CN107057027A - 一种高固含量低粘度水性聚氨酯的制备方法 - Google Patents

一种高固含量低粘度水性聚氨酯的制备方法 Download PDF

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CN107057027A
CN107057027A CN201710029631.XA CN201710029631A CN107057027A CN 107057027 A CN107057027 A CN 107057027A CN 201710029631 A CN201710029631 A CN 201710029631A CN 107057027 A CN107057027 A CN 107057027A
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柴春鹏
马飞
马一飞
李国平
罗运军
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Abstract

本发明涉及一种高固含量低粘度水性聚氨酯的制备方法，属于涂料或胶粘剂领域。首先对原料进行除水处理；然后制备小粒径乳液S；同时制备预分散的大粒径乳液L；再向预分散的大粒径乳液L中滴加适量的乳液S，滴加完毕即可停止乳化，在35～45℃下旋蒸除去溶剂，得到的乳液H即为所述高固含量水性聚氨酯。制备的水性聚氨酯固含量高、粘度低、储存稳定性好、无毒环保、力学性能好。其固含量可达64.1％，粘度290mPa·s，胶膜的拉伸强度36.3MPa，断裂伸长率1130％，吸水率10.6％。

Description

一种高固含量低粘度水性聚氨酯的制备方法
技术领域
本发明涉及一种高固含量低粘度水性聚氨酯的制备方法，属于涂料或胶粘剂领域。
背景技术
水性聚氨酯是一种性能优异、绿色环保的新型水性材料，可以应用于涂料、胶粘剂、皮革涂饰等诸多领域。它不仅继承了聚氨酯材料良好的粘接性能、耐磨性能和低温力学性能，而且集合了水性材料低VOC、无毒、不燃、绿色环保等优点。然而水性聚氨酯在应用上仍存在很多缺点，如干燥时间长、成本高、初粘力小、力学性能较低、耐水性差等，无法满足实际应用的需求。
目前的研究中，高固含量水性聚氨酯的制备方法一般通过亲水单体、基础配方、乳化工艺等三个方面进行改进，如卫晓利等人以1,2-二羟基-3-丙磺酸钠(DHPA)为亲水扩链剂合成了固含量达61％的磺酸型水性聚氨酯(卫晓利,张发兴.用磺酸型亲水扩链剂制备高固含量聚氨酯乳液[J].合成橡胶工业,2010,33(1):29-32)，但文中使用的亲水扩链剂价格昂贵且用量较多；再如，Q.A.Li等以六亚甲基二异氰酸酯与异佛尔酮二异氰酸酯以30︰70的比例混合实验，合成了50％高固含量的水性聚氨酯(Li Q A,Su D C.Synthesis andcharacterization of high solid content aqueous polyurethane dispersion[J].Journal of Applied Polymer Science,2007,105(5):2516-2524)；瞿金清等采用聚酯二元醇(Oxyester T-1136)和聚醚二元醇(N-210)为混合软段制备高固含量水性聚氨酯(瞿金清,陈焕钦.高固含量水性聚氨酯分散体的合成[J].化工学报,2003,54(6):868-871)。这些方法通过对基础配方进行微调来提高固含量，一方面对固含量提升不大，另一方面当具体到水性聚氨酯的某项应用，偏重性能的配方与偏向高固含量的配方不一致，并不能广泛应用该方法。
发明内容
本发明的目的是为了解决现有的高固含量水性聚氨酯的制备方法不能被广泛应用的问题，提供一种高固含量低粘度水性聚氨酯的制备方法。
本专利基于乳液粒子堆积模型，提出了一种较为通用的制备高固含量低粘度水性聚氨酯的方法，即在预聚体乳化分散基本完成、乳液粘度减小的阶段加入粘度较低的小粒径乳液，使小粒子分散于大粒子之间，提高乳液粒子的空间利用率，最终提高乳液的固含量。本方法可用于制备多种类型和配方的水性聚氨酯，制备的水性聚氨酯固含量高，贮存稳定性好，无毒环保，力学性能达标，并且该方法适用于多种类型及配方的水性聚氨酯制备，目前还未见有人报道。
本发明的目的是通过下述技术方案实现的。
一种高固含量低粘度水性聚氨酯的制备方法，具体步骤如下：
步骤一、将大分子二元醇、亲水扩链剂、亲油扩链剂和溶剂进行除水处理；
步骤二、小粒径乳液S的制备：以大分子二元醇、异氰酸酯、亲油性扩链剂、亲水性扩链剂和催化剂为原料在70～80℃制备预聚体A，加入溶剂稀释，2000～3000r/min搅拌下一次性加入去离子水乳化分散，除去溶剂制得低固含量、小粒径的乳液S；
步骤三、大粒径乳液L的预分散：以大分子二元醇、异氰酸酯、亲油性扩链剂、亲水性扩链剂和催化剂为原料在70～80℃制备预聚体B，加入溶剂稀释，在200～1000r/min搅拌下滴加去离子水乳化分散，得到预分散的大粒径乳液L；
步骤四、高固含低粘度水性聚氨酯的制备：向步骤三的预分散的大粒径乳液L中滴加的步骤二的乳液S，滴加完毕即停止乳化，然后在35～45℃下旋蒸除去溶剂，得到高固含量低粘度水性聚氨酯。
所述乳液S的固含量为30～35％。
所述乳液S的粒径为30～160nm。
步骤二中所述大分子二元醇、异氰酸酯、亲油性扩链剂、亲水性扩链剂、催化剂和中和剂的质量百分比为：大分子二元醇56.64～66.81％，亲油扩链剂2.94～5.10％，亲水扩链剂1.99～5.04％，异氰酸酯25.09～35.25％，催化剂0.05～0.20％，中和剂0～3.80％，且各原料总质量为100％。
所述去离子水质量与预聚体A的质量比为1.857～2.333:1。
步骤三中所述大分子二元醇、异氰酸酯、亲油性扩链剂、亲水性扩链剂、催化剂和中和剂的质量百分比为：大分子二元醇41.38～68.63％，亲油扩链剂1.78～11.09％，亲水扩链剂1.50～2.99％，异氰酸酯25.54～46.13％，催化剂0.05～0.20％，中和剂0～2.26％，且各原料总质量为100％。
所述溶剂质量与预聚体B的质量比为0.82～1.22：1；所述去离子水质量与预聚体B的质量比为0.70～1.00：1。
步骤四中所述乳液S与大粒径乳液L的质量比为0.06～0.24。
所述亲水扩链剂为羧酸型亲水扩链剂如二羟甲基丙酸(DMPA)、磺酸型亲水扩链剂如乙二胺基乙磺酸钠(AAS)或大分子亲水单体如磺酸盐聚酯二元醇(PESS)。
所述大分子二元醇为聚醚二元醇或聚酯二元醇，聚酯二元醇如聚(1,6-己二醇/新戊二醇-己二酸)(PHNA)或聚己二酸-1，4-丁二醇酯二醇(PBA)，聚醚二元醇如聚丙二醇(PPG)或聚四氢呋喃二醇(PTMG)。
所述亲油扩链剂为1,4-丁二醇(BDO)、一缩乙二醇(DEG)、三羟甲基丙烷(TMP)或乙二胺(EDA)。
所述异氰酸酯包括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)、二苯基甲烷二异氰酸酯(MDI)或异佛尔酮二异氰酸酯(IPDI)与六亚甲基二异氰酸酯(HDI)的混合溶液。
所述溶剂为丙酮或丁酮。
有益效果
1、一种本发明所述的高固含量水性聚氨酯的制备方法，可用于高固含量羧酸型、磺酸型及羧酸/磺酸型水性聚氨酯的制备，所制备的水性聚氨酯可作为涂料、胶粘剂应用于多种领域。
2、按照本发明所述方法制备的水性聚氨酯固含量高、粘度低、储存稳定性好、无毒环保、力学性能好，其固含量可达到64.1％，粘度290mPa·s，胶膜的拉伸强度36.3MPa，断裂伸长率1130％，吸水率10.6％。此种方法既符合水性材料的发展趋势，又能降低水性聚氨酯应用的成本，扩展其在各领域的应用，具有巨大的经济和社会效益前景。
具体实施方式
下面结合具体实施例对本发明作进一步阐述。
固含量测试方法：取一定质量(m0)的聚氨酯乳液放入105℃的烘箱中，3小时后取出，降温至室温，测得质量为m1，它的固含量为：
固含量＝(m0-m1)/m0×100％
粒径测试方法：用Zetasizer Nano SZ型激光粒度仪对按1:1000稀释的透明乳液进行粒径测试，测试温度25℃。
粘度测试方法：用BROOKFIELD R/S+流变仪对乳液进行测试，测试温度25℃，剪切速率150r/min。
吸水率测试方法：将水性聚氨酯胶膜裁成约2cm×2cm的试样，测定干膜质量(m0)。于室温下在去离子水中浸泡24h后取出，用滤纸吸取湿膜表面水分，测定湿膜质量(m1)。吸水率/％＝(m1–m0)/m0×100％
力学性能测试方法：拉伸性能测试按照GB/T 528-2009进行。使用WDW-E100D型电子式万能试验机对样条进行拉伸试验，记录最大拉伸强度和断裂伸长率。
实施例1：
取1.54g DMPA、40.0g PBA(分子量2000)、1.80g BDO混合均匀，升温至80℃，加入17.17g IPDI，滴加0.06g催化剂二月桂酸二丁基锡(T-12，0.5wt％)，保持80℃反应约4h，停止加热并加入40ml丁酮稀释，降至室温，加入1.16g中和剂三乙胺(TEA)，反应40min。在2500r/min搅拌下向预聚体溶液中加入102.4g水，乳化25min。旋蒸除去溶剂丁酮，得到小粒径乳液S1，测其固含量为35％，粒径92nm。
取1.54g DMPA、40.0g PBA(分子量2000)、1.80g BDO混合均匀，升温至80℃，加入17.17g IPDI，滴加0.06g T-12，保持80℃反应约4h，停止加热并加入60ml丁酮稀释，降至室温，加入1.16gTEA，中和40min。在1000r/min搅拌下向预聚体溶液中逐滴滴加47.9g的水，得预分散的大粒径乳液L1；
向150.0g L1中滴加9.0g的乳液S1，全部滴加完毕后停止乳化。旋蒸除去丙酮，得水性聚氨酯乳液H1。
乳液H1的固含量为63.9％，粘度282mPa·s，胶膜的拉伸强度24.5MPa，断裂伸长率985％，吸水率4.70％。
实施例2：
取3.54g DMPA、40.0g PHNA(分子量2000)、1.20g BDO混合均匀，升温至80℃，加入21.25g IPDI，滴加0.06g T-12，保持80℃反应约4h，停止加热并加入40ml丁酮稀释，降至室温，加入2.67g TEA，中和40min。在2500r/min搅拌下向预聚体溶液中加入165.2g水和1.60gEDA，乳化25min。旋蒸除去溶剂丁酮，得到小粒径乳液S2，测其固含量为34％，粒径39nm。
取15.00g PPG(分子量1000)、16.72g的TDI混合均匀，升温至70℃反应2h。加入4.02g TMP和0.06g T-12，70℃反应2h，加入56ml丙酮降低预聚体粘度。降低温度至60℃，加入1.09g的AAS(50wt％)，反应25min。在1000r/min搅拌下向预聚体溶液中逐滴滴加25.4g的水，得预分散的大粒径乳液L2；
向100.0g L2中滴加15.0g的乳液S2，全部滴加完毕后停止乳化。旋蒸除去丙酮，得水性聚氨酯乳液H2。
乳液H2的固含量为61.9％，粘度289mPa·s，胶膜的拉伸强度13.3MPa，断裂伸长率635％，吸水率15.4％。
实施例3：
取40g PTMG(分子量2000)、16.88g IPDI混合均匀，升温至80℃反应2h。加入1.80gBDO和0.06g T-12，80℃反应2h，加入40ml丙酮降低预聚体粘度。降低温度至60℃，加入4.89g的AAS(50wt％)，反应25min。在3000r/min搅拌下向预聚体溶液中加入112.5g水，乳化25min。旋蒸除去溶剂丙酮，得到小粒径乳液S3，测其固含量为30％，粒径41nm。
取1.78g DMPA、40.0g PTMG(分子质量2000)、1.06g DEG混合均匀，升温至70℃，加入15.16g MDI，滴加0.06g T-12，70℃反应约4h，停止加热并加入73ml丁酮稀释，降至室温，加入1.34g TEA，中和40min。在200r/min搅拌下向预聚体溶液中逐滴加入59.3g水，得预分散的大粒径乳液L3。
向160.0g L3中逐滴加入15.0g乳液S3，滴加完毕即可停止乳化。旋蒸除去丁酮，得水性聚氨酯乳液H3。
乳液H3的固含量为62.5％，粘度305mPa·s，胶膜的拉伸强度26.4MPa，断裂伸长率1060％，吸水率5.22％。
实施例4：
取1.00g DMPA、33.3g PHNA(分子量2000)、1.18g DEG混合均匀，升温至80℃，加入12.56g IPDI，滴加0.06gT-12，保持80℃反应约4h，停止加热并加入40ml丁酮稀释，降至室温，加入0.75g TEA，中和40min。在2500r/min搅拌下向预聚体溶液中加入147.0g水和1.27gEDA，乳化25min。旋蒸除去溶剂丁酮，得到小粒径乳液S4，测其固含量为32％，粒径159nm。
取1.20g DMPA、30.0g PHNA(分子量2000)、10.0g PESS(分子量2000)、1.20g BDO混合均匀，升温至80℃，加入15.03g IPDI，滴加0.06g T-12，保持80℃反应约4h，停止加热并加入72ml丁酮稀释，降至室温，加入0.85g TEA，中和40min。在400r/min搅拌下向预聚体溶液中逐滴加入46.6g水，得预分散的大粒径乳液L4。
向150.0g的L4中逐滴加入24.0g乳液S4，滴加完毕即可停止乳化。旋蒸除去丁酮，得水性聚氨酯乳液H4。
乳液H4的固含量为64.1％，粘度290mPa·s，胶膜的拉伸强度36.3MPa，断裂伸长率1130％，吸水率10.6％。
实施例5：
取0.89g DMPA、30.0g PPG(分子量2000)、1.35g BDO混合均匀，升温至70℃，加入11.39g TDI，滴加0.06g T-12，保持80℃反应约4h，停止加热并加入40ml丙酮稀释，降至50℃，加入0.67gTEA，中和40min。加入2.74g AAS(50wt％)，50℃反应30min。在2000r/min搅拌下向预聚体溶液中加入84.0g水，乳化25min。旋蒸除去溶剂丙酮，得到小粒径乳液S5，测其固含量为35％，粒径45nm。
取0.98g DMPA、20.0g PPG(分子量2000)、1.80g BDO混合均匀，升温至80℃，加入15.18g IPDI，滴加0.06g T-12，保持80℃反应约4h，停止加热并加入43ml丁酮稀释，降至室温，加入0.74g TEA，中和40min。在600r/min搅拌下向预聚体溶液中逐滴加入38.7g水，得预分散的大粒径乳液L5。
向100.0g的L5中逐滴加入24.0g乳液S5，滴加完毕即可停止乳化。旋蒸除去丁酮，得水性聚氨酯乳液H5。
乳液H5的固含量为63.0％，粘度278mPa·s，胶膜的拉伸强度23.2MPa，断裂伸长率960％，吸水率4.39％。
实施例6：
取15.0g PTMG(分子量2000)、15.0g PESS(分子量2000)，2.70g BDO混合均匀，升温至80℃，加入18.67g IPDI，滴加0.06g T-12，保持80℃反应约4h，停止加热并加入40ml丙酮稀释，降至60℃，加入3.18g AAS(50wt％)，反应25min。在3000r/min搅拌下向预聚体溶液中加入123.6g水，乳化25min。旋蒸除去溶剂丙酮，得到小粒径乳液S6，测其固含量为30％，粒径53nm。
取30g PHNA(分子量1500)、9.34g的IPDI和3.03g的HDI混合均匀，升温至80℃反应2h。加入1.80g BDO和0.06g T-12，80℃反应2h，加入63ml丙酮降低预聚体粘度。降低温度至60℃，加入1.80g的AAS(50wt％)，反应25min。在800r/min搅拌下向预聚体溶液中逐滴滴加31.5g的水，得预分散的大粒径乳液L6。
向120g的L6中滴加27.0g的乳液S6，全部滴加完毕后停止乳化。旋蒸除去丙酮，得水性聚氨酯乳液H6。
乳液H6的固含量为62.8％，粘度273mPa·s，胶膜的拉伸强度12.8MPa，断裂伸长率654％，吸水率13.4％。
本发明包括但不限于以上实施例，凡是在本发明精神的原则之下进行的任何等同替换或局部改进，都将视为在本发明的保护范围之内。

Claims (7)

1.一种高固含量低粘度水性聚氨酯的制备方法，其特征在于：具体步骤如下：
步骤一、将大分子二元醇、亲水扩链剂、亲油扩链剂和溶剂进行除水处理；
步骤二、小粒径乳液S的制备：以大分子二元醇、异氰酸酯、亲油性扩链剂和亲水性扩链剂为原料在70～80℃制备预聚体A，加入溶剂稀释，2000～3000r/min搅拌下一次性加入去离子水乳化分散，除去溶剂制得低固含量、小粒径的乳液S；
步骤三、大粒径乳液L的预分散：以大分子二元醇、异氰酸酯、亲油性扩链剂和亲水性扩链剂为原料在70～80℃制备预聚体B，加入溶剂稀释，在200～1000r/min搅拌下滴加去离子水乳化分散，得到预分散的大粒径乳液L；
步骤四、高固含量低粘度水性聚氨酯的制备：向步骤三的预分散的大粒径乳液L中滴加的步骤二的乳液S，滴加完毕即停止乳化，然后在35～45℃下旋蒸除去溶剂，得到高固含量低粘度水性聚氨酯。
2.如权利要求1所述的一种高固含量低粘度水性聚氨酯的制备方法，其特征在于：所述乳液S的固含量为30～35％；所述乳液S的粒径为30～160nm。
3.如权利要求1所述的一种高固含量低粘度水性聚氨酯的制备方法，其特征在于：步骤二中所述大分子二元醇、异氰酸酯、亲油性扩链剂和亲水性扩链剂及其他原料的质量百分比为：大分子二元醇56.64～66.81％，亲油扩链剂2.94～5.10％，亲水扩链剂1.99～5.04％，异氰酸酯25.09～35.25％，催化剂0.05～0.20％，中和剂0～3.80％，且各原料总质量为100％。
4.如权利要求1所述的一种高固含量低粘度水性聚氨酯的制备方法，其特征在于：步骤三中所述大分子二元醇、异氰酸酯、亲油性扩链剂和亲水性扩链剂及其他原料的质量百分比为：大分子二元醇41.38～68.63％，亲油扩链剂1.78～11.09％，亲水扩链剂1.50～2.99％，异氰酸酯25.54～46.13％，催化剂0.05～0.20％，中和剂0～2.26％，且各原料总质量为100％。
5.如权利要求1或3或4所述的一种高固含量低粘度水性聚氨酯的制备方法，其特征在于：所述步骤二中去离子水质量与预聚体A的质量比为1.857～2.333:1；所述步骤三中溶剂质量与预聚体B的质量比为0.82～1.22：1；所述步骤三中去离子水质量与预聚体B的质量比为0.70～1.00：1。
6.如权利要求1所述的一种高固含量低粘度水性聚氨酯的制备方法，其特征在于：步骤四中所述乳液S与大粒径乳液L的质量比为0.06～0.24。
7.如权利要求1或2或3或4或6所述的一种高固含量低粘度水性聚氨酯的制备方法，其特征在于：所述亲水扩链剂为羧酸型亲水扩链剂如二羟甲基丙酸、磺酸型亲水扩链剂如乙二胺基乙磺酸钠或大分子亲水单体如磺酸盐聚酯二元醇；
所述大分子二元醇为聚醚二元醇或聚酯二元醇，聚酯二元醇如聚(1,6-己二醇/新戊二醇-己二酸)或聚己二酸-1，4-丁二醇酯二醇，聚醚二元醇如聚丙二醇或聚四氢呋喃二醇；
所述亲油扩链剂为1,4-丁二醇、一缩乙二醇、三羟甲基丙烷或乙二胺；
所述异氰酸酯包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯或异佛尔酮二异氰酸酯与六亚甲基二异氰酸酯的混合溶液；
所述溶剂为丙酮或丁酮。
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