CN115322123B - 一种卤素改性偶氮类二胺扩链剂、其制备方法及用途 - Google Patents
一种卤素改性偶氮类二胺扩链剂、其制备方法及用途 Download PDFInfo
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Abstract
本发明涉及一种卤素改性偶氮类二胺扩链剂、其制备方法及用途,所得到的卤素改性偶氮类二胺扩链剂可以与异氰酸酯及可生物降解聚酯多元醇共同使用,生产聚氨酯相关制品。因扩链剂特殊的结构设计,使其可进一步提升聚氨酯制品力学性能,防火性能的同时,可有效提升其制品的可降解能力,促进制品的降解速度。同时在降解过程中的产物,因可起到肥料作用,使其降解后产物更有利于进行填埋处理,及使填埋土地更有效的进行农行利用。该类制品可应用于聚氨酯涂料、体育铺装材料等领域。
Description
技术领域
本发明属于聚氨酯领域,具体的涉及一种卤素改性偶氮类二胺扩链剂及其制备方法。
背景技术
扩链剂是聚氨酯配方中常用的助剂。扩链剂可起到使聚合物硬段分子链延伸,生成分子量更大的线性分子,增加硬段含量,提升力学性能的作用。其中二胺是一种重要的扩链剂种类。其较强的活性可应用于聚氨酯涂料、聚氨酯弹性体、体育铺装材料等领域。
聚氨酯是由异氰酸酯、聚酯或者聚醚多元醇通过热固化反应得到的交联体型结构聚合物材料,原材料完全依赖于石油基资源。随着社会的进步和发展,石油资源日渐枯竭,严重限制了聚氨酯工业的发展。同时聚氨酯材料废弃后不可回收利用,在自然环境下难以降解,造成“白色污染”。处理聚氨酯废弃物的方法以填埋和焚烧为主,“填埋处理”占用土地资源,造成土壤劣化,而“焚烧处理”产生大量有毒气体,造成严重空气污染。因此,开发环境友好的可生物降解聚氨酯材料成为材料领域的焦点。
近年来可降解聚氨酯研究成为了研究的热点内容。专利CN102977330A提供了一种利用液化生物质与淀粉的共混物为原料制备可降解聚氨酯材料,以液化生物质与淀粉的共混物为多元醇,在催化剂、表面活性剂和发泡剂的存在下,与多异氰酸酯聚合,调整原料的质量份数比,可得到发泡类、软质类、半硬质类和硬质类聚氨酯制品。但该体系中可降解部分仅为其中的多元醇组分,即聚氨酯中的软段部分。其中还保留大量无法进行降解的硬段部分,从而整个体系降解效果有限。专利CN104387553A提供了一种生物可降解不饱和聚氨酯材料的制备方法,即采用不饱和聚酯多元醇聚富马酸丙二醇酯作为软段,利用其聚酯的可降解性,实现材料的生物降解功能。同时聚氨酯主链结构带有大量不饱和缺电子双键,可便于对材料进行进一步改性。该专利虽然在主链结构中引入不饱和双键结构,但并未对聚氨酯的降解性起到有利作用。
发明内容
本发明的目的在于提供一种卤素改性偶氮类二胺扩链剂。该扩链剂因其自身结构包含的多芳环结构,提升了硬段的刚性,可有效提升聚氨酯产品的拉伸强度,硬度等力学性能。同时使用该扩链剂的聚氨酯产品可保证在一定外界条件作用下进行分解,因扩链剂属聚氨酯硬段部分,通过其自身的降解可解决聚氨酯硬段降解问题;其在降解过程中所分解出的尿素单体因其自身的碱性可有效促进体系中存在的聚酯多元醇的分解,从而可在软硬链段两方面均实现有效降解,提升聚氨酯制品的整体的降解能力。
为了克服现有技术的不足,本发明提供以下方案:
一方面,本发明提供一种卤素改性偶氮类二胺扩链剂,其结构式为:
其中R1为C1-C20的烷基,X为F,Cl,Br,I等卤素元素;进一步的,R1优选C1-C4的烷基,更优选甲基、乙基、丙基、异丙基或丁基。
在一些具体的实施方式中,所述卤素改性偶氮类二胺的结构如下:
另一方面,本发明提供了卤素改性偶氮类二胺扩链剂的制备方法,所述制备方法包括以下步骤:将伯胺基卤代二胺、尿素与锌粉催化剂加入到反应器中,在60~120℃条件下,反应2-3小时,生成卤素改性偶氮类二胺。
其中,伯胺基卤代二胺结构为:
其中R1为C1-C20的烷基,X为F,Cl,Br,I等卤素元素;进一步的,R1优选C1-C4的烷基,更优选甲基、乙基、丙基、异丙基或丁基。
其中,伯胺基卤代二胺与尿素摩尔比为1:1~3;
催化剂的加入量是伯胺基卤代二胺和尿素物质量之和的1~5%。
在一个具体的实施方式中,反应方程式为:
伯胺基卤代二胺制备方法包括:(1)将苯胺与冰醋酸单体在金属锌催化作用下,在80~120℃条件,反应2-3小时,生成乙酰苯胺;
(2)生成的乙酰苯胺经硝酸与硫酸混合酸液体的反向滴定,在30~50℃条件下,反应1-2小时,进行硝化反应,生成邻硝基苯胺;
(3)生成的邻硝基苯胺与溴化铜硫酸溶液在60~100℃条件下,反应1-2小时,生成邻溴苯胺。
(4)生成的邻溴苯胺与甲醛在80~120℃条件下,反应2-4小时,生成伯胺基卤代二胺。
优选的,所述步骤(1)中苯胺与冰醋酸单体摩尔比为1:1~2;
所述步骤(1)中的金属锌催化剂为锌粉,用量是苯胺与冰醋酸单体物质量之和的1-5%;所述步骤(1)的反应路线如下:
所述步骤(2)中混合酸液体中硝酸与硫酸的摩尔比为1:1~2;乙酰基苯胺与混合酸液体的摩尔比为10:1~3。
所述步骤(2)的反应路线如下:
所述步骤(3)中邻硝基苯胺与溴化铜硫酸溶液摩尔比为1:2~3;溴化铜与硫酸的摩尔比为1:1~2。
所述步骤(3)的反应路线如下:
所述步骤(4)中邻溴苯胺与甲醛的重量比为1:1~3。
所述步骤(4)的反应路线如下:
再一方面,本发明还提供了卤素改性偶氮类二胺扩链剂作为扩链剂在制备聚氨酯中的应用。
最后,本发明提供了一种聚氨酯的制备方法,所述方法包含以下步骤:
先合成MDI预聚体,即将聚醚加热除水后加入MDI单体,在一定温度下反应1-2小时后制得;固化剂组分的制备是将聚醚,扩链剂,粉料等组分搅拌加热除水。再将两组分按一定比例混合,同时加入少量催化剂。在室温条件下养护,制得聚氨酯制品。
本发明的卤代改性偶氮类二胺扩链剂既可单独使用也可与其他扩链剂配合使用,与聚醚、增塑剂混合后作为固化剂组分用于生产聚氨酯相关制品,相关制品可应用于复合材料、弹性体和体育铺装材料等领域。
本发明的有益效果在于:
1.本发明提供了一种卤素改性偶氮类二胺扩链剂。该扩链剂在与异氰酸酯、多元醇混合后反应,因其含有的多苯环结构可增强硬段本身强度,提升制品的力学性能。同时经卤素改性后,扩链剂中的伯胺因卤素元素的吸电子效应,其活性明显降低,保证了其与异氰酸酯单体间有足够时间充分进行反应,使软硬段间充分进行相分离,有利于提升制品力学性能。同时可延长操作时间,使其在使用过程中具备可操作性。
2.本发明中的偶氮类二胺结构在一定外界条件作用下(例如在碱性条件下,环境温度50℃~70℃偶氮键即发生断裂,生成两个伯胺基结构)可进行分解,其中的偶氮键断裂,体系中释放出尿素单体,即以扩链剂分解的方式使硬段发生分解。同时由于尿素单体的存在使体系呈碱性,而在碱性条件下可有效促进聚乳酸、聚己内酯等聚酯类链段的分解,从实现硬段分解的同时,起到对含有聚酯链节的软段降解的有效促进作用,加强聚氨酯制品整体的降解能力。
3.聚氨酯制品降解后的残余物多采用土地填埋的方式进行处理。但其残余物填埋后会对土地本身造成影响,不利于植被的种植。本专利中扩链剂在分解后所产生的尿素单体,一直残留于体系当中。而尿素可作为一种高效肥料应用于农业生产当中。制品降解残余物中的尿素组分,在填埋到土地中以后,在土地中分解为碳酸铵,可被植被所吸收利用。由此可提升制品填埋土地的利用能力。
具体实施方式
下面的实施例将对本发明所提供的方法予以进一步说明,但本发明不限于所列出的实施例,还应包括在本发明所要求的权利范围内其它任何公知的改变。
部分原料来源:
苯胺,来自万华化学集团股份有限公司。
尿素,购买自中化集团
MDI预聚体:将200gC2020聚醚,400gF3135聚醚经120℃除水2小时后,降温至80℃加入200g MDI50进行聚合反应,生成MDI预聚体。其中聚醚与MDI50均来自万华化学集团股份有限公司。
冰醋酸来自同心化工,硫酸硝酸来自天鹤化工,溴化铜来自润泰精细化工,氟化铜来自艺康化工,碘化铜来自南通润丰石油化工,甲醛来自盛样化工,碳酸钙来自中天矿业,摩卡来自苏州湘源新材料有限公司。
实施例1
(1)将2mol苯胺与4mol冰醋酸加入到干燥的反应器中,加入0.06mol锌粉催化剂,在80℃温度条件下,反应2小时。精馏后,制得乙酰苯胺;
(2)取用步骤1制备的2mol乙酰苯胺,将0.2mol硫酸硝酸混合酸液体滴加进去,其中硝酸0.1mol、硝酸0.1mol,在30℃温度条件下,反应1小时,精馏后制得邻硝基苯胺;
(3)取用步骤2制备的2mol邻硝基苯胺与4mol溴化铜硫酸溶液加入到干燥反应器中,其中溴化铜与硫酸各为1mol。在60℃温度条件下,反应1小时,精馏后制得邻溴苯胺;
(4)取用步骤3制备的2mol邻溴苯胺,与2mol甲醛加入干燥反应器中,在80℃温度条件下,反应2小时,精馏后制得伯胺基溴代二胺。
(5)取用步骤4制备的2mol伯胺基溴代二胺,与2mol尿素,加入0.04mol锌粉催化剂,在60℃温度条件下,反应2小时,制得溴改性偶氮类二胺扩链剂。
(6)将2g步骤(5)制得的扩链剂与20g C2020聚醚,23g长链氯化石蜡,55g400目碳酸钙填料混合搅拌,100℃除水2小时后,与MDI预聚体以5:1的质量比混合后,利用搅拌器混合均匀。
实施例1核磁碳谱数据如下:
13CNMR(CDCl3,600MHz,TMS):44.4(2C),117.8(2C),118.1(2C),119(2C),127.3(2C),128.1(2C),129(2C),131.5(2C),133(2C),133.8(4C),143.8(2C),144.8(2C),193(1C)。
实施例2
(1)将1mol苯胺与4mol冰醋酸加入到干燥的反应器中,加入0.25mol锌粉催化剂,在120℃温度条件下,反应3小时。精馏后,制得乙酰苯胺;
(2)取用步骤1制备的2mol乙酰苯胺,将0.6mol硫酸硝酸混合酸液体滴加进去,其中硝酸0.2mol、硝酸0.4mol,在50℃温度条件下,反应2小时,精馏后制得邻硝基苯胺;
(3)取用步骤2制备的2mol邻硝基苯胺与6mol碘化铜硫酸溶液加入到干燥反应器中,其中碘化铜与硫酸各为1mol与2mol。在100℃温度条件下,反应2小时,精馏后制得邻碘苯胺;
(4)取用步骤3制备的2mol邻碘苯胺,与6mol甲醛加入干燥反应器中,在120℃温度条件下,反应4小时,精馏后制得伯胺基碘代二胺。
(5)取用步骤4制备的2mol伯胺基碘代二胺,与6mol尿素,加入0.4mol锌粉催化剂,在120℃温度条件下,反应3小时,制得碘改性偶氮类二胺扩链剂。
(6)将2g步骤(5)制得的扩链剂与30g C2020聚醚,40g长链氯化石蜡,60g400目碳酸钙填料混合搅拌,100℃除水2小时后,与MDI预聚体以5:1的质量比混合后,利用搅拌器混合均匀。
实施例3
(1)将1mol苯胺与3mol冰醋酸加入到干燥的反应器中,加入0.12mol锌粉催化剂,在100℃温度条件下,反应2.5小时。精馏后,制得乙酰苯胺;
(2)取用步骤1制备的2mol乙酰苯胺,将0.9mol硫酸硝酸混合酸液体滴加进去,其中硝酸0.75mol、硝酸0.15mol,在40℃温度条件下,反应1.5小时,精馏后制得邻硝基苯胺;
(3)取用步骤2制备的2mol邻硝基苯胺与5mol氟化铜硫酸溶液加入到干燥反应器中,其中氟化铜与硫酸各为1mol与1.5mol。在70℃温度条件下,反应1.5小时,精馏后制得邻氟苯胺;
(4)取用步骤3制备的2mol邻氟苯胺,与4mol甲醛加入干燥反应器中,在100℃温度条件下,反应3小时,精馏后制得伯胺基氟代二胺。
(5)取用步骤4制备的2mol伯胺基氟代二胺,与6mol尿素,加入0.18mol锌粉催化剂,在100℃温度条件下,反应2.5小时,制得氟改性偶氮类二胺扩链剂。
(6)将3g步骤(5)制得的扩链剂与40g C2020聚醚,60g长链氯化石蜡,80g400目碳酸钙填料混合搅拌,100℃除水2小时后,与MDI预聚体以5:1的质量比混合后,利用搅拌器混合均匀。
对比例
将2g 3,3'-二氯-4,4'-二氨基二苯基甲烷与20g C2020聚醚,23g长链氯化石蜡,55g 400目碳酸钙填料混合搅拌,100℃除水2小时后,与MDI预聚体以5:1的质量比混合后,利用搅拌器混合均匀。
按国标GB 36246-2018要求,浇铸13mm厚标准力学性能测试样条,在室温条件下固化7天后,进行力学性能测试。通过万能拉力机,以国标要求拉伸速度范围内进行测试试样拉伸剪切强度、断裂伸长率。
降解测试:在样板上切取10mm×10mm×5mm的小样快,浸入到25ml磷酸盐缓冲溶液(PH值=7.2)中,在37±1℃环境中放置,每隔6~7d取出,80℃真空干燥后至恒重后称重,计算其质量减少百分数。
拉伸强度(Mpa) | 断裂伸长率(%) | 失重率(%) | |
实施例1 | 1.5 | 134 | 15.1 |
实施例2 | 1.4 | 145 | 14.8 |
实施例3 | 1.6 | 160 | 16.3 |
对比例1 | 1.5 | 155 | 3.2 |
Claims (13)
1.一种卤素改性偶氮类二胺扩链剂,其特征在于,结构式为:
其中R1为C1-C20的亚烷基,X为F,Cl,Br,I卤素元素。
2.如权利要求1所述的卤素改性偶氮类二胺扩链剂,其特征在于,R1为C1-C4的亚烷基。
3.如权利要求2所述的卤素改性偶氮类二胺扩链剂,其特征在于,R1为亚甲基、亚乙基、亚丙基、亚异丙基或亚丁基。
4.如权利要求1所述的卤素改性偶氮类二胺扩链剂,其特征在于,其结构为
5.如权利要求1-4任一项所述的卤素改性偶氮类二胺扩链剂的制备方法,所述制备方法包括以下步骤:将伯胺基卤代二胺、尿素与锌粉催化剂加入到反应器中,在60~120℃条件下,反应2-3小时,生成卤素改性偶氮类二胺,所述伯胺基卤代二胺结构为:
其中R1为C1-C20的亚烷基,X为F,Cl,Br,I卤素元素。
6.如权利要求5所述的制备方法,其特征在于,R1为C1-C4的亚烷基。
7.如权利要求6所述的制备方法,其特征在于,R1为亚甲基、亚乙基、亚丙基、亚异丙基或亚丁基。
8.如权利要求5-7任一项所述的制备方法,其特征在于,所述伯胺基卤代二胺与尿素摩尔比为1:1~3。
9.如权利要求5-7任一项所述的制备方法,其特征在于,所述锌粉催化剂的加入量是伯胺基卤代二胺和尿素物质量之和的1~5%。
10.如权利要求5-7任一项所述的制备方法,其特征在于,所述伯胺基卤代二胺制备方法包括:(1)将苯胺与冰醋酸单体在金属锌粉催化作用下,在80~120℃条件,反应2-3小时,生成乙酰苯胺;
(2)生成的乙酰苯胺经硝酸与硫酸混合酸液体的反向滴定,在30~50℃条件下,反应1-2小时,进行硝化反应,生成邻硝基苯胺;
(3)生成的邻硝基苯胺与溴化铜硫酸溶液在60~100℃条件下,反应1-2小时,生成邻溴苯胺;
(4)生成的邻溴苯胺与甲醛在80~120℃条件下,反应2-4小时,生成伯胺基卤代二胺。
11.如权利要求10所述的制备方法,其特征在于,所述步骤(1)中苯胺与冰醋酸单体摩尔比为1:1~2;和/或,所述步骤(2)中混合酸液体中硝酸与硫酸的摩尔比为1:1~2;乙酰基苯胺与混合酸液体的摩尔比为10:1~3;和/或,所述步骤(3)中邻硝基苯胺与溴化铜硫酸溶液摩尔比为1:2~3;溴化铜与硫酸的摩尔比为1:1~2;和/或,所述步骤(4)中邻溴苯胺与甲醛的重量比为1:1~3。
12.如权利要求1-4任一项所述的卤素改性偶氮类二胺扩链剂或如权利要求5-11任一项所述的制备方法制备的卤素改性偶氮类二胺扩链剂作为扩链剂在制备聚氨酯中的应用。
13.一种聚氨酯的制备方法,其包含以下步骤:将MDI预聚体与聚醚、扩链剂、粉料混合,加入催化剂,在室温条件下养护,制得聚氨酯制品,所述扩链剂包含如权利要求1-4任一项所述的卤素改性偶氮类二胺扩链剂或如权利要求5-11任一项所述的制备方法制备的卤素改性偶氮类二胺扩链剂。
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