CN117024944A - 基于聚氨酯回收再利用的聚苯颗粒复合保温板 - Google Patents
基于聚氨酯回收再利用的聚苯颗粒复合保温板 Download PDFInfo
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Abstract
本发明公开了一种基于聚氨酯回收再利用的聚苯颗粒复合保温板,属于保温板技术领域。由聚氨酯、聚苯颗粒、玻璃纤维复合制得,聚苯颗粒赋予了其保温性,玻璃纤维增加了其强度;通过对聚氨酯硬泡进行醇降解,获得降解后的低聚物多元醇,再以该低聚物多元醇为主要原料,合成聚氨酯,体现其再生性;此外,在合成再生聚氨酯的过程中,掺入了自制的改性多元醇作为原料之一,该分子能直接参与低聚物多元醇和二异氰酸酯聚合反应过程,赋予保温板极强且长久的阻燃性;基团呈枝状分布,提高聚氨酯的力学性能和耐热性能,具备重要的应用意义。
Description
技术领域
本发明属于保温板技术领域,具体地,涉及一种基于聚氨酯回收再利用的聚苯颗粒复合保温板。
背景技术
聚苯颗粒全称为膨胀聚苯乙烯泡沫颗粒,该材料是由可发性聚苯乙烯树脂珠粒为基础原料膨胀发泡制成的,因其具有良好的保温性,便宜的价格,在世界上被广泛使用,深受建筑行业的青睐,然而聚苯颗粒也有一定的不足之处,它耐热性差、阻燃能力差、不环保,因此现在常用聚苯颗粒与其他材料复合来解决这些问题,聚氨酯作为一种可回收材料,就常常与聚苯颗粒复合。
现在技术在对聚氨酯进行回收时,通常都是将废旧聚氨酯材料与新生聚氨酯材料以及其余助剂和功能添加剂共混,得到功能性再生聚氨酯材料,例如赋予其阻燃性能。但是该种方式导致加入的阻燃剂容易析出,且对聚氨酯材料的强度等造成不良影响;此外,废旧聚氨酯材料直接与新生聚氨酯材料混合,实现的是物理上的融合,也难以保证得到的再生聚氨酯材料的性能。
发明内容
本发明的目的在于克服现有技术的缺陷,提供了一种基于聚氨酯回收再利用的聚苯颗粒复合保温板。
本发明的目的可以通过以下技术方案实现:
一种基于聚氨酯回收再利用的聚苯颗粒复合保温板,通过以下步骤制得:
A1、将废旧聚氨酯硬泡洗净、干燥后粉碎,备用;然后将一缩二乙二醇和2,3-环氧丙基三甲基氯化铵混合均匀后,加入搅拌釜中,升温至120℃,再加入粉碎后的废旧聚氨酯硬泡,升温至150℃反应4h,获得再生低聚物多元醇;粉碎后的废旧聚氨酯硬泡、一缩二乙二醇、2,3-环氧丙基三甲基氯化铵的用量之比为1000g:800g:200g;
以一缩二乙二醇作为醇解剂、2,3-环氧丙基三甲基氯化铵作为助醇解剂对废旧聚氨酯硬泡进行醇降解,得到再生低聚物多元醇;
A2、将A1制得的再生低聚物多元醇,改性多元醇、十二烷基硫酸钠(发泡剂)、聚苯颗粒、玻璃纤维、水搅拌混合均匀,然后加入IPDI,在电动搅拌机上搅拌5min,随后倒入模具中,发泡5h,熟化后,得到基于聚氨酯回收再利用的聚苯颗粒复合保温板;再生低聚物多元醇、改性多元醇、十二烷基硫酸钠、聚苯颗粒、玻璃纤维、水、IPDI的用量比为500g:100g-200g:50g:400g:150g:2L:500g;
发泡过程,IPDI受到发泡剂的影响而突然汽化,从而使反应物料中气体浓度很快增加,当气体浓度增加到超过平衡饱和浓度后,溶液中开始形成微细的气泡,这过程中多元醇和IPDI发生聚合反应,生成聚氨酯;
聚氨酯硬质泡沫进行醇降解,获得降解后的低聚物多元醇,再以该低聚物多元醇为主要原料,合成聚氨酯,能够实现聚氨酯废旧泡沫的再生利用,符合环保和节能要求。
进一步地,所述改性多元醇通过如下步骤制备:
S1、在有回流装置的三口烧瓶中加入二氯甲基膦,乙二醇单乙酸酯与氯苯混合,加入三氯化铝作为催化剂,搅拌,缓慢加热至100℃,反应时间为6h,至无明显HCl逸出,停止反应,减压蒸除未反应的二氯甲基膦和部分溶剂,得到中间体1;二氯甲基膦、乙二醇乙酸酯、氯苯、三氯化铝的用量之比为13.2g:10.4g:100mL:0.26g;
在三氯化铝的催化下二氯甲基膦与乙二醇乙酸酯发生酯化反应,通过控制二者的摩尔比接近1:1且二氯甲基膦略微过量,使二氯甲基膦上只有一个-Cl参与到反应,得到中间体1;具体反应过程如下所示:
S2、室温、氮气保护下,在装有搅拌及回流装置的三口烧瓶中加入四氯化碳、三聚氰胺、中间体1,混合搅拌均匀,升温至80℃,回流反应6h后停止加热,待反应瓶内温度降至30℃后,抽滤,滤饼用蒸馏水洗涤三次,真空干燥,得到中间体2;四氯化碳、三聚氰胺、中间体1、蒸馏水的用量之比为200mL:12.6g:60.2g:30mL;
三聚氰胺和中间体1发生酰化反应,通过控制二者的摩尔比接近1:3且中间体1略微过量,使三聚氰胺上有三个-NH2参与到反应,得到中间体2;具体反应过程如下所示:
S3、将中间体2溶解在DMSO中,加入NaOH溶液(质量分数18%),混合搅拌均匀,加热至80℃,反应1h,反应完全后,先旋蒸去除部分溶剂,再通过柱层析提纯(洗脱液采用甲醇/***的混合溶剂,二者的体积比为2:1),旋蒸除去洗脱液,干燥,得到改性多元醇;中间体2、DMSO、NaOH溶液的用量之比为60.8g:200mL:50mL;
在碱性条件下中间体2的酯基发生水解反应,得到改性多元醇;具体反应过程如下所示:
改性多元醇分子上含有3个未反应完全的-CH3CH2OH基团,能够直接参与低聚物多元醇和二异氰酸酯聚合反应过程,增加其相容性、3个基团呈枝状分布,这种结构能够促进交联反应的发生,提高聚氨酯的力学性能和耐热性能;引入了大量的N和P,在受热时可以产生P-N协效阻燃效果,极大的加强了改性多元醇的阻燃性,并且这种结构是直接聚合到聚氨酯分子链上的,不易析出,保证阻燃的持久性。
本发明的有益效果:
本发明通过对聚氨酯硬泡进行醇降解,获得降解后的低聚物多元醇,再以该低聚物多元醇为主要原料,合成聚氨酯,能够实现废旧聚氨酯的再生利用,符合环保要求;此外,玻璃纤维能赋予保温板一定的力学性能,聚苯颗粒赋予了其保温性;另外,在合成再生聚氨酯的过程中,掺入了自制的改性多元醇作为原料之一,该改性多元醇分子上含有3个未反应完全的-CH3CH2OH基团,能够直接参与低聚物多元醇和二异氰酸酯聚合反应过程,增加其相容性,3个基团呈枝状分布,提高聚氨酯的力学性能和耐热性能;在受热时可以产生P-N协效阻燃效果,极大的加强了改性多元醇的阻燃性,并且这种结构是直接聚合到聚氨酯分子链上的,不易析出,保证阻燃的持久性。因此,该保温板具有可回收性、稳定高效的阻燃性、保温性,并且拥有一定的力学性能和耐热性,具备重要的应用意义。
具体实施方式
下面将结合本发明实施例,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
制备改性多元醇:
S1、在有回流装置的三口烧瓶中加入13.2g二氯甲基膦,10.4g乙二醇单乙酸酯与100mL氯苯混合,加入0.26g三氯化铝作为催化剂,搅拌,缓慢加热至100℃,反应时间为6h,至无明显HCl逸出,停止反应,减压蒸除未反应的二氯甲基膦和部分溶剂,得到中间体1;
S2、室温、氮气保护下,在装有搅拌及回流装置的三口烧瓶中加入200mL四氯化碳、12.6g三聚氰胺、60.2g中间体1,混合搅拌均匀,升温至80℃,回流反应6h后停止加热,待反应瓶内温度降至30℃后,抽滤,滤饼用30mL蒸馏水洗涤三次,真空干燥,得到中间体2;
S3、将60.8g中间体2溶解在200mLDMSO中,加入50mLNaOH溶液(质量分数18%),混合搅拌均匀,加热至80℃,反应1h,反应完全后,先旋蒸去除部分溶剂,再通过柱层析提纯(洗脱液采用甲醇/***的混合溶剂,二者的体积比为2:1),旋蒸除去洗脱液,干燥,得到改性多元醇。
实施例2
制备改性多元醇:
S1、在有回流装置的三口烧瓶中加入26.4g二氯甲基膦,20.8g乙二醇单乙酸酯与200mL氯苯混合,加入0.52g三氯化铝作为催化剂,搅拌,缓慢加热至100℃,反应时间为6h,至无明显HCl逸出,停止反应,减压蒸除未反应的二氯甲基膦和部分溶剂,得到中间体1;
S2、室温、氮气保护下,在装有搅拌及回流装置的三口烧瓶中加入300mL四氯化碳、25.2g三聚氰胺、120.4g中间体1,混合搅拌均匀,升温至80℃,回流反应6h后停止加热,待反应瓶内温度降至30℃后,抽滤,滤饼用60mL蒸馏水洗涤三次,真空干燥,得到中间体2;
S3、将121.6g中间体2溶解在400mLDMSO中,加入100mLNaOH溶液(质量分数18%),混合搅拌均匀,加热至80℃,反应1h,反应完全后,先旋蒸去除部分溶剂,再通过柱层析提纯(洗脱液采用甲醇/***的混合溶剂,二者的体积比为2:1),旋蒸除去洗脱液,干燥,得到改性多元醇。
实施例3
制备基于聚氨酯回收再利用的聚苯颗粒复合保温板:
A1、将废旧聚氨酯硬泡洗净、干燥后粉碎,备用;然后将800g的一缩二乙二醇和200g的2,3-环氧丙基三甲基氯化铵混合均匀后,加入搅拌釜中,升温至120℃,再加入1000g粉碎后的废旧聚氨酯硬泡,升温至150℃反应4h,获得再生低聚物多元醇;
A2、将500g由A1制得的再生低聚物多元醇,100g改性多元醇、50g十二烷基硫酸钠(发泡剂)、400g聚苯颗粒、150g玻璃纤维、2L水搅拌混合均匀,然后加入500gIPDI,在电动搅拌机上搅拌5min,随后倒入模具中,发泡5h,熟化后,得到基于聚氨酯回收再利用的聚苯颗粒复合保温板。
实施例4
制备基于聚氨酯回收再利用的聚苯颗粒复合保温板:
A1、将废旧聚氨酯硬泡洗净、干燥后粉碎,备用;然后将800g的一缩二乙二醇和200g的2,3-环氧丙基三甲基氯化铵混合均匀后,加入搅拌釜中,升温至120℃,再加入1000g粉碎后的废旧聚氨酯硬泡,升温至150℃反应4h,获得再生低聚物多元醇;
A2、将500g由A1制得的再生低聚物多元醇,150g改性多元醇、50g十二烷基硫酸钠(发泡剂)、400g聚苯颗粒、150g玻璃纤维、2L水搅拌混合均匀,然后加入500gIPDI,在电动搅拌机上搅拌5min,随后倒入模具中,发泡5h,熟化后,得到基于聚氨酯回收再利用的聚苯颗粒复合保温板。
实施例5
制备基于聚氨酯回收再利用的聚苯颗粒复合保温板:
A1、将废旧聚氨酯硬泡洗净、干燥后粉碎,备用;然后将800g的一缩二乙二醇和200g的2,3-环氧丙基三甲基氯化铵混合均匀后,加入搅拌釜中,升温至120℃,再加入1000g粉碎后的废旧聚氨酯硬泡,升温至150℃反应4h,获得再生低聚物多元醇;
A2、将500g由A1制得的再生低聚物多元醇,200g改性多元醇、50g十二烷基硫酸钠(发泡剂)、400g聚苯颗粒、150g玻璃纤维、2L水搅拌混合均匀,然后加入500gIPDI,在电动搅拌机上搅拌5min,随后倒入模具中,发泡5h,熟化后,得到基于聚氨酯回收再利用的聚苯颗粒复合保温板。
对比例1
将实施例3中的改性多元醇换成三乙醇胺,其余步骤不变,并按照实施例5制成复合保温板。
对比例2
将实施例3中的改性多元醇去除,其余步骤不变,并按照实施例5制成复合保温板。
对实施例3-5和对比例1-2获得的复合保温板,制成测试样品,进行如下性能测试:
采用国家标准GB/T2406-2008《塑料燃烧性能试验方法》测定试样的极限氧指数;
升温至60℃,采用国家标准GB/T9641-1988《泡沫塑料-硬质材料拉伸性能的测定》测定试样的抗拉强度;
在密闭保温室内,用保温板把密闭保温室进行分隔成AB两个室,AB两室内体积相同,A室内初始温度为100℃,B室内初始温度为25℃,30min后,再分别对B室进行测量;
测试项目 | 极限氧指数 | 60℃时抗拉强度 | B室温度 |
实施例3 | 32 | 0.2601MPa | 30℃ |
实施例4 | 33 | 0.2554MPa | 28℃ |
实施例5 | 31 | 0.2642MPa | 29℃ |
对比例1 | 26 | 0.2011MPa | 45℃ |
对比例2 | 24 | 0.2003MPa | 49℃ |
由上表可知,该保温板具有高效的阻燃性、保温性,并且拥有一定的力学性能和耐热性,具备重要的应用意义。
在说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”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一定指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何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明,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 (7)
1.基于聚氨酯回收再利用的聚苯颗粒复合保温板,其特征在于,通过如下步骤制成:
A1、将废旧聚氨酯硬泡洗净、干燥后粉碎,备用;然后将一缩二乙二醇和2,3-环氧丙基三甲基氯化铵混合均匀后,加入搅拌釜中,加热,再加入粉碎后的废旧聚氨酯硬泡,150℃反应4h,获得再生低聚物多元醇;
A2、将A1制得的再生低聚物多元醇,改性多元醇、十二烷基硫酸钠、聚苯颗粒、玻璃纤维、水搅拌混合均匀,然后加入IPDI,在电动搅拌机上搅拌5min,随后倒入模具中,发泡5h,熟化后,得到基于聚氨酯回收再利用的聚苯颗粒复合保温板。
2.根据权利要求1所述的基于聚氨酯回收再利用的聚苯颗粒复合保温板,其特征在于,步骤A1中,粉碎后的废旧聚氨酯硬泡、一缩二乙二醇、2,3-环氧丙基三甲基氯化铵的用量之比为1000g:800g:200g。
3.根据权利要求1所述的基于聚氨酯回收再利用的聚苯颗粒复合保温板,其特征在于,步骤A2中,再生低聚物多元醇、改性多元醇、十二烷基硫酸钠、聚苯颗粒、玻璃纤维、水、IPDI的用量比为500g:100g-200g:50g:400g:150g:2L:500g。
4.根据权利要求1所述的基于聚氨酯回收再利用的聚苯颗粒复合保温板,其特征在于,所述改性多元醇通过如下步骤制备:
S1、在三口烧瓶中加入二氯甲基膦,乙二醇单乙酸酯与氯苯混合,加入三氯化铝作为催化剂,搅拌,在100℃回流反应6h,至无明显HCl逸出,停止反应,减压蒸除未反应的二氯甲基膦和部分溶剂,得到中间体1;
S2、室温、氮气保护下,在装有搅拌及回流装置的三口烧瓶中加入四氯化碳、三聚氰胺、中间体1,混合搅拌均匀,升温至80℃,回流反应6h后停止加热,待反应瓶内温度降至30℃后,抽滤,滤饼用蒸馏水洗涤三次,真空干燥,得到中间体2;
S3、将中间体2溶解在DMSO中,加入NaOH溶液,混合搅拌均匀,加热至80℃,反应1h,反应完全后,先旋蒸去除部分溶剂,再通过柱层析提纯,旋蒸除去洗脱液,干燥,得到改性多元醇。
5.根据权利要求4所述的基于聚氨酯回收再利用的聚苯颗粒复合保温板,其特征在于,步骤S1中,二氯甲基膦、乙二醇乙酸酯、氯苯、三氯化铝的用量之比为13.2g:10.4g:100mL:0.26g。
6.根据权利要求4所述的基于聚氨酯回收再利用的聚苯颗粒复合保温板,其特征在于,步骤S2中,四氯化碳、三聚氰胺、中间体1、蒸馏水的用量之比为200mL:12.6g:60.2g:30mL。
7.根据权利要求4所述的基于聚氨酯回收再利用的聚苯颗粒复合保温板,其特征在于,步骤S3中,中间体2、DMSO、NaOH溶液的用量之比为60.8g:200mL:50mL。
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