CN114835878A - 一种耐低温高回弹聚氨酯弹性体及其制备方法 - Google Patents
一种耐低温高回弹聚氨酯弹性体及其制备方法 Download PDFInfo
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Abstract
本发明涉及聚氨酯应用技术领域,具体涉及一种耐低温高回弹聚氨酯弹性体及其制备方法。本申请中制备聚氨酯弹性体的原料包括以下质量百分比的组分:聚氨酯预聚物92~96%,扩链剂4~8%,其中所述扩链剂为端叠氮基聚乙二醇和端叠氮基聚四氢呋喃环氧乙烷共聚醚的混合物。通过两种扩链剂相互协同,使得聚氨酯弹性体具有较好的耐低温性,同时力学性能高,满足了一些在寒带周围冬季气温零下地区对力学性能要求较高的应用领域的聚氨酯弹性体的需求。
Description
技术领域
本发明涉及聚氨酯弹性体技术领域,具体涉及一种耐低温高回弹聚氨酯弹性体及其制备方法。
背景技术
聚氨酯弹性体分子主链是由柔性链段(软段)和刚性链段(硬段)交替组成的嵌段共聚物,软段是聚酯或聚醚相对分子质量较高的多元醇,它提供弹性体的韧性、弹性和低温性能,硬段由二异氰酸酯和小相对分子质量的二元胺或二元醇构成,贡献弹性体的刚性、强度和耐热性能。由于市场上大部分热塑性聚氨酯弹性体普遍存在耐低温性能差,在低温环境中物性急剧下降,导致该产品受气候影响比较大;而耐低温性能相对较好的热塑性聚氨酯弹性体的成本又比较高,限制了耐低温热塑性聚氨酯弹性体的普及和应用。因此,开发耐低温效果好的热塑性聚氨酯弹性体膜仍是本领域研究的热点。
公开日为2016年04月13日的中国专利201511031062.X公开了一种耐低温聚氨酯弹性体及其制备方法,该聚氨酯弹性体由组分A和组分B组成,其中组分A为聚氨酯预聚体,由聚酯多元醇、二异氰酸酯和增塑剂制成,组分B为扩链剂,所述的聚酯多元醇由已二酸与1,4丁二醇或由己二酸、乙二醇和1,4丁二醇制备而成,该方法简单易行,且制备的聚氨酯弹性体耐低温性有所提高,但是机械性能较差。
发明内容
为了在提高耐低温性能的同时,使聚氨酯弹性体具有优异的机械性能,本发明提供一种耐低温高回弹聚氨酯弹性体及其制备方法。
一种耐低温高回弹聚氨酯弹性体,原料包括以下质量百分比的组分:聚氨酯预聚物92~96%,扩链剂4~8%;所述聚氨酯预聚物的原料各组分按质量百分比计包括:聚醚多元醇50~70%,二异氰酸酯19~25%,其余为增塑剂;所述扩链剂为端叠氮基聚乙二醇和端叠氮基聚四氢呋喃环氧乙烷共聚醚的混合物,其中各组分按质量百分比计,端叠氮基聚乙二醇占10~90%,端叠氮基聚四氢呋喃环氧乙烷共聚醚占10~90%。
优选的,所述扩链剂为端叠氮基聚乙二醇和端叠氮基聚四氢呋喃环氧乙烷共聚醚的混合物,其中各组分按质量百分比计,端叠氮基聚乙二醇占50%,端叠氮基聚四氢呋喃环氧乙烷共聚醚占50%。
优选的,所述端叠氮基聚四氢呋喃环氧乙烷共聚醚的制备包括以下步骤:
将端羟基环氧乙烷-四氢呋喃共聚物和甲苯混合,加入氯化亚砜进行氯代反应,反应结束除去甲苯和氯化亚砜,洗涤干燥得端氯基聚四氢呋喃环氧乙烷共聚醚;
向端氯基四氢呋喃环氧乙烷共聚醚内加入N,N-二甲基甲酰胺和叠氮化钠进行叠氮反应,产物用二氯甲烷萃取有机相,用去离子水清洗除去N,N-二甲基甲酰胺,旋蒸除去二氯甲烷,得到端叠氮基聚四氢呋喃环氧乙烷共聚醚。
优选的,所述端叠氮基聚乙二醇的数均分子量为150~300。
优选的,所述端叠氮基聚四氢呋喃环氧乙烷共聚醚的数均分子量为3500~4500。
优选的,所述聚醚多元醇为3-甲基四氢呋喃和四氢呋喃的共聚醚二醇。
优选的,所述二异氰酸酯为碳化二亚胺改性二苯甲烷二异氰酸酯或脲酮亚胺改性二苯甲烷二异氰酸酯中的一种。
一种耐低温高回弹聚氨酯弹性体的制备方法,包括以下步骤:
S1:将聚醚多元醇真空脱水,冷却;加入二异氰酸酯和增塑剂升温反应,当NCO含量达到理论值4.0~6.5%时停止反应,得到聚氨酯预聚物;
S2:将聚氨酯预聚物加热,当异氰酸酯指数达到0.90~1.20时;加入预热后的扩链剂,搅拌均匀,浇筑至模具中于凝胶点合模;放置在硫化机上加压硫化脱模;再放置在烘箱中进行二次硫化,得到聚氨酯弹性体。
优选的,步骤S1中,所述真空脱水过程中,脱水温度为100~110℃,真空脱水时间为1~2h,冷却温度为40~50℃;升温反应过程中,温度为75~85℃,反应时间为2~3h。
优选的,步骤S2中,所述聚氨酯预聚物的加热温度为75~85℃;扩链剂的预热温度为95~105℃;硫化机的工作温度为100℃,加压硫化的时间为45~60min;烘箱的温度为100℃,二次硫化的时间为20~24h。
与现有技术相比,本申请具有以下有益效果:
大分子扩链剂端叠氮基聚环氧乙烷四氢呋喃共聚醚(AzTPET)的相对分子质量较大,其扩链的弹性体交联点间的相对分子质量增加,弹性体的体积溶胀率的提高,聚氨酯弹性体的延伸率得到大幅度提高,但是强度有所降低。端叠氮基聚乙二醇(ATPEG)作为小分子扩链剂,扩链后交联点间形成较为均匀的链长,所得的聚氨酯弹性体具有较高的表观密度,使弹性体的拉伸强度保持稳定。两种扩链剂相互协同,在保持耐低温的性能的同时解决了聚醚型聚氨酯弹性体具有较好的耐低温性,抗拉伸强度和抗撕裂能力低的问题,满足了一些在寒带周围冬季气温零下地区对力学性要求较高的应用领域的聚氨酯弹性体的需求。
具体实施方式
下面结合具体实施例对本申请进一步进行描述。
原料:
3-甲基四氢呋喃和四氢呋喃的共聚醚二醇,Mn=2000,购自INVISTA公司;
碳化二亚胺改性二苯甲烷二异氰酸酯购自巴斯夫;
脲酮亚胺改性二苯甲烷二异氰酸酯购自HUNTSMAN公司;
端叠氮基聚乙二醇,数均分子量150~300,购自碳水科技;
端羟基环氧乙烷-四氢呋喃共聚物,数均分子量3500~4000,购自黎明化工研究院;
聚四氢呋喃醚二醇,数均分子量2000,购自巴斯夫;
增塑剂选用邻苯二甲酸二丁酯;
其余化学品均为市售工业级。
以下实施例中的端叠氮基聚四氢呋喃环氧乙烷共聚醚采用如下方法制备而得:
首先向三口烧瓶中加入20mmol端羟基环氧乙烷-四氢呋喃共聚物和50mL甲苯,在搅拌器上混合均匀,同时,将100mmol氯化亚砜溶于10mL甲苯中,在室温下滴加到端羟基环氧乙烷-四氢呋喃共聚物-甲苯溶液中,在85℃下搅拌回流,反应时间为10h,反应结束除去甲苯和多余的二氯亚砜,产物萃取,洗涤并干燥得到端氯基聚四氢呋喃环氧乙烷共聚醚。
然后取5mmol的端氯基聚四氢呋喃环氧乙烷共聚醚加入至三口烧瓶中,再加入200mLN,N-二甲基甲酰胺,室温下,加入25mmol叠氮化钠,升温至85℃搅拌回流,反应时间为24h。将反应物冷却至室温,产物用二氯甲烷萃取有机相,用去离子水清洗除去N,N-二甲基甲酰胺,旋蒸除去二氯甲烷,得到端叠氮基聚四氢呋喃环氧乙烷共聚醚。
实施例1
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将70.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至110℃,在真空中脱水2h,然后将温度冷却至50℃,将19.0g脲酮亚胺改性二苯甲烷二异氰酸酯和11.0g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至85℃,反应时间为3h,计算并控制体系中的NCO含量为4.0%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将92g的聚氨酯预聚物加热至80℃,控制异氰酸酯指数为1.00,将8g扩链剂加热至95℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化60min脱模后,再放置在加热至100℃的烘箱内二次硫化22h,得到聚氨酯弹性体,其中扩链剂包括:50%的端叠氮基聚四氢呋喃环氧乙烷共聚醚、50%的端叠氮基聚乙二醇(Mn=200),本实施例中端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为4000。
实施例2
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将70.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至100℃,在真空中脱水1.5h,然后将温度冷却至40℃,将22.0g碳化二亚胺改性二苯甲烷二异氰酸酯和8.0g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至85℃,反应时间为2h,计算并控制体系中的NCO含量为4.0%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将92g的聚氨酯预聚物加热至85℃,控制异氰酸酯指数为1.00,将8g扩链剂加热至105℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化60min脱模后,再放置在加热至100℃的烘箱内二次硫化24h,得到聚氨酯弹性体,其中扩链剂包括:50%的端叠氮基聚四氢呋喃环氧乙烷共聚醚、50%的端叠氮基聚乙二醇(Mn=150),本实施例中端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为3500。
实施例3
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将50.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至105℃,在真空中脱水1h,然后将温度冷却至45℃,将25.0g脲酮亚胺改性二苯甲烷二异氰酸酯和25.0g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至80℃,反应时间为2.5h,计算并控制体系中的NCO含量为5.0%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将94g的聚氨酯预聚物加热至85℃,控制异氰酸酯指数为1.20,将6g扩链剂加热至95℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化45min脱模后,再放置在加热至100℃的烘箱内二次硫化24h,得到聚氨酯弹性体,其中扩链剂包括:90%的端叠氮基聚四氢呋喃环氧乙烷共聚醚、10%的端叠氮基聚乙二醇(Mn=300),本实施例中端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为4000。
实施例4
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将60.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至110℃,在真空中脱水2h,然后将温度冷却至50℃,将25.0g碳化二亚胺改性二苯甲烷二异氰酸酯和15.0g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至82℃,反应时间为3h,计算并控制体系中的NCO含量为4.0%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将96g的聚氨酯预聚物加热至75℃,控制异氰酸酯指数为0.90,将4g扩链剂加热至100℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化50min脱模后,再放置在加热至100℃的烘箱内二次硫化20h,得到聚氨酯弹性体。其中扩链剂包括:40%的端叠氮基聚四氢呋喃环氧乙烷共聚醚、60%的端叠氮基聚乙二醇(Mn=200),本实施例中端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为4500。
实施例5
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将70.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至110℃,在真空中脱水2h,然后将温度冷却至50℃,将19.5g脲酮亚胺改性二苯甲烷二异氰酸酯和10.5g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至75℃,反应时间为3h,计算并控制体系中的NCO含量为6.5%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将95g的聚氨酯预聚物加热至80℃,控制异氰酸酯指数为1.00,将5g扩链剂加热至100℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化60min脱模后,再放置在加热至100℃的烘箱内二次硫化24h,得到聚氨酯弹性体,其中扩链剂包括:10%的端叠氮基聚四氢呋喃环氧乙烷共聚醚、90%的端叠氮基聚乙二醇(Mn=150),本实施例中端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为3500。
实施例6
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将70.0g的聚四氢呋喃醚二醇加热至110℃,在真空中脱水2h,然后将温度冷却至50℃,将19.5g二苯基甲烷二异氰酸酯和10.5g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至75℃,反应时间为3h,计算并控制体系中的NCO含量为6.5%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将95g的聚氨酯预聚物加热至80℃,控制异氰酸酯指数为1.00,将5g扩链剂加热至100℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化60min脱模后,再放置在加热至100℃的烘箱内二次硫化24h,得到聚氨酯弹性体,其中扩链剂包括:60%的端叠氮基聚四氢呋喃环氧乙烷共聚醚、40%的端叠氮基聚乙二醇(Mn=200),本实施例中端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为4000。
对比例1
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将70.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至110℃,在真空中脱水2h,然后将温度冷却至50℃,将19.0g脲酮亚胺改性二苯甲烷二异氰酸酯和11.0g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至85℃,反应时间为3h,计算并控制体系中的NCO含量为4.0%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将92g的聚氨酯预聚物加热至80℃,控制异氰酸酯指数为1.00,将8g扩链剂4,4'-二氨基-3,3'-二氯二苯甲烷(MOCA)加热至95℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化60min脱模后,再放置在加热至100℃的烘箱内二次硫化22h,得到聚氨酯弹性体。
对比例2
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将70.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至110℃,在真空中脱水2h,然后将温度冷却至50℃,将19.0g脲酮亚胺改性二苯甲烷二异氰酸酯和11.0g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至85℃,反应时间为3h,计算并控制体系中的NCO含量为4.0%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将92g的聚氨酯预聚物加热至80℃,控制异氰酸酯指数为1.00,将8g扩链剂端叠氮基聚四氢呋喃环氧乙烷共聚醚加热至95℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化60min脱模后,再放置在加热至100℃的烘箱内二次硫化22h,得到聚氨酯弹性体,本对比例中端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为4000。
对比例3
一种耐低温高回弹聚氨酯弹性体的制备包括以下步骤:
步骤一:将70.0g的3-甲基四氢呋喃/四氢呋喃共聚醚二醇加热至110℃,在真空中脱水2h,然后将温度冷却至50℃,将19.0g脲酮亚胺改性二苯甲烷二异氰酸酯和11.0g增塑剂加入到3-甲基四氢呋喃/四氢呋喃共聚醚二醇中,加热温度至85℃,反应时间为3h,计算并控制体系中的NCO含量为4.0%,当达到理论值时停止反应,得到聚氨酯预聚物。
步骤二:将92g的聚氨酯预聚物加热至80℃,控制异氰酸酯指数为1.00,将8g扩链剂端叠氮基聚乙二醇加热至95℃加入到预聚物中搅拌均匀,浇注于预热温度至100℃的模具中于凝胶点合模后,放置在硫化剂上加压硫化60min脱模后,再放置在加热至100℃的烘箱内二次硫化22h,得到聚氨酯弹性体,本对比例中端叠氮基聚乙二醇的数均分子量为200。
对实施例1-6和对比例1-2所得聚氨酯弹性体进行力学性能和耐寒性能测试,测试结果见表1。
拉伸性能按照GB/T528—2009进行测试;
硬度按照GB/T531.1—2008进行测试;
压缩耐寒系数参照HG/T3866—2008的方法测试;
压缩永久变形参照GB/T1683—2018进行测试。
表1耐寒性能和力学性能测试结果
与对比例1相比,对比例2的压缩耐寒系数有所升高,说明以端叠氮基聚环氧乙烷四氢呋喃共聚醚作为扩链剂,在一定程度上可以提高聚氨酯弹性体的耐低温性。
与对比例1相比,对比例3的强度性能有所提升,说明以端叠氮基聚乙二醇作为扩链剂,可以使弹性体具有较好的拉伸强度。
与对比例2和对比例3相比,实施例1-6的强度性能和压缩耐寒系数均有显著升高,说明同时使用端叠氮基聚环氧乙烷四氢呋喃共聚醚(AzTPET)和端叠氮基聚乙二醇(ATPEG)作为扩链剂,通过两者协同作用可使聚氨酯弹性体具有耐低温性,并且具有较好的强度性能。
以上具体实施方式仅仅是对本申请的解释,其并不是对本申请的限制,本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改,但只要在本申请的权利要求范围内都受到专利法的保护。
Claims (10)
1.一种耐低温高回弹聚氨酯弹性体,其特征在于:原料包括以下质量百分比的组分:聚氨酯预聚物92~96%,扩链剂4~8%;所述聚氨酯预聚物的原料各组分按质量百分比计包括:聚醚多元醇50~70%,二异氰酸酯19~25%,其余为增塑剂;所述扩链剂为端叠氮基聚乙二醇和端叠氮基聚四氢呋喃环氧乙烷共聚醚的混合物,其中各组分按质量百分比计,端叠氮基聚乙二醇占10~90%,端叠氮基聚四氢呋喃环氧乙烷共聚醚占10~90%。
2.根据权利要求1所述的一种耐低温高回弹聚氨酯弹性体,其特征在于:所述扩链剂为端叠氮基聚乙二醇和端叠氮基聚四氢呋喃环氧乙烷共聚醚的混合物,其中各组分按质量百分比计,端叠氮基聚乙二醇占50%,端叠氮基聚四氢呋喃环氧乙烷共聚醚占50%。
3.根据权利要求1所述的一种耐低温高回弹聚氨酯弹性体,其特征在于:所述端叠氮基聚四氢呋喃环氧乙烷共聚醚的制备包括以下步骤:
将端羟基环氧乙烷-四氢呋喃共聚物和甲苯混合,加入氯化亚砜进行氯代反应,反应结束除去甲苯和氯化亚砜,洗涤干燥得端氯基聚四氢呋喃环氧乙烷共聚醚;
向端氯基四氢呋喃环氧乙烷共聚醚内加入N,N-二甲基甲酰胺和叠氮化钠进行叠氮反应,产物用二氯甲烷萃取有机相,用去离子水清洗除去N,N-二甲基甲酰胺,旋蒸除去二氯甲烷,得到端叠氮基聚四氢呋喃环氧乙烷共聚醚。
4.根据权利要求1所述的一种耐低温高回弹聚氨酯弹性体,其特征在于:所述端叠氮基聚乙二醇的数均分子量为150~300。
5.根据权利要求3所述的一种耐低温高回弹聚氨酯弹性体,其特征在于:所述端羟基环氧乙烷-四氢呋喃共聚物的数均分子量为3500~4500。
6.根据权利要求1所述的一种耐低温高回弹聚氨酯弹性体,其特征在于:所述聚醚多元醇为3-甲基四氢呋喃和四氢呋喃的共聚醚二醇。
7.根据权利要求1所述的一种耐低温高回弹聚氨酯弹性体,其特征在于:所述二异氰酸酯为碳化二亚胺改性二苯甲烷二异氰酸酯或脲酮亚胺改性二苯甲烷二异氰酸酯中的一种。
8.根据权利要求1-7任一项所述的一种耐低温高回弹聚氨酯弹性体的制备方法,其特征在于:包括以下步骤:
S1:将聚醚多元醇真空脱水,冷却;加入二异氰酸酯和增塑剂升温反应,当NCO含量达到理论值4.0~6.5%时停止反应,得到聚氨酯预聚物;
S2:将聚氨酯预聚物加热,当异氰酸酯指数达到0.90~1.20时;加入预热后的扩链剂,搅拌均匀,浇筑至模具中于凝胶点合模;放置在硫化机上加压硫化脱模;再放置在烘箱中进行二次硫化,得到聚氨酯弹性体。
9.根据权利要求8所述的一种耐低温高回弹聚氨酯弹性体的制备方法,其特征在于:步骤S1中,所述真空脱水过程中,脱水温度为100~110℃,真空脱水时间为1~2h,冷却温度为40~50℃;升温反应过程中,温度为75~85℃,反应时间为2~3h。
10.根据权利要求8所述的一种耐低温高回弹聚氨酯弹性体的制备方法,其特征在于:步骤S2中,所述聚氨酯预聚物的加热温度为75~85℃;扩链剂的预热温度为95~105℃;硫化机的工作温度为100℃,加压硫化的时间为45~60min;烘箱的温度为100℃,二次硫化的时间为20~24h。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115819715A (zh) * | 2023-02-14 | 2023-03-21 | 旭川化学(苏州)有限公司 | 一种凝胶冰垫聚氨酯原液及其制备方法和凝胶冰垫 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5223056A (en) * | 1992-01-21 | 1993-06-29 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government | Azido thermoplastic elastomers |
US5240523A (en) * | 1988-07-11 | 1993-08-31 | Thiokol Corporation | Binders for high-energy composition utilizing cis-,cis-1,3,5-tri(isocyanatomethyl)cyclohexane |
US20010047072A1 (en) * | 2000-05-02 | 2001-11-29 | Sanderson Andrew J. | Chain-extended poly(bis-azidomethyloxetane), and combustible cartridge cases and ammunition comprising the same |
KR20110119064A (ko) * | 2010-04-26 | 2011-11-02 | 국방과학연구소 | 아지도 디올 사슬연장제를 함유하는 에너지 함유 폴리우레탄 열가소성 탄성체 |
CN102241820A (zh) * | 2011-03-03 | 2011-11-16 | 华东理工大学 | 一种新型聚三唑弹性体及其制备方法 |
CN105542114A (zh) * | 2016-01-29 | 2016-05-04 | 上海益弹新材料有限公司 | 一种软段中含有氰基的热塑性聚氨酯弹性体及其制备方法 |
CN108976406A (zh) * | 2018-07-24 | 2018-12-11 | 西安近代化学研究所 | 一种氯化聚醚二元醇及其合成方法 |
CN110591041A (zh) * | 2018-06-13 | 2019-12-20 | 南京理工大学 | 一种具有自修复性的热塑性叠氮聚氨酯弹性体及其制备方法 |
CN112266461A (zh) * | 2020-09-29 | 2021-01-26 | 广东互典缓冲材料技术有限公司 | 一种能够低温环境下使用的缓冲材料及其制备方法与应用 |
US20210155737A1 (en) * | 2019-11-25 | 2021-05-27 | Covestro Llc | Azido-alkyne click and oxysilane hybrid compositions |
US20210155738A1 (en) * | 2019-11-25 | 2021-05-27 | Covestro Llc | Allophanate carbamate azido-alkyne click compositions |
-
2022
- 2022-04-27 CN CN202210459073.1A patent/CN114835878A/zh active Pending
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5240523A (en) * | 1988-07-11 | 1993-08-31 | Thiokol Corporation | Binders for high-energy composition utilizing cis-,cis-1,3,5-tri(isocyanatomethyl)cyclohexane |
US5223056A (en) * | 1992-01-21 | 1993-06-29 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence Of Her Majesty's Canadian Government | Azido thermoplastic elastomers |
US20010047072A1 (en) * | 2000-05-02 | 2001-11-29 | Sanderson Andrew J. | Chain-extended poly(bis-azidomethyloxetane), and combustible cartridge cases and ammunition comprising the same |
KR20110119064A (ko) * | 2010-04-26 | 2011-11-02 | 국방과학연구소 | 아지도 디올 사슬연장제를 함유하는 에너지 함유 폴리우레탄 열가소성 탄성체 |
CN102241820A (zh) * | 2011-03-03 | 2011-11-16 | 华东理工大学 | 一种新型聚三唑弹性体及其制备方法 |
CN105542114A (zh) * | 2016-01-29 | 2016-05-04 | 上海益弹新材料有限公司 | 一种软段中含有氰基的热塑性聚氨酯弹性体及其制备方法 |
CN110591041A (zh) * | 2018-06-13 | 2019-12-20 | 南京理工大学 | 一种具有自修复性的热塑性叠氮聚氨酯弹性体及其制备方法 |
CN108976406A (zh) * | 2018-07-24 | 2018-12-11 | 西安近代化学研究所 | 一种氯化聚醚二元醇及其合成方法 |
US20210155737A1 (en) * | 2019-11-25 | 2021-05-27 | Covestro Llc | Azido-alkyne click and oxysilane hybrid compositions |
US20210155738A1 (en) * | 2019-11-25 | 2021-05-27 | Covestro Llc | Allophanate carbamate azido-alkyne click compositions |
CN112266461A (zh) * | 2020-09-29 | 2021-01-26 | 广东互典缓冲材料技术有限公司 | 一种能够低温环境下使用的缓冲材料及其制备方法与应用 |
Non-Patent Citations (1)
Title |
---|
蔡如琳 等: "PBT 基叠氮型聚氨酯弹性体的形态结构与微相分离", 《固体火箭技术》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115819715A (zh) * | 2023-02-14 | 2023-03-21 | 旭川化学(苏州)有限公司 | 一种凝胶冰垫聚氨酯原液及其制备方法和凝胶冰垫 |
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