CN106433547A - 一种改性聚氨酯胶黏剂及其制备方法 - Google Patents

一种改性聚氨酯胶黏剂及其制备方法 Download PDF

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CN106433547A
CN106433547A CN201610865678.5A CN201610865678A CN106433547A CN 106433547 A CN106433547 A CN 106433547A CN 201610865678 A CN201610865678 A CN 201610865678A CN 106433547 A CN106433547 A CN 106433547A
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mdi
carbodiimides
uretonimine
methyl diphenylene
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顾飚
董卫龙
巢雄飞
夏洋
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Changzhou Shunxiang New Material Technology Co Ltd
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Abstract

一种改性聚氨酯胶黏剂及其制备方法，所述聚氨酯胶黏剂各组成及质量百分比为：60％～85％低聚物多元醇、8％～30％二异氰酸酯化合物、3％～7％双羟基硅氧烷、0.6％～3％功能性助剂，其中所述聚氨酯胶黏剂中异氰酸酯基含量4％～8％。本发明制备的聚氨酯胶黏剂不含TDI、重金属催化剂、增塑剂等有毒物质，用本发明方法制备的聚氨酯塑胶跑道具有较高的拉伸强度、断裂伸长率、回弹性和耐久性。

Description

一种改性聚氨酯胶黏剂及其制备方法
技术领域
本发明涉及一种聚氨酯胶黏剂及其制备方法，特别涉及一种环保塑胶跑道用侧链硅氧烷改性聚氨酯粘结剂及其制备方法。
技术背景
聚氨酯塑胶跑道具有弹性好、耐磨、防滑、耐候性好、易施工等优点，已广泛应用于体育运动场地建设。目前随着环保意识的增强，对运动场地尤其是对聚氨酯塑胶跑道的环保要求日益严格。
传统的塑胶跑道产品都是TDI型的，由于TDI的蒸气压较高(20℃约1.33Pa)，对人的呼吸系统有严重的刺激性，在塑胶跑道浆料的生产和施工过程中对人的健康造成了极大的危害。而且在塑胶跑道使用过程中会慢慢释放出有害气体影响人的身体健康。IST(国际运动跑道技术协会)早在1994年针对“是用聚氨酯树脂铺设运动跑道”的问题提出“不接受使用含单体TDI成分的聚氨酯系统的运动跑道”的建议。而MDI的蒸气压低(25℃约1.33×10-3a)，对人的健康危害小。以MDI为基础的塑胶跑道符合环保要求。
近几年，国内学校“毒跑道”事件频发，严重危害学生的身体健康，为此，国家和各省市已相续出台更严格的聚氨酯塑胶跑道的环保标准。因此，开发新型环保、综合性能好、具有较好耐久性的聚氨酯塑胶跑道已成为目前聚氨酯塑胶跑道迫切需要解决的问题。
有鉴于上述的缺陷，本设计人，积极加以研究创新，以期创设一种改性聚氨酯胶黏剂及其制备方法，使其更具有产业上的利用价值。
发明内容
为解决上述技术问题，本发明的目的是为了解决现有技术的不足提供一种环保、机械性能优异的聚氨酯胶黏剂。
本发明的技术方案如下：
一种改性聚氨酯胶黏剂，其特征在于，所述聚氨酯胶黏剂各组成及质量百分比为：
其中所述聚氨酯胶黏剂中异氰酸酯基含量为4％～8％。
进一步的，包括以下步骤：
S1：双羟基硅氧烷的合成，冰浴下将氨基硅氧烷和阻聚剂加入带有温度显示的烧瓶中，在烧瓶中缓慢滴加含羟基丙烯酸酯单体，滴加完后控制在一定温度下反应，再加入过量氨基硅氧烷继续反应；反应结束后用正己烷除去未反应的氨基硅氧烷，并在真空环境下干燥，得到淡黄色的双羟基硅氧烷液体；
S2：在二异氰酸酯化合物中，滴加双羟基硅氧烷，滴加完毕后在50℃下反应1-2小时，然后逐渐升温至80℃，加入低聚物多元醇反应4-5小时，生成预聚体；
S3：用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到室温，加入功能性助剂制得侧链硅氧烷改性聚氨酯粘结剂。
进一步的，所述步骤S1中滴加完后反应温度控制为40℃，反应时间为6小时。
进一步的，所述步骤S1中含所述羟基丙烯酸酯单体与氨基硅氧烷的配比为2～2.5。
进一步的，所述步骤S1中所述氨基硅氧烷为3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、3-氨丙基甲基二乙氧基硅烷和3-氨丙基甲基二甲氧基硅烷中的一种或多种。
进一步的，所述步骤S1中所述含羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯中的一种或多种。
进一步的，所述步骤S1中所述阻聚剂为对羟基苯甲酚、对甲氧基苯酚、叔丁基邻苯二酚和2,6—二叔丁基—4—甲基苯酚中的一种或多种，其用量为含羟基丙烯酸酯单体质量的0.05％-0.2％。
进一步的，所述步骤S2中所述低聚物多元醇为聚醚二元醇、聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇和α,ω-二羟基聚二甲基硅氧烷之一种或几种，其分子量范围为400-10000。
进一步的，所述步骤S2中所述二异氰酸酯化合物为二苯基甲烷二异氰酸酯、碳化二亚胺-脲酮亚胺改性MDI、MDI-50、异佛尔酮二异氰酸酯、甲基环己基二异氰酸酯、2,2,4-三甲基己二异氰酸酯中的一种或几种。
进一步的，所述步骤S3中所述功能性助剂为催化剂和除水剂；所述催化剂为二丁基锡二月桂酸酯或辛酸亚锡，其用量为所述二异氰酸酯与低聚物多元醇质量之和的0.05％～0.2％；所述除水剂为甲基苯磺酰异氰酸酯或原甲酸三乙酯，其用量为所述二异氰酸酯与低聚物多元醇质量之和的1％～3％。
借由上述方案，本发明至少具有以下优点：
(1)本发明先合成双羟基封端的硅氧烷；将其与异氰酸酯化合物、聚醚多元醇混合、预聚制得异氰酸酯基封端侧链硅氧烷改性的聚氨酯粘接剂；侧链硅氧烷可以通过自身水解-缩合反应产生交联网络结构，因此，侧链硅氧烷的引入可以有效降低异氰酸酯基的含量，有效提高聚氨酯粘结剂的拉伸强度、断裂伸长率及与橡胶粒子、ETPU弹性聚氨酯发泡粒子的粘结强度，显著提高了塑胶跑道的力学性能和耐久性。
(2)本发明制备的聚氨酯胶黏剂不含TDI、重金属催化剂、增塑剂等有毒物质，用本发明方法制备的聚氨酯塑胶跑道具有较高的拉伸强度、断裂伸长率、回弹性和耐久性。
具体实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1
S1：双羟基硅氧烷的合成，冰浴下将17.4克3-氨丙基三乙氧基硅烷(APTES)和0.07克2,6—二叔丁基—4—甲基苯酚加入装有温度计的250℃的四口烧瓶中，在烧瓶中缓慢滴加18.27克的丙烯酸羟乙酯(HEA)，将该反应移入40℃的油浴中搅拌，反应6h。加入2.3克的3-氨丙基三乙氧基硅烷(APTES)，继续反应20min。将用正己烷除去未反应的3-氨丙基三乙氧基硅烷(APTES)等，得到的30克两端带羟基的侧链硅氧烷在真空环境下干燥，得到淡黄色的液体。
S2：在114克二苯基甲烷二异氰酸酯化合物(MDI 100LL)中，滴加30g双羟基硅氧烷，滴加完毕后在50℃下反应1-2小时，然后逐渐升温至80℃，加入850聚醚二元醇反应4-5小时，生成预聚体；
S3：用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到室温，加入1.6克催化剂(二丁基锡二月桂酸酯)及4.4克除水剂(对甲基苯磺酰异氰酸酯)混合均匀，制得侧链硅氧烷改性聚氨酯粘结剂。
实施例2
S1：双羟基硅氧烷的合成，冰浴下将40.5克3-氨丙基三乙氧基硅烷(APTES)和0.16克2,6—二叔丁基—4—甲基苯酚加入装有温度计的250℃的四口烧瓶中，在烧瓶中缓慢滴加42.6克的丙烯酸羟乙酯(HEA)，将该反应移入40℃的油浴中搅拌，反应6h。加入5.4克的3-氨丙基三乙氧基硅烷(APTES)，继续反应20min。将用正己烷除去未反应的3-氨丙基三乙氧基硅烷(APTES)等，得到的70克两端带羟基的侧链硅氧烷在真空环境下干燥，得到淡黄色的液体。
S2：在300克二苯基甲烷二异氰酸酯化合物(MDI 100LL)中，滴加70g双羟基硅氧烷，滴加完毕后在50℃下反应1-2小时，然后逐渐升温至80℃，加入500聚醚二元醇反应4-5小时，生成预聚体；
S3：用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到室温，加入8克催化剂(二丁基锡二月桂酸酯)及22克除水剂(对甲基苯磺酰异氰酸酯)混合均匀，制得侧链硅氧烷改性聚氨酯粘结剂。
实施例3
S1：双羟基硅氧烷的合成，冰浴下将23.1克3-氨丙基三乙氧基硅烷(APTES)和0.16克2,6—二叔丁基—4—甲基苯酚加入装有温度计的250℃的四口烧瓶中，在烧瓶中缓慢滴加42.6克的丙烯酸羟乙酯(HEA)，将该反应移入40℃的油浴中搅拌，反应6h。加入5.4克的3-氨丙基三乙氧基硅烷(APTES)，继续反应20min。将用正己烷除去未反应的3-氨丙基三乙氧基硅烷(APTES)等，得到的40克两端带羟基的侧链硅氧烷在真空环境下干燥，得到淡黄色的液体。
S2：在160克二苯基甲烷二异氰酸酯化合物(MDI 100LL)中，滴加40g双羟基硅氧烷，滴加完毕后在50℃下反应1-2小时，然后逐渐升温至80℃，加入780聚醚二元醇反应4-5小时，生成预聚体；
S3：用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到室温，加入5.3克催化剂(二丁基锡二月桂酸酯)及14.7克除水剂(对甲基苯磺酰异氰酸酯)混合均匀，制得侧链硅氧烷改性聚氨酯粘结剂。
在制作塑胶跑道时，将以上聚氨酯粘接剂与聚氨酯发泡粒子按重量比32:68混合均匀，铺装，固化即可。
对比例1
聚氨酯粘结剂的制备：在107克二苯基甲烷二异氰酸酯化合物(MDI 100LL)中，加入1095克聚醚二元醇(N220)，在80℃进行反应4-5小时，用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到室温，加入1.2克催化剂(二丁基锡二月桂酸酯)及15.6克除水剂(对甲基苯磺酰异氰酸酯)混合均匀，得到聚氨酯粘结剂。
实施例与对比例制的标准样板力学性能测试指标与国标对比如下：

Claims (10)

1.一种改性聚氨酯胶黏剂，其特征在于，所述聚氨酯胶黏剂各组成及质量百分比为：
其中所述聚氨酯胶黏剂中异氰酸酯基含量为4％～8％。
2.根据权利要求1所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于，包括以下步骤：
S1：双羟基硅氧烷的合成，冰浴下将氨基硅氧烷和阻聚剂加入带有温度显示的烧瓶中，在烧瓶中缓慢滴加含羟基丙烯酸酯单体，滴加完后控制在一定温度下反应，再加入过量氨基硅氧烷继续反应；反应结束后用正己烷除去未反应的氨基硅氧烷，并在真空环境下干燥，得到淡黄色的双羟基硅氧烷液体；
S2：在二异氰酸酯化合物中，滴加双羟基硅氧烷，滴加完毕后在50℃下反应1-2小时，然后逐渐升温至80℃，加入低聚物多元醇反应4-5小时，生成预聚体；
S3：用甲苯-二正丁胺法测定生成预聚体的异氰酸酯基(NCO)含量，当接近NCO理论值时，将反应温度降低到室温，加入功能性助剂制得侧链硅氧烷改性聚氨酯粘结剂。
3.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S1中滴加完后反应温度控制为40℃，反应时间为6小时。
4.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S1中含所述羟基丙烯酸酯单体与氨基硅氧烷的配比为2～2.5。
5.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S1中所述氨基硅氧烷为3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、3-氨丙基甲基二乙氧基硅烷和3-氨丙基甲基二甲氧基硅烷中的一种或多种。
6.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S1中所述含羟基丙烯酸酯单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯中的一种或多种。
7.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S1中所述阻聚剂为对羟基苯甲酚、对甲氧基苯酚、叔丁基邻苯二酚和2,6—二叔丁基—4—甲基苯酚中的一种或多种，其用量为含羟基丙烯酸酯单体质量的0.05％-0.2％。
8.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S2中所述低聚物多元醇为聚醚二元醇、聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇和α,ω-二羟基聚二甲基硅氧烷之一种或几种，其分子量范围为400-10000。
9.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S2中所述二异氰酸酯化合物为二苯基甲烷二异氰酸酯、碳化二亚胺-脲酮亚胺改性MDI、MDI-50、异佛尔酮二异氰酸酯、甲基环己基二异氰酸酯、2,2,4-三甲基己二异氰酸酯中的一种或几种。
10.根据权利要求2所述的一种改性聚氨酯胶黏剂的制备方法，其特征在于：所述步骤S3中所述功能性助剂为催化剂和除水剂；所述催化剂为二丁基锡二月桂酸酯或辛酸亚锡，其用量为所述二异氰酸酯与低聚物多元醇质量之和的0.05％～0.2％；所述除水剂为甲基苯磺酰异氰酸酯或原甲酸三乙酯，其用量为所述二异氰酸酯与低聚物多元醇质量之和的1％～3％。
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