CN106243312A - 一种超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法 - Google Patents
一种超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法 Download PDFInfo
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- CN106243312A CN106243312A CN201610720480.8A CN201610720480A CN106243312A CN 106243312 A CN106243312 A CN 106243312A CN 201610720480 A CN201610720480 A CN 201610720480A CN 106243312 A CN106243312 A CN 106243312A
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- Prior art keywords
- acid
- preparation
- ultrahigh hardness
- polyurethane emulsion
- waterborne polyurethane
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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Abstract
本发明涉及化工技术领域，具体涉及一种超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，本发明采用一种由液体双金属氰化物催化剂催化制得的新型聚碳酸酯多元醇‑聚碳酸环己酯多元醇，制备水性聚氨酯乳液，该多元醇是在催化剂作用下，以小分子多元醇等作为起始剂，由二氧化碳与氧化环己烯进行开环调节聚合制备而成，其分子内含有比例较高的碳酸酯基团，结构均匀，分子间或分子内聚能比较高，并且分子链带有脂肪环侧基团，赋予水性聚氨酯材料超高硬度、优异的物理强度和优越的耐溶剂性能，是制备高性能水性聚氨酯材料的优选原料。
Description
技术领域
本发明涉及化工技术领域，具体涉及一种超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法。
背景技术
聚氨酯为主链含—NHCOO—重复结构单元的一类聚合物，英文缩写PU，包括硬质聚氨酯塑料、软质聚氨酯塑料、聚氨酯弹性体等多种形态，并分为热塑性和热固性两大类，其原料一般以树脂状态呈现。水性聚氨酯是以水代替有机溶剂作为分散介质的新型聚氨酯体系，也称水分散聚氨酯、水系聚氨酯或水基聚氨酯。水性聚氨酯以水为溶剂，无污染、安全可靠、机械性能优良、相容性好、易于改性等优点。
聚氨酯树脂的水性化已逐步取代溶剂型，成为聚氨酯工业发展的重要方向，水性聚氨酯具有无污染、安全可靠、物理性能优良、相容性和成膜性胶好等优点，目前已逐步取代溶剂型聚氨酯，成为聚氨酯工业发展的重要方向，可广泛应用于木器漆、建筑漆、粘合剂、皮革涂饰剂、纺织品涂层整理剂、纸张和玻璃纤维表面处理剂等。然而，目前市场上的水性聚氨酯普遍存在膜硬度低、耐溶剂性能差的缺点。
发明内容
本发明第一个目的是针对现有技术水性聚氨酯存在的表面硬度低、耐溶剂性差等问题，以聚碳酸环己酯多元醇为主要初始原料，采用聚己内酯多元醇复配，有效提高水性聚氨酯涂层的硬度、强度以及耐溶剂性能，同时具备较好的柔顺性和弹性，同时具有成本低廉，工艺简单可控等优点。
本发明另一个目的是针对现有技术的不足提供一种新型的、实用的聚碳酸环己酯型水性聚氨酯乳液的制备方法，获取高性能的超高硬度水性聚氨酯乳液。
为了实现以上目的，本发明提供以下技术方案：
一种超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，包括以下步骤：
A1、本体聚合制备聚氨酯树脂：将100份聚碳酸环己酯多元醇和20-100份聚己内酯多元醇加入反应釜，升温至60-100℃，再加入8-30份羧酸型或磺酸型的亲水端羟基化合物，加入40-80份脂肪族多异氰酸酯或异氰酸酯封端预聚物进行初步反应，反应0.5-5h后再加入0.05-5份铋类催化剂继续反应完全，添加1-10份小分子多元醇或多元胺，扩大聚合物分子链，得到聚氨酯树脂；
A2、乳液聚合制备聚氨酯乳液：将上述聚氨酯树脂降温至5-25℃，加入20-90份溶剂，加入0.1-30份中和成盐剂调节pH值至7-8，再次加入5-50份小分子多元醇或多元胺的水溶液，进行乳液聚合反应；
A3、脱溶及完全反应阶段：将残余溶剂进行升温降压脱除，温度控制在40-70℃，通过水分散相将残余异氰酸酯基团完全反应，制得超高硬度的聚碳酸酯型水性聚氨酯乳液。
其中，所述聚碳酸环己酯多元醇以二氧化碳为起始原料，在引发剂、液体双金属氰化物催化剂作用下与氧化环己烯共聚合成，数均分子量为500-10000，羟基官能度为2-6，分子量分布指数(MWD)为1.05-2。
其中，所述液体双金属氰化物催化剂结构为：
aM1·bM2·cX·d(CN)·fTBA·gL·hH2O·IOH·OR；
其中，M1为两价金属，具体为锌、镉、钴、镍、铜、铁中的任意一种或多种的混合物；
M2为三价或变价金属，具体为铁、钴、铬、铝、锡中的任意一种或多种的混合物；
X为卤素，L为含有n个配位体原子有机螯合剂，n≥2，具体为氧、硫、氮、磷的有机螯合剂；
R为脱除一个羟基的小分子或单分子醇，具体为丁二醇、丙二醇、聚丙二醇、聚乙二醇、二丙二醇、二乙二醇、己二醇、戊二醇等中的任意一种或多种的混合物；
a、b、c、d、f、g、h、I为0.01-10的数值。
其中，所述聚己内酯多元醇己内酯单体、起始剂、四苯基锡催化剂经开环聚合而成，数均分子量为500-3000，羟基官能度为2-3。
其中，所述羧酸型亲水端羟基化合物为N，N-二羟基单马来酰胺酸、二氨基苯甲酸、酒石酸、二羟甲基丙酸、二羟甲基丁酸、含羧基半酯二醇、中的任意一种或几种的混合物；
所述磺酸型亲水端羟基化合物为含磺酸基聚酯二醇、1，2-二羟基-3-丙磺酸钠、乙二氨基乙磺酸钠、1,4-丁二醇-2-磺酸钠、中的任意一种或几种的混合物。
其中，所述脂肪族多异氰酸酯为六亚甲基二异氰酸酯、反式环己烷二异氰酸酯、三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的任意一种或几种混合物。
所述的异氰酸酯封端预聚物为六亚甲基二异氰酸酯、反式环己烷二异氰酸酯、三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的任意一种，与聚碳酸环己酯多元醇反应，所得到的异氰酸酯基团封端的预聚物。
其中，所述铋类催化剂为异辛酸铋，二月桂酸铋，新癸酸铋，环烷酸铋，氧化铋，硝酸铋的任意一种或几种的混合物。
其中，所述小分子多元醇或多元胺为类氨羟基二醇、一缩二乙二醇、一缩二丙二醇、1，4-丁二醇、1，6-己二醇、甘油、三羟甲基丙烷、二甘醇、三甘醇、新戊二醇、山梨醇、二乙氨基乙醇、乙二胺、N，N-二羟基(二异丙基)苯胺、氢醌-双(β-羟乙基)醚的任意一种或几种的混合物，其中，小分子多元醇或多元胺的水溶液中，水与小分子多元醇或多元胺的重量比例为5:1。
其中，所述中和成盐剂为碳酸钠、氨水、氢氧化钠、氢氧化钾、碳酸氢钠、醋酸钠、焦磷酸钠、盐酸、磷酸、甲酸、醋酸、二乙醇胺、三乙醇胺、氨基乙酸的任意一种或几种的混合物。
其中，所述溶剂为乙酸乙酯、乙酸丁酯、丙酮、丁酮、苯、甲苯、二甲苯、N,N-二甲基甲酰胺、甲基吡咯烷酮的任意一种或几种的混合物。
本发明采用一种由液体双金属氰化物催化剂催化制得的新型聚碳酸酯多元醇-聚碳酸环己酯多元醇，制备水性聚氨酯乳液，该多元醇是在催化剂作用下，以小分子多元醇等作为起始剂，由二氧化碳与氧化环己烯进行开环调节聚合制备而成，其分子内含有比例较高的碳酸酯基团，结构均匀，分子间或分子内聚能比较高，并且分子链带有脂肪环侧基团，赋予水性聚氨酯材料超高硬度、优异的物理强度和优越的耐溶剂性能，是制备高性能水性聚氨酯材料的优选原料。
与现有技术相比，本发明具有的有益效果为：
一、本发明的聚碳酸酯型水性聚氨酯乳液，具有超高的表面硬度、优良的耐溶剂性能、膜物理强度、附着力和耐磨性，可应用于木器漆、建筑涂料等，在高要求水性聚氨酯产品既能满足性能要求又具有成本优势；
二、本发明产品使用的聚碳酸环己酯多元醇是以二氧化碳为原料，采用液体双金属氰化物催化剂催化制备，催化效率高，残余催化剂小，液体催化剂能够更好分散，合成条件稳定简单，成本低廉，并且所得产品结构均匀，性能优越，具有良好的市场应用前景；
三、本发明采用聚碳酸环己酯多元醇和聚己内酯多元醇复配使用，在提高表面硬度的同时确保具备优良的柔韧性和回弹性，应用范围广泛。
具体实施方式
下面结合具体实施例对本发明做进一步的详细说明，但不构成的对本发明的任何限制。
实施例1。
第一步、本体聚合制备聚氨酯树脂：按质量分数称取100份分子量为1000的聚碳酸环己酯多元醇和40份分子量为1000的聚己内酯多元醇加入反应釜，升温至60℃，再加入12份的N，N-二羟基单马来酰胺酸，加入50份六亚甲基二异氰酸酯进行初步反应，反应2h后再加入1份异辛酸铋催化剂继续保证物料完全反应，根据分子量设计需求添加1份类氨羟基二醇，扩大聚合物分子链，得到聚氨酯树脂。
第二步、乳液聚合制备聚氨酯乳液，将上述聚氨酯树脂降温至5℃，加入20份丙酮，加入3份起调节物料PH值作用的碳酸钠，根据需要再次加入8份类氨羟基二醇的水溶液(其中水与类氨羟基二醇的重量比例为5:1)，进行乳液聚合反应。
第三步、脱溶及完全反应阶段，将残余丙酮进行升温降压脱除，温度控制在40℃，并且利用水分散相将残余异氰酸酯基团完全反应，得到本发明的超高硬度的聚碳酸酯型水性聚氨酯乳液。
实施例2。
第一步、本体聚合制备聚氨酯树脂：按质量分数称取100份分子量为1000的聚碳酸环己酯多元醇和20份分子量为1000的聚己内酯多元醇加入反应釜，升温至70℃，再加入8份的乙二氨基乙磺酸钠，加入40份异佛尔酮二异氰酸酯进行初步反应，反应0.5h后再加入0.05份异辛酸铋催化剂继续保证物料完全反应，根据分子量设计需求添加1份类氨羟基二醇，扩大聚合物分子链，得到聚氨酯树脂。
第二步、乳液聚合制备聚氨酯乳液，将上述聚氨酯树脂降温至15℃，加入80份苯，加入0.1份起调节物料PH值作用的三乙醇胺，根据需要再次加入5份氢醌-双(β-羟乙基)醚的水溶液(其中水与氢醌-双(β-羟乙基)醚的重量比例为5:1)，进行乳液聚合反应。
第三步、脱溶及完全反应阶段，将残余苯进行升温降压脱除，温度控制在60℃，并且利用水分散相将残余异氰酸酯基团完全反应，得到本发明的超高硬度的聚碳酸酯型水性聚氨酯乳液。
实施例3。
第一步、本体聚合制备聚氨酯树脂：按质量分数称取100份分子量为1000的聚碳酸环己酯多元醇和100份分子量为1000的聚己内酯多元醇加入反应釜，升温至100℃，再加入30份的乙二氨基乙磺酸钠，加入80份异佛尔酮二异氰酸酯进行初步反应，反应5h后再加入5份异辛酸铋催化剂继续保证物料完全反应，根据分子量设计需求添加10份N，N-二羟基(二异丙基)苯胺，扩大聚合物分子链，得到聚氨酯树脂。
第二步、乳液聚合制备聚氨酯乳液，将上述聚氨酯树脂降温至25℃，加入90份乙酸乙酯，加入30份起调节物料PH值作用的碳酸钠，根据需要再次加入50份二乙氨基乙醇的水溶液(其中水与二乙氨基乙醇的重量比例为5:1)，进行乳液聚合反应。
第三步、脱溶及完全反应阶段，将残余乙酸乙酯进行升温降压脱除，温度控制在65℃，并且利用水分散相将残余异氰酸酯基团完全反应，得到本发明的超高硬度的聚碳酸酯型水性聚氨酯乳液。
实施例4。
第一步、本体聚合制备聚氨酯树脂：按质量分数称取100份分子量为2000的聚碳酸环己酯多元醇和60份分子量为1000的聚己内酯多元醇加入反应釜，升温至85℃，再加入9份的二羟甲基丙酸，加入55份六亚甲基二异氰酸酯进行初步反应，反应3h后再加入1.5份硝酸铋催化剂继续保证物料完全反应，根据分子量设计需求添加5份类氨羟基二醇，扩大聚合物分子链，得到聚氨酯树脂。
第二步、乳液聚合制备聚氨酯乳液，将上述聚氨酯树脂降温至20℃，加入50份丁酮，加入4份起调节物料PH值作用的焦磷酸钠，根据需要再次加入10份类氨羟基二醇的水溶液(其中水与类氨羟基二醇的重量比例为5:1)，进行乳液聚合反应。
第三步、脱溶及完全反应阶段，将残余丁酮进行升温降压脱除，温度控制在70℃，并且利用水分散相将残余异氰酸酯基团完全反应，得到本发明的超高硬度的聚碳酸酯型水性聚氨酯乳液。
实施例5。
第一步、本体聚合制备聚氨酯树脂：按质量分数称取100份分子量为3000的聚碳酸环己酯多元醇和20份分子量为3000的聚己内酯多元醇加入反应釜，升温至90℃，再加入10份的N，N-二羟基单马来酰胺酸，加入60份六亚甲基二异氰酸酯进行初步反应，反应1h后再加入0.05份异辛酸铋催化剂继续保证物料完全反应，根据分子量设计需求添加4份乙二胺，扩大聚合物分子链，得到聚氨酯树脂。
第二步、乳液聚合制备聚氨酯乳液，将上述聚氨酯树脂降温至12℃，加入65份N,N-二甲基甲酰胺，加入4份起调节物料PH值作用的碳酸钠，根据需要再次加入8份一缩二乙二醇的水溶液(其中水与一缩二乙二醇的重量比例为5:1)，进行乳液聚合反应。
第三步、脱溶及完全反应阶段，将残余N,N-二甲基甲酰胺进行升温降压脱除，温度控制在68℃，并且利用水分散相将残余异氰酸酯基团完全反应，得到本发明的超高硬度的聚碳酸酯型水性聚氨酯乳液。
实施例6。
第一步、本体聚合制备聚氨酯树脂：按质量分数称取100份分子量为1000的聚碳酸环己酯多元醇和20份分子量为500的聚己内酯多元醇加入反应釜，升温至80℃，再加入14份的含羧基半酯二醇，加入70份三甲基六亚甲基二异氰酸酯进行初步反应，反应4h后再加入1份硝酸铋催化剂继续保证物料完全反应，根据分子量设计需求添加4份氢醌-双(β-羟乙基)醚，扩大聚合物分子链，得到聚氨酯树脂。
第二步、乳液聚合制备聚氨酯乳液，将上述聚氨酯树脂降温至12℃，加入35份甲基吡咯烷酮，加入2份起调节物料PH值作用的焦磷酸钠，根据需要再次加入10份类氨羟基二醇的水溶液(其中水与类氨羟基二醇的重量比例为5:1)，进行乳液聚合反应。
第三步、脱溶及完全反应阶段，将残余甲基吡咯烷酮进行升温降压脱除，温度控制在50℃，并且利用水分散相将残余异氰酸酯基团完全反应，得到本发明的超高硬度的聚碳酸酯型水性聚氨酯乳液。
按照相应的国家标准方法对本发明的超高硬度的聚碳酸酯型水性聚氨酯乳液进行性能测试，测试结果如下：
由上表可以看出，本发明制备的聚碳酸酯型水性聚氨酯乳液具有超高的硬度，硬度达到3H，远高于同类产品，这是得益于分子链上的脂肪环基团。其次，采用聚己内酯多元醇的复配，加上聚碳酸环己酯多元醇本身的碳酸脂基团，赋予材料优越的强度和附着力，是制备高性能水性聚氨酯材料的优选原料，具有良好的应用前景。
上述的实施例仅为本发明的优选实施例，不能以此来限定本发明的权利范围，因此，依本发明申请专利范围所作的等同变化，仍属本发明所涵盖的范围。
Claims (10)
1.一种超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，包括以下步骤：
A1、本体聚合制备聚氨酯树脂：将100份聚碳酸环己酯多元醇和20-100份聚己内酯多元醇加入反应釜，升温至60-100℃，再加入8-30份羧酸型或磺酸型的亲水端羟基化合物，加入40-80份脂肪族多异氰酸酯或异氰酸酯封端预聚物进行初步反应，反应0.5-5h后再加入0.05-5份铋类催化剂继续反应完全，添加1-10份小分子多元醇或多元胺，扩大聚合物分子链，得到聚氨酯树脂；
A2、乳液聚合制备聚氨酯乳液：将上述聚氨酯树脂降温至5-25℃，加入20-90份溶剂，加入0.1-30份中和成盐剂调节pH值至7-8，再次加入5-50份小分子多元醇或多元胺的水溶液，进行乳液聚合反应；
A3、脱溶及完全反应阶段：将残余溶剂进行升温降压脱除，温度控制在40-70℃，通过水分散相将残余异氰酸酯基团完全反应，制得超高硬度的聚碳酸酯型水性聚氨酯乳液。
2.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述聚碳酸环己酯多元醇以二氧化碳为起始原料，在引发剂、液体双金属氰化物催化剂作用下与氧化环己烯共聚合成，数均分子量为500-10000，羟基官能度为2-6，分子量分布指数为1.05-2。
3.根据权利要求2所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述液体双金属氰化物催化剂结构为：
aM1·bM2·cX·d(CN)·fTBA·gL·hH2O·IOH·OR；
其中，M1为两价金属，具体为锌、镉、钴、镍、铜、铁中的任意一种或多种的混合物；
M2为三价或变价金属，具体为铁、钴、铬、铝、锡中的任意一种或多种的混合物；
X为卤素，L为含有n个配位体原子有机螯合剂，n≥2，具体为氧、硫、氮、磷的有机螯合剂；
R为脱除一个羟基的小分子或单分子醇，具体为丁二醇、丙二醇、聚丙二醇、聚乙二醇、二丙二醇、二乙二醇、己二醇、戊二醇等中的任意一种或多种的混合物；
a、b、c、d、f、g、h、I为0.01-10的数值。
4.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述聚己内酯多元醇己内酯单体、起始剂、四苯基锡催化剂经开环聚合而成，数均分子量为500-3000，羟基官能度为2-3。
5.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述羧酸型亲水端羟基化合物为N，N-二羟基单马来酰胺酸、二氨基苯甲酸、酒石酸、二羟甲基丙酸、二羟甲基丁酸、含羧基半酯二醇、中的任意一种或几种的混合物；
所述磺酸型亲水端羟基化合物为含磺酸基聚酯二醇、1，2-二羟基-3-丙磺酸钠、乙二氨基乙磺酸钠、1,4-丁二醇-2-磺酸钠、中的任意一种或几种的混合物。
6.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述脂肪族多异氰酸酯为六亚甲基二异氰酸酯、反式环己烷二异氰酸酯、三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的任意一种或几种混合物。
所述的异氰酸酯封端预聚物为六亚甲基二异氰酸酯、反式环己烷二异氰酸酯、三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯中的任意一种，与聚碳酸环己酯多元醇反应，所得到的异氰酸酯基团封端的预聚物。
7.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述铋类催化剂为异辛酸铋，二月桂酸铋，新癸酸铋，环烷酸铋，氧化铋，硝酸铋的任意一种或几种的混合物。
8.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述小分子多元醇或多元胺为类氨羟基二醇、一缩二乙二醇、一缩二丙二醇、1，4-丁二醇、1，6-己二醇、甘油、三羟甲基丙烷、二甘醇、三甘醇、新戊二醇、山梨醇、二乙氨基乙醇、乙二胺、N，N-二羟基(二异丙基)苯胺、氢醌-双(β-羟乙基)醚的任意一种或几种的混合物，其中，小分子多元醇或多元胺的水溶液中，水与小分子多元醇或多元胺的重量比例为5:1。
9.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述中和成盐剂为碳酸钠、氨水、氢氧化钠、氢氧化钾、碳酸氢钠、醋酸钠、焦磷酸钠、盐酸、磷酸、甲酸、醋酸、二乙醇胺、三乙醇胺、氨基乙酸的任意一种或几种的混合物。
10.根据权利要求1所述的超高硬度的聚碳酸酯型水性聚氨酯乳液的制备方法，其特征在于，所述溶剂为乙酸乙酯、乙酸丁酯、丙酮、丁酮、苯、甲苯、二甲苯、N,N-二甲基甲酰胺、甲基吡咯烷酮的任意一种或几种的混合物。
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| CN110511350A (zh) * | 2019-07-25 | 2019-11-29 | 华南理工大学 | 一种聚碳型水性聚氨酯及其制备方法 |
| CN110511350B (zh) * | 2019-07-25 | 2021-10-26 | 华南理工大学 | 一种聚碳型水性聚氨酯及其制备方法 |
| CN115584160A (zh) * | 2022-02-25 | 2023-01-10 | 上海欧畅新材料科技有限公司 | 一种应用于健身球的快干型水性喷涂油墨 |
| CN115584160B (zh) * | 2022-02-25 | 2023-08-29 | 上海欧畅新材料科技有限公司 | 一种应用于健身球的快干型水性喷涂油墨 |
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