CN108178821A - 耐磨型双组份聚氨酯抗静电板材原液的制备方法 - Google Patents

耐磨型双组份聚氨酯抗静电板材原液的制备方法 Download PDF

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CN108178821A
CN108178821A CN201711465636.3A CN201711465636A CN108178821A CN 108178821 A CN108178821 A CN 108178821A CN 201711465636 A CN201711465636 A CN 201711465636A CN 108178821 A CN108178821 A CN 108178821A
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徐明奎
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Abstract

一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,包括以下步骤:(1)制备分子量为2000的聚酯多元醇;(2)制备分子量为1500的聚酯多元醇;(3)制备A组份聚酯多元醇混合物;(4)制备B组份异氰酸酯预聚体;(5)制备耐磨型双组份聚氨酯抗静电板材原液。本发明提供的耐磨型双组份聚氨酯抗静电板材原液所制成的聚氨酯板材具有耐磨性能好,抗静电性能优异,产品经久耐用等优点。

Description

耐磨型双组份聚氨酯抗静电板材原液的制备方法
技术领域
本发明属于化工合成技术领域,具体涉及一种耐磨型双组份聚氨酯抗静电板材原液的制备方法。
背景技术
聚氨酯又称聚氨基甲酸酯,是在大分子主链中含有氨基甲酸酯基的聚合物,聚氨酯具有很多优异的性能,所以被广泛运用包括聚氨酯板材的多个领域。聚氨酯板材在运输、使用的过程中因为摩擦产生了大量的静电荷,如果不将这些静电荷释放掉,就有可能发生燃烧或者粉尘爆炸,造成严重后果,而现在市场上的聚氨酯板材耐磨性和抗静电性能不佳,影响了聚氨酯板材产品的使用和寿命。因此,开发一款有着优异抗静电性能的耐磨型聚氨酯板材,成为本领域急需解决的技术问题。
发明内容
本发明的目的是为了克服现有技术的不足,通过改变聚酯多元醇的结构和调整双组份的配方,提供了一种耐磨型双组份聚氨酯抗静电板材原液,使用这种原液制成的聚氨酯板材具有耐磨性能好,抗静电性能优异,产品经久耐用等优点。
本发明的目的通过以下技术方案来实现,一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,包括以下步骤:
(1)乙二醇、1,4-丁二醇和精己二酸在催化剂四异丙基钛酸酯的作用下进行聚酯化反应,反应至聚酯多元醇酸值达到0.23-0.87,羟值达到540-582,得到分子量为2000的聚酯多元醇,反应式如下:
聚酯化反应采用以下方法进行:将1,4-丁二醇和精己二酸投入反应釜中,关闭加料盖,导入氮气,分阶段加热升温到225℃,恒温225℃后,加入四异丙基钛酸酯作为催化剂,在氮气保护状态下,恒温225℃下抽真空反应,取样分析,至聚酯多元醇酸值达到0.23-0.87,羟值达到540-582,然后降温至120℃出料计量包装备用,得分子量为2000的聚酯多元醇。
优选的,所述各反应物所占的质量百分数分别为:20.5%的乙二醇、24.5%的1,4-丁二醇和55%的精己二酸;所述催化剂四异丙基钛酸酯的质量为反应物投料总质量的0.0035%。
(2)二甲基硅氧烷、甲基丙二醇和精己二酸在催化剂四异丙基钛酸酯的作用下进行聚酯化反应,反应至聚酯多元醇酸值达到0.3-0.7,羟值达到74-76,得到分子量为1500的聚酯多元醇,反应式如下:
聚酯化反应可采用以下方法进行:将二甲基硅氧烷、甲基丙二醇和精己二酸投入反应釜中,关闭加料盖,导入氮气,分阶段加热升温到225℃,恒温225℃后,加入四异丙基钛酸酯作为催化剂,在氮气保护状态下,恒温225℃下抽真空反应,取样分析,至聚酯多元醇酸值达到0.3-0.7,羟值达到74-76,然后降温至120℃出料计量包装备用,得分子量为1500的聚酯多元醇。
优选的,所述各反应物所占的质量百分数分别为:2.5%的二甲基硅氧烷,37.5%甲基丙二醇和60%的精己二酸;所述催化剂四异丙基钛酸酯为反应物投料总量的0.0035%。
(3)取步骤(1)中2000分子量的聚酯多元醇、步骤(2)中1500分子量的聚酯多元醇和水、二甲基硅油、乙二醇、抗静电剂在催化剂三乙醇胺的作用下进行混合搅拌,至粘度为7.0-9.0Pa.s/50℃,水份含量为0.36-0.38%,得到A组份聚酯多元醇混合物。
所述水作为发泡剂、二甲基硅油作为匀泡剂、乙二醇作为扩链剂、三乙醇胺作为催化剂。
A组份聚酯多元醇混合物的制备可采用以下方法进行:将步骤(1)制备的2000分子量的聚酯多元醇、步骤(2)制备的1500分子量的聚酯多元醇、水、二甲基硅油、乙二醇、三乙醇胺和抗静电剂依次加入反应釜中,关闭加料盖,导入氮气保护,在60-65℃温度下混合搅拌,取样分析,粘度为7.0-9.0Pa.s/50℃,水份含量为0.36-0.38%时出料包装,得A组份聚酯多元醇混合物。
优选的,所述各反应物所占的质量百分数分别为::45%的1500分子量的聚酯多元醇、45%的2000分子量的聚酯多元醇、0.17%的三乙醇胺、0.35%的水、1.0%的二甲基硅油、2%的抗静电剂和6.48%的乙二醇。
(4)取步骤(1)中2000分子量的聚酯多元醇、步骤(2)中1500分子量的聚酯多元醇和二苯基甲烷二异氰酸酯、液化二苯基甲烷二异氰酸酯在催化剂磷酸的作用下进行预聚,反应至NCO含量达到19.2-19.4%,粘度为1.8-2.8Pa.s/50℃,得到B组份异氰酸酯预聚体,反应式如下:
所述预聚反应可使用如下方法进行:在氮气的保护下,将二苯基甲烷二异氰酸酯投入至反应釜中,反应釜温度控制在65-70℃,在搅拌状态下加入磷酸,再投入步骤(1)制备的2000分子量的聚酯多元醇、步骤(2)制备的1500分子量的聚酯多元醇搅拌反应2.5小时左右,再投入液化二苯基甲烷二异氰酸酯,温度控制在60-65℃搅拌反应,取样测试,NCO含量达到19.2-19.4%,粘度为1.8-2.8Pa.s/50℃时出料包装,得B组份异氰酸酯预聚体。
优选的,所述各反应物所占的质量百分数分别为:50.8%的二苯基甲烷二异氰酸酯、19.2%的分子量为1500的聚酯多元醇,19.2%分子量为2000的聚酯多元醇和10.8%的液化二苯基甲烷二异氰酸酯;所述催化剂磷酸的质量为反应物投料总质量的0.0038%。
(5)取步骤(3)中的A组份聚酯多元醇混合物与步骤(4)中的B组份异氰酸酯预聚体在聚氨酯发泡机中混合并发生凝胶反应,得到耐磨型双组份聚氨酯抗静电板材原液,反应式如下:
2RNCO+H2O→RNHCONHR+CO2↑。
优选的,所述A组份聚酯多元醇混合物和B组份异氰酸酯预聚体的质量比为100:65-70。
优选的,所述凝胶反应中加入三乙烯二胺作为催化剂。
优选的,所述三乙烯二胺的质量为反应物投料总质量的0.6±0.1%。
与现有技术相比,本发明提供的耐磨型双组份聚氨酯抗静电板材原液制得的聚氨酯板材具有以下优势:
1、通过本发明的板材原液制得的聚氨酯板材耐磨性能好,较普通聚氨酯板材,耐磨指数(DIN)从300-400提升到了100-200。
2、通过本发明的板材原液制得的聚氨酯板材抗静电性能优异,较普通聚氨酯板材,抗静电指数由<10E+9提升到了<9E+9。
3、通过本发明的板材原液制得的聚氨酯板材安全可靠,抗撕裂,强度高,使用寿命长,可广泛运用于工业、民用建筑中的各个领域。
具体实施方式
下面通过具体实施方式的描述对本发明作进一步说明,但这并非是对本发明的限制,本领域技术人员根据本发明的基本思想,可以做出各种修改或者改进,但是只要不脱离本发明的基本思想,均在本发明的范围之内。
本发明实施例中所用的各种原料和试剂如无特别说明均为市售购买。
实施例1 分子量为2000的聚酯多元醇的制备
将乙二醇、1,4-丁二醇和精己二酸按照质量配比(20.5%的乙二醇、24.5%的1,4-丁二醇和55%的精己二酸)投入反应釜中,关闭加料盖,导入氮气,并分如下阶段加热升温:在常温至140℃,升温2-3小时;在140℃时,恒温1小时,并保持分馏塔塔顶温度100-102℃,一小时后继续升温,140-180℃升温阶段控制在3小时,180-225℃升温阶段控制在2小时,当温度达到225℃时,开始恒温,并加入反应物投料总量的0.0035%四异丙基钛酸酯作为催化剂,在225℃恒温一小时,取样分析,调整;在氮气保护状态下,在225℃恒温分如下阶段抽真空:在0.02MPa时反应0.5小时,在0.04MPa时反应0.5小时,在0.06MPa时反应0.5小时,在0.08MPa时反应0.5小时,在0.09MPa时反应0.5小时,再充入氮气使反应釜恢复常压状态,取样分析,至聚酯多元醇酸值达到0.23-0.87,羟值达到540-582,然后降温至120℃出料计量包装备用,制备得分子量为2000的聚酯多元醇。
实施例2 分子量为1500的聚酯多元醇的制备
将二甲基硅氧烷、甲基丙二醇和精己二酸按照质量配比(2.5%的二甲基硅氧烷,37.5%甲基丙二醇和60%的精精己二酸)投入反应釜中,关闭加料盖,导入氮气,并分如下阶段加热升温:在常温至140℃,升温2-3小时;在140℃时,恒温1小时,并保持分馏塔塔顶温度100-102℃,一小时后继续升温,140-180℃升温阶段控制在3小时,180-225℃升温阶段控制在2小时,当温度达到225℃时,开始恒温,并加入反应物投料总量的0.0035%的四异丙基钛酸酯作为催化剂,在225℃恒温一小时,取样分析,调整;在氮气保护状态下,在225℃恒温分如下阶段抽真空:在0.02MPa时反应0.5小时,在0.04MPa时反应0.5小时,在0.06MPa时反应0.5小时,在0.08MPa时反应0.5小时,在0.09MPa时反应0.5小时,再充入氮气使反应釜恢复常压状态,取样分析,至聚酯多元醇酸值达到0.3-0.7,羟值达到74-76,然后降温至120℃出料计量包装备用,制备得分子量为1500的聚酯多元醇。
实施例3 A组份聚酯多元醇混合物的制备
将实施例1中制备得到的2000分子量的聚酯多元醇、实施例2中制备得到的1500分子量的聚酯多元醇和水、二甲基硅油、乙二醇、抗静电剂、三乙醇胺按照质量配比(45%的1500分子量的聚酯多元醇、45%的2000分子量的聚酯多元醇、0.17%的三乙醇胺、0.35%的水、1.0%的二甲基硅油、2%的抗静电剂和6.48%的乙二醇)依次加入反应釜中,关闭加料盖,导入氮气保护,在60-65℃温度下混合搅拌2小时后,取样分析,至粘度为7.0-9.0Pa.s/50℃,水份含量为0.36-0.38%,出料包装,制备得A组份聚酯多元醇混合物。
实施例4 B组份异氰酸酯预聚体的制备
按照质量配比(50.8%的二苯基甲烷二异氰酸酯、19.2%的分子量为1500的聚酯多元醇,19.2%分子量为2000的聚酯多元醇和10.8%的液化二苯基甲烷二异氰酸酯)准备反应物。在氮气的保护下,将二苯基甲烷二异氰酸酯投入至反应釜中,反应釜温度控制在65-70℃温度,在搅拌状态下加入磷酸,再投入实施例1中制备得到的2000分子量的聚酯多元醇、实施例2中制备得到的1500分子量的聚酯多元醇搅拌反应2.5小时,再投入液化二苯基甲烷二异氰酸酯,温度控制在60-65℃,搅拌0.5小时,取样测试异氰酸酯基含量,至NCO含量为19.2-19.4%,粘度为1.8-2.8Pa.s/50℃,出料包装,制备得B组份异氰酸酯预聚体。
实施例5 聚氨酯抗静电板材原液的制备
将A组份聚酯多元醇混合物与B组份异氰酸酯预聚体按照质量配比100:65-70加入到聚氨酯发泡机中,加入占投料总质量0.6±0.1%的三乙烯二胺,在聚氨酯发泡机中混合并发生凝胶反应,得到耐磨型双组份聚氨酯抗静电板材原液。
通过本发明制得的耐磨型双组份聚氨酯抗静电板材原液与现有聚氨酯双组份板材原液的技术数据对比如下表(表中百分数均指质量百分数):
需要说明的是,上述发明内容及具体实施方式意在证明本发明所提供技术方案的实际应用,不应解释为对本发明保护范围的限定。本领域技术人员在本发明的精神和原理内,当可作各种修改、等同替换、或改进。

Claims (8)

1.一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,包括以下步骤:
(1)乙二醇、1,4-丁二醇和精己二酸在催化剂四异丙基钛酸酯的作用下进行聚酯化反应,反应至聚酯多元醇酸值达到0.23-0.87,羟值达到540-582,得到分子量为2000的聚酯多元醇,反应式如下:
(2)二甲基硅氧烷、甲基丙二醇和精己二酸在催化剂四异丙基钛酸酯的作用下进行聚酯化反应,反应至聚酯多元醇酸值达到0.3-0.7,羟值达到74-76,得到分子量为1500的聚酯多元醇,反应式如下:
(3)取步骤(1)中2000分子量的聚酯多元醇、步骤(2)中1500分子量的聚酯多元醇和水、二甲基硅油、乙二醇、抗静电剂在催化剂三乙醇胺的作用下进行混合搅拌,至粘度为7.0-9.0Pa.s/50℃,水份含量为0.36-0.38%,得到A组份聚酯多元醇混合物;
(4)取步骤(1)中2000分子量的聚酯多元醇、步骤(2)中1500分子量的聚酯多元醇和二苯基甲烷二异氰酸酯、液化二苯基甲烷二异氰酸酯在催化剂磷酸的作用下进行预聚,反应至NCO含量达到19.2-19.4%,粘度为1.8-2.8Pa.s/50℃,得到B组份异氰酸酯预聚体,反应式如下:
(5)取步骤(3)中的A组份聚酯多元醇混合物与步骤(4)中的B组份异氰酸酯预聚体在聚氨酯发泡机中混合并发生凝胶反应,得到耐磨型双组份聚氨酯抗静电板材原液,反应式如下:
2RNCO+H2O→RNHCONHR+CO2↑。
2.根据权利要求1所述的一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,其特征在于,步骤(1)中所述各反应物所占的质量百分数分别为:20.5%的乙二醇、24.5%的1,4-丁二醇和55%的精己二酸;所述催化剂四异丙基钛酸酯的质量为反应物投料总质量的0.0035%。
3.根据权利要求1所述的一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,其特征在于,步骤(2)所述各反应物所占的质量百分数分别为:2.5%的二甲基硅氧烷,37.5%甲基丙二醇和60%的精精己二酸;所述催化剂四异丙基钛酸酯的质量为反应物投料总质量的0.0035%。
4.根据权利要求1所述的一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,其特征在于,步骤(3)中所述各反应物所占的质量百分数分别为:45%的1500分子量的聚酯多元醇、45%的2000分子量的聚酯多元醇、0.17%的三乙醇胺、0.35%的水、1.0%的二甲基硅油、2%的抗静电剂和6.48%的乙二醇。
5.根据权利要求1所述的一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,其特征在于,步骤(4)中所述各反应物所占的质量百分数分别为:50.8%的二苯基甲烷二异氰酸酯、19.2%的分子量为1500的聚酯多元醇,19.2%分子量为2000的聚酯多元醇和10.8%的液化二苯基甲烷二异氰酸酯;所述催化剂磷酸的质量为反应物投料总质量的0.0038%。
6.根据权利要求1所述的一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,其特征在于,步骤(5)中所述A组份聚酯多元醇混合物和B组份异氰酸酯预聚体的质量比为100:65-70。
7.根据权利要求1所述的一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,其特征在于,步骤(5)中所述的凝胶反应中加入三乙烯二胺作为催化剂。
8.根据权利要求8所述的一种耐磨型双组份聚氨酯抗静电板材原液的制备方法,其特征在于,所述三乙烯二胺的质量为反应物投料总质量的0.6±0.1%。
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