CN113444483A - 一种阻燃聚氨酯胶粘剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种阻燃聚氨酯胶粘剂及其制备方法,涉及聚氨酯胶粘剂技术领域,其制备包括以下步骤:将低聚八氨基苯基硅倍半氧烷加入到乙醇溶液中,升温,加入氨基磺酸,搅拌反应,然后加入氰尿酸,搅拌反应,抽滤,洗涤,干燥,制得阻燃剂;将聚己二酸一缩二乙二醇酯二醇加入到反应容器中,然后加入二异氰酸酯和催化剂,升温反应,加入阻燃剂,保温反应,再加入1,4‑丁二醇和乙酸乙酯,保温反应,降温,加入三乙胺中和,得聚氨酯预聚体;向聚氨酯预聚体中加入水进行高速分散乳化,然后减压蒸馏除去乙酸乙酯,即得。本发明在聚氨酯预聚体制备过程中加入阻燃剂,其参与反应接枝到聚氨酯预聚体上,制得的胶粘剂具有良好的力学性能和阻燃性能。
Description
技术领域
本发明涉及聚氨酯胶粘剂技术领域,尤其涉及一种阻燃聚氨酯胶粘剂及其制备方法。
背景技术
聚氨酯(PU)胶粘剂是指在分子链中含有氨基甲酸酯基团(-NHCOO-)或异氰酸酯基(-NCO)的胶粘剂,可分为多异氰酸酯和聚氨酯两大类。由于聚氨酯胶粘剂含有这两个基团显示出较高的活性与极性,所以其应用于许多种基材,如泡沫、塑料、木材、皮革、织物、纸张、陶瓷等多孔材料,以及金属、玻璃、橡胶、塑料等表面光洁的材料,对它们具有优良的粘结力。聚氨酯与被粘合材料之间产生的氢键作用会使分子内聚力增强,从而使粘接更加牢固。聚氨酯胶粘剂的多样性为许多粘接难题都准备了解决的方法,且特别适用于其他类型胶粘剂不能粘接或粘接有困难的地方。此外,聚氨酯胶粘剂还具有良好的韧性、可调节性、粘合工艺简便、极佳的耐低温性能以及优良的稳定性等特性。正是由于聚氨酯胶粘剂这种优良的粘接性能和对多种基材的粘接适应性,使其应用领域不断扩大,在国内外成为发展最快的胶粘剂。
然而,未经阻燃处理的聚氨酯是可燃物,遇火会燃烧并产生大量有毒雾,因此为使聚氨酯胶粘剂在更广的范围内得到应用,需研制阻燃性能优异的聚氨酯胶粘剂。
发明内容
基于背景技术存在的技术问题,本发明提出了一种阻燃聚氨酯胶粘剂及其制备方法,其具有良好的力学性能和阻燃性能。
本发明提出的一种阻燃聚氨酯胶粘剂的制备方法,包括以下步骤:
S1、将低聚八氨基苯基硅倍半氧烷加入到乙醇溶液中,升温至65-70℃,加入氨基磺酸,搅拌反应2-3h,然后加入氰尿酸,搅拌反应2-3h,停止搅拌,冷却至室温抽滤,洗涤,干燥,制得阻燃剂;
S2、将经脱水处理后的聚己二酸一缩二乙二醇酯二醇加入到反应容器中,然后加入二异氰酸酯和催化剂,升温至70-80℃反应30-40min,然后加入阻燃剂,保温反应30-40min,再加入1,4-丁二醇和乙酸乙酯,保温反应60-90min,然后降温至40-45℃,加入三乙胺中和,反应2-3h,得聚氨酯预聚体;
S3、向聚氨酯预聚体中加入水进行高速分散乳化,然后减压蒸馏除去乙酸乙酯,即得。
优选地,S1中,低聚八氨基苯基硅倍半氧烷、氨基磺酸、氰尿酸的重量比为100:9-13:11-16。
优选地,S2中,聚己二酸一缩二乙二醇酯二醇的数均分子量为3000。
优选地,S2中,二异氰酸酯是由甲苯二异氰酸酯和六亚甲基二异氰酸酯按照3-5:5-7的重量百分比组成的。
优选地,S2中,聚己二酸一缩二乙二醇酯二醇、二异氰酸酯、阻燃剂、1,4-丁二醇的重量比为10:20-40:2-7:0.5-2。
优选地,S2中,加入乙酸乙酯调节体系的固含量为37-42%。
优选地,S3中,还包括在加水的同时加入增塑剂进行高速分散乳化。
优选地,S3中,高速分散乳化是采用5000-10000r/min转速搅拌30-60min。
本发明还提出了一种采用上述方法制备的阻燃聚氨酯胶粘剂。
有益效果:本发明以聚己二酸一缩二乙二醇酯二醇、二异氰酸酯、1,4-丁二醇为主要原料合成聚氨酯预聚体,且在聚己二酸一缩二乙二醇酯二醇和二异氰酸酯反应过程中添加阻燃剂参与反应;该阻燃剂是以低聚八氨基苯基硅倍半氧烷为原料,利用氨基磺酸上的酸根与其反应,再加入氰尿酸并控制添加量得到硅倍半氧烷的氰尿酸盐,将其加入聚氨酯的合成过程中,阻燃剂上的氨基和羟基参与反应,从而接枝到聚氨酯预聚体上。本发明制得的聚氨酯胶粘剂具有良好的力学性能和阻燃性能,可用于金属、塑料、木材、橡胶、陶瓷灯材质的粘结,其力学性能和阻燃性能。
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
本发明提出的一种阻燃聚氨酯胶粘剂的制备方法,包括以下步骤:
S1、将低聚八氨基苯基硅倍半氧烷加入到乙醇溶液中,升温至65℃,加入氨基磺酸,搅拌反应2h,然后加入氰尿酸,搅拌反应3h,停止搅拌,冷却至室温抽滤,洗涤,干燥,制得阻燃剂;其中,低聚八氨基苯基硅倍半氧烷、氨基磺酸、氰尿酸的重量比为100:9:11;
S2、将经脱水处理后的聚己二酸一缩二乙二醇酯二醇(数均分子量为3000)加入到反应容器中,然后加入甲苯二异氰酸酯、六亚甲基二异氰酸酯和催化剂,升温至70℃反应30min,然后加入阻燃剂,保温反应30min,再加入1,4-丁二醇,并加入乙酸乙酯调节体系的固含量为37%,保温反应60min,然后降温至40℃,加入三乙胺中和,反应2h,得聚氨酯预聚体;其中,聚己二酸一缩二乙二醇酯二醇、甲苯二异氰酸酯、六亚甲基二异氰酸酯、阻燃剂、1,4-丁二醇的重量比为10:9:12:2:0.5;
S3、向聚氨酯预聚体中加入水和增塑剂,采用5000r/min转速搅拌30min高速分散乳化,然后减压蒸馏除去乙酸乙酯,即得。
实施例2
本发明提出的一种阻燃聚氨酯胶粘剂的制备方法,包括以下步骤:
S1、将低聚八氨基苯基硅倍半氧烷加入到乙醇溶液中,升温至65℃,加入氨基磺酸,搅拌反应3h,然后加入氰尿酸,搅拌反应3h,停止搅拌,冷却至室温抽滤,洗涤,干燥,制得阻燃剂;其中,低聚八氨基苯基硅倍半氧烷、氨基磺酸、氰尿酸的重量比为100:10:12;
S2、将经脱水处理后的聚己二酸一缩二乙二醇酯二醇(数均分子量为3000)加入到反应容器中,然后加入甲苯二异氰酸酯、六亚甲基二异氰酸酯和催化剂,升温至70℃反应35min,然后加入阻燃剂,保温反应35min,再加入1,4-丁二醇,并加入乙酸乙酯调节体系的固含量为38%,保温反应70min,然后降温至40℃,加入三乙胺中和,反应2.5h,得聚氨酯预聚体;其中,聚己二酸一缩二乙二醇酯二醇、甲苯二异氰酸酯、六亚甲基二异氰酸酯、阻燃剂、1,4-丁二醇的重量比为10:14:14:4:1;
S3、向聚氨酯预聚体中加入水和增塑剂,采用7000r/min转速搅拌40min高速分散乳化,然后减压蒸馏除去乙酸乙酯,即得。
实施例3
本发明提出的一种阻燃聚氨酯胶粘剂的制备方法,包括以下步骤:
S1、将低聚八氨基苯基硅倍半氧烷加入到乙醇溶液中,升温至70℃,加入氨基磺酸,搅拌反应2.5h,然后加入氰尿酸,搅拌反应2.5h,停止搅拌,冷却至室温抽滤,洗涤,干燥,制得阻燃剂;其中,低聚八氨基苯基硅倍半氧烷、氨基磺酸、氰尿酸的重量比为100:11.5:15;
S2、将经脱水处理后的聚己二酸一缩二乙二醇酯二醇(数均分子量为3000)加入到反应容器中,然后加入甲苯二异氰酸酯、六亚甲基二异氰酸酯和催化剂,升温至75℃反应35min,然后加入阻燃剂,保温反应40min,再加入1,4-丁二醇,并加入乙酸乙酯调节体系的固含量为40%,保温反应80min,然后降温至45℃,加入三乙胺中和,反应2.5h,得聚氨酯预聚体;其中,聚己二酸一缩二乙二醇酯二醇、甲苯二异氰酸酯、六亚甲基二异氰酸酯、阻燃剂、1,4-丁二醇的重量比为10:14:21:6:1.5;
S3、向聚氨酯预聚体中加入水和增塑剂,采用8000r/min转速搅拌50min高速分散乳化,然后减压蒸馏除去乙酸乙酯,即得。
实施例4
本发明提出的一种阻燃聚氨酯胶粘剂的制备方法,包括以下步骤:
S1、将低聚八氨基苯基硅倍半氧烷加入到乙醇溶液中,升温至70℃,加入氨基磺酸,搅拌反应3h,然后加入氰尿酸,搅拌反应2h,停止搅拌,冷却至室温抽滤,洗涤,干燥,制得阻燃剂;其中,低聚八氨基苯基硅倍半氧烷、氨基磺酸、氰尿酸的重量比为100:13:16;
S2、将经脱水处理后的聚己二酸一缩二乙二醇酯二醇(数均分子量为3000)加入到反应容器中,然后加入甲苯二异氰酸酯、六亚甲基二异氰酸酯和催化剂,升温至80℃反应40min,然后加入阻燃剂,保温反应40min,再加入1,4-丁二醇,并加入乙酸乙酯调节体系的固含量为42%,保温反应90min,然后降温至45℃,加入三乙胺中和,反应3h,得聚氨酯预聚体;其中,聚己二酸一缩二乙二醇酯二醇、甲苯二异氰酸酯、六亚甲基二异氰酸酯、阻燃剂、1,4-丁二醇的重量比为10:20:20:7:2;
S3、向聚氨酯预聚体中加入水和增塑剂,采用10000r/min转速搅拌60min高速分散乳化,然后减压蒸馏除去乙酸乙酯,即得。
对比例
与实施例1相比,区别仅在于不含有S1步骤,S2中所采用的阻燃剂为低聚八氨基苯基硅倍半氧烷。
对本发明实施例1-4和对比例制备的阻燃聚氨酯交联剂的性能进行检测,结果如表1所示。
1.拉伸强度:根据GB/T 528-1998的方法进行测试;
2.伸长率:根据GB 528-82的方法进行测试;
3.剪切强度:根据GB/T 7124-2008的方法进行测试,将ABS板材制成12.5mm×25.0mm,胶层为0.2mm,拉力机的剪切力速率为9.2MPa/min;
4.氧指数:根据GB/T2406-93的方法,采用氧指数测定仪进行垂直燃烧测试。
表1性能测试结果
实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例 | |
拉伸强度/MPa | 38.8 | 39.3 | 40.5 | 40.6 | 35.1 |
伸长率/% | 640 | 686 | 720 | 651 | 584 |
剪切强度/MPa | 2.41 | 2.95 | 3.05 | 2.83 | 2.04 |
氧指数/% | 30.7 | 31.6 | 31.5 | 30.9 | 29.2 |
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 (9)
1.一种阻燃聚氨酯胶粘剂的制备方法,其特征在于,包括以下步骤:
S1、将低聚八氨基苯基硅倍半氧烷加入到乙醇溶液中,升温至65-70℃,加入氨基磺酸,搅拌反应2-3h,然后加入氰尿酸,搅拌反应2-3h,停止搅拌,冷却至室温抽滤,洗涤,干燥,制得阻燃剂;
S2、将经脱水处理后的聚己二酸一缩二乙二醇酯二醇加入到反应容器中,然后加入二异氰酸酯和催化剂,升温至70-80℃反应30-40min,然后加入阻燃剂,保温反应30-40min,再加入1,4-丁二醇和乙酸乙酯,保温反应60-90min,然后降温至40-45℃,加入三乙胺中和,反应2-3h,得聚氨酯预聚体;
S3、向聚氨酯预聚体中加入水进行高速分散乳化,然后减压蒸馏除去乙酸乙酯,即得。
2.根据权利要求1所述的阻燃聚氨酯胶粘剂的制备方法,其特征在于,S1中,低聚八氨基苯基硅倍半氧烷、氨基磺酸、氰尿酸的重量比为100:9-13:11-16。
3.根据权利要求1所述的阻燃聚氨酯胶粘剂的制备方法,其特征在于,S2中,聚己二酸一缩二乙二醇酯二醇的数均分子量为3000。
4.根据权利要求1所述的阻燃聚氨酯胶粘剂的制备方法,其特征在于,S2中,二异氰酸酯是由甲苯二异氰酸酯和六亚甲基二异氰酸酯按照3-5:5-7的重量百分比组成的。
5.根据权利要求1所述的阻燃聚氨酯胶粘剂的制备方法,其特征在于,S2中,聚己二酸一缩二乙二醇酯二醇、二异氰酸酯、阻燃剂、1,4-丁二醇的重量比为10:20-40:2-7:0.5-2。
6.根据权利要求1所述的阻燃聚氨酯胶粘剂的制备方法,其特征在于,S2中,加入乙酸乙酯调节体系的固含量为37-42%。
7.根据权利要求1所述的阻燃聚氨酯胶粘剂的制备方法,其特征在于,S3中,还包括在加水的同时加入增塑剂进行高速分散乳化。
8.根据权利要求1或7所述的阻燃聚氨酯胶粘剂的制备方法,其特征在于,S3中,高速分散乳化是采用5000-10000r/min转速搅拌30-60min。
9.一种基于权利要求1-8任一项所述方法制备的阻燃聚氨酯胶粘剂。
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