CN108102065B - 用于防弹玻璃的纤维增强型热塑性聚氨酯及其制备方法 - Google Patents

用于防弹玻璃的纤维增强型热塑性聚氨酯及其制备方法 Download PDF

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CN108102065B
CN108102065B CN201711099948.7A CN201711099948A CN108102065B CN 108102065 B CN108102065 B CN 108102065B CN 201711099948 A CN201711099948 A CN 201711099948A CN 108102065 B CN108102065 B CN 108102065B
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郎增科
郎东辉
郎潇
赵莉莉
贾振兴
杨帆
任鹏
田克
韩风安
张钰琳
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Abstract

本发明公开了用于防弹玻璃的纤维增强型热塑性聚氨酯，包括以下重量份原料组分：脂肪族二异氰酸酯20～35份、平均分子量2000～4000的聚四氢呋喃环氧乙烷共聚醚50～55份、1,4‑丁二醇6～12份、由γ‑氨丙基三乙氧基硅烷改性的玻璃纤维5～15份、以及占其它原料组分总重0.03～0.08％的二月桂酸二丁基锡。获得的纤维增强型热塑性聚氨酯，不仅对玻璃板和聚碳酸酯板具有优良地粘接性，还具有高透明度、高耐黄变性能、和耐老化性能，而且拥有极其优异的拉伸强度、断裂韧性、抗冲击强度，可显著提高防弹玻璃的各项使用性能，促进防弹玻璃的应用发展。本发明热塑性聚氨酯材料的制备，通过限定不同原料组分的混合与加入顺序，得到更适用于防弹玻璃的夹层材料。

Description

用于防弹玻璃的纤维增强型热塑性聚氨酯及其制备方法
技术领域
本发明涉及热塑性聚氨酯材料技术领域，尤其涉及用于防弹玻璃的纤维增强型热塑性聚氨酯，同时还涉及该材料的制备方法及其用途。
背景技术
防弹玻璃，不仅具有普通玻璃的外观和传送光的行为，还以多层复合结构来吸收冲击和***过程中所产生的部分能量和冲击波压力，具备良好的抗冲击性、抗穿透性和安全性，从而具有防盗、防弹和防爆功能，可广泛用于航空、车船、安保等领域。传统防弹玻璃采用透明胶合材料将多层玻璃粘接制造，依靠玻璃厚度、夹层层数和胶合材料的性能来提升防弹能力。由于玻璃材质的高密度性往往造成由多层玻璃构成的防弹玻璃过于厚重，给安装和使用常带来不便。
新型防弹玻璃结构中，使用聚碳酸酯板代替最后一层玻璃板，可在同等重量和厚度下显著提升防弹玻璃的抗冲击性，而该结构的防弹玻璃中，作为夹层材料的透明胶合材料，其性能对防弹能力、使用性能的影响尤为重要。目前常使用聚乙烯醇缩丁醛(PVB)制备的薄膜用作防弹玻璃的夹层，而PVB胶片存在一个致命的缺点——低温柔顺性差，当环境温度低于0℃时脆性显著提高，即PVB胶片对玻璃和聚碳酸酯板的粘结强度随着温度的降低而降低。这就导致了使用PVB胶片制备的防弹玻璃不能在低温下使用。
热塑性聚氨酯(TPU)具有优良的耐低温性、高拉伸强度，以及同聚碳酸酯有优良的粘接性，是替代PVB胶片应用于防弹玻璃的潜在材料之一。而防弹玻璃除了对强度有特殊要求外，还对光学性能有特殊的要求，目前还没有性能优异的适用于防弹玻璃的TPU材料。
发明内容
为解决现有技术存在的不足，本发明提供了一种用于防弹玻璃的纤维增强型热塑性聚氨酯，该热塑性聚氨酯材料具有高透明度、高耐黄变性、高粘接性和高抗冲击性，适用于防弹玻璃的特殊性能要求。
为实现上述目的，本发明提供了一种用于防弹玻璃的纤维增强型热塑性聚氨酯，包括以下重量份原料组分：
脂肪族二异氰酸酯20～35份；
平均分子量2000～4000的聚四氢呋喃环氧乙烷共聚醚50～55份；
1,4-丁二醇6～12份；
由γ-氨丙基三乙氧基硅烷改性的玻璃纤维5～15份；
以及占其它原料组分总重0.03～0.08％的二月桂酸二丁基锡。
作为防弹玻璃的夹层材料，除需与玻璃板、与聚碳酸酯板均具有优良的粘接性以保证防弹玻璃的结构稳固外，还需具有良好的透明度和耐黄变性、耐老化性，提供防弹玻璃的基础使用性能和使用寿命，更重要的还需具备优异的拉伸和抗冲击性能，从而赋予防弹玻璃更有效的防弹能力。本发明以不含有芳香族官能团的聚四氢呋喃环氧乙烷共聚醚和脂肪族二异氰酸酯为原料，以1,4-丁二醇为扩链剂，以二月桂酸二丁基锡为催化剂，并特别增加由γ-氨丙基三乙氧基硅烷改性的玻璃纤维，制备热塑性聚氨酯材料，各原料经缩合、交联反应后，得到不仅能够优良地粘接玻璃板和聚碳酸酯板，并具有高透明度和高耐黄变性能、耐老化性能的TPU材料，而且该TPU材料属于纤维增强型，其拉伸强度、断裂韧性、抗冲击强度极其优异，用作防弹玻璃的夹层材料能够显著提高防弹玻璃的各项使用性能，促进防弹玻璃的应用发展。
作为对上述技术方案的限定，所述脂肪族二异氰酸酯为六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)、二环己基甲烷-4,4’-二异氰酸酯(HMDI)、1,3-二(异氰酸甲基)环己烷中的至少一种。
作为对上述技术方案的限定，所述聚四氢呋喃环氧乙烷共聚醚的官能度为2.0～2.3。
作为对上述技术方案的限定，所述聚四氢呋喃环氧乙烷共聚醚的分子量为3100，羟值为40.12mg KOH/g。
作为对上述技术方案的限定，所述玻璃纤维为短切玻璃纤维，纤维长度为2～6mm。
作为对上述技术方案的限定，所述短切玻璃纤维的纤维长度为3mm。
进一步限定原料脂肪族二异氰酸酯、聚四氢呋喃环氧乙烷共聚醚、玻璃纤维的物质选择，以利于热塑性聚氨酯材料的性能优化。
同时，本发明还提供了一种如上所述的用于防弹玻璃的纤维增强型热塑性聚氨酯的制备方法，包括以下步骤：
a、获取由γ-氨丙基三乙氧基硅烷改性的玻璃纤维；
b、将由γ-氨丙基三乙氧基硅烷改性的玻璃纤维与1,4-丁二醇混合得到物料A，将二月桂酸二丁基锡与聚四氢呋喃环氧乙烷共聚醚混合得到物料B，以脂肪族二异氰酸酯为物料C，通过控制物料A，B，C的比例，将三种物料同时注入到双螺杆连续反应挤出机中，在温度为160～260℃、模头压力为2MPa下进行反应，反应后挤出产物再经切粒、烘干后得到纤维增强型热塑性聚氨酯的颗粒产品。
本发明的热塑性聚氨酯材料，在制备过程，通过限定不同原料的混合与加入顺序，将改性玻璃纤维先与扩链剂混合，再控制各物料流量按原料配比共同加入到双螺杆挤出机中，在特定的反应温度和压力下，以扩链剂引导原料聚四氢呋喃环氧乙烷共聚醚和脂肪族二异氰酸酯发生聚合、交联反应，反应中改性玻璃纤维在扩链剂的促进及辅助分散作用下均匀构建在热塑性聚氨酯分子链中，得到纤维增强型热塑性聚氨酯材料，可保证材料粘接性、透明度、耐黄变性及耐老化性的同时，极大提高材料的拉伸强度、断裂韧性、抗冲击强度等性能，得到更适用于防弹玻璃的TPU材料。
作为对上述技术方案的限定，所述由γ-氨丙基三乙氧基硅烷改性的玻璃纤维的制备采用如下方法：
将玻璃纤维加入到γ-氨丙基三乙氧基硅烷的乙醇溶液中，于室温下进行超声振荡处理，然后取出、干燥，得到由γ-氨丙基三乙氧基硅烷改性的玻璃纤维；所述超声振荡处理方式为室温下、以超声功率600W连续进行90次超声振荡，每次超声振荡持续60s，间隔20s。
作为对上述技术方案的限定，所述γ-氨丙基三乙氧基硅烷的用量为玻璃纤维重量的15％，所述γ-氨丙基三乙氧基硅烷的乙醇溶液的体积浓度为20％。
采用γ-氨丙基三乙氧基硅烷为改性剂，对普通玻璃纤维经由特定超声振荡处理进行改性，并进一步限定改性剂的使用量及使用浓度，以获取性能更适用的改性玻璃纤维，利于改性玻璃纤维与原料的交联反应，促进后期纤维增强型热塑性聚氨酯材料的制备。
同时，本发明还提供了如上所述用于防弹玻璃的纤维增强型热塑性聚氨酯的用途，即所述纤维增强型热塑性聚氨酯用于防弹玻璃制作中玻璃层与聚碳酸酯层的粘接。
综上所述，采用本发明的技术方案，获得的用于防弹玻璃的纤维增强型热塑性聚氨酯，是以不含有芳香族官能团的聚四氢呋喃环氧乙烷共聚醚和脂肪族二异氰酸酯为原料，以1,4-丁二醇为扩链剂，以二月桂酸二丁基锡为催化剂，并特别增加由γ-氨丙基三乙氧基硅烷改性的玻璃纤维，经缩合、交联反应得到，用作防弹玻璃的夹层材料，不仅能够优良地粘接玻璃板和聚碳酸酯板，并具有高透明度和高耐黄变性能、耐老化性能，而且其拉伸强度、断裂韧性、抗冲击强度极其优异，可显著提高防弹玻璃的各项使用性能，促进高性能防弹玻璃的应用发展。本发明的热塑性聚氨酯材料，制备过程简单，通过限定不同原料的混合与加入顺序，将改性玻璃纤维与扩链剂先混合，然后均匀构建在热塑性聚氨酯分子链中，以得到更适用于防弹玻璃的夹层材料。
具体实施方式
下面将结合实施例，对本发明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做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。
实施例一
本实施例涉及用于防弹玻璃的纤维增强型热塑性聚氨酯及其制备。
一种用于防弹玻璃的纤维增强型热塑性聚氨酯，包括以下重量份原料组分：
脂肪族二异氰酸酯20～35份；
平均分子量2000～-4000的聚四氢呋喃环氧乙烷共聚醚50～55份；
1,4-丁二醇6～12份；
由γ-氨丙基三乙氧基硅烷改性的玻璃纤维5～15份；
以及占其它原料组分总重0.03～0.08％的二月桂酸二丁基锡。
其制备包括以下步骤：
a、获取由γ-氨丙基三乙氧基硅烷改性的玻璃纤维；
b、将由γ-氨丙基三乙氧基硅烷改性的玻璃纤维与1,4-丁二醇混合得到物料A，将二月桂酸二丁基锡与聚四氢呋喃环氧乙烷共聚醚混合得到物料B，以脂肪族二异氰酸酯为物料C，控制物料A，物料B和物料C的比例，将三种物料同时注入到双螺杆连续反应挤出机中，在温度为160～-260℃、模头压力为2MPa下进行反应，待反应完全后挤出产物，再经切粒、烘干后获得纤维增强型热塑性聚氨酯的颗粒产品。
按上述方法制备不同实施例的纤维增强型热塑性聚氨酯，各实施例的物料及用量如下表所示：
Figure BDA0001463160020000061
Figure BDA0001463160020000071
实施例二
本实施例涉及实施例一获得的纤维增强型热塑性聚氨酯材料的性能，如下表所示，其中试片的雾度和YI由x-rite Ci 7600系列分光仪测试得到，其他性能按国标要求测试得到。
Figure BDA0001463160020000072
由上表可见，本发明的纤维增强型热塑性聚氨酯在拉伸强度、光学性能、耐低温性能上明显优于普通的PVB胶片，替代PVB胶片用于防弹玻璃，能够显著提高防弹玻璃的使用性能。
综上所述，本发明的纤维增强型热塑性聚氨酯能够优良地粘接玻璃板和聚碳酸酯板，并具有高透明度和高耐黄变性能、耐老化性能，而且其拉伸强度、断裂韧性、抗冲击强度极其优异，可显著提高防弹玻璃的各项使用性能，促进防弹玻璃的应用发展。本发明的热塑性聚氨酯材料，制备过程简单，通过限定不同原料的混合与加入顺序，将改性玻璃纤维与扩链剂先混合，然后均匀构建在热塑性聚氨酯分子链中，以得到更适用于防弹玻璃的夹层材料。

Claims (8)

1.一种用于防弹玻璃的纤维增强型热塑性聚氨酯，其特征在于，包括以下重量份原料组分：
脂肪族二异氰酸酯20~35份；
聚四氢呋喃环氧乙烷共聚醚57.91份、56.71份或57.59份，其分子量为3100，羟值为40.12 mg KOH/g；
1,4-丁二醇6~12份；
由γ-氨丙基三乙氧基硅烷改性的玻璃纤维5~15份；
以及占其它原料组分总重0.03~0.08%的二月桂酸二丁基锡；
所述脂肪族二异氰酸酯为六亚甲基二异氰酸酯、二环己基甲烷-4,4’-二异氰酸酯、1,3-二(异氰酸甲基)环己烷中的至少一种。
2.根据权利要求1所述的用于防弹玻璃的纤维增强型热塑性聚氨酯，其特征在于：所述聚四氢呋喃环氧乙烷共聚醚的官能度为2.0~2.3。
3.根据权利要求1所述的用于防弹玻璃的纤维增强型热塑性聚氨酯，其特征在于：所述玻璃纤维为短切玻璃纤维，纤维长度为2~6 mm。
4.根据权利要求3所述的用于防弹玻璃的纤维增强型热塑性聚氨酯，其特征在于：所述短切玻璃纤维的纤维长度为3mm。
5.一种如权利要求1至4中任一项所述的用于防弹玻璃的纤维增强型热塑性聚氨酯的制备方法，其特征在于，包括以下步骤：
a、获取由γ-氨丙基三乙氧基硅烷改性的玻璃纤维；
b、将由γ-氨丙基三乙氧基硅烷改性的玻璃纤维与1,4-丁二醇混合得到物料A，将二月桂酸二丁基锡与聚四氢呋喃环氧乙烷共聚醚混合得到物料B，以脂肪族二异氰酸酯为物料C，通过控制物料A，B，C的比例，将三种物料同时注入到双螺杆连续反应挤出机中，在温度为160~260℃、模头压力为2 MPa下进行反应，反应后挤出产物再经切粒、烘干后得到纤维增强型热塑性聚氨酯的颗粒产品。
6.根据权利要求5所述的用于防弹玻璃的纤维增强型热塑性聚氨酯的制备方法，其特征在于，所述由γ-氨丙基三乙氧基硅烷改性的玻璃纤维的制备采用如下方法：
将玻璃纤维加入到γ-氨丙基三乙氧基硅烷的乙醇溶液中，于室温下进行超声振荡处理，然后取出、干燥，得到由γ-氨丙基三乙氧基硅烷改性的玻璃纤维；所述超声振荡处理方式为室温下、以超声功率600W连续进行90次超声振荡，每次超声振荡持续60s，间隔20s。
7.根据权利要求6所述的用于防弹玻璃的纤维增强型热塑性聚氨酯的制备方法，其特征在于：所述γ-氨丙基三乙氧基硅烷的用量为玻璃纤维重量的15%，所述γ-氨丙基三乙氧基硅烷的乙醇溶液的体积浓度为20%。
8.一种如权利要求1至4中任一项所述的用于防弹玻璃的纤维增强型热塑性聚氨酯的用途，其特征在于：所述纤维增强型热塑性聚氨酯用于防弹玻璃制作中玻璃层与聚碳酸酯层的粘接。
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