CN107488255A - 一种无毒工艺制备水性聚氨酯的方法 - Google Patents
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Abstract
本发明公开了一种无毒工艺制备水性聚氨酯的方法以及由该方法制备的水性聚氨酯,所述方法包括:将二环己基甲烷二异氰酸酯与脂肪族二元醇按照摩尔比2.5‑4混合,在70‑90℃下反应3‑5小时得到预聚体,加入含亲水基团的二羟甲基丁酸,反应3‑5小时,加入KOH的水溶液乳化分散,滴加二胺扩链剂扩链和聚乙酰胺,得到一种水性聚氨酯乳液。本发明采用脂肪族异氰酸酯二环己基甲烷二异氰酸脂、脂肪族聚合二元醇,不含制备水性聚氨酯常用的NMP、丙酮等有机溶剂,也不含三乙胺等常用中和剂,可以制得完全无毒的聚氨酯材料,其可广泛用于医药卫生、食品、家居用品领域。
Description
技术领域
本发明涉及一种水性聚氨酯的制备方法,具体涉及一种无毒工艺制备水性聚氨酯的方法及由该方法获得的聚氨酯。
背景技术
水性聚氨酯以水为分散介质,与溶剂型聚氨酯相比,具有不燃、气味小,节能,操作方便等优点,已广泛用作皮革涂饰剂、涂料和粘合剂等。
尽管与溶剂型聚氨酯相比,水性聚氨酯的产品性能如耐水性还有差距。近年来,随着人们对健康、环保的要求日益提高以及国家有关法律法规的颁布,对水性聚氨酯的制备研究有很多报道。
专利CN10113A、CN1405196A、CN1930257A、CN1827690A、CN1918251A、CN151A、CN1980964A等对水性聚氨酯的制备均有报道。在这些专利及其他文献报道中,提到的水性聚氨酯制备方法大多采用丙酮法,以二羟甲基丁酸(DMPA)为含亲水单体物质以引入亲水羧基、以叔胺类物质为中和剂。由于DMPA在酮类、低聚物二元醇中的溶解度较低,通常在将DMPA加入预聚体中时都是以N-甲基吡咯烷酮(NMP)为助溶剂。N-甲基吡咯烷酮慢性作用可致中枢神经系统机能障碍,引起呼吸器官、肾脏和血管系统的病变,而N-甲基吡咯烷酮沸点高、最终不易脱除而滞留在材料中,从而带有一定得生物毒性。其次水性聚氨酯通常以叔胺类物质如三乙胺为中和剂,而三乙胺有强烈氨臭,在水中溶解度小,此类水性聚氨酯会散发出胺的臭味,在生产过程中对人和环境会造成危害,同时使制品有一定毒性。第三,在以往专利中大多使用HDI、IPDI脂肪族异氰酸脂或TDI等芳香族异氰酸酯为原料,一方面HDI、IPDI和TDI等异氰酸脂蒸汽压高、易挥发,在生产过程中易对人和环境造成危害,而且以芳香族异氰酸酯TDI或MDI为原料的聚氨酯材料,在使用过程中可能分解产生致癌的芳香胺类物质。由此可见,虽然常用的水性聚氨酯中的有机溶剂等对人体、环境有害物质大大减小了,但生产、制品使用过程中,仍然会产生一定量对人体、环境有害的物质,从而限制了在某些领域特别是医疗卫生、食品等领域的应用。
专利CN1995086A公开了一种水性无毒可降解聚氨酯弹性体的制备方法,该方法以KOH、NaOH为中和剂、生产过程中不使用有机溶剂,通过这些方法以消除毒性。但该发明为了避免使用助溶剂NMP而不使用含亲水单体扩链剂,乳化时直接加水到预聚体中同时通过强力搅拌以实现乳化分散,或者在使用了DMPA的条件下不使用助溶剂而直接用于预聚体扩链,由于其醇溶性差,预聚体系呈现浑浊状,不利于扩链反应,该发明的缺点是其制备的乳液粒径大、乳液不稳定而易沉淀、分层。
发明内容
针对以上技术缺陷,本发明提供一种无毒工艺制备水性聚氨酯的方法。
本发明所述无毒工艺制备水性聚氨酯的方法包括如下步骤:
a)将二环己基甲烷二异氰酸酯与脂肪族聚合二元醇混合,加入催化剂并在60-90℃,优选70-90℃下反应1-3小时得到预聚体;
b)向预聚体中加入含亲水基团的DMBA,在70-90℃下继续反应2-4小时;
c)降低温度到25-35℃,在FLUKE高速搅拌机进行搅拌同时加入含中和剂的去离子水,中和剂浓度为0.1-0.3mol/l,至乳液固含量约25-45%,乳化0.2-0.5小时;
d)在乳液中加入二胺类扩链剂,继续乳化、扩链0.5-2小时得到水性聚氨酯;
或为
a)将二环己基甲烷二异氰酸酯与脂肪族聚合二元醇、含亲水基团的DMBA混合,并加入催化剂在60-90℃下反应2-5小时得到预聚体;
b)降低温度到25-35℃,在FLUKE高速搅拌机进行搅拌同时加入含中和剂的去离子水,中和剂浓度为0.1-0.3mol/l,至乳液固含量约25-45%,乳化0.2-0.5小时;
c)在乳液中加入二胺类扩链剂和聚乙酰胺,继续乳化、扩链0.5-2小时得到水性聚氨酯;
其中,所述二环己基甲烷二异氰酸酯与脂肪族聚合二元醇摩尔比2.5-4∶1,优选为2.8-3.2∶1;聚合二元醇、DMBA的摩尔比为0.5-2.5∶1,优选为1.2-1.8∶1,二环己基甲烷二异氰酸酯与二元醇、DMBA、脂肪族二胺扩链剂总量的摩尔比为1.0-1.1,优选为1.01-1.05∶1;DMBA用量为固体份质量的2.5-8%,优选为3-4.5%;中和剂的摩尔数为DMBA摩尔数的1110%,乳液固含量为25-45%。
本发明采用脂肪族异氰酸酯为原料,与MDI、TDI等芳香族异氰酸酯相比,脂肪族异氰酸酯制品在使用过程中不会产生芳香胺类致癌物质。
所述脂肪族异氰酸酯包括但不限于二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯或己二异氰酸酯,优选二环己基甲烷二异氰酸酯;二环己基甲烷二异氰酸酯制得的水性聚氨酯具有更好的力学、耐水性、耐黄变性能,二环己基甲烷二异氰酸脂相对异佛尔酮二异氰酸酯和己二异氰酸酯挥发更少,这在水性聚氨酯生产过程中对于操作人员更加安全和环保。
本发明方法采用二羟甲基丁酸(DMBA),与二羟甲基丙酸相比,DMBA在低聚物二元醇中的溶解度较高,熔点较低,因此在将DMBA引入预聚反应体系时,可以少用或者不用N-甲基吡咯烷酮(NMP)助溶剂来溶解DMBA,减少有毒害有机物质的使用,并且由DMBA制得水性聚氨酯的耐水性比DMPA制得的有改善,同时具有高模量、高强度、低模量的特性。
在水性聚氨酯制备中,可以将二环己基甲烷二异氰酸酯与脂肪族聚醚二元醇或聚酯二元醇、亲水单体扩链剂DMBA一次混合后反应制备预聚物,再将预聚物乳化、中和、扩链制得水性聚氨酯乳液的一步法制备的水性聚氨酯预聚体粘度大、亲水基团在分子量中的分布不均匀,乳化效果较差。
以分步加料法,先将二环己基甲烷二异氰酸酯与脂肪族聚醚二元醇或聚酯二元醇反应制得预聚体,再将预聚体与含亲水单体的小分子二醇扩链剂扩链,将扩链后的预聚物乳化分散、中和、扩链得到水性聚氨酯乳液,以分步加料方式制得的预聚物中亲水单体分布较均匀、乳化效果较好。
本发明方法中所述中和剂包括但不限于NaHCO3、KHCO3或KOH,其中本发明所述中和剂优选为KOH,以KOH为中和剂的乳液稳定性、分散性更好,能得到泛蓝光、半透明乳液,实际对中和剂进行选择时发现,以NaOH为中和剂的乳液的外观较差、粒径大、稳定性差。
本发明方法中,所述脂肪族聚合二元醇为6子量的脂肪族聚醚二元醇或聚酯二元醇;或6子量的脂肪族聚醚二元醇或聚酯二元醇与分子量低于4元醇的混合物;
进一步优选为所述脂肪族聚合二元醇为12子量的脂肪族聚醚二元醇或聚酯二元醇;或12子量的脂肪族聚醚二元醇或聚酯二元醇与分子量低于4元醇的混合物;
其中,所述脂肪族聚酯二元醇为6子量的聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸酯中一种或多种;所述脂肪族聚醚二元醇为6子量的聚四氢呋喃醚;更进一步优选所述的脂肪族聚酯二元醇为12子量的聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇、聚己二酸丙二醇酯二元醇或聚己二酸丁二醇酯二元醇;所述聚醚二元醇为12子量的聚四氢呋喃醚。
本发明方法中,所述分子量低于4元醇为乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、己二醇、一缩二乙二醇或新戊二醇。
本发明所述二胺扩链剂为肼、乙二胺、丁二胺、己二胺或异佛尔酮二胺,它们具有易溶于水,反应速度快,能很快完成预聚体的扩链反应,残留小的特点。
本发明所述催化剂为二月桂酸二丁基锡;优选二月桂酸二丁基锡的用量为1m。
本发明还提供一种由上述方法所制得的水性聚氨酯,所述水性聚氨酯可广泛用于对健康要求较高的食品、医药卫生和家具用品领域。
本发明方法克服了以往水性聚氨酯制备专利技术可能产生毒性的缺点,对以往水性聚氨酯生产工艺中可能产生毒害作用的原料、工艺等进行改进,以提供一种完全没有毒性的水性聚氨酯。
首先,本专利中采用的DMBA熔点低,在低聚物二元醇中溶解度较大,不需要以NMP为溶剂,消除了有机溶剂NMP的残留;
其次,本专利采用KOH为中和剂,消除了有机胺类物质的挥发和残留,没有生物毒性。
再次,本专利采用二环己基甲烷二异氰酸酯,与其它两种常用于水性聚氨酯的异氰酸酯IPDI和TDI相比,H12MDI的蒸气压低,挥发性小,在生产过程中对环境和生产人员产生的毒害作用小。
最后,与传统芳香族异氰酸酯相比,以H12MDI为原料,不会在乳液和制品的制备、储存、使用中分解产生致癌的芳香胺类物质。
与以往专利相比,本专利技术具有如下的优势:
一.本专利采用的二环己基甲烷二异氰酸酯为脂肪族异氰酸酯,不会在乳液和制品的制备、储存中产生致癌的芳香胺类物质,同时它与另外一种常用于水性聚氨酯的脂肪族异氰酸酯IPDI相比,其结构规整、刚性较大,具有更好的力学、热学等性能。此外H12MDI的蒸汽压低、挥发性小,与TDI、IPDI等原料相比,其对环境的毒害作用更小。
二.本专利采用含羧基的DMBA为扩链剂,在分子链中引入亲水基团。与DMPA相比,DMBA的熔点低、在低聚物二元醇中的溶解度较大,不需要以NMP为助溶剂,可以有效减小有机溶剂的使用。
三.本专利采用KOH为中和剂,制品没有生物毒性,同时也可以有效消除水性聚氨酯生产过程中的有机胺类物质挥发对环境造成的危害。
四.本专利采用了分步投料、自乳化的制备工艺,制得的聚氨酯乳液粒径小、储存稳定性、分散性更好。
具体实施方式
为了更好实施本发明,通过以下实施例对本发明做进一步说明但不局限于这些实施例,据本发明的内容对本发明所作的一些非本质的改进和调整,仍属于本发明保护范围。
实施例中所涉及的主要原料来源如下:
二环己基甲烷二异氰酸酯(H12MDI),烟台万华聚氨酯股份有限公司生产。
聚醚二元醇:
聚四氢呋喃二醇(PTMEG,分子量62韩国PTG生产,工业品;
聚丙二醇(分子量12,天津三石化生产,工业品。聚酯二元醇:聚碳酸酯二醇(PCDL,分子量12,NPU,工业品;
聚己内酯二醇(PCL,分子量12,Solvay公司,工业品。
二羟甲基丁酸(DMBA):瑞典柏斯托公司,工业品。
中和剂:KOH,天津科密欧化学试剂有限公司,试剂。
扩链剂:1,4-丁二醇(BDO),己二胺,乙二胺,天津科密欧化学试剂有限公司,试剂。
FLUKE高速乳化分散机,上海弗鲁克流体机械制造有限公司;
固含量测试方法:依照GB/T 1725-79.
拉伸性能测试:测试仪器采用ZWICK公司Z万能材料试验机、按照ASTM D882标准进行测试。
乳液粒径测试:测试仪器是马尔文仪器公司zatasizer nano ZS激光纳米粒度测定仪,测试温度为25℃。
储存稳定性:取乳液置于离心分离机中,在3pm/min下离心分离15分钟,若无沉淀产生则说明储存稳定性在6个月以上。
实施例1
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI235.8克与3TMEG1加入4滴T12催化剂,在70℃下反应1小时,将预聚体加热至80℃,加入28.7克融化的DMBA反应3小时,再加入9.54克BDO和聚乙酰胺反应1小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下将含有12克KOH的水溶液1388克加入预聚体中,分散20分钟后加入乙二胺15.4克继续搅拌反应20分钟得到白色水性聚氨酯乳液。测得乳液固含量为30%、DMBA含量4.87%、粒径80-110nm,膜拉伸强度28MPa,断裂伸长率860%。
实施例2
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI 235.8克与216克PTMEG6入4滴T12催化剂,在70℃下反应1小时,将预聚体加热至80℃,加入24.6克融化的DMBA反应3小时,再加入14.9克BDO和聚乙酰胺反应1小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下,将含有10.2克KOH的水溶液1180克加入预聚体,分散20分钟后加入乙二胺9.9克继续搅拌反应20分钟得到半透明、半乳白色水性聚氨酯乳液。测得乳液固含量为30.5%、DMBA含量4.9%、粒径80-1,膜拉伸强度30.4MPa,断裂伸长率830%。
实施例3
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI235.8克与6TMEG2加入4滴T12催化剂,在80℃下反应1小时后,在预聚体中加入35克融化的DMBA反应3.5小时,再加入6.86克BDO和聚乙酰胺反应1.5小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下将含有14.6克KOH的水溶液1673克加入预聚体,分散20分钟后加入乙二胺4.15克继续搅拌反应20分钟得到半透明、半乳白色水性聚氨酯乳液。测得乳液固含量为35.2%、DMBA含量、粒径95-120nm,膜拉伸强度24MPa,断裂伸长率890%。
实施例4
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI 262克与250克PPG1加入4滴T12催化剂,在80℃下反应1小时后,在80℃下往预聚体中加入28克融化的DMBA应3.5小时,再加入20.5克BDO和聚乙酰胺反应1.5小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下,将含有11.6克KOH的水溶液1397克加入预聚体中,分散20分钟后加入己二胺33.1克继续搅拌反应20分钟,得到半透明、半乳白色水性聚氨酯乳液。测得乳液固含量为30%、DMBA含量4.7%、粒径85-110nm,膜拉伸强度25MPa,断裂伸长率960%。
实施例5
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI238.4克与303克PCDL1加入3滴T12催化剂,在60℃下反应1小时,将预聚体升温到70℃,加入26.49克融化的DMBA反应3小时,在80℃下再加入19.65克BDO和聚乙酰胺反应2小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下加入含有10.6克KOH的水溶液1427克,分散20分钟后加入己二胺19.33克继续搅拌反应20分钟得到白色水性聚氨酯乳液。测得乳液固含量为30%、DMBA含量4.37%、粒径80-110nm,膜拉伸强度35MPa,断裂伸长率820%。
实施例6
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI238.4克与606克PCDL2加入3滴T12催化剂,在60℃下反应1.5小时,将预聚体升温到70℃,加入40.3克融化的DMBA反应3.5小时,在80℃下再加入11.25克BDO和聚乙酰胺反应2.5小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下加入含有16.8克KOH的水溶液1717克,分散20分钟后加入己二胺19.33克继续搅拌反应20分钟得到白色水性聚氨酯乳液。测得乳液固含量为30%、DMBA含量4.4%、粒径80-110nm,膜拉伸强度28MPa,断裂伸长率860%。
实施例7
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI262克与333克PCL1加入3滴T12催化剂,在60℃下反应1小时,将预聚体升温到70℃,加入31.9克融化的DMBA反应3小时,在80℃下再加入10.6克BDO和聚乙酰胺反应2小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下加入含有13.3克KOH的水溶液1540克,分散20分钟后加入乙二胺17.1克继续搅拌反应20分钟得到白色水性聚氨酯乳液。测得乳液固含量为30%、DMBA含量4.4%、粒径80-1,膜拉伸强度36MPa,断裂伸长率820%。
实施例8
在装有搅拌器、冷凝回流管、热电偶的3l四口烧瓶中,加入H12MDI262克与666克PCL2加入3滴T12催化剂,在60℃下反应1.5小时,将预聚体升温到70℃,加入44.7克融化的DMBA反应3.5小时,在80℃下再加入12.5克BDO和聚乙酰胺反应2.5小时。将上述扩链反应后的预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下加入含有18.5克KOH的水溶液1780克,分散20分钟后加入己二胺21.6克继续搅拌反应20分钟得到白色水性聚氨酯乳液。测得乳液固含量为34%、DMBA含量4.4%、粒径90-110nm,膜拉伸强度29MPa,断裂伸长率860%。
实施例9
在装有搅拌器、冷凝回流管、热电偶的5四口烧瓶中,加入H12MDI238.4克与303克PCDL1加入3滴催化剂T12,在70℃下加入26.49克融化的DMBA、19.65克BDO 2.5和聚乙酰胺小时。将上述预聚体降温至30℃,在FLUKE高速乳化分散机在1r/min高速搅拌下加入含有10.6克KOH的水溶液1427克,分散20分钟后加入己二胺19.33克继续搅拌反应20分钟得到白色水性聚氨酯乳液。测得乳液固含量为30%、DMBA含量4.37%、粒径90-120nm,膜拉伸强度33MPa,断裂伸长率840%。
Claims (10)
1.一种无毒工艺制备水性聚氨酯的方法,其特征在于,所述方法包括:
a)将二环己基甲烷二异氰酸酯与脂肪族聚合二元醇混合,然后加入催化剂并在60-90℃下反应1-3小时,得到预聚体;
b)向预聚体中加入二羟甲基丁酸,在70-90℃下继续反应2-4小时;
c)降低温度到25-35℃,采用FLUKE高速搅拌机进行搅拌同时加入含中和剂的去离子水,中和剂浓度为0.1-0.3mol/l,至乳液固含量为25-45%,乳化0.2-0.5小时;
d)在乳液中加入二胺类扩链剂和聚乙酰胺,继续乳化、扩链0.5-2小时得到水性聚氨酯;或为
a)二环己基甲烷二异氰酸酯与脂肪族聚合二元醇、含亲水基团的DMBA混合物加入催化剂在60-90℃下反应2-5小时得到预聚体;
b)降低温度到25-35℃,在FLUKE高速搅拌机进行搅拌同时加入含中和剂的去离子水,中和剂浓度为0.1-0.3mol/l,至乳液固含量为25-45%,乳化0.2-0.5小时;
c)在乳液中加入二胺类扩链剂,继续乳化、扩链0.5-2小时得到水性聚氨酯;
其中,所述二环己基甲烷二异氰酸酯与脂肪族聚合二元醇摩尔比2.5-4∶1,所述脂肪族聚合二元醇、二羟甲基丁酸的摩尔比为0.5-2.5∶1,二环己基甲烷二异氰酸酯与所述脂肪族聚合二元醇、二羟甲基丁酸、脂肪族二胺扩链剂总量的摩尔比为1.0-1.1,二羟甲基丁酸用量为固体份质量的2.5-8%,中和剂的摩尔数为二羟甲基丁酸摩尔数的100%-110%,乳液固含量为25-45%。
2.根据权利要求1所述的制备方法,其特征在于,所述中和剂为NaHCO3、KHCO3或KOH。
3.根据权利要求2所述的制备方法,其特征在于,所述脂肪族聚合二元醇为600-3000分子量的脂肪族聚醚二元醇或聚酯二元醇;或600-3000分子量的脂肪族聚醚二元醇或聚酯二元醇与分子量低于400的二元醇的混合物。
4.根据权利要求3所述的制备方法,其特征在于,所述脂肪族聚合二元醇为1000-2000分子量的脂肪族聚醚二元醇或聚酯二元醇;或1000-2000分子量的脂肪族聚醚二元醇或聚酯二元醇与分子量低于400的二元醇的混合物。
5.根据权利要求3所述的制备方法,其特征在于,所述的脂肪族聚酯二元醇为600-3000分子量的聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸酯中一种或多种;所述脂肪族聚醚二元醇为600-3000分子量的聚四氢呋喃醚。
6.根据权利要求5所述的制备方法,其特征在于,所述的脂肪族聚酯二元醇为1000-2000分子量的聚己内酯二元醇、聚碳酸酯二元醇、聚己二酸乙二醇、聚己二酸丙二醇酯二元醇或聚己二酸丁二醇酯二元醇;所述聚醚二元醇为1000-2000分子量的聚四氢呋喃醚。
7.根据权利要求6所述的制备方法,其特征在于,所述分子量低于400的二元醇为乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、1,5-戊二醇、己二醇、一缩二乙二醇或新戊二醇。
8.根据权利要求7所述的制备方法,其特征在于,所述二胺扩链剂为肼、乙二胺、丁二胺、己二胺或异佛尔酮二胺。
9.根据权利要求8所述的制备方法,其特征在于,所述催化剂为二月桂酸二丁基锡。
10.根据权利要求9所述的制备方法,其特征在于,所述二月桂酸二丁基锡的用量为100-300PPm。
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