CN109535387A - 一种tgic副产物制备聚氨酯泡沫塑料的方法 - Google Patents

一种tgic副产物制备聚氨酯泡沫塑料的方法 Download PDF

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CN109535387A
CN109535387A CN201811323168.0A CN201811323168A CN109535387A CN 109535387 A CN109535387 A CN 109535387A CN 201811323168 A CN201811323168 A CN 201811323168A CN 109535387 A CN109535387 A CN 109535387A
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赵刚
李娜
张钧康
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Abstract

本发明公开了一种利用异氰脲酸三缩水甘油酯(TGIC)副产物制备聚氨酯泡沫塑料的方法。所述聚氨酯泡沫塑料是用TGIC副产物部分替代聚醚多元醇来制备的TGIC副产物/聚醚多元醇/异氰酸酯的共聚聚氨酯泡沫塑料。将TGIC副产物用于聚氨酯泡沫的制备既降低了环境污染，又实现了市场效益。该方法生产设备及工艺简单，能耗低，周期短，生产效率高，成本低，无三废排放，环境友好。

Description

一种TGIC副产物制备聚氨酯泡沫塑料的方法
技术领域
本发明涉及化工固体废弃物再利用领域，尤其涉及一种TGIC副产物制备聚氨酯泡沫塑料的方法。
背景技术
异氰尿酸三缩水甘油酯，又称三(2，3-环氧丙基)异氰尿酸酯，简称TGIC，俗称“呔哔克”。在已经市场化的的二十多种重要的三聚氰酸衍生物中，它是一种占有广大消费品市场的化工产品。由于TGIC具有三个高度活性的环氧基，三嗪环也很稳定。它不但具有一般环氧树脂的理化性质，能和胺类、羧酸、酚醛、酸酐、树脂等环氧类固化剂产生固化反应。生成交联状的不溶不熔物，固化反应速度较快，而且与往常的环氧树脂相比，TGIC环氧当量低，分子量小，环氧值高，具有更好的耐候性、耐热性、粘结性等特点，所以TGIC作为粉末涂料的固化剂，有着很广泛的用途。
生产TGIC，传统的方法所使用的初始原材料是环氧氯丙烷(ECH)和异氰酸酯。将二者及相应的助剂、催化剂等一同放入反应装置中，进行相应的开环反应。待此反应结束后，利用氢氧化钠，进行闭环合成。最后，对反应装置中的混合物进行精炼，即可以得到TGIC成品。在成品的整个生产过程中，主要产生两种副产物：经过精制TGIC后所残留的副产物和层积盐。层积盐可以利用于工业生产，但是副产物至今却一直危害周边环境。如何将此副产物有效利用起来，是生产TGIC后续工作的重中之重。副产物中可能存在的主要化学基团和成分是：单环氧基团产物；双环氧基团产物；另有，甲醇等小分子。经过分析，TGIC副产物中含有很多环氧基团，经过改性，能更好的寻求它的应用价值。
TGIC产品产量逐年提高，相应的副产物的产量也会随之提高。每年都会产出近万吨副产物难以处理，严重危害环境。如何将如此庞大的副产物有效地利用起来，确实是眼下必须处理好的一个难题。TGIC副产物作为一种无毒无害的化学产品，如果可以加之利用，那么，正好符合现在人们对于相对较高的生活水平的要求。根据TGIC副产物自身的结构特点和性能，可以看出它有着很大的利用空间。这样就能将这种副产物变废为宝，实现很好的利用，产生实际的社会经济效益。
据报道，王宇提出TGIC副产物中添加抗氧剂可改性制备热熔胶，但是TGIC副产物在受热的情况下不稳定，容易发生爆聚，存在安全隐患，难以实际生产应用。田志红等人提出TGIC副产物与甲苯二异氰酸酯改性可制备纸塑复合胶黏剂，任强等人提出TGIC副产物与尿素反应制备胶黏剂。这些改性都需要进行化学反应，工艺复杂，生产成本较高，附加值较低。
发明内容
本发明的目的在于克服现有技术存在的不足，解决TGIC副产物利用中工艺复杂，附加值低等问题，将TGIC副产物应用于塑料行业，提供一种TGIC副产物制备的聚氨酯泡沫塑料的方法。
为实现上述目的，本发明采取了以下的技术方案：
一种TGIC副产物制备的聚氨酯泡沫塑料，其特征在于所述泡沫塑料是在泡沫塑料研制的基础上，用TGIC副产物部分替代聚醚多元醇来制备的TGIC副产物/聚醚多元醇/异氰酸酯共聚聚氨酯泡沫塑料。
所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，以TGIC副产物、聚醚多元醇和异氰酸酯为单体，加入匀泡剂、催化剂、发泡剂和助剂等，经过发泡后得到聚氨酯泡沫塑料。
所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于由TGIC副产物-聚醚多元醇-异氰酸酯经过三元共聚制得，其中TGIC副产物10-40份，聚醚多元醇10-40份，异氰酸酯20-60份。
所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的匀泡剂为硅基泡沫稳定剂，优选二甲基聚硅氧烷和聚醚的嵌段共聚物。
所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的催化剂为胺类催化剂和有机金属类催化剂的任意配比的混合物或其中一种；进一步优化，所述的胺类催化剂是三乙醇胺、二甲基环己胺、三亚乙基二胺、三乙烯二胺等一种或者两种任意比例的混合物；所述的有机金属类催化剂是二丁基二月桂酸酯、辛酸亚锡、异辛酸钾-二丙二醇溶液等中的一种或者两种任意比例的混合物。
所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的发泡剂为HCFC-141b、HCFC-245fa、环戊烷、正戊烷、二氧化碳或者水的至少一种。
所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的助剂是碳酸钙、硫酸镁、硅微粉、氧化铝等。
上述各原料的质量份如下所示：
与现有技术相比，本发明具有如下有益效果：
(1)在传统的聚氨酯泡沫塑料体系中引入价格低廉的TGIC副产物，有利于节约资源，降低成本，生产效率高，无三废排放，环境友好，能产生实际的经济效益。
(2)根据TGIC副产物加入比例不同，可以制备出一系列的性价比高的PU泡沫塑料，丰富泡沫塑料的种类，满足不同的市场需求。
(3)通过简单的混合工艺可将TGIC副产物转化为附加值高的PU泡沫塑料产品。
具体实施方式
下面结合具体实施例，对本发明的具体实施方式作进一步描述。以下实施例仅用于说明本发明，并不限制本发明的保护范围。
实施例1
将20份TGIC副产物、29份聚醚多元醇、50份多苯基多亚甲基多异氰酸酯、0.5份硅氧泡沫稳定剂、0.1份三乙醇胺、0.4份水，依次加入三口烧瓶中，室温搅拌30s，迅速转移至容器内，得到密度为85Kg/m3的聚氨酯泡沫塑料。
实施例2
将40份TGIC副产物、10份聚醚多元醇、47份多苯基多亚甲基多异氰酸酯、2份硅氧泡沫稳定剂、0.2份二丁基二月桂酸酯、0.1份三乙醇胺、2份水，依次加入三口烧瓶中，室温搅拌20s，迅速转移至容器内，得到密度为98Kg/m3的聚氨酯泡沫塑料。
实施例3
将30份TGIC副产物、15份聚醚多元醇、39.8份多苯基多亚甲基多异氰酸酯、2份硅氧泡沫稳定剂、0.2份二丁基二月桂酸酯、0.2份三亚乙基二胺0.8份、水2份水，依次加入三口烧瓶中，室温搅拌10s，迅速转移至容器内，得到密度为55Kg/m3的聚氨酯泡沫塑料。
实施例4
将30份TGIC副产物、12份聚醚多元醇、45份多苯基多亚甲基多异氰酸酯、2份硅氧泡沫稳定剂、0.1份二丁基二月桂酸酯、0.1份三亚乙基二胺0.8份、2份HCFC-141b、8份碳酸钙，依次加入三口烧瓶中，室温搅拌10s，迅速转移至容器内，得到密度为102Kg/m3的聚氨酯泡沫塑料。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管已经用一般性说明及具体实施方案对本发明进行了详细说明，但对于本领域的技术人员来说，在本发明基础上，在不脱离本发明精神的前提下，还可以做出若干修改、改进或等同替换。所做的所有修改、改进、等同替换等，均应属于本发明的保护范围。

Claims (8)

1.一种TGIC副产物制备聚氨酯泡沫塑料的方法，其特征在于用TGIC副产物部分替代聚醚多元醇来制备TGIC副产物/聚醚多元醇/异氰酸酯共聚聚氨酯泡沫塑料的方法。
2.根据权利要求1所述的一种TGIC副产物制备聚氨酯泡沫塑料的方法，其特征在于由TGIC副产物-聚醚多元醇-异氰酸酯经过三元共聚制得，其中TGIC副产物10-40份，聚醚多元醇10-40份，异氰酸酯20-60份。。
3.根据权利要求1所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于以TGIC副产物、聚醚多元醇和异氰酸酯为单体，加入匀泡剂、催化剂、发泡剂和助剂等，经过发泡后得到聚氨酯泡沫塑料。
4.根据权利要求3所述的一种低成本聚甲基丙烯酰亚胺泡沫塑料的制备方法，所述的TGIC副产物，聚醚多元醇，异氰酸酯单体的质量比为(10-30)∶(10-30)∶(20-60)。
5.根据权利要求3所述的所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的匀泡剂为硅基泡沫稳定剂，优选二甲基聚硅氧烷和聚醚的嵌段共聚物。
6.根据权利要求3所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的催化剂为胺类催化剂和有机金属类催化剂的任意配比的混合物或其中一种；进一步优化，所述的胺类催化剂是三乙醇胺、二甲基环己胺、三亚乙基二胺、三乙烯二胺等一种或者两种任意比例的混合物；所述的有机金属类催化剂是二丁基二月桂酸酯、辛酸亚锡、异辛酸钾-二丙二醇溶液等中的一种或者两种任意比例的混合物。
7.根据权利要求3所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的发泡剂为HCFC-141b、HCFC-245fa、环戊烷、正戊烷、二氧化碳或者水的至少一种。
8.根据权利要求3所述的一种TGIC副产物制备的聚氨酯泡沫塑料的方法，其特征在于所述的助剂是碳酸钙、硫酸镁、硅微粉、氧化铝等。
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