CN108129645A - 一种可辐射固化聚己内酯二元醇及其制备方法和应用 - Google Patents
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Abstract
本发明涉及一种可辐射固化聚己内酯二元醇及其制备方法和应用,所述可辐射固化聚己内酯二元醇的数均分子量为300~6000,所述可辐射固化聚己内酯二元醇的结构式如下:
Description
技术领域
本发明涉及高分子材料技术领域,具体地,涉及一种可辐射固化聚己内酯二元醇及其制备方法和应用。
背景技术
聚己内酯二元醇被广泛应用于聚氨酯弹性体、涂料、胶黏剂等领域。以该原料制备的弹性体具有优异的水解稳定性和高、低温性能。它比聚醚型和普通聚醚型PU拥有更加平衡的性能,一方面它能表现出普通聚己内酯型PU的优良抗撕裂和应力-应变行为,同时又表现出聚醚型PU突出的压缩永久变形和回弹性能,因而在市场中得到了广泛的应用。尤其是在一些对材料的高温性能、动态性能、耐磨耗和抗曲挠性能具有较高要求的场合,聚己内酯型PU已成为首选材料。
聚己内酯二元醇获得的PU制品一般来说柔韧性较好,经过适度交联后聚氨酯的拉伸强度、模量、耐溶剂性、耐高温性等许多性能都能得到大幅提高;一般而言,通过异氰酸酯和亚氨基、羟基封端聚氨酯预聚体或加入多元醇交联剂等方法可以实现聚氨酯在成型过程中实现交联;但是成型中进行分子间的交联受到反应性基团被包覆、基团之间距离较大,最终的转化率因此受到了限制,因此制品在微细结构上出现缺陷容易导致制品的部分性能下降。
因此,研发一种可辐射固化聚己内酯二元醇从而改善以其为原料制备得到的聚氨酯的力学性能、耐化学性能和尺寸稳定性等性能就显得尤为必要。
发明内容
本发明的目的在于克服现有技术的不足,提供一种可辐射固化聚己内酯聚己内酯二元醇,本发明提供的可辐射固化聚己内酯二元醇主链含有不饱和双键,在热、辐射条件下聚合物主链中的不饱和双键发生交联从而提高产品的力学性能、耐化学性能和尺寸稳定性。
本发明的另一目的在于提供上述可辐射固化聚己内酯二元醇的制备方法。
本发明的另一目的在于提供上述可辐射固化聚己内酯二元醇直接或作为聚氨酯原料在热、辐射固化涂料、胶黏剂中的应用。
为实现上述目的,本发明采用如下技术方案:
一种可辐射固化聚己内酯二元醇,所述可辐射固化聚己内酯二元醇的数均分子量为300~6000,所述可辐射固化聚己内酯二元醇的结构式如下:
;
其中, x+y为1~50的整数。
为解决上述技术问题,本发明的发明人进行了制品工艺及聚己内酯二元醇的结构设计,本发明提供的可辐射固化聚己内酯二元醇的主链含有不饱和双键,不饱和双键随后可以通过热、辐射(UV光固化、EB电子束)交联提高产品的力学性能、耐化学性能和尺寸稳定性;并且由于聚合物主链中只含有一个不饱和双键,确保了在后序热、辐射固化中速率可控。并且因双键交联密度可控,制品的综合物理化学性能如拉伸强度更高、模量更大、耐溶剂性更好、耐高温性能更佳、酸值更低,抗黄变性能优异。另外,本发明提供的可辐射固化聚己内酯二元醇因主链具有支链,导致结晶温度降低、使用更为方便。
本发明提供的可辐射固化聚己内酯二元醇能够通过热、辐射等技术手段应用于可交联型热塑性聚氨酯制品领域,聚氨酯可以先热塑性成型、不饱和双键随后可以通过热、辐射(UV光固化、EB电子束)交联从而提高聚氨酯成品的力学性能、耐化学性能和尺寸稳定性等性能。
优选地,所述可辐射固化聚己内酯二元醇的数均分子量为1000~4000,x+y为8~35的整数。
上述可辐射固化聚己内酯二元醇的制备方法,所述方法如下:将ε-己内酯、催化剂以及引发剂混合均匀并升温至80~120℃,减压除水除杂;然后于氮气保护下升温至80~200℃,保温1~48h,抽真空0.5~2.0h,即得所述可辐射固化聚己内酯。
优选地,所述引发剂为含不饱和双键的二元醇,所述二元醇为三羟甲基丙烷单烯丙基醚。
优选地,所述催化剂为有机碱土金属、有机铝、锡、钛、锆化合物或无机酸如盐酸、磷酸等。
优选地,所述催化剂的用量为10~3000ppm。
本发明提供的可辐射固化聚己内酯二元醇能够通过热、辐射等技术手段应用于可交联型热塑性聚氨酯制品领域,聚氨酯可以先热塑性成型、不饱和双键随后可以通过热、辐射(UV光固化、EB电子束)交联从而提高聚氨酯成品的力学性能、耐化学性能和尺寸稳定性等性能。因此,本发明同时保护上述可辐射固化聚己内酯二元醇直接或作为聚氨酯原料在热、辐射固化涂料、胶黏剂中的应用。
与现有技术相比,本发明具有如下有益效果:
本发明提供的可辐射固化聚己内酯二元醇的主链含有不饱和双键,不饱和双键随后可以通过热、辐射(UV光固化、EB电子束)交联提高产品的力学性能、耐化学性能和尺寸稳定性;并且由于聚合物主链中只含有一个不饱和双键,确保了在后序热、辐射固化中速率可控。该工艺的实施,避免了复杂的前期除水工艺且控制了产品的酸值,达到降低下游应用中易黄变的技术难题;另外,本发明提供的可辐射固化聚己内酯二元醇因主链具有支链,导致结晶温度降低、使用更为方便。
本发明提供的可辐射固化聚己内酯二元醇能够通过热、辐射等技术手段应用于可交联型热塑性聚氨酯制品领域,聚氨酯可以先热塑性成型、不饱和双键随后可以通过热、辐射(UV光固化、EB电子束)交联从而提高聚氨酯成品的力学性能、耐化学性能和尺寸稳定性等性能。
具体实施方式
以下结合具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,本发明所用试剂和材料均为市购。
实施例1 可辐射固化聚己内酯二元醇Q1
一种可辐射固化聚己内酯二元醇,所述可辐射固化聚己内酯二元醇的数均分子量为500,所述可辐射固化聚己内酯二元醇的结构式如下:
上述可辐射固化聚己内酯二元醇的制备方法如下:
反应釜中将三羟甲基丙烷单烯丙基醚 1.0 mol、辛酸亚锡 200.0 ppm和己内酯10.0mol ,搅拌升温至90.0 ℃,真空30min后充入氮气,升温至120℃,反应6.0h,真空1.0h。得到可交联型聚己内酯二元醇Q1。
实施例2 可辐射固化聚己内酯二元醇Q2
一种可辐射固化聚己内酯二元醇,所述可辐射固化聚己内酯二元醇的数均分子量为1000,所述可辐射固化聚己内酯二元醇的结构式如下:
上述可辐射固化聚己内酯二元醇的制备方法如下:
反应釜中将三羟甲基丙烷单烯丙基醚 1.0 mol、磷酸 200.0 ppm和己内酯20.0 mol ,搅拌升温至90.0 ℃,真空30min后充入氮气,升温至150℃,反应12.0h,真空1.0h。得到可交联型聚己内酯二元醇Q3。
实施例3 可辐射固化聚己内酯二元醇Q3
一种可辐射固化聚己内酯二元醇,所述可辐射固化聚己内酯二元醇的数均分子量为2500,所述可辐射固化聚己内酯二元醇的结构式如下:
上述可辐射固化聚己内酯二元醇的制备方法如下:
反应釜中将三羟甲基丙烷单烯丙基醚 1.0 mol、月桂酸二丁基锡50.0 ppm和己内酯40.0 mol ,搅拌升温至90.0 ℃,真空30min后充入氮气,升温至120℃,反应6.0h,真空1.0h。得到可交联型聚己内酯二元醇Q3。
实施例4 可辐射固化聚己内酯二元醇Q4
一种可辐射固化聚己内酯二元醇,所述可辐射固化聚己内酯二元醇的数均分子量为2500,所述可辐射固化聚己内酯二元醇的结构式如下:
上述可辐射固化聚己内酯二元醇的制备方法如下
反应釜中将三羟甲基丙烷单烯丙基醚 1.0 mol、辛酸铝2000.0 ppm和己内酯40.0 mol,搅拌升温至90.0 ℃,真空30min后充入氮气,升温至120℃,反应6.0h,真空1.0h。得到可交联型聚己内酯二元醇Q4。
对实施例1~4制备得到的可辐射固化聚己内酯二元醇的物化性能进行测试,测试方法如下,测试结果见下表1。
(1)色度 GB/T 2794-1995;
(2)分子量及其分布 常温GPC,THF为流动相;
(3)熔点:差示扫描量热法
表1 实施例1~4制备得到的可辐射固化聚己内酯二元醇的物化性能
应用试验例 聚氨酯的制备
分别将上述各实施例制备得到的可辐射固化聚己内酯二元醇为原料制备聚氨酯弹性体,其中聚己内酯二元醇1.0mol,甲苯二异氰酸酯1.5mol,三羟甲基丙烷0.4mol。并以普通未经任何改性的聚己内酯二元醇为原料制备聚氨酯弹性体,作为对比例1。对制备得到的聚氨酯弹性体进行均进行EB电子束进行二次固化的物化性能进行测试,测试方法如下,测试结果见下表2。
测试方法:
(1)尺寸稳定性、耐化学性GB-T 11547-2008
(2)拉伸强度GB1040-92
表2 实施例1~4提供的可交联型聚己内酯二元醇制备得到的聚氨酯的性能测试
上述实施例为本发明较佳的实施方式,但是本发明并不限制于为实现本发明所公开的具体实施方式,其他的任何未背离本发明的精神实质和原理下所作的改变、修饰、替代、组合、简化,均视为等效的置换方法,都包含在本发明的保护范围之内。
Claims (8)
1.一种可辐射固化聚己内酯二元醇,其特征在于,所述可辐射固化聚己内酯二元醇的数均分子量为300~6000,所述可辐射固化聚己内酯二元醇的结构式如下:
;
其中, x+y为1~50的整数。
2.根据权利要求1所述可辐射固化聚己内酯二元醇,其特征在于,所述可辐射固化聚己内酯二元醇的数均分子量为1000~4000,x+y为8~35的整数。
3.权利要求1或2所述可辐射固化聚己内酯二元醇的制备方法,其特征在于,所述方法如下:
将ε-己内酯、催化剂以及引发剂混合均匀并升温至80~120℃,减压除水除杂;然后于氮气保护下升温至80~200℃,保温1~48h,抽真空0.5~2.0h,即得所述可辐射固化聚己内酯。
4.根据权利要求3所述制备方法,其特征在于,所述引发剂为含不饱和双键的二元醇。
5.根据权利要求4所述制备方法,其特征在于,所述二元醇为三羟甲基丙烷单烯丙基醚。
6.根据权利要求3所述制备方法,其特征在于,所述催化剂为有机碱土金属、有机铝、锡、钛、锆化合物或无机酸。
7.根据权利要求3所述制备方法,其特征在于,所述催化剂的用量为10~3000ppm。
8.权利要求1或2所述可辐射固化聚己内酯二元醇直接或作为聚氨酯原料在热、辐射固化涂料、胶黏剂中的应用。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108912316A (zh) * | 2018-07-05 | 2018-11-30 | 广东博兴新材料科技有限公司 | 一种聚己内酯多元醇及其制备方法和应用 |
CN109054001A (zh) * | 2018-07-05 | 2018-12-21 | 广东博兴新材料科技有限公司 | 一种聚己内酯多元醇及其制备方法和应用 |
CN114437332A (zh) * | 2022-03-11 | 2022-05-06 | 三河亮克威泽工业涂料有限公司 | 聚酯低聚物及其制备方法、光固化腻子及其制备方法、固化方法和应用 |
CN116693835A (zh) * | 2023-07-04 | 2023-09-05 | 湖南聚仁化工新材料科技有限公司 | 一种辐射交联用聚己内酯及其制备和辐照交联方法 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030148126A1 (en) * | 2002-02-01 | 2003-08-07 | Dong Tian | Multi-functional unsaturated polyester polyols |
CN103483537A (zh) * | 2013-09-26 | 2014-01-01 | 湖南本安亚大新材料有限公司 | 一种紫外光固化树脂、其制备方法以及用其所制备的涂料 |
CN105837778A (zh) * | 2016-04-11 | 2016-08-10 | 常州大学 | 一种辐射固化形状记忆性聚合物的制备方法 |
CN107400192A (zh) * | 2017-08-29 | 2017-11-28 | 杭州重力脚轮科技有限公司 | 一种聚己内酯型聚氨酯弹性体及其制备方法和应用 |
-
2017
- 2017-12-06 CN CN201711277351.7A patent/CN108129645A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030148126A1 (en) * | 2002-02-01 | 2003-08-07 | Dong Tian | Multi-functional unsaturated polyester polyols |
CN103483537A (zh) * | 2013-09-26 | 2014-01-01 | 湖南本安亚大新材料有限公司 | 一种紫外光固化树脂、其制备方法以及用其所制备的涂料 |
CN105837778A (zh) * | 2016-04-11 | 2016-08-10 | 常州大学 | 一种辐射固化形状记忆性聚合物的制备方法 |
CN107400192A (zh) * | 2017-08-29 | 2017-11-28 | 杭州重力脚轮科技有限公司 | 一种聚己内酯型聚氨酯弹性体及其制备方法和应用 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108912316A (zh) * | 2018-07-05 | 2018-11-30 | 广东博兴新材料科技有限公司 | 一种聚己内酯多元醇及其制备方法和应用 |
CN109054001A (zh) * | 2018-07-05 | 2018-12-21 | 广东博兴新材料科技有限公司 | 一种聚己内酯多元醇及其制备方法和应用 |
CN114437332A (zh) * | 2022-03-11 | 2022-05-06 | 三河亮克威泽工业涂料有限公司 | 聚酯低聚物及其制备方法、光固化腻子及其制备方法、固化方法和应用 |
CN114437332B (zh) * | 2022-03-11 | 2023-09-19 | 三河亮克威泽工业涂料有限公司 | 聚酯低聚物及其制备方法、光固化腻子及其制备方法、固化方法和应用 |
CN116693835A (zh) * | 2023-07-04 | 2023-09-05 | 湖南聚仁化工新材料科技有限公司 | 一种辐射交联用聚己内酯及其制备和辐照交联方法 |
CN116693835B (zh) * | 2023-07-04 | 2024-05-03 | 湖南聚仁新材料股份公司 | 一种辐射交联用聚己内酯及其制备和辐照交联方法 |
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