CN106750126B - 一种无助溶剂水性聚氨酯的制备方法 - Google Patents
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Abstract
本发明涉及一种无助溶剂水性聚氨酯的制备方法,包括:室温下,将2,2‑二羟甲基丙酸DMPA和脂肪族二元醇共混,在搅拌、氮气保护的条件下,加热至DMPA完全熔融,冷却至室温,得到低熔点扩链剂;将低熔点扩链剂与齐聚物多元醇混合后减压脱水,加入二异氰酸酯,在氮气保护条件下,70‑90℃反应1‑3h,得到聚氨酯预聚体;将聚氨酯预聚体降至室温,加入三乙胺中和,然后加入去离子水并分散在去离子水中,加入乙二胺进行扩链,得到水性聚氨酯。本发明的方法简单,制备得到的水性聚氨酯安全,环保,适用于工业生产。
Description
技术领域
本发明属于水性聚氨酯的制备领域,特别涉及一种无助溶剂水性聚氨酯的制备方法。
背景技术
水性聚氨酯不同于传统的溶剂型聚氨酯,是以水代替有机溶剂作为分散介质的一种环境友好型材料。水性聚氨酯种类有很多,其中阴离子型水性聚氨酯使用的最为广泛。目前工业上普遍采用丙酮法制备阴离子型水性聚氨酯,在众多阴离子型扩链剂中,二羟甲基丙酸(DMPA)是使用最广泛的一种,但其弊端在于DMPA的熔点高(160℃-170℃),在丙酮中的溶解度较低,很难加热溶解,这就需要加入助溶剂如N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)等来溶解DMPA,加快DMPA的扩链反应。但NMP、DMF是有毒、有害的有机溶剂,并且其沸点高,很难从制备出的水性聚氨酯中除去,在使用过程中会给环境保护和人体安全带来极大地隐患,因此迫切需要一种新工艺来解决DMPA溶解难的问题。
目前关于有关制备不含助溶剂的水性聚氨酯的研究并不多,例如,Lee和Kim等人使用二羟甲基丁酸(DMBA)为扩链剂,制备水性聚氨酯,DMBA结构与DMPA类似,侧链上的甲基换成了乙基,使得其熔点降为(105℃-115℃),制备过程中无需使用NMP或DMF等助溶剂来溶解,可直接加入到体系中参与反应。([1]Lee S J,Kim B K.Covalent incorporation ofstarch derivative into waterborne polyurethane for biodegradability[J].Carbohydrate Polymers,2011,87(2):1803–1809.[2]Kim B S,Kim B K.Enhancement ofhydrolytic stability and adhesion of waterborne polyurethanes[J].Journal ofApplied Polymer Science,2005,97(5):1961–1969.)Xiao等人使用2,4-二氨基苯磺酸钠(SDBS)为扩链剂,制备水性聚氨酯,SDBS的熔点较低且能溶解于去离子水中直接加入到反应体系中,从而避免使用助溶剂([3]Xiao Y,Fu X,Zhang Y,et al.Preparation ofwaterborne polyurethanes based on the organic solvent-free process[J].GreenChemistry,2016,18(2):412-416.)。但二羟甲基丁酸(DMBA)和2,4-二氨基苯磺酸钠(SDBS)价格昂贵,经济性较差,难以在工业上得到广泛的应用。此外还有研究利用DMPA和活泼单体如:己内酯、环氧乙烷、环氧丙烷以及四氢呋喃的开环反应降低扩链剂的熔点,从而进一步制备无助溶剂的水性聚氨酯([4]陈大俊,吴键儒.一种用于水性聚氨酯的扩链剂的制备方法:CN103214668,2015.),但此方法工艺复杂,成本高。因此,需要一种经济性高且工艺简单的方法来解决DMPA溶解难的问题。
发明内容
本发明所要解决的技术问题是提供一种无助溶剂水性聚氨酯的制备方法,该方法工艺易行,设备简单,生产的水性聚氨酯不含高沸点的有毒助溶剂,更加安全、环保。
本发明的一种无助溶剂水性聚氨酯的制备方法,包括:
(1)室温下,将2,2-二羟甲基丙酸DMPA和脂肪族二元醇共混,在(机械)搅拌、氮气保护的条件下,加热至DMPA完全熔融,冷却至室温,得到低熔点扩链剂;
(2)将步骤(1)中的低熔点扩链剂与齐聚物多元醇混合后减压脱水,加入二异氰酸酯,在氮气保护条件下,70~90℃反应1~3h(优选80℃反应2h),得到聚氨酯预聚体;
(3)将步骤(2)中的聚氨酯预聚体降至室温,加入三乙胺中和,然后加入去离子水并分散在去离子水中(高速分散于水中),加入乙二胺进行扩链,得到水性聚氨酯。
所述步骤(1)中DMPA和脂肪族二元醇的摩尔比为0.25-4∶1。
所述步骤(1)中脂肪族二元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇或1,6-己二醇。
所述步骤(1)中加热的温度为160~170℃,时间为10~20min;冷却的速率为10~20℃/min。
所述步骤(1)中低熔点扩链剂的熔点为110~140℃。
所述步骤(2)中低熔点扩链剂、二异氰酸酯与齐聚物多元醇的摩尔比为1∶2.2∶1。
所述步骤(2)中齐聚物多元醇的分子量为600~3000。
所述齐聚物多元醇为聚己内酯二醇PCL、聚己二酸-1,4-丁二醇酯二醇PBA、聚己二酸乙二醇酯二醇PEA、聚己二酸丙二醇酯二醇PPA、聚四氢呋喃二醇PTMG或聚氧化丙烯二元醇PPG。
所述步骤(2)中二异氰酸酯为异佛尔酮二异氰酸酯IPDI、甲苯二异氰酸酯TDI、六亚甲基二异氰酸酯HDI或4,4-二苯基甲烷二异氰酸酯MDI。
所述步骤(2)中减压脱水的条件为:温度为110~120℃,时间为2~3h,相对真空度需达到-90Kpa;优选120℃减压脱水2h。
所述步骤(3)中三乙胺与DMPA的摩尔比为1∶1;乙二胺与二异氰酸酯的摩尔比为1∶11。
所述步骤(3)中中和的时间为20~40min,扩链的反应时间为30~50min;中和反应的时间优选为30min,扩链反应的时间优选为40min。
本发明通过将DMPA和脂肪族二醇按一定比例共混,在氮气保护下加热至160-170℃,待DMPA完全融化后以10-20℃/min的降温速率冷却至室温,冷却的过程中由于脂肪族二醇阻碍了DMPA的结晶,使得DMPA的结晶程度降低,从而制得熔点较低的水性聚氨酯扩链剂。在后续制备水性聚氨酯的过程中,不需要加入N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)等有机助溶剂,使材料的环保性和安全性得到了提升。
有益效果
(1)本发明的制备方法工艺简单、成本低廉,可在工业上得到广泛的应用;
(2)本发明生产的水性聚氨酯不含高沸点的有毒助溶剂如:N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF),更加环保、安全和经济。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
将DMPA与1,4-丁二醇以2∶1的摩尔比混合,在氮气保护下,升温至165℃,机械搅拌至DMPA完全融化后,以20℃/min的降温速率冷却至室温,制得扩链剂A1,熔点为136℃。
实施例2
将DMPA与1,4-丁二醇以0.5∶1的摩尔比混合,在氮气保护下,升温至170℃,机械搅拌至DMPA完全融化后,以10℃/min的降温速率冷却至室温,制得扩链剂A2,熔点为114℃。
实施例3
将DMPA与乙二醇以1∶1的摩尔比混合,在氮气保护下,升温至160℃,机械搅拌至DMPA完全融化后,以20℃/min的降温速率冷却至室温,制得扩链剂B,熔点为122℃。
实施例4
将DMPA与1,6-己二醇以1∶1的摩尔比混合,在氮气保护下,升温至165℃,机械搅拌至DMPA完全融化后,以10℃/min的降温速率冷却至室温,制得扩链剂C,熔点为128℃。
实施例5
将聚己内酯二醇(分子量为1000)20g和扩链剂A12.38g加入到三口烧瓶中,120℃时减压脱水2h后(相对真空度为-95Kpa),加入9.78g异氟尔酮二异氰酸酯(IPDI),在氮气的保护下,于80℃反应2h后,降温至室温,后加入中和剂三乙胺1.35g,机械搅拌下中和30min,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为56.27nm,胶膜拉伸强度为15.81Mpa。
实施例6
将聚己内酯二醇(分子量为1000)20g和扩链剂A22.09g加入到三口烧瓶中,120℃时减压脱水2h后(相对真空度为-95Kpa),加入9.78g异氟尔酮二异氰酸酯(IPDI),在氮气的保护下,于80℃反应2h后,降温至室温,后加入中和剂三乙胺0.67g,机械搅拌下中和30min,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为127.3nm,胶膜拉伸强度为32.77Mpa。
实施例7
将聚己内酯二醇(分子量为1000)20g和扩链剂B1.96g加入到三口烧瓶中,120℃时减压脱水2h后(相对真空度为-95Kpa),加入9.78g异氟尔酮二异氰酸酯(IPDI),在氮气的保护下,于80℃反应2h后,降温至室温,后加入中和剂三乙胺1.01g,机械搅拌下中和30min,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为68.36nm,胶膜拉伸强度为18.53Mpa。
实施例8
将聚己内酯二醇(分子量为1000)20g和扩链剂C2.52g加入到三口烧瓶中,120℃时减压脱水2h后(相对真空度为-95Kpa),加入9.78g异氟尔酮二异氰酸酯(IPDI),在氮气的保护下,于80℃反应2h后,降温至室温,后加入中和剂三乙胺1.01g,机械搅拌下中和30min,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为74.42nm,胶膜拉伸强度为20.36Mpa。
实施例9
将聚己内酯二醇(分子量为2000)40g和扩链剂A12.38g加入到三口烧瓶中,120℃时减压脱水2h后(相对真空度为-95Kpa),加入9.78g异氟尔酮二异氰酸酯(IPDI),在氮气的保护下,于80℃反应2h后,降温至室温,后加入中和剂三乙胺1.35g,机械搅拌下中和30min,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为80.36nm,胶膜拉伸强度为24.52Mpa。
实施例10
将聚己内酯二醇(分子量为3000)60g和扩链剂A12.38g加入到三口烧瓶中,120℃时减压脱水2h后(相对真空度为-95Kpa),加入9.78g异氟尔酮二异氰酸酯(IPDI),在氮气的保护下,于80℃反应2h后,降温至室温,后加入中和剂三乙胺1.35g,机械搅拌下中和30min,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为129.42nm,胶膜拉伸强度为30.64Mpa。
实施例11
将聚四氢呋喃二醇PTMG(分子量为2000)40g和扩链剂A12.24g加入到三口烧瓶中,120℃时减压脱水2h后,加入7.4g六亚甲基二异氰酸酯(HDI),在氮气的保护下,于80℃反应2h后(相对真空度为-95Kpa),降温至室温,后加入中和剂三乙胺0.7g,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为154.4nm,胶膜拉伸强度为20.32Mpa。
实施例12
将聚己二酸-1,4-丁二醇酯二醇(分子量为2000)40g和扩链剂A12.38g加入到三口烧瓶中,120℃时减压脱水2h后(相对真空度为-95Kpa),加入7.66g甲苯二异氰酸酯(TDI),在氮气的保护下,于80℃反应2h后,降温至室温,后加入中和剂三乙胺1.35g,机械搅拌下中和30min,在高速剪切(1500r/min)的作用下加入去离子水进行乳化,再加入0.24g乙二胺进行扩链反应40min,得到水性聚氨酯。测得乳液粒径为116.23nm,胶膜拉伸强度为22.34Mpa。
Claims (9)
1.一种无助溶剂水性聚氨酯的制备方法,包括:
(1)室温下,将2,2-二羟甲基丙酸DMPA和脂肪族二元醇共混,在搅拌、氮气保护的条件下,加热至DMPA完全熔融,冷却至室温,得到低熔点扩链剂;其中,DMPA和脂肪族二元醇的摩尔比为0.25-4∶1;冷却的速率为10~20℃/min;
(2)将步骤(1)中的低熔点扩链剂与齐聚物多元醇混合后减压脱水,加入二异氰酸酯,在氮气保护条件下,70-90℃反应1-3h,得到聚氨酯预聚体;
(3)将步骤(2)中的聚氨酯预聚体降至室温,再加入三乙胺中和,然后加入去离子水并分散在去离子水中,加入乙二胺进行扩链,得到水性聚氨酯。
2.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述步骤(1)中脂肪族二元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇或1,6-己二醇。
3.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述步骤(1)中加热的温度为160~170℃,时间为10~20min。
4.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述步骤(1)中低熔点扩链剂的熔点为110~140℃。
5.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述步骤(2)中低熔点扩链剂、二异氰酸酯与齐聚物多元醇的摩尔比为1∶2.2∶1。
6.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述齐聚物多元醇为聚己内酯二醇PCL、聚己二酸-1,4-丁二醇酯二醇PBA、聚己二酸乙二醇酯二醇PEA、聚己二酸丙二醇酯二醇PPA、聚四氢呋喃二醇PTMG或聚氧化丙烯二元醇PPG;二异氰酸酯为异佛尔酮二异氰酸酯IPDI、甲苯二异氰酸酯TDI、六亚甲基二异氰酸酯HDI或4,4-二苯基甲烷二异氰酸酯MDI。
7.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述步骤(2)中减压脱水的条件为:温度为110~120℃,时间为2~3h,相对真空度为-90Kpa。
8.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述步(3)中三乙胺与DMPA的摩尔比为1∶1;乙二胺与二异氰酸酯的摩尔比为1∶11。
9.根据权利要求1所述的一种无助溶剂水性聚氨酯的制备方法,其特征在于,所述步骤(3)中中和的时间为20-40min,扩链的反应时间为30-50min。
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