CN106634780A - 耐水解抑菌型聚氨酯热熔胶及其制备方法 - Google Patents

耐水解抑菌型聚氨酯热熔胶及其制备方法 Download PDF

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CN106634780A
CN106634780A CN201611256258.3A CN201611256258A CN106634780A CN 106634780 A CN106634780 A CN 106634780A CN 201611256258 A CN201611256258 A CN 201611256258A CN 106634780 A CN106634780 A CN 106634780A
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陈海良
陈淑海
高振胜
宋小娜
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Shandong Inov Polyurethane Co Ltd
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Abstract

本发明涉及一种耐水解抑菌型聚氨酯热熔胶及其制备方法，属于热塑性聚氨酯弹性体技术领域。本发明所述的耐水解抑菌型聚氨酯热熔胶，由以下重量百分含量的原料制成：聚酯多元醇80‑87.5％，二异氰酸酯9‑14.8％，扩链剂2.2‑4.2％，抗氧化剂0.2‑0.5％，抗水解剂0.2‑0.8％，复合抗菌剂0.3‑1％，催化剂0.06‑0.1％。本发明所述的耐水解抑菌型聚氨酯热熔胶，具有优异的抗水解性能和抗霉变性能，在潮湿环境中长期使用保持良好的机械性能，原料简单易得，成本低；本发明同时提供了简单易行的制备方法。

Description

耐水解抑菌型聚氨酯热熔胶及其制备方法
技术领域
本发明涉及一种耐水解抑菌型聚氨酯热熔胶及其制备方法，属于热塑性聚氨酯弹性体技术领域。
背景技术
热塑性聚氨酯热熔胶是将线型的或带有少量支链的聚合物二元醇、低相对分子质量的扩链剂与异氰酸酯反应，生成链状的高分子化合物氨基甲酸酯。聚氨酯热熔胶常温为固态，使用时加热至一定温度可熔化，可涂布于基材表面或制成薄膜、片材或胶条等多种形状，经冷却而固化。热塑性聚氨酯热熔胶受热一定温度后变成粘稠状液体，冷却后又恢复原来的物性，因而利用此种特性可以反复加热-冷却固化，此种热熔胶具有粘接强度较高，耐低温、耐磨等优点。且加工方式灵活，综合性能优良，可与多种辅料混合加工，成品粘接工艺简便，浪费少，不含有机溶剂，属于环境友好材料，而且所生产的产品能够被回收或二次利用。
聚氨酯热熔胶已在鞋材、服装、包装印刷等领域得到了广泛的关注和应用，但是目前市场上的聚氨酯热熔胶在使用过程中容易受水汽的侵蚀而发生性能降解；另外，现有聚氨酯热熔胶在日常使用过程中会受到环境中微生物的侵蚀，导致物质变质、发霉，从而影响聚氨酯热熔胶制品表面洁净，严重时还会导致材料性能降解而无法使用。
发明内容
本发明的目的是提供一种耐水解抑菌型聚氨酯热熔胶，其具有优异的抗水解性能和抗霉变性能，在潮湿环境中长期使用保持良好的机械性能，原料简单易得，成本低；本发明同时提供了简单易行的制备方法。
本发明所述的耐水解抑菌型聚氨酯热熔胶，由以下重量百分含量的原料制成：
所述聚酯多元醇为羟值为18-38.4mg KOH/g，酸值为0.1-0.7mg KOH/g的脂肪族聚酯型二醇。优选为聚己二酸丁二醇酯二醇、聚己二酸己二醇酯二醇、聚辛二酸丁二醇酯二醇或聚辛二酸己二醇酯二醇中的一种或多种。
所述二异氰酸酯为4,4'-二苯基甲烷二异氰酸酯、亚苯基-1，4-二异氰酸酯、甲苯二异氰酸酯、1，4-环己基-二异氰酸酯或癸烷-1，10-二异氰酸酯。优选为4,4'-二苯基甲烷二异氰酸酯。
所述扩链剂为小分子量直链脂肪族二元醇。优选为1，4-丁二醇，乙二醇，1，2-丙二醇或1，6-己二醇。更优选为丁二醇、己二醇或它们的混合物。
所述扩链剂为1,2-丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、1,6-己二醇或3-甲基-1,5-戊二醇中的一种或多种。
所述抗氧化剂为受阻酚类、亚磷酸酯类或含硫类抗氧化剂，优选为1010、1076、168、626、DLTDP或DMTDP中的一种或多种。
所述抗霉菌剂为有机与无机复合型，有机抗霉菌剂为抗霉菌剂总质量的25％-65％。优选的，有机抗菌剂为8-羟基喹啉铜、10,10’-氧代双吩恶砒或季铵盐类抗菌剂；无机抗菌剂为纳米氧化锌、纳米二氧化钛或银离子型氧化物。
所述抗水解剂为单碳化二亚胺或聚碳化二亚胺中的一种或两种。
所述催化剂为有机铋、有机锡或钛酸酯类催化剂。
所述的耐水解抑菌型聚氨酯热熔胶的制备方法，是将聚酯多元醇、抗氧化剂、抗水解剂、复合抗菌剂和催化剂混合加热至100-115℃，充分混合；二异氰酸酯加热至60-75℃；扩链剂加热至40-60℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到目标产品。
本发明制备的耐水解抑菌型聚氨酯热熔胶，硬度为邵尔80-97A，起始流动温度为90-120℃。
本发明具有以下有益效果：
(1)通过引入高效有机/无机复合型抗菌剂，提高了聚氨酯热熔胶持久抗霉变性能；选择的纳米级无机抗菌剂在热熔胶中能充分分散，使用简单、成本低、与其他添加剂相容性高；
(2)在原位聚合反应过程中引入高效抗水解剂，使热熔胶最终制品保持了非常高的抗水解性能，长期在潮湿环境中也能保持优良的机械性能；
(3)本发明通过复配高效抗菌剂和耐水解剂获得了具有持久耐水解和抗霉变的性能，二者具有良好的协同效果，大大拓宽了热熔胶的应用领域和使用寿命；
(4)所述的耐水解抑菌型聚氨酯热熔胶的制备方法，采用连续水下切造粒，生产效率高，操作简单，可广泛应用于防水器材、鞋材、服装和包装贴合领域。
具体实施方式
下面结合实施例对本发明作进一步的说明，但其并不限制本发明的实施。
实施例1
所述的耐水解抑菌型聚氨酯热熔胶，由以下重量百分含量的原料制成：
制备步骤如下：
将聚己二酸丁二醇酯二醇、T-9、1010、纳米二氧化钛、8-羟基喹啉铜和P200充分混合加热至105℃；二异氰酸酯加热至65℃保温；扩链剂加热至45℃保温；将加热后的各原料组分通过精确计量混合后注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到产品。所得产品的硬度为87A，起始流动温度为91℃。
实施例2
所述的耐水解抑菌型聚氨酯热熔胶，由以下重量百分含量的原料制成：
制备步骤如下：
将聚己二酸丁二醇酯二醇、T-9、1010、纳米二氧化钛、聚季铵盐和P200充分混合加热至105℃；二异氰酸酯加热至65℃保温；扩链剂加热至45℃保温；将加热后的各原料组分通过精确计量混合后注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到产品。所得产品的硬度为90A，起始流动温度为97℃。
实施例3
所述的耐水解抑菌型聚氨酯热熔胶，由以下重量百分含量的原料制成：
制备步骤如下：
将聚己二酸己二醇酯二醇、T-9、1010、DLTDP、纳米氧化锌、聚季铵盐和Stabaxol 1充分混合加热至110℃；二异氰酸酯加热至65℃保温；扩链剂加热至45℃保温；将加热后的各原料组分通过精确计量混合后注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到产品。所得产品的硬度为97A，起始流动温度为118℃。
对比例1
所述的耐水解抑菌型聚氨酯热熔胶，由以下重量百分含量的原料制成：
制备步骤如下：
将聚己二酸丁二醇酯二醇、T-9、1010、充分混合加热至110℃；二异氰酸酯加热至65℃保温；扩链剂加热至45℃保温；将加热后的各原料组分通过精确计量混合后注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到产品。所得产品的硬度为90A，起始流动温度为96℃。
将实施例1-3和对比例1所得粒子做成片材，分别进行耐水解和抗霉菌性能检测。其中耐水解测试条件为40℃水浴放置7天，抗霉菌测试为淤泥中埋放90天。检测结果见表1。
表1实施例和对比例1所得产品的性能检测结果
本发明采用高效耐水解剂和复合型抗菌剂，合成了具有持久抗霉变性能的聚氨酯热熔胶。产品经长期水汽或霉菌的侵蚀仍维持了较高的力学性能，且表面保持清洁规整。该发明提供的生产方法简单、高效，原料价廉易得，能有效拓宽聚氨酯热熔胶在潮湿多菌环境中的应用，产品能够广泛应用于服装、鞋材、防水胶条和包装印刷等领域。

Claims (10)

1.一种耐水解抑菌型聚氨酯热熔胶，其特征在于由以下重量百分含量的原料制成：
所述聚酯多元醇为羟值为18-38.4mg KOH/g，酸值为0.1-0.7mg KOH/g的脂肪族聚酯型二醇。
2.根据权利要求1所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：二异氰酸酯为4,4'-二苯基甲烷二异氰酸酯、亚苯基-1，4-二异氰酸酯、甲苯二异氰酸酯、1，4-环己基-二异氰酸酯或癸烷-1，10-二异氰酸酯。
3.根据权利要求1所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：扩链剂为小分子量直链脂肪族二元醇。
4.根据权利要求3所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：扩链剂为1,2-丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、1,6-己二醇或3-甲基-1,5-戊二醇中的一种或多种。
5.根据权利要求1所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：抗氧化剂为受阻酚类、亚磷酸酯类或含硫类抗氧化剂。
6.根据权利要求1所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：抗霉菌剂为有机与无机复合型，有机抗霉菌剂为抗霉菌剂总质量的25％-65％。
7.根据权利要求6所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：有机抗菌剂为8-羟基喹啉铜、10,10’-氧代双吩恶砒或季铵盐类抗菌剂；无机抗菌剂为纳米氧化锌、纳米二氧化钛或银离子型氧化物。
8.根据权利要求1所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：抗水解剂为单碳化二亚胺或聚碳化二亚胺中的一种或两种。
9.根据权利要求1所述的耐水解抑菌型聚氨酯热熔胶，其特征在于：催化剂为有机铋、有机锡或钛酸酯类催化剂。
10.一种权利要求1-9任一所述的耐水解抑菌型聚氨酯热熔胶的制备方法，其特征在于：将聚酯多元醇、抗氧化剂、抗水解剂、复合抗菌剂和催化剂混合加热至100-115℃，混合；二异氰酸酯加热至60-75℃；扩链剂加热至40-60℃；将加热后的各原料组分通过精确计量混合注入双螺杆反应机，混合物料在双螺杆反应机内反应塑化，经水下切粒后得到目标产品。
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CN107312154A (zh) * 2017-07-17 2017-11-03 中天科盛（上海）企业发展股份有限公司 一种抗菌耐水解热塑性聚氨酯弹性体
CN109486464A (zh) * 2018-10-30 2019-03-19 浙江华峰热塑性聚氨酯有限公司 服装用抗菌性热塑性聚氨酯网膜及制备方法
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CN110684499A (zh) * 2019-11-12 2020-01-14 东莞市米儿塑胶原料有限公司 一种改性聚氨酯树脂热熔胶
CN110923946A (zh) * 2019-11-20 2020-03-27 苏州市雄林新材料科技有限公司 一种纳米抗菌透气tpu薄膜及其制备方法
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CN116967930A (zh) * 2023-09-21 2023-10-31 上海芯谦集成电路有限公司 特殊热熔胶加工工艺的抛光垫及其制备方法
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