CN116284681A - 一种耐高温聚氨酯树脂的制备方法与应用 - Google Patents
一种耐高温聚氨酯树脂的制备方法与应用 Download PDFInfo
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Abstract
本发明涉及高分子材料技术领域,公开了一种耐高温聚氨酯树脂的制备方法与应用,采用甲基丙烯酸羟乙酯为封端剂,制备端烯基聚氨酯预聚体乳液,使用1,2‑二马来酰亚胺基乙烷为交联剂,与端烯基聚氨酯预聚体乳液相互交联聚合,采用二‑1‑金刚烷基膦对端羟基聚丁二烯进行改性,使端羟基聚丁二烯结构中含有丰富的金刚烷基膦,由于金刚烷结构中含有稳定的六元环,需要吸收大量的能量才能发生键的断裂,因此,以改性端羟基聚丁二烯为原料制备的聚氨酯树脂具有优异的耐高温性能,另外,二‑1‑金刚烷基膦含有磷元素,可以一定程度上增强聚氨酯树脂的阻燃性能。
Description
技术领域
本发明涉及高分子材料技术领域,具体涉及一种耐高温聚氨酯树脂的制备方法与应用。
背景技术
聚氨酯的结构中含有大量高极性的氨基甲酸酯基团和反应活性较高的异氰酸酯基团,因此对木材等多种材料具有良好的粘力,附着力十分优异,因此在塑料、纸张、皮革、金属、玻璃和木材等材料的粘结领域具有广泛的应用,并且聚氨酯合成简单,加工容易,目前聚氨酯的合成主要采用聚醚多元醇为原料,其较低的内聚能会导致合成的聚氨酯树脂耐热性能较差,导致以聚氨酯树脂为原料制备的胶黏剂在高温环境下易发生水解,进而产生脱胶的现象,不利于聚氨酯树脂在胶黏剂领域的进一步应用,因此需要对聚氨酯进行改性。
通过调节聚氨酯的反应原料,改变聚氨酯的分子链结构,可以提高聚氨酯树脂的耐高温性能,申请号为CN202110635524.8的中国发明专利公开了一种耐高温隔热性聚氨酯密封胶及制备方法,通过对二苯甲烷二异氰酸酯结构中加入硅烷,使其端部与有机硅烷端封剂连接,再进行后续的预聚合、聚合,使用苯酐聚酯多元醇为原料,配合聚醚三醇和小分子扩链剂的使用,使制得的聚氨酯链具有树枝状的结构,进而从结构上提高了聚氨酯密封胶的耐高温隔热性,从而使制备的聚氨酯其具有良好的耐高温性能,但是聚醚三醇本身的低内聚能难免会对聚氨酯树脂的耐热性产生影响,因此,需要改变聚氨酯的大分子二元醇/多元醇原料,才能有效增强聚氨酯树脂的耐高温性能。
发明内容
本发明的目的在于提供一种耐高温聚氨酯树脂的制备方法与应用,通过以1,2-二马来酰亚胺基乙烷为交联剂,以金刚烷改性端羟基聚丁二烯为二元醇原料,使制备的聚氨酯树脂具有优异的耐高温性能。
本发明的目的可以通过以下技术方案实现:
一种耐高温聚氨酯树脂的制备方法包括以下步骤:
(1)将改性端羟基聚丁二烯与甲苯-2,4-二异氰酸酯置于反应器中,搅匀,滴入二月桂酸二丁基锡,将反应器中的温度升高至70-75℃,反应1-4h,待反应器中温度降低至50-60℃,加入溶有1,4-丁二醇的丙酮溶液,反应30-40mi n,使用甲基丙烯酸羟乙酯进行封端处理30-60mi n,反应结束后降温处理,得端烯基聚氨酯预聚体乳液;
(2)将1,2-二马来酰亚胺基乙烷加入端烯基聚氨酯乳液中,搅匀,继续向体系中加入引发剂,升高体系的反应温度至60-80℃,在氮气保护下,反应4-12h,反应结束后降温出料,真空干燥,得耐高温聚氨酯树脂。
进一步地,步骤(2)中,所述引发剂为二叔丁基过氧化物、偶氮二异丁腈或者过氧化苯甲酰中的任意一种。
通过上述技术方案,以改性端羟基聚丁二烯为二元醇原料,甲苯-2,4-二异氰酸酯为二元异氰酸酯原料,配合1,4-丁二醇扩链剂和甲基丙烯酸羟乙酯封端剂,制备端烯基聚氨酯预聚体乳液,以1,2-二马来酰亚胺基乙烷为交联剂,在引发剂的作用下,发生交联聚合,得马来酰亚胺交联耐高温聚氨酯树脂。
进一步地,步骤(1)中,所述改性端羟基聚丁二烯的制备方法包括以下步骤:
S1:将端羟基聚丁二烯倒入甲苯中,升高温度至80-90℃,搅拌至完全溶解,待反应液中温度降低至40-50℃,加入甲酸水溶液,待温度降低至室温后,加入浓度为30%的双氧水,继续反应6-18h,反应结束后,使用去离子水分离反应液中的双氧水和甲酸,倒入乙醇中析出固体产物,得环氧化端羟基聚丁二烯;
S2:将环氧化聚丁二烯溶解在甲苯中,继续加入二-1-金刚烷基膦混匀,升高温度进行反应,反应结束后,减压蒸馏除去溶剂,真空干燥,得改性端羟基聚丁二烯。
进一步地,步骤S1中,所述端羟基聚丁二烯的平均分子量为2700-3300,羟值为0.47-0.53mmo l/g。
进一步地,步骤S1中,所述甲酸溶液的质量浓度为80-90%。
进一步地,步骤S2中,所述环氧化聚丁二烯和二-1-金刚烷基膦的质量比为1:0.02-0.05。
进一步地,步骤S2中,所述反应的温度为100-110℃,回流反应6-18h。
通过上述技术方案,以甲酸-双氧水为氧化体系,将端羟基聚丁二烯结构中的烯基氧化成环氧基团,得端羟基环氧化聚丁二烯,在高温条件下,其结构中的环氧基团可以与二-1-金刚烷基膦结构中的P-H键发生开环加成反应,从而将二-1-金刚烷基膦共价连接在端羟基聚丁二烯分子链中,得改性端羟基聚丁二烯。
一种耐高温聚氨酯树脂的应用,是将制得的耐高温聚氨酯树脂应用于胶黏剂领域。
本发明的有益效果:
(1)本发明采用甲基丙烯酸羟乙酯为封端剂,制备端烯基聚氨酯预聚体乳液,使用1,2-二马来酰亚胺基乙烷为交联剂,与端烯基聚氨酯预聚体乳液相互交联聚合,使得制备的聚氨酯树脂结构中含有相互缠绕的三维交联网络,进而提高了聚氨酯分子链的交联密度,能够对聚氨酯分子链的运动起到一定的限位作用,阻碍聚氨酯分子链的运动,此外,交联密度的提高有利于聚氨酯树脂承受更高的外界冲击力,因此制备的聚氨酯树脂具有良好的耐高温性能和耐冲击性能,而交联剂1,2-二马来酰亚胺基乙烷结构中含有耐高温性能较强的双马来酰亚胺基团,可以进一步增强聚氨酯树脂的耐高温性能。
(2)本发明采用二-1-金刚烷基膦对端羟基聚丁二烯进行改性,使端羟基聚丁二烯结构中含有丰富的金刚烷基膦,由于金刚烷结构中含有稳定的六元环,需要吸收大量的能量才能发生键的断裂,因此,以改性端羟基聚丁二烯为原料制备的聚氨酯树脂具有更高的耐高温性能,另外,二-1-金刚烷基膦含有磷元素,可以一定程度上增强聚氨酯树脂的阻燃性能,而且摒弃了传统的聚醚多元醇原料,避免了聚醚多元醇内聚能较低,对聚氨酯树脂耐高温性能产生影响。
当然,实施本发明的任一产品并不一定需要同时达到以上所述的所有优点。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例描述所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明实施例1制备的改性端羟基聚丁二烯红外光谱图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中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作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一、改性端羟基聚丁二烯的制备
S1:将端羟基聚丁二烯倒入甲苯中,升高温度至90℃,搅拌至完全溶解,待反应液中温度降低至40℃,加入88%的甲酸水溶液,待温度降低至室温后,加入浓度为30%的双氧水,继续反应12h,反应结束后,使用去离子水分离反应液中的双氧水和甲酸,倒入乙醇中析出固体产物,得环氧化端羟基聚丁二烯,其中端羟基聚丁二烯的平均分子量为3000,羟值为0.5mmo l/g;
S2:将2g环氧化聚丁二烯溶解在甲苯中,继续加入0.06g二-1-金刚烷基膦混匀,升高温度至110℃,回流反应8h,反应结束后,减压蒸馏除去溶剂,真空干燥,得改性端羟基聚丁二烯,图1为改性端羟基聚丁二烯的红外光谱图,其中3481cm-1处为羟基的吸收峰,2995cm-1处为-CH2-的吸收峰,989cm-1处为碳碳双键的吸收峰,代表改性端羟基聚丁二烯中含有未被氧化的碳碳双键,1356cm-1处为金刚烷的吸收峰,代表改性端羟基聚丁二烯结构中含有金刚烷基团,826cm-1处为环氧基团的吸收峰,代表改性端羟基聚丁二烯含有未与二-1-金刚烷基膦反应的环氧基团。
二、耐高温聚氨酯树脂的制备
(1)将10g改性端羟基聚丁二烯与4g甲苯-2,4-二异氰酸酯置于反应器中,搅匀,滴入0.1g二月桂酸二丁基锡,将反应器中的温度升高至70℃,反应1h,待反应器中温度降低至50℃,加入溶有0.6g的1,4-丁二醇的丙酮溶液,反应30mi n,使用0.1g甲基丙烯酸羟乙酯进行封端处理30mi n,反应结束后降温处理,得端烯基聚氨酯预聚体乳液;
(2)将0.5g的1,2-二马来酰亚胺基乙烷加入10g端烯基聚氨酯乳液中,搅匀,继续向体系中加入0.1g偶氮二异丁腈,升高体系的反应温度至60℃,在氮气保护下,反应4h,反应结束后降温出料,真空干燥,得耐高温聚氨酯树脂。
实施例2
耐高温聚氨酯树脂的制备
(1)将10g改性端羟基聚丁二烯与5g甲苯-2,4-二异氰酸酯置于反应器中,搅匀,滴入0.2g二月桂酸二丁基锡,将反应器中的温度升高至70℃,反应3h,待反应器中温度降低至55℃,加入溶有0.8g的1,4-丁二醇的丙酮溶液,反应35mi n,使用0.2g甲基丙烯酸羟乙酯进行封端处理40mi n,反应结束后降温处理,得端烯基聚氨酯预聚体乳液;
(2)将0.6g的1,2-二马来酰亚胺基乙烷加入10g端烯基聚氨酯乳液中,搅匀,继续向体系中加入0.2g过氧化苯甲酰,升高体系的反应温度至70℃,在氮气保护下,反应8h,反应结束后降温出料,真空干燥,得耐高温聚氨酯树脂。
改性端羟基聚丁二烯的制备方法与实施例1相同。
实施例3
耐高温聚氨酯树脂的制备
(1)将10g改性端羟基聚丁二烯与6g甲苯-2,4-二异氰酸酯置于反应器中,搅匀,滴入0.3g二月桂酸二丁基锡,将反应器中的温度升高至75℃,反应4h,待反应器中温度降低至60℃,加入溶有1g的1,4-丁二醇的丙酮溶液,反应40mi n,使用0.3g甲基丙烯酸羟乙酯进行封端处理60mi n,反应结束后降温处理,得端烯基聚氨酯预聚体乳液;
(2)将0.8g的1,2-二马来酰亚胺基乙烷加入端烯基聚氨酯乳液中,搅匀,继续向体系中加入0.3g二叔丁基过氧化物,升高体系的反应温度至80℃,在氮气保护下,反应12h,反应结束后降温出料,真空干燥,得耐高温聚氨酯树脂。
改性端羟基聚丁二烯的制备方法与实施例1相同。
对比例1
耐高温聚氨酯树脂的制备
(1)将10g端羟基聚丁二烯与5g甲苯-2,4-二异氰酸酯置于反应器中,搅匀,滴入0.2g二月桂酸二丁基锡,将反应器中的温度升高至70℃,反应2h,待反应器中温度降低至55℃,加入溶有0.8g的1,4-丁二醇的丙酮溶液,反应35mi n,使用甲基丙烯酸羟乙酯进行封端处理40mi n,反应结束后降温处理,得端烯基聚氨酯预聚体乳液;
(2)将0.6g的1,2-二马来酰亚胺基乙烷加入端烯基聚氨酯乳液中,搅匀,继续向体系中加入0.2g过氧化苯甲酰,升高体系的反应温度至70℃,在氮气保护下,反应8h,反应结束后降温出料,真空干燥,得耐高温聚氨酯树脂。
性能检测:
a、参考标准ASTM D256,使用YK-3653型冲击试验机,测试实施例1-实施例3以及对比例1制备的耐高温聚氨酯树脂的冲击性能,测试结果如下:
从上表中的数据可知,本发明实施例1-实施例3和对比例1制备的耐高温聚氨酯树脂冲击强度相对于市售聚氨酯树脂较高,推测是由于实施例1-实施例3和对比例1制备的耐高温聚氨酯树脂使用1,2-二马来酰亚胺基乙烷交联,具有较高的交联密度,因此冲击强度更高。
b、称取0.5g实施例1-实施例3和对比例1制备的耐高温聚氨酯树脂,将其放置于TGA-1350型热重分析仪中,设置温度范围为30-600℃,升温速率为10℃/mi n,测试其初始分解温度,测试结果如下:
从上表中的数据可知,本发明实施例1-实施例3制备的耐高温聚氨酯树脂初始分解温度较高,因此具有良好的耐高温性能,而对比例1使用普通的端羟基聚丁二烯为原料,因此制备的聚氨酯树脂结构中不含高稳定性的金刚烷基团,因此耐高温性能较差,但是使用1,2-二马来酰亚胺基乙烷进行交联,因此耐高温性能依旧强于市售聚氨酯树脂。
c、参考国家标准GB/T 2406-2009,将实施例1-实施例3和对比例1制备的耐高温聚氨酯树脂注塑成规格为130mm×10mm×3mm的试样,使用CS I-101G极限氧指数仪测试试样的极限氧指数,评价试样的阻燃性能,测试结果如下:
从上表中的数据可知,本发明实施例1-实施例3制备的耐高温聚氨酯树脂极限氧指数较高,而对比例1制备的耐高温聚氨酯树脂与市售聚氨酯树脂的极限氧指数较低,推测是由于本发明实施例1-实施例3使用改性端羟基聚丁二烯为原料,其结构中含有磷元素,因此阻燃性能较好。
注:上述测试中市售聚氨酯树脂购买自湖北巨胜科技有限公司。
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外,在不相互矛盾的情况下,本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (8)
1.一种耐高温聚氨酯树脂的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将改性端羟基聚丁二烯与甲苯-2,4-二异氰酸酯置于反应器中,搅匀,滴入二月桂酸二丁基锡,将反应器中的温度升高至70-75℃,反应1-4h,待反应器中温度降低至50-60℃,加入溶有1,4-丁二醇的丙酮溶液,反应30-40min,使用甲基丙烯酸羟乙酯进行封端处理30-60min,反应结束后降温处理,得端烯基聚氨酯预聚体乳液;
(2)将1,2-二马来酰亚胺基乙烷加入端烯基聚氨酯乳液中,搅匀,继续向体系中加入引发剂,升高体系的反应温度至60-80℃,在氮气保护下,反应4-12h,反应结束后降温出料,真空干燥,得耐高温聚氨酯树脂。
2.根据权利要求1所述的一种耐高温聚氨酯树脂的制备方法,其特征在于,步骤(2)中,所述引发剂为二叔丁基过氧化物、偶氮二异丁腈或者过氧化苯甲酰中的任意一种。
3.根据权利要求1所述的一种耐高温聚氨酯树脂的制备方法,其特征在于,步骤(1)中,所述改性端羟基聚丁二烯的制备方法包括以下步骤:
S1:将端羟基聚丁二烯倒入甲苯中,升高温度至80-90℃,搅拌至完全溶解,待反应液中温度降低至40-50℃,加入甲酸水溶液,待温度降低至室温后,加入浓度为30%的双氧水,继续反应6-18h,反应结束后,使用去离子水分离反应液中的双氧水和甲酸,倒入乙醇中析出固体产物,得环氧化端羟基聚丁二烯;
S2:将环氧化聚丁二烯溶解在甲苯中,继续加入二-1-金刚烷基膦混匀,升高温度进行反应,反应结束后,减压蒸馏除去溶剂,真空干燥,得改性端羟基聚丁二烯。
4.根据权利要求3所述的一种耐高温聚氨酯树脂的制备方法,其特征在于,步骤S1中,所述端羟基聚丁二烯的平均分子量为2700-3300,羟值为0.47-0.53mmol/g。
5.根据权利要求3所述的一种耐高温聚氨酯树脂的制备方法,其特征在于,步骤S1中,所述甲酸溶液的质量浓度为80-90%。
6.根据权利要求3所述的一种耐高温聚氨酯树脂的制备方法,其特征在于,步骤S2中,所述环氧化聚丁二烯和二-1-金刚烷基膦的质量比为1:0.02-0.05。
7.根据权利要求2所述的一种耐高温聚氨酯树脂的制备方法,其特征在于,步骤S2中,所述反应的温度为100-110℃,回流反应6-18h。
8.一种如权利要求1所述的耐高温聚氨酯树脂的应用,其特征在于,将制得的所述耐高温聚氨酯树脂应用于胶黏剂领域。
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