CN106496502A - 一种制备高稳定性的螺吡喃聚氨酯复合物的方法 - Google Patents
一种制备高稳定性的螺吡喃聚氨酯复合物的方法 Download PDFInfo
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Abstract
本发明公开了一种制备高稳定性的螺吡喃聚氨酯复合物的方法,包括:螺吡喃按照质量比为1:10~1000添加到聚氨酯预聚体中,得到螺吡喃复合的聚氨酯预聚体。再将质量比1:1~50的功能性倍半硅氧烷和扩链剂添加到螺吡喃复合的聚氨酯预聚体中得到功能性倍半硅氧烷复合的螺吡喃聚氨酯。反应温度为25℃~100℃,反应时间为1h~36h,最终得到耐高温、抗老化的螺吡喃聚氨酯。本方法工艺简单,反应条件温和,原料易得,最终得到的螺吡喃聚氨酯复合物具有耐高温、抗氧化的特性,可广泛应用于高温下的响应型弹性体,高温光敏涂料、保护涂层等领域。
Description
技术领域
本发明属于聚合物复合物以及响应型聚合物技术领域,具体涉及一种提高螺吡喃在聚氨酯中稳定性的方法。
背景技术
螺吡喃是一种光响应、pH响应以及力学响应型化合物,其在外界条件的刺激下会由闭合结构的螺吡喃转变为具有共轭结构的部花菁。螺吡喃作为一种新型化合物被广泛应用于聚合物中,2009年首次被应用于聚甲基丙烯酸酯中得到紫外响应型和力学响应型的聚合物。自此,螺吡喃在各类力学响应聚合物中被广泛应用并深入研究,其中螺吡喃复合聚氨酯因其回复性好,响应速度快等优点更受到研究者的青睐(C.K.Lee,D.A.Davis,S.R.White,J.S.Moore,N.R.Sottos,P.V.Braun,Journal of the American ChemicalSociety,2010,132,16107-16111),其在光学传感器、力学传感器以及3D打印等领域具有广阔的应用前景。
当前制备螺吡喃复合聚合物主要有以下几类:螺吡喃以嵌段形式反应到聚合物主链中;螺吡喃以侧链接枝到聚合物侧链中以及螺吡喃与聚合物物理混合。其中化学反应型螺吡喃聚合物复合物具有稳定性好,不易分相等优点。
尽管螺吡喃在聚合物中具有光学响应和力学响应的特征。然而,Lukas Metzler(Lukas Metzler,Thomas Reichenbach,Oliver Brügner,Hartmut Komber,FlorianLombeck,Stefan Müllers,Ralf Hanselmann,Har-ald Hillebrecht,Michael Walterband Michael Sommer,Polym.Chem.,2015,6,3694–3707)等人报道了螺吡喃在高温下易发生分解,Jeffrey S.Moore(Brett A.Beiermann,Douglas A.Davis,SharlotteL.B.Kramer,Jeffrey S.Moore,Nancy R.Sottos and Scott R.White,J.Mater.Chem.,2011,21,8443–8447)等人报道了螺吡喃在酸性条件下易发生水解裂解,这些苛刻的条件会导致螺吡喃在聚合物中发生老化,从而使得光学、力学响应能力变弱,最终导致材料的使用寿命降低。因此需要一种来提高螺吡喃在聚合物中稳定性的方法来提高材料的使用寿命。
发明内容
发明目的:针对现有螺吡喃在聚合物中不稳定的缺点,本发明的目的是提供一种制备高稳定性的螺吡喃聚氨酯复合物的方法,具有简单快捷,反应条件温和,原料便宜易得等优点,得到的螺吡喃聚氨酯复合物的稳定性得到了明显的提升。
技术方案:为了实现上述发明目的,本发明采用的技术方案如下:
一种制备高稳定性的螺吡喃聚氨酯复合物的方法,包括以下步骤:
1)将质量比为1:10~1000的螺吡喃单体加入到聚氨酯预聚体中,反应温度为25℃-90℃,搅拌反应1h~10h,得到螺吡喃复合的聚氨酯预聚体;
2)向步骤1)的螺吡喃复合的聚氨酯预聚体中加入功能化倍半硅氧烷和扩链剂,其中功能性倍半硅氧烷与螺吡喃复合的聚氨酯预聚体的质量比为1:1~50,扩链剂与聚氨酯预聚体的质量比不大于6/100;反应温度为25℃~100℃,反应时间为1h~36h,得到螺吡喃聚氨酯复合物。
所用的螺吡喃的结构式如下:
式中,R1,R2,R3均选自H、羟基、酚羟基、氨基活性基团,且R1,R2,R3不同时为H。
步骤1)中,选用的聚氨酯预聚体为异氰酸酯封端的聚氨酯预聚体,其由多异氰酸酯和聚合物多元醇反应而成。所选用的多异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯,六亚甲基二异氰酸酯中的一种或者几种的混合。
步骤1)中,所选用的预聚体中的聚合物多元醇为聚四氢呋喃醚二醇、聚酯二元醇、端羟基聚二甲基硅烷、聚环氧丙烷多元醇以及端氨基聚环氧丙烷其中的一种或几种的混合。
步骤2)中,所用的功能化倍半硅氧烷符合通式(RSiO1.5)n,其中n=4-16的整数,R选自苯胺甲基、氨丙基、环己胺甲基、苯胺丙基。如果选用惰性的倍半硅氧烷则不能很好地分散到聚合物中并与聚合物反应,因而对螺吡喃的保护作用会削弱。
步骤2)中,所用的扩链剂为1,4-丁二醇、乙二醇、乙二胺、甘油中的一种或几种混合。
步骤(1)中,螺吡喃单体与聚氨酯预聚体的比例为1:10~1000,螺吡喃不宜在聚合物中添加过多,否则容易导致聚合物颜色太深,而且会因为位阻原因导致聚合物的分子量无法长大。
步骤(2)中所述的功能化倍半硅氧烷:螺吡喃聚氨酯预聚物质量比为1:1~50,功能化倍半硅氧烷不宜添加太多,否则会导致体系发生分相,从而影响材料的力学性能。
反应温度为25℃~90℃,反应温度太低会使得反应无法进行,而温度太高会导致反应中螺吡喃结构被破坏。
有益效果:与现有技术相比,本发明的优点包括工艺方法简单快捷,反应条件温和,所用的原料易得,使得螺吡喃在聚氨酯体系中长期稳定存在。该方法亦可广泛应用于其他螺吡喃基聚合物中如螺吡喃聚丙烯酸酯,螺吡喃硅橡胶等体系,具有很好的实用性。
附图说明
图1是苯胺甲基倍半硅氧烷复合的螺吡喃聚氨酯紫外照射前后实物照片图;
图2是不同聚氨酯体系螺吡喃热稳定性对比图。
具体实施方式
下面结合具体的实施例对本发明做进一步的说明。
实施例1
将0.1g羟基修饰的螺吡喃单体与2.5g MDI混合,加热到60℃反应2h,继而加入60g聚四氢呋喃醚(分子量=1000)和18.48g六亚甲基二异氰酸酯(HDI),并在45℃下反应2h,得到螺吡喃修饰的聚氨酯预聚物。向上述预聚物中加入3.8g苯胺甲基倍半硅氧烷和4.3g 1,4-丁二醇继续在80℃下反应12h,得到苯胺甲基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例2
将0.1g羟基修饰的螺吡喃单体与2.5g甲苯二异氰酸酯(TDI)混合,加热到60℃反应2h,继而加入60g聚四氢呋喃醚(分子量=1000)和18.48g六亚甲基二异氰酸酯(HDI),并在45℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入7.6g苯胺甲基倍半硅氧烷和3.2g 1,4-丁二醇继续在25℃下反应36h,得到苯胺甲基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例3
将0.1g羟基修饰的螺吡喃单体与2.5g二苯甲烷二异氰酸酯MDI混合,加热到60℃反应2h,继而加入60g聚四氢呋喃醚(分子量=1000)和18.48g六亚甲基二异氰酸酯(HDI),并在45℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入7.0g环己胺甲基倍半硅氧烷和3.2g 1,4-丁二醇继续在100℃下反应1h,得到环己胺甲基甲基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例4
将0.1g胺基螺吡喃单体与2.5g二苯甲烷二异氰酸酯MDI混合,加热到40℃反应2h,继而加入120g聚酯二元醇(分子量=2000)和18.48g六亚甲基二异氰酸酯(HDI),并在60℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入8.0g苯胺丙基倍半硅氧烷和3.0g 1,4-丁二醇继续在60℃下反应8h,得到苯胺丙基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例5
将0.1g羟基修饰的螺吡喃单体与2.5g二苯甲烷二异氰酸酯MDI混合,加热到60℃反应2h,继而加入60g端羟基聚二甲基硅烷(分子量=1000)和18.48g六亚甲基二异氰酸酯(HDI),并在45℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入5.0g氨丙基倍半硅氧烷和2.0g 1,4-丁二醇继续在30℃下反应12h,得到氨丙基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例6
将0.2g酚羟基修饰的螺吡喃单体与2.5g六亚甲基二异氰酸酯(HDI)混合,加热到90℃反应10h,继而加入60g聚四氢呋喃醚二醇(分子量=1000)和13.4g异佛尔酮二异氰酸酯(IPDI),并在45℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入11.3g苯胺甲基倍半硅氧烷和2.1g 1,4-丁二醇继续在70℃下反应20h,得到苯胺甲基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例7
将0.2g胺基修饰的螺吡喃单体与2.5g甲苯二异氰酸酯(TDI)混合,加热到25℃反应1h,继而加入60g聚四氢呋喃醚二醇(分子量=1000)和13.4g异佛尔酮二异氰酸酯(IPDI),并在45℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入76.1g苯胺甲基倍半硅氧烷继续在80℃下反应12h,得到苯胺甲基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例8
将0.1g羟基修饰的螺吡喃单体与2.5g二苯甲烷二异氰酸酯(MDI)混合,加热到90℃反应1h,继而加入60g聚四氢呋喃醚(分子量=1000)和18.48g六亚甲基二异氰酸酯(HDI),并在45℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入3.8g苯胺甲基倍半硅氧烷和4.3g 1,4-丁二醇继续在80℃下反应12h,得到苯胺甲基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例9
将0.1g羟基修饰的螺吡喃单体与2.5g二苯甲烷二异氰酸酯(MDI)混合,加热到50℃反应5h,继而加入60g聚乙二醇(分子量=1000)和18.48g六亚甲基二异氰酸酯(HDI),并在45℃下反应2h。得到螺吡喃修饰的聚氨酯预聚物;向上述预聚物中加入3.8g苯基倍半硅氧烷和3.68g甘油继续在65℃下反应24h,得到苯基倍半硅氧烷复合的螺吡喃聚氨酯。
实施例10
不添加功能性倍半硅氧烷螺吡喃聚氨酯的制备。将0.1g羟基修饰的螺吡喃单体与2.5g MDI混合,加热到60℃反应2h,继而加入60g聚四氢呋喃醚(分子量=1000)和18.48g六亚甲基二异氰酸酯(HDI),并在45℃下反应2h,得到螺吡喃修饰的聚氨酯预聚物。向上述预聚物中加入3.68g甘油继续在90℃下反应12h,得到未添加功能性倍半硅氧烷复合的螺吡喃聚氨酯。
实施例11
取实施例中1-9中任一制备的功能化倍半硅氧烷复合的螺吡喃聚氨酯以及实施例10中制备的未添加功能性倍半硅氧烷的螺吡喃聚氨酯,进行高温螺吡喃热稳定性实验。将样品在室温下,白光条件下照射12h以确保体系中所有的螺吡喃都保持闭环结构。如图1所示,左图为螺吡喃聚氨酯复合物在白光照射12h后的照片,为无色透明状态。将样品放置在70℃下加热不同时间(0h,0.5h,1h,1.5h,2h)后,用紫外灯照射5min,由于螺吡喃具有紫外响应性,材料变为紫色(如图1右图所示),并记录加热后材料在最大吸收峰位置的吸收值。如图2所示,对比添加和不添加功能化倍半硅氧烷体系的吸收强度变化,添加功能性倍半硅氧烷体系的紫外吸收强度衰减程度远高于未添加功能性倍半硅氧烷体系,可见本发明制备出了高稳定性的螺吡喃聚氨酯复合物。
Claims (7)
1.一种制备高稳定性的螺吡喃聚氨酯复合物的方法,其特征在于,包括以下步骤:
1)将质量比为1:10~1000的螺吡喃单体加入到聚氨酯预聚体中,反应温度为25℃-90℃,搅拌反应1h~10h,得到螺吡喃复合的聚氨酯预聚体;
2)向步骤1)的螺吡喃复合的聚氨酯预聚体中加入功能化倍半硅氧烷和扩链剂,其中功能性倍半硅氧烷与螺吡喃复合的聚氨酯预聚体的质量比为1:1~50,扩链剂与聚氨酯预聚体的质量比不大于6/100;反应温度为25℃~100℃,反应时间为1h~36h,得到螺吡喃聚氨酯复合物。
2.根据权利要求1所述的提高螺吡喃在聚氨酯中稳定性的方法,其特征在于:所用的螺吡喃的结构式如下:
式中,R1,R2,R3均选自H、羟基、酚羟基、氨基活性基团,且R1,R2,R3不同时为H。
3.根据权利要求1所述的制备高稳定性的螺吡喃聚氨酯复合物的方法,其特征在于:步骤1)中,选用的聚氨酯预聚体为异氰酸酯封端的聚氨酯预聚体,其由多异氰酸酯和聚合物多元醇反应而成。
4.根据权利要求1所述的制备高稳定性的螺吡喃聚氨酯复合物的方法,其特征在于:所选用的多异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯,六亚甲基二异氰酸酯中的一种或者几种的混合。
5.根据权利要求1所述的制备高稳定性的螺吡喃聚氨酯复合物的方法,其特征在于,步骤1)中,所选用的预聚体中的聚合物多元醇为聚四氢呋喃醚二醇、聚酯二元醇、端羟基聚二甲基硅烷、聚环氧丙烷多元醇以及端氨基聚环氧丙烷其中的一种或几种的混合。
6.根据权利要求1所述的制备高稳定性的螺吡喃聚氨酯复合物的方法,其特征在于:步骤2)中,所用的功能化倍半硅氧烷符合通式(RSiO1.5)n,其中n=4-16的整数,R选自苯胺甲基、氨丙基、环己胺甲基、苯胺丙基。
7.根据权利要求1所述的制备高稳定性的螺吡喃聚氨酯复合物的方法,其特征在于:步骤2)中,所用的扩链剂为1,4-丁二醇、乙二醇、乙二胺、甘油其中的一种或几种混合。
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