乙二醇、丙三醇、三羟甲基丙烷,1,4-环己二醇、2,2-二羟甲基丁酸、2,2-二羟甲基丙酸、油酸二乙醇酰胺中的至少一种。
在其中一些实施例中,所述有机胺类化合物为中的二乙醇胺、三乙醇胺、甲基二乙醇胺、二异丙胺、1,2-二甲基丙胺、1,2-丙二胺、1,4-丁二胺、己二胺中的至少一种。
在其中一些实施例中,所述肟基化合物为乙醛肟、二甲基酮肟、丁二酮肟、丁醛肟中的至少一种。
在其中一些实施例中,所述乳化剂为十二磺基硫酸钠、硫酸-2-对壬基酚氧-乙酯铵、2-丙烯酰胺基-甲基-丙基硫酸钠、2-丙烯酰胺基-甲基-丙基硫酸铵中的一种或多种。
本发明还提供了一种木质素基水性聚氨酯的制备方法,所述制备方法包括如下步骤:
先通入氮气5-20分钟除去反应釜内的空气,按配方重量,在多功能反应釜中依次加入去离子水、乳化剂和异氰酸改性木质素,在搅拌速度为500-1000转/分钟搅拌下进行乳化,并快速升温至80-100℃,恒温0.5-1小时;再将多元异氰酸酯和低聚物多元醇加入混合反应,并升温至110-120℃,恒温反应1-3小时,再加入扩链剂,快速升温至120-150℃后加入肟基化合物,继续恒温反应1-2小时后,加入有机胺类化合物,继续反应1-3小时后,每隔半小时测反应液的黏度,当黏度为5-30S/25℃,降温到50-60℃并保温;然后通入氮气20-30分钟,除去反应釜内的水蒸气,将反应物从反应釜中倒出,在高速分散机中进行分散乳化,减压蒸馏除去水,即得到木质素基水性聚氨酯乳液;在玻璃板涂布木质素基水性聚氨酯乳液并固化即得到木质素基水性聚氨酯薄膜。
本发明具有以下优点:
(1)以水作为溶剂,不仅反应过程比较的绿色环保,而且可减少后续聚氨酯在使用过程中VOC的排放;
(2)对木质素进行异氰酸改性,作为反应物进行反应而不是简单地将木质素作为填料,可增强聚氨酯的强度性能;
(3)对木质素进行高值化利用,转换成生物质资源,减少造纸工业中木质素对环境的污染,减少碳排放。
附图说明
图1实施例1制备的异氰酸改性木质素的电镜图;
图2实施例1制备的异氰酸改性前后木质素的红外光谱图;
图3实施例2制备的聚氨酯薄膜的拉伸曲线图;
图4实施例3制备的聚氨酯薄膜的拉伸曲线图;
图5实施例4制备的聚氨酯薄膜的拉伸曲线图
图6实施例5制备的聚氨酯薄膜的拉伸曲线图
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
将200g木质素分散在500g的聚乙烯醇中,在90℃下恒温处理2小时,过滤除去滤液将滤渣依次经过榨油机和胶体磨进行粉碎处理后,再将滤渣分散于500g份甲乙酮中,以500W的功率超声处理3小时,得到微纳木质素在甲乙酮中的分散液。将得到的微纳木质素甲乙酮分散液加入多功能反应釜中,并依次加入450份的二苯基甲烷二异氰酸酯和2份的二月桂酸二丁基锡,然后将混合物加热至100℃并反应24小时,反应后混合物冷却至25℃,将400份的正己烷在搅拌速度为1500转/分钟的搅拌下将其加入混合物中,连续搅拌1小时,最后,过滤混合物,用正己烷洗涤至少三次,并在50℃下干燥12小时,得到干燥的异氰酸改性木质素。对制备的异氰酸木质素颗粒进行扫描电镜测试,结果如图1所示;进行红外光谱表征如图2所示。对比木质素改性前后的红外光谱图,1680,1100和910cm-1分别是C=C,C-C和C-H的振动;而1480cm-1是C-N的振动,很明显改性后上述峰强度强于未改性的木质素,表明异氰酸改性木质素成功。
实施例2
本实施例提供一种木质素基水性聚氨酯及其制备方法,其原料配比如表1所示:
表1实施例2的原料配比
四氢呋喃醚二醇 | 90份 |
六亚甲基二异氰酸酯 | 70份 |
丙二醇 | 5份 |
三乙醇胺 | 5份 |
二甲基酮肟 | 30份 |
十二磺基硫酸钠 | 5份 |
异氰酸改性木质素 | 100份 |
去离子水 | 500份 |
本实施例中异氰酸改性木质素为实施例1制备的异氰酸改性木质素。
本实施例基于木质素基水性聚氨酯及其制备方法如下:先通入氮气5-20分钟除去反应釜内的空气,按配方重量,在多功能反应釜中依次加入去离子水、十二磺基硫酸钠和异氰酸改性木质素,在搅拌速度为1000转/分钟搅拌下进行乳化,并快速升温至90℃,恒温1小时;再将六亚甲基二异氰酸酯和四氢呋喃醚二醇加入混合反应,并升温至110℃,恒温反应1-3小时,再加入丙二醇,快速升温至120-150℃后加入二甲基酮肟,继续恒温反应1-2小时后,加入三乙醇胺,继续反应3小时后,每隔半小时测反应液的黏度,当黏度为5~30S/25℃,降温到50℃并保温;然后通入氮气20分钟,除去反应釜内的水蒸气,将反应物从反应釜中倒出,在高速分散机中进行分散乳化,减压蒸馏除去水,即得到木质素基水性聚氨酯乳液;在玻璃板涂布木质素基水性聚氨酯乳液并固化即得到木质素基水性聚氨酯薄膜。通过万能拉伸试验机测试薄膜的拉伸强度如图3所示,强度约为172MPa。
根据GB/T 23985-2009《色漆和清漆挥发性有机化合物(VOC)含量的测定差值法》对制备的醇酸树脂的VOC进行测试,结果为VOC≤229。
实施例3
本实施例提供一种木质素基水性聚氨酯及其制备方法,其原料配比如表2所示:
表2实施例3的原料配比
聚丙二醇 | 100份 |
甲苯二异氰酸酯 | 90份 |
一缩二乙二醇 | 10份 |
甲基二乙醇胺 | 15份 |
丁醛肟 | 30份 |
硫酸-2-对壬基酚氧-乙酯铵 | 5份 |
异氰酸改性木质素 | 110份 |
去离子水 | 600份 |
本实施例中异氰酸改性木质素为实施例1制备的异氰酸改性木质素。
本实施例基于木质素基水性聚氨酯及其制备方法如下:先通入氮气5-20分钟除去反应釜内的空气,按配方重量,在多功能反应釜中依次加入去离子水、硫酸-2-对壬基酚氧-乙酯铵和异氰酸改性木质素,在搅拌速度为500-1000转/分钟搅拌下进行乳化,并快速升温至80℃,恒温0.5小时;再将甲苯二异氰酸酯和聚丙二醇加入混合反应,并升温至120℃,恒温反应2小时,再加入一缩二乙二醇,快速升温至150℃后加入丁醛肟,继续恒温反应1小时后,加入甲基二乙醇胺,继续反应2小时后,每隔半小时测反应液的黏度,当黏度为5-30S/25℃,降温到50℃并保温;然后通入氮气20分钟,除去反应釜内的水蒸气,将反应物从反应釜中倒出,在高速分散机中进行分散乳化,减压蒸馏除去水,即得到木质素基水性聚氨酯乳液;在玻璃板涂布木质素基水性聚氨酯乳液并固化即得到木质素基水性聚氨酯薄膜。通过万能拉伸试验机测试薄膜的拉伸强度如图4所示,强度约为153MPa。
根据GB/T 23985-2009《色漆和清漆挥发性有机化合物(VOC)含量的测定差值法》对制备的醇酸树脂的VOC进行测试,结果为VOC≤187。
实施例4
本实施例提供一种木质素基水性聚氨酯及其制备方法,其原料配比如表3所示:
表3实施例4的原料配比
本实施例中异氰酸改性木质素为实施例1制备的异氰酸改性木质素。
本实施例基于木质素基水性聚氨酯及其制备方法如下:先通入氮气20分钟除去反应釜内的空气,按配方重量,在多功能反应釜中依次加入去离子水、2-丙烯酰胺基-甲基-丙基硫酸铵和异氰酸改性木质素,在搅拌速度为1000转/分钟搅拌下进行乳化,并快速升温至100℃,恒温1小时;再将二环己基甲烷二异氰酸酯和聚碳酸酯二醇加入混合反应,并升温至110℃,恒温反应1小时,再加入2,2-二羟甲基丙酸,快速升温至150℃后加入丁二酮肟,继续恒温反应2小时后,加入1,2-二甲基丙胺,继续反应1小时后,每隔半小时测反应液的黏度,当黏度为5-30S/25℃,降温到50~60℃并保温;然后通入氮气30分钟,除去反应釜内的水蒸气,将反应物从反应釜中倒出,在高速分散机中进行分散乳化,减压蒸馏除去水,即得到木质素基水性聚氨酯乳液;在玻璃板涂布木质素基水性聚氨酯乳液并固化即得到木质素基水性聚氨酯薄膜。通过万能拉伸试验机测试薄膜的拉伸强度如图5所示,强度约为168MPa。
根据GB/T 23985-2009《色漆和清漆挥发性有机化合物(VOC)含量的测定差值法》对制备的醇酸树脂的VOC进行测试,结果为VOC≤221。
实施例5
本实施例提供一种木质素基水性聚氨酯及其制备方法,其原料配比如表4所示:
本实施例基于木质素基水性聚氨酯及其制备方法如下:先通入氮气20分钟除去反应釜内的空气,按配方重量,在多功能反应釜中依次加入去离子水、十二磺基硫酸钠和异氰酸改性木质素,在搅拌速度为1000转/分钟搅拌下进行乳化,并快速升温至100℃,恒温1小时;再将六亚甲基二异氰酸酯和聚己二酸丁二醇酯加入混合反应,并升温至90℃,恒温反应1小时,再加入三羟甲基丙烷,快速升温至150℃后加入乙醛肟,继续恒温反应2小时后,加入1,2-丙二胺,继续反应3小时后,每隔半小时测反应液的黏度,当黏度为5-30S/25℃,降温到50℃并保温;然后通入氮气30分钟,除去反应釜内的水蒸气,将反应物从反应釜中倒出,在高速分散机中进行分散乳化,减压蒸馏除去水,即得到木质素基水性聚氨酯乳液;在玻璃板涂布木质素基水性聚氨酯乳液并固化即得到木质素基水性聚氨酯薄膜。通过万能拉伸试验机测试薄膜的拉伸强度如图6所示,强度约为134MPa。
根据GB/T 23985-2009《色漆和清漆挥发性有机化合物(VOC)含量的测定差值法》对制备的醇酸树脂的VOC进行测试,结果为VOC≤203。
表4实施例5的原料配比
聚己二酸丁二醇酯 | 120份 |
六亚甲基二异氰酸酯 | 90份 |
三羟甲基丙烷 | 20份 |
1,2-丙二胺 | 20份 |
乙醛肟 | 80份 |
十二磺基硫酸钠 | 5份 |
异氰酸改性木质素 | 120份 |
去离子水 | 800份 |
本实施例中异氰酸改性木质素为实施例1制备的异氰酸改性木质素。
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 (7)
1.一种木质素基水性聚氨酯,其特征在于,由以下重量份数的原料组成:低聚物多元醇80-120份,多元异氰酸酯70-90份,扩链剂5-20份,有机胺类化合物5-20份,肟基化合物30-80份,乳化剂1-5份,异氰酸改性木质素100-120份,去离子水300-800份,所述多元异氰酸酯为六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、多亚甲基多苯基多氰酸酯中的至少一种;
所述异氰酸改性木质素的制备步骤包括:
(1)木质素的微纳化处理:将200-300份木质素分散在500-600份的聚乙烯醇中,在80-100℃下恒温处理1-3小时,过滤除去滤液将滤渣依次经过榨油机和胶体磨进行粉碎处理后,再将滤渣分散于400-600份甲乙酮中,以400-500W的功率超声处理1-3小时,得到微纳木质素在甲乙酮中的分散液;
(2)木质素的异氰酸改性:将步骤(1)得到的微纳木质素甲乙酮分散液加入多功能反应釜中,并依次加入300-450份的多元异氰酸酯和1-3份的二月桂酸二丁基锡,然后将混合物加热至80-100℃并反应24小时,反应后混合物冷却至25℃,将200-500份的正己烷在搅拌速度为1000-2000转/分钟的搅拌下将其加入混合物中,连续搅拌0.5-1小时,最后,过滤混合物,用正己烷洗涤至少三次,并在50-80℃下干燥10-12小时,得到干燥的异氰酸改性木质素;
所述步骤(2)中的多元异氰酸酯为六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯的至少一种。
2.如权利要求1所述的木质素基水性聚氨酯,其特征在于,所述低聚物多元醇为聚四氢呋喃醚二醇、聚丙二醇、聚己二酸已二醇酯、聚碳酸酯二醇、聚己二酸丁二醇酯、聚己内酯二醇中的至少一种。
3.如权利要求1所述的木质素基水性聚氨酯,其特征在于,所述扩链剂为乙二醇、丙二醇、1,4-丁二醇,一缩二乙二醇、丙三醇、三羟甲基丙烷,1,4-环己二醇、2,2-二羟甲基丁酸、2,2-二羟甲基丙酸、油酸二乙醇酰胺中的至少一种。
4.如权利要求1所述的木质素基水性聚氨酯,其特征在于,所述有机胺类化合物为中的二乙醇胺、三乙醇胺、甲基二乙醇胺、二异丙胺、1,2-二甲基丙胺、1,2-丙二胺、1,4-丁二胺、己二胺中的至少一种。
5.如权利要求1所述的木质素基水性聚氨酯,其特征在于,所述肟基化合物为乙醛肟、二甲基酮肟、丁二酮肟、丁醛肟中的至少一种。
6.如权利要求1所述的木质素基水性聚氨酯,其特征在于,所述乳化剂为十二磺基硫酸钠、硫酸-2-对壬基酚氧-乙酯铵、2-丙烯酰胺基-甲基-丙基硫酸钠、2-丙烯酰胺基-甲基-丙基硫酸铵中的一种或多种。
7.权利要求1~6任一项所述的木质素基水性聚氨酯的制备方法,其特征在于,步骤如下:
先通入氮气5-20分钟除去反应釜内的空气,在多功能反应釜中依次加入去离子水、乳化剂和异氰酸改性木质素,在搅拌速度为500-1000转/分钟搅拌下进行乳化,并快速升温至80-100℃,恒温0.5-1小时;再将多元异氰酸酯和低聚物多元醇加入混合反应,并升温至110-120℃,恒温反应1-3小时,再加入扩链剂,快速升温至120-150℃后加入肟基化合物,继续恒温反应1-2小时后,加入有机胺类化合物,继续反应1-3小时后,每隔半小时测反应液的黏度,当黏度为5-30S/25℃,降温到50-60℃并保温;然后通入氮气20-30分钟,除去反应釜内的水蒸气,将反应物从反应釜中倒出,在高速分散机中进行分散乳化,减压蒸馏除去水,即得到木质素基水性聚氨酯乳液;在玻璃板涂布木质素基水性聚氨酯乳液并固化即得到木质素基水性聚氨酯薄膜。
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