CN105837781A - 一种高强度聚氨酯复合材料 - Google Patents

一种高强度聚氨酯复合材料 Download PDF

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CN105837781A
CN105837781A CN201610249122.3A CN201610249122A CN105837781A CN 105837781 A CN105837781 A CN 105837781A CN 201610249122 A CN201610249122 A CN 201610249122A CN 105837781 A CN105837781 A CN 105837781A
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polyurethane composite
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龚文祥
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Chuzhou Huanqiu Polyurethane Technology Co Ltd
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Abstract

本发明公开了一种高强度聚氨酯复合材料，其原料包括：端羟基聚丁二烯、聚四氢呋喃醚二醇、甲苯二异氰酸酯、4,4′–二苯基甲烷二异氰酸酯、1,4–丁二醇、二溴新戊二醇、二月桂酸二丁基锡、二甲硫基甲苯二胺、改性复合填料；改性复合填料按照以下工艺进行制备：将硅烷偶联剂TM551和苯胺甲基三乙氧基硅烷加入甲苯中搅拌均匀，加入炭黑、中超耐磨炉黑、多壁碳纳米管、硫酸钡、纳米二氧化钛，超声分散后在室温下搅拌反应得到。本发明提出的高强度聚氨酯复合材料，其强度高，耐热性好，能满足多种领域的使用要求。

Description

一种高强度聚氨酯复合材料
技术领域
本发明涉及聚氨酯技术领域，尤其涉及一种高强度聚氨酯复合材料。
背景技术
聚氨酯是主链上含有重复氨基甲酸酯基团的大分子化合物的统称，具有优异的耐磨、耐油、耐撕裂、耐化学腐蚀等特性，其用途非常广，可以代替橡胶、塑料、尼龙等，用于机场、酒店、建材、汽车厂、煤矿厂、水泥厂、高级公寓、别墅、园林美化、彩石艺术、公园等领域。但普通的聚氨酯材料其强度不是很高，且在使用的过程中，容易出现泛黄、变硬、力学性能迅速降低的缺陷，大大限制了聚氨酯材料在实际中的应用。
发明内容
基于背景技术存在的技术问题，本发明提出了一种高强度聚氨酯复合材料，其强度高，耐热性和耐候性好，能满足多种领域的使用要求。
本发明提出的一种高强度聚氨酯复合材料，其原料按重量份包括：端羟基聚丁二烯30-50份、聚四氢呋喃醚二醇10-25份、甲苯二异氰酸酯20-35份、4,4′–二苯基甲烷二异氰酸酯10-25份、1,4–丁二醇2-5份、二溴新戊二醇1-5份、二月桂酸二丁基锡0.01-0.1份、二甲硫基甲苯二胺1-3.5份、改性复合填料10-25份；
其中，所述改性复合填料按照以下工艺进行制备：按重量份将2-5份硅烷偶联剂TM551和2-10份苯胺甲基三乙氧基硅烷加入30-50份甲苯中搅拌均匀，然后加入5-15份炭黑、3-12份中超耐磨炉黑、2-12份多壁碳纳米管、3-12份硫酸钡、1-5份纳米二氧化钛，超声分散2-5min后在室温下搅拌反应10-20h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
优选地，其原料中，端羟基聚丁二烯、聚四氢呋喃醚二醇、甲苯二异氰酸酯、4,4′–二苯基甲烷二异氰酸酯的重量比为34-45：13-22：25-33：13-21。
优选地，其原料按重量份包括：端羟基聚丁二烯39-42份、聚四氢呋喃醚二醇17-20份、甲苯二异氰酸酯28-32份、4,4′–二苯基甲烷二异氰酸酯16-20份、1,4–丁二醇3.2-4份、二溴新戊二醇3-3.8份、二月桂酸二丁基锡0.03-0.07份、二甲硫基甲苯二胺2.1-2.6份、改性复合填料18-22份。
优选地，其原料按重量份包括：端羟基聚丁二烯40份、聚四氢呋喃醚二醇18份、甲苯二异氰酸酯30份、4,4′–二苯基甲烷二异氰酸酯17.5份、1,4–丁二醇3.7份、二溴新戊二醇3.3份、二月桂酸二丁基锡0.055份、二甲硫基甲苯二胺2.4份、改性复合填料19份。
优选地，改性复合填料按照以下工艺进行制备：按重量份将3.2-4份硅烷偶联剂TM551和5.5-7份苯胺甲基三乙氧基硅烷加入38-43份甲苯中搅拌均匀，然后加入7-10份炭黑、7-11份中超耐磨炉黑、5.5-7份多壁碳纳米管、6-8.5份硫酸钡、3.2-4份纳米二氧化钛，超声分散3-5min后在室温下搅拌反应15-18h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
优选地，改性复合填料按照以下工艺进行制备：按重量份将3.8份硅烷偶联剂TM551和6份苯胺甲基三乙氧基硅烷加入40份甲苯中搅拌均匀，然后加入8.5份炭黑、10份中超耐磨炉黑、6.3份多壁碳纳米管、7.2份硫酸钡、3.6份纳米二氧化钛，超声分散4min后在室温下搅拌反应16.3h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
优选地，所述炭黑为炭黑N220、炭黑N330、炭黑N990、炭黑N550中的一种或者多种的混合物。
优选地，所述纳米二氧化钛的平均粒径为30-50nm，比表面积为85-120m2/g。
本发明所述高强度聚氨酯复合材料可以按照常规的聚氨酯制备工艺制备而成。
本发明中，以端羟基聚丁二烯、聚四氢呋喃醚二醇、甲苯二异氰酸酯、4,4′–二苯基甲烷二异氰酸酯为聚氨酯单体，得到的聚氨酯具有卓越的机械强度，同时具有优异的耐热性和耐水性，以二溴新戊二醇与1,4–丁二醇和二甲硫基甲苯二胺为扩链剂，扩链速度快，得到的复合材料具有优异的阻燃性和耐热性；在改性复合填料的制备过程中，以硅烷偶联剂TM551和苯胺甲基三乙氧基硅烷为改性剂，以炭黑、中超耐磨炉黑、多壁碳纳米管、硫酸钡、纳米二氧化钛为无机填料，通过控制反应的条件，使改性剂水解的羟基与无机填料表面的活性基团发生了反应，从而在无机填料的表面引入了大量的氨基和苯环得到了改性复合填料，将复合填料加入体系中，在体系中，分散均匀，一方面，因在其表面引入了大量的氨基，其能与体系中的异氰酸根反应生成脲键，从而在体系中形成新的交联点，显著提高了复合材料的力学性能，另一方面，因在体系中引入了苯环结构，进一步提高了复合材料的强度、耐热性和耐老化性。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种高强度聚氨酯复合材料，其原料按重量份包括：端羟基聚丁二烯30份、聚四氢呋喃醚二醇25份、甲苯二异氰酸酯20份、4,4′–二苯基甲烷二异氰酸酯25份、1,4–丁二醇2份、二溴新戊二醇5份、二月桂酸二丁基锡0.01份、二甲硫基甲苯二胺3.5份、改性复合填料10份；
其中，改性复合填料按照以下工艺进行制备：按重量份将2份硅烷偶联剂TM551和10份苯胺甲基三乙氧基硅烷加入30份甲苯中搅拌均匀，然后加入15份炭黑、3份中超耐磨炉黑、12份多壁碳纳米管、12份硫酸钡、1份纳米二氧化钛，超声分散5min后在室温下搅拌反应10h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
实施例2
本发明提出的一种高强度聚氨酯复合材料，其原料按重量份包括：端羟基聚丁二烯50份、聚四氢呋喃醚二醇10份、甲苯二异氰酸酯35份、4,4′–二苯基甲烷二异氰酸酯10份、1,4–丁二醇5份、二溴新戊二醇1份、二月桂酸二丁基锡0.1份、二甲硫基甲苯二胺1份、改性复合填料25份；
其中，改性复合填料按照以下工艺进行制备：按重量份将5份硅烷偶联剂TM551和2份苯胺甲基三乙氧基硅烷加入50份甲苯中搅拌均匀，然后加入5份炭黑、12份中超耐磨炉黑、2份多壁碳纳米管、3份硫酸钡、5份纳米二氧化钛，超声分散2min后在室温下搅拌反应20h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
实施例3
本发明提出的一种高强度聚氨酯复合材料，其原料按重量份包括：端羟基聚丁二烯39份、聚四氢呋喃醚二醇20份、甲苯二异氰酸酯28份、4,4′–二苯基甲烷二异氰酸酯20份、1,4–丁二醇3.2份、二溴新戊二醇3.8份、二月桂酸二丁基锡0.03份、二甲硫基甲苯二胺2.6份、改性复合填料18份；
其中，改性复合填料按照以下工艺进行制备：按重量份将3.2份硅烷偶联剂TM551和7份苯胺甲基三乙氧基硅烷加入38份甲苯中搅拌均匀，然后加入3份炭黑N990、7份炭黑N550、7份中超耐磨炉黑、7份多壁碳纳米管、6份硫酸钡、4份纳米二氧化钛，超声分散3min后在室温下搅拌反应18h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料；所述纳米二氧化钛的平均粒径为50nm，比表面积为120m2/g。
实施例4
本发明提出的一种高强度聚氨酯复合材料，其原料按重量份包括：端羟基聚丁二烯42份、聚四氢呋喃醚二醇17份、甲苯二异氰酸酯32份、4,4′–二苯基甲烷二异氰酸酯16份、1,4–丁二醇4份、二溴新戊二醇3份、二月桂酸二丁基锡0.07份、二甲硫基甲苯二胺2.1份、改性复合填料22份；
其中，改性复合填料按照以下工艺进行制备：按重量份将4份硅烷偶联剂TM551和5.5份苯胺甲基三乙氧基硅烷加入43份甲苯中搅拌均匀，然后加入2份炭黑N330、3份炭黑N990、2份炭黑N550、11份中超耐磨炉黑、5.5份多壁碳纳米管、8.5份硫酸钡、3.2份纳米二氧化钛，超声分散5min后在室温下搅拌反应15h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料；所述纳米二氧化钛的平均粒径为30nm，比表面积为85m2/g。
实施例5
本发明提出的一种高强度聚氨酯复合材料，其原料按重量份包括：端羟基聚丁二烯40份、聚四氢呋喃醚二醇18份、甲苯二异氰酸酯30份、4,4′–二苯基甲烷二异氰酸酯17.5份、1,4–丁二醇3.7份、二溴新戊二醇3.3份、二月桂酸二丁基锡0.055份、二甲硫基甲苯二胺2.4份、改性复合填料19份；
其中，改性复合填料按照以下工艺进行制备：按重量份将3.8份硅烷偶联剂TM551和6份苯胺甲基三乙氧基硅烷加入40份甲苯中搅拌均匀，然后加入8.5份炭黑N220、10份中超耐磨炉黑、6.3份多壁碳纳米管、7.2份硫酸钡、3.6份纳米二氧化钛，超声分散4min后在室温下搅拌反应16.3h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料；所述纳米二氧化钛的平均粒径为45nm，比表面积为100m2/g。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (8)

1.一种高强度聚氨酯复合材料，其特征在于，其原料按重量份包括：端羟基聚丁二烯30-50份、聚四氢呋喃醚二醇10-25份、甲苯二异氰酸酯20-35份、4,4′–二苯基甲烷二异氰酸酯10-25份、1,4–丁二醇2-5份、二溴新戊二醇1-5份、二月桂酸二丁基锡0.01-0.1份、二甲硫基甲苯二胺1-3.5份、改性复合填料10-25份；
其中，所述改性复合填料按照以下工艺进行制备：按重量份将2-5份硅烷偶联剂TM551和2-10份苯胺甲基三乙氧基硅烷加入30-50份甲苯中搅拌均匀，然后加入5-15份炭黑、3-12份中超耐磨炉黑、2-12份多壁碳纳米管、3-12份硫酸钡、1-5份纳米二氧化钛，超声分散2-5min后在室温下搅拌反应10-20h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
2.根据权利要求1所述高强度聚氨酯复合材料，其特征在于，其原料中，端羟基聚丁二烯、聚四氢呋喃醚二醇、甲苯二异氰酸酯、4,4′–二苯基甲烷二异氰酸酯的重量比为34-45：13-22：25-33：13-21。
3.根据权利要求1或2所述高强度聚氨酯复合材料，其特征在于，其原料按重量份包括：端羟基聚丁二烯39-42份、聚四氢呋喃醚二醇17-20份、甲苯二异氰酸酯28-32份、4,4′–二苯基甲烷二异氰酸酯16-20份、1,4–丁二醇3.2-4份、二溴新戊二醇3-3.8份、二月桂酸二丁基锡0.03-0.07份、二甲硫基甲苯二胺2.1-2.6份、改性复合填料18-22份。
4.根据权利要求1-3中任一项所述高强度聚氨酯复合材料，其特征在于，其原料按重量份包括：端羟基聚丁二烯40份、聚四氢呋喃醚二醇18份、甲苯二异氰酸酯30份、4,4′–二苯基甲烷二异氰酸酯17.5份、1,4–丁二醇3.7份、二溴新戊二醇3.3份、二月桂酸二丁基锡0.055份、二甲硫基甲苯二胺2.4份、改性复合填料19份。
5.根据权利要求1-4中任一项所述高强度聚氨酯复合材料，其特征在于，所述改性复合填料按照以下工艺进行制备：按重量份将3.2-4份硅烷偶联剂TM551和5.5-7份苯胺甲基三乙氧基硅烷加入38-43份甲苯中搅拌均匀，然后加入7-10份炭黑、7-11份中超耐磨炉黑、5.5-7份多壁碳纳米管、6-8.5份硫酸钡、3.2-4份纳米二氧化钛，超声分散3-5min后在室温下搅拌反应15-18h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
6.根据权利要求1-5中任一项所述高强度聚氨酯复合材料，其特征在于，改性复合填料按照以下工艺进行制备：按重量份将3.8份硅烷偶联剂TM551和6份苯胺甲基三乙氧基硅烷加入40份甲苯中搅拌均匀，然后加入8.5份炭黑、10份中超耐磨炉黑、6.3份多壁碳纳米管、7.2份硫酸钡、3.6份纳米二氧化钛，超声分散4min后在室温下搅拌反应16.3h，反应结束后经离心、洗涤、干燥、研磨得到所述改性复合填料。
7.根据权利要求1-6中任一项所述高强度聚氨酯复合材料，其特征在于，所述炭黑为炭黑N220、炭黑N330、炭黑N990、炭黑N550中的一种或者多种的混合物。
8.根据权利要求1-7中任一项所述高强度聚氨酯复合材料，其特征在于，所述纳米二氧化钛的平均粒径为30-50nm，比表面积为85-120m2/g。
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Application publication date: 20160810