CN116589659B - 一种自修复聚氨酯弹性体的制备方法 - Google Patents
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Abstract
本发明涉及化工技术领域,尤其涉及一种自修复聚氨酯弹性体的制备方法,包括如下步骤:S1、以2,2'‑联吡啶‑5,5'‑二甲醇、γ‑丁内酯为原料合成聚酯多元醇;S2、以乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯、三羟甲基丙烷为原料合成光固化二元醇扩链剂;S3、以聚酯多元醇、二苯基甲烷二异氰酸酯、光固化二元醇扩链剂为原料合成热塑性聚氨酯基体;S4、以热塑性聚氨酯基体、2‑羟甲基呋喃、1,4‑双(马来酰亚胺基)丁烷为原料合成自修复聚氨酯弹性体。本发明有益效果:本发明的自修复聚氨酯弹性体具有优异的性能,一次循环拉伸后,拉伸强度自修复后可达12.18MPa,断裂伸长可达950.41%,10次循环拉伸后的形状恢复量可达95%,切断自修复后,拉伸强度可达11.85MPa。
Description
技术领域
本发明涉及化工技术领域,尤其涉及一种自修复聚氨酯弹性体的制备方法。
背景技术
高分子材料因易加工、易塑形、耐磨和重量轻等特点而被广泛应用在纺织、汽车、医疗器械、航天航空、建筑等领域。但是其在生产及应用的过程中难免会受到损伤,特别是对于材料内部发生的一些微裂纹损伤人们无法通过肉眼观察到,在后续使用过程中微裂纹会进一步恶化发展成裂缝,这会大大降低材料的力学性能。从长期服役的角度来看,将自修复功能引入高分子材料中能使产品的安全性和可靠性提高,使用周期更长。
自修复材料,最早是在基体材料中植入包覆有修复剂和催化剂的微胶囊,实现了材料的自修复功能,但体系中包埋的修复剂有限,并且一经释放便无法补充,再加上修复剂等异物质的引入导致材料的自身力学性能不佳,远不能满足实际使用性能要求。
聚氨酯因其特有的软硬段可设计性,综合性能优异等特点成为当前自修复聚合物材料开发研究的重点。而目前报道的大多数聚氨酯文献中能在温和温度下自修复的高分子材料的力学性能较低,具有高力学强度的自修复材料所需要的刺激温度又较高,并且刺激时间长。这也限制了其在更多应用领域的发展,特别是对材料力学性能要求较高的领域。
发明内容
为了解决上述背景技术中提到的问题,本发明提供一种自修复聚氨酯弹性体的制备方法。
为了实现上述目的,本发明采用了如下技术方案:
1.一种自修复聚氨酯弹性体的制备方法,包括如下步骤:
S1、以2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯为原料合成聚酯多元醇;
S2、以乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯、三羟甲基丙烷为原料合成光固化二元醇扩链剂;
S3、以聚酯多元醇、二苯基甲烷二异氰酸酯、光固化二元醇扩链剂为原料合成热塑性聚氨酯基体;
S4、以热塑性聚氨酯基体、2-羟甲基呋喃、1,4-双(马来酰亚胺基)丁烷为原料合成自修复聚氨酯弹性体。
优选的,所述步骤S1中,2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:2n,n的取值范围为5-20。
优选的,所述步骤S2中,乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯、三羟甲基丙烷的摩尔比为1:1:1。
优选的,所述步骤S3中,聚酯多元醇、二苯基甲烷二异氰酸酯、光固化二元醇扩链剂的摩尔比为2:4:1。
优选的,所述步骤S4中,热塑性聚氨酯基体、2-羟甲基呋喃、1,4-双(马来酰亚胺基)丁烷的摩尔比为2:4:1。
优选的,2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯在零下5-零下10℃,氢化钠、1-(2-甲基环己基)-3-苯基脲催化下,生成聚酯多元醇。
优选的,所述步骤S2的反应过程为:乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯在20-30℃,二月桂酸二丁基锡催化下,生成中间体A,加热至40-50℃,滴加三羟甲基丙烷,生成光固化二元醇扩链剂。
优选的,所述步骤S3的反应过程为:聚酯多元醇、二苯基甲烷二异氰酸在60-70℃,二月桂酸二丁基锡催化下,生成预聚物B,冷却至30-40℃,滴加光固化二元醇扩链剂,生成热塑性聚氨酯基体。
优选的,所述步骤S4的反应过程为:热塑性聚氨酯基体、2-羟甲基呋喃在60-70℃,二月桂酸二丁基锡催化下,生成预聚物C,滴加1,4-双(马来酰亚胺基)丁烷,加入光引发剂2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮,固化成膜后,用270nm波长UV灯照射,得到自修复聚氨酯弹性体。
与现有技术相比,本发明的有益效果是:
1、本发明采用了γ-丁内酯为主要原料合成了高柔顺性的聚醚,聚醚为软段,确保室温下高分子链段的迁移,通过聚酯多元醇、二苯基甲烷二异氰酸酯、光固化二元醇扩链剂合成了聚氨酯基体,光固化二元醇扩链剂的引入,增加了光固化位点和氢键,通过D-A加成反应将动态D-A键引入,在UV照射后进行二次交联,使大量氢键缔合位点聚集,提升链段氢键聚合程度,大量氢键的产生使分子链间距缩小引起链段重排,由于软段上分子段存在对称结构特征,因此使得聚醚链段出现部分结晶,增强弹性体的微相分离结构,增加弹性体形状记忆性能,使得弹性体具有优良的自我修复性能。
2、本发明的自修复聚氨酯弹性体具有优异的性能,一次循环拉伸后,拉伸强度自修复后可达12.18MPa,断裂伸长可达950.41%,10次循环拉伸后的形状恢复量可达95%,切断自修复后,拉伸强度可达11.85MPa。
具体实施方式
如无特别说明,本发明中采用的试剂均来自于市场购买。
本发明聚氨酯弹性体的反应方程式如下:
S1、聚酯多元醇的合成
S2、光固化二元醇扩链剂的合成
S3、塑性聚氨酯基体的合成
S4、自修复聚氨酯弹性体的合成
实施例1
一种自修复聚氨酯弹性体的制备方法,包括如下步骤:
S1、聚酯多元醇的合成:
将2,2'-联吡啶-5,5'-二甲醇、氢化钠、1-(2-甲基环己基)-3-苯基脲溶解在四氢呋喃中,在零下10℃平衡20mi n,然后滴加γ-丁内酯,待反应结束后,加入少量乙酸终止,将反应液滴入冰甲醇中沉降离心,烘干,得到聚酯多元醇;
2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:20;
氢化钠的添加量为γ-丁内酯质量的3%;
1-(2-甲基环己基)-3-苯基脲的添加量为γ-丁内酯质量的2%;
S2、光固化二元醇扩链剂的合成:
将乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯溶解在醋酸中,在25℃,二月桂酸二丁基锡催化下,生成中间体A,加热至45℃,将三羟甲基丙烷使用醋酸溶解后加入,并加入少量2,6-二叔丁基对甲酚作为阻聚剂防止爆聚,反应结束后,用去离子水对产物进行冲洗,除去醋酸、2,6-二叔丁基对甲酚,烘干,得到光固化二元醇扩链剂;
乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯、三羟甲基丙烷的摩尔比为1:1:1;
二月桂酸二丁基锡的添加量为乙二醇单烯丙基醚质量的3%;
S3、热塑性聚氨酯基体的合成:
将聚酯多元醇、二苯基甲烷二异氰酸溶解在醋酸中,在65℃,二月桂酸二丁基锡催化下,生成预聚物B,冷却至35℃,将光固化二元醇扩链剂使用醋酸溶解后加入,反应结束后,减压蒸馏除去醋酸,得到热塑性聚氨酯基体;
聚酯多元醇、二苯基甲烷二异氰酸酯、光固化二元醇扩链剂的摩尔比为2:4:1;
二月桂酸二丁基锡的添加量为聚酯多元醇质量的2%;
S4、自修复聚氨酯弹性体的合成:
将热塑性聚氨酯基体、2-羟甲基呋喃溶解在醋酸中,在65℃,二月桂酸二丁基锡催化下,生成预聚物C,将1,4-双(马来酰亚胺基)丁烷用DMF溶解后加入,然后加入光引发剂2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮,真空加热脱去醋酸、DMF并进行固化成膜,用270nm波长UV灯照射,得到厚度为1mm的自修复聚氨酯弹性体;
热塑性聚氨酯基体、2-羟甲基呋喃、1,4-双(马来酰亚胺基)丁烷的摩尔比为2:4:1;
二月桂酸二丁基锡的添加量为热塑性聚氨酯基体质量的2%;
2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮的的添加量为2-羟甲基呋喃质量的0.5%。
实施例2
本实施例与实施例1的不同之处在于:2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:10,其余部分与实施例1完全相同。
实施例3
本实施例与实施例1的不同之处在于:2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:16,其余部分与实施例1完全相同。
实施例4
本实施例与实施例1的不同之处在于:2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:26,其余部分与实施例1完全相同。
实施例5
本实施例与实施例1的不同之处在于:2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:30,其余部分与实施例1完全相同。
实施例6
本实施例与实施例1的不同之处在于:2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:36,其余部分与实施例1完全相同。
实施例7
本实施例与实施例1的不同之处在于:2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:40,其余部分与实施例1完全相同。
结果与检测
使用万能力学试验机对实施例1-7获得的自修复聚氨酯弹性体进行力学拉伸测试。记录弹性体的拉伸强度和断裂伸长率,每个实施例获得的弹性体样品测7次,去掉最大值、最小值后,取其平均值作为最终数据,自修复数据为将自修复聚氨酯弹性体进行一次循环拉伸后的力学测试,结果如表1所示。
表1
使用万能力学试验机对实施例1-7获得的自修复聚氨酯弹性体进行循环拉伸测试。室温下以初始形变为起点进行定速循环,递进值为10%,对材料进行10次循环拉伸,结果如表2所示。
形状恢复量=(10次循环拉伸后试样长度/初始试样长度)*100%
表2
形状恢复量% | |
实施例1 | 95 |
实施例2 | 88 |
实施例3 | 84 |
实施例4 | 81 |
实施例5 | 80 |
实施例6 | 85 |
实施例7 | 84 |
将实施例1-7获得的自修复聚氨酯弹性体沿中部垂直于拉伸轴线的方向切断,对断口进行120℃、10s加热,在3Mpa下进行原位拼接,冷却至室温并保持1h,通过拉伸测试,研究材料的自修复性能。
表3
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 (8)
1.一种自修复聚氨酯弹性体的制备方法,其特征在于,包括如下步骤:
S1、以2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯为原料合成聚酯多元醇;
S2、以乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯、三羟甲基丙烷为原料合成光固化二元醇扩链剂;
S3、以聚酯多元醇、二苯基甲烷二异氰酸酯、光固化二元醇扩链剂为原料合成热塑性聚氨酯基体;
S4、以热塑性聚氨酯基体、2-羟甲基呋喃、1,4-双(马来酰亚胺基)丁烷为原料合成自修复聚氨酯弹性体;
所述步骤S3中,聚酯多元醇、二苯基甲烷二异氰酸酯、光固化二元醇扩链剂的摩尔比为2:4:1。
2.根据权利要求1所述的一种自修复聚氨酯弹性体的制备方法,其特征在于,所述步骤S1中,2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯的摩尔比为1:2n,n的取值范围为5-20。
3.根据权利要求1所述的一种自修复聚氨酯弹性体的制备方法,其特征在于,所述步骤S2中,乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯、三羟甲基丙烷的摩尔比为1:1:1。
4.根据权利要求1所述的一种自修复聚氨酯弹性体的制备方法,其特征在于,所述步骤S4中,热塑性聚氨酯基体、2-羟甲基呋喃、1,4-双(马来酰亚胺基)丁烷的摩尔比为2:4:1。
5.根据权利要求1所述的一种自修复聚氨酯弹性体的制备方法,其特征在于,2,2'-联吡啶-5,5'-二甲醇、γ-丁内酯在零下5-零下10℃,氢化钠、1-(2-甲基环己基)-3-苯基脲催化下,生成聚酯多元醇。
6.根据权利要求1所述的一种自修复聚氨酯弹性体的制备方法,其特征在于,所述步骤S2的反应过程为:乙二醇单烯丙基醚、二苯基甲烷二异氰酸酯在20-30℃,二月桂酸二丁基锡催化下,生成中间体A,加热至40-50℃,滴加三羟甲基丙烷,生成光固化二元醇扩链剂。
7.根据权利要求1所述的一种自修复聚氨酯弹性体的制备方法,其特征在于,所述步骤S3的反应过程为:聚酯多元醇、二苯基甲烷二异氰酸在60-70℃,二月桂酸二丁基锡催化下,生成预聚物B,冷却至30-40℃,滴加光固化二元醇扩链剂,生成热塑性聚氨酯基体。
8.根据权利要求1所述的一种自修复聚氨酯弹性体的制备方法,其特征在于,所述步骤S4的反应过程为:热塑性聚氨酯基体、2-羟甲基呋喃在60-70℃,二月桂酸二丁基锡催化下,生成预聚物C,滴加1,4-双(马来酰亚胺基)丁烷,加入光引发剂2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮,固化成膜后,用270nm波长UV灯照射,得到自修复聚氨酯弹性体。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4273909A (en) * | 1980-04-22 | 1981-06-16 | Minnesota Mining And Manufacturing Company | One-part solvent-free thermosettable blocked prepolymer composition containing a diene, together with chain extender, chain terminator and a dienophile |
CN106893307A (zh) * | 2017-01-18 | 2017-06-27 | 福建师范大学泉港石化研究院 | 一种低熔点高强度的聚氨酯3d打印材料及其制备方法 |
CN108558932A (zh) * | 2018-05-16 | 2018-09-21 | 华东理工大学 | 二(2-吡啶基)甲基取代氨基酚氧基镁络合物及其制备方法和应用 |
CN110790888A (zh) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | 基于多重动态可逆作用的高强度室温自修复聚氨酯弹性体及其制备与应用 |
CN110804163A (zh) * | 2019-12-04 | 2020-02-18 | 青岛科技大学 | 一种含可修饰官能团的生物基共聚酯的制备方法 |
CN114133507A (zh) * | 2021-12-29 | 2022-03-04 | 青岛科技大学 | 一种生物基可降解聚氨酯的一锅制备法 |
CN114874512A (zh) * | 2022-06-14 | 2022-08-09 | 江苏顺隆轮胎有限公司 | 一种高弹性自修复内胎材料及其制备方法 |
CN114940740A (zh) * | 2022-06-29 | 2022-08-26 | 华南理工大学 | 一种基于多重可逆作用的高性能透明室温自修复聚氨酯弹性体及制备方法 |
CN115353609A (zh) * | 2022-07-22 | 2022-11-18 | 华东师范大学 | 一种可修复增强的高性能聚氨酯弹性体及制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011146577A2 (en) * | 2010-05-19 | 2011-11-24 | Drexel University | Remendable interfaces for polymer composites |
-
2023
- 2023-06-13 CN CN202310696182.XA patent/CN116589659B/zh active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4273909A (en) * | 1980-04-22 | 1981-06-16 | Minnesota Mining And Manufacturing Company | One-part solvent-free thermosettable blocked prepolymer composition containing a diene, together with chain extender, chain terminator and a dienophile |
CN106893307A (zh) * | 2017-01-18 | 2017-06-27 | 福建师范大学泉港石化研究院 | 一种低熔点高强度的聚氨酯3d打印材料及其制备方法 |
CN108558932A (zh) * | 2018-05-16 | 2018-09-21 | 华东理工大学 | 二(2-吡啶基)甲基取代氨基酚氧基镁络合物及其制备方法和应用 |
CN110790888A (zh) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | 基于多重动态可逆作用的高强度室温自修复聚氨酯弹性体及其制备与应用 |
CN110804163A (zh) * | 2019-12-04 | 2020-02-18 | 青岛科技大学 | 一种含可修饰官能团的生物基共聚酯的制备方法 |
CN114133507A (zh) * | 2021-12-29 | 2022-03-04 | 青岛科技大学 | 一种生物基可降解聚氨酯的一锅制备法 |
CN114874512A (zh) * | 2022-06-14 | 2022-08-09 | 江苏顺隆轮胎有限公司 | 一种高弹性自修复内胎材料及其制备方法 |
CN114940740A (zh) * | 2022-06-29 | 2022-08-26 | 华南理工大学 | 一种基于多重可逆作用的高性能透明室温自修复聚氨酯弹性体及制备方法 |
CN115353609A (zh) * | 2022-07-22 | 2022-11-18 | 华东师范大学 | 一种可修复增强的高性能聚氨酯弹性体及制备方法 |
Non-Patent Citations (5)
Title |
---|
Kinetic study of Diels–Alder reaction involving in maleimide–furan compounds and linear polyurethane;Xuanxuan Liu,等;《Polym. Bull.》;第70卷;2319–2335 * |
Synthesis and Characterization of an Electroluminescent Polyester Containing the Ru(II) Complex;Jin-Kyu Lee,等;《Chem. Mater.》;第9卷(第8期);1710-1712 * |
Synthesis and properties of thermotropic liquid-crystalline polymers containing transition metals;Kenji Hanabma,等;《Makromol. Chem.》;第190卷(第1期);1-8 * |
Synthesis of performance-advantaged polyurethanes and polyesters from biomass-derived monomers by aldol-condensation of 5-hydroxymethyl furfural and hydrogenation;Hochan Chang,等;《Green Chemistry》;第23卷;4355-4363 * |
动态可逆交联聚合物的研究进展;郝树杰,等;《热固性树脂》;第36卷(第2期);52-59 * |
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