CN104341983B - 一锅式生物催化过氧化物介导的固化组合物及其制备方法 - Google Patents

一锅式生物催化过氧化物介导的固化组合物及其制备方法 Download PDF

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CN104341983B
CN104341983B CN201410334723.5A CN201410334723A CN104341983B CN 104341983 B CN104341983 B CN 104341983B CN 201410334723 A CN201410334723 A CN 201410334723A CN 104341983 B CN104341983 B CN 104341983B
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S·阿鲁姆甘
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Abstract

本发明涉及一种组合物，该组合物包含可交联聚合物颗粒的稳定水性分散体、过氧化物酶、以及具有至少100℃的10小时半衰期温度的疏水性氢过氧化物。该组合物为具有大量可聚合的官能团的胶乳颗粒提供稳健的一锅式过氧化物酶介导的固化。

Description

一锅式生物催化过氧化物介导的固化组合物及其制备方法
背景技术
本发明涉及一种用于水性胶乳制剂的一锅式酶可固化的干燥剂包。
对于水性涂料获得低VOC/零VOC的推动必须使用软的共聚物以在没有挥发性聚结剂的情况下实现膜的形成，这是以较低的Tg为代价(其会对硬度产生负面影响)。因此，在固化过程中，通常使用交联剂来赋予硬度。在高性能涂料中的环境固化取决于聚合物前体中的反应性官能团，以建立三维交联网络。常规固化剂包括氧化催化剂(过渡金属干燥剂)、自由基引发剂和能得到所需结果的化学交联剂。大多数传统方法需要双组分体系，因为通常很难将适用期(pot life)从固化时间中分离。由于预交联、依赖于双组分结构以及与金属干燥剂联用的毒性(如环烷酸钴)，很多这些常用固化添加剂都具有缺陷。
EP2589629描述了氧化酶的使用，例如过氧化物酶和漆酶(laccases)作为醇酸体系中环境固化金属干燥剂的环境友好的替代物。WO01/28960A1描述了合成漆(syntheticurushi)的酶催化的环境交联，该合成漆包含可氧化的酚基团。不过，通过酶致氧化的环境固化通常是缓慢的或在无其他添加剂的情况下是无效的，其对固化过程可能有负面影响。
因此，在本领域中找到用于低VOC水性粘结剂制剂的环境固化的一锅式方法将是一大进步。
发明内容
在一个方面，本发明通过提供一种组合物解决了本领域的需求，该组合物含有可交联的聚合物颗粒的稳定的水性分散体、过氧化物酶、以及具有至少100℃的10小时半衰期温度的疏水性氢过氧化物。
另一方面，本发明涉及一种方法，该方法包括以下步骤：1)将可交联的聚合物颗粒的稳定的水性分散体、过氧化物酶、具有至少100℃的10小时半衰期温度的疏水性氢过氧化物、颜料和流变改性剂一起接触；和2)将步骤1)得到混合物施涂在基材上以形成固化的涂层。
本发明通过使稳健的一锅式室温过氧化物酶介导的固化用于具有各种可聚合的官能团的胶乳颗粒来解决本领域的需求。
发明详述
在一个方面，本发明是一种组合物，其包含可交联的聚合物颗粒的稳定的水性分散体、过氧化物酶、以及具有至少100℃的10小时半衰期温度的疏水性氢过氧化物。如本文中所用，“可交联的聚合物颗粒”是指被活性亚甲基(如由醇酸树脂产生的二烯丙基)；乙酰乙酰氧基(例如由单体产生的，如甲基丙烯酸乙酰乙酰氧基乙酯)；端烯基；或聚乙烯基二甲基硅氧烷基团官能化的聚合物颗粒。因此，可交联的聚合物颗粒的分散体是基于醇酸树脂、乙酰乙酰氧基官能化的丙烯酸、乙烯基硅氧烷、或乙酸乙烯酯的胶乳。
所述过氧化物酶是水溶性的铁-卟啉酶(iron-porphyrin enzyme)，其在疏水性氢过氧化物存在下催化各种有机基材的氧化。过氧化物酶的例子包括辣根过氧化物酶、细胞色素c过氧化物酶和谷胱甘肽过氧化物酶。以胶乳的重量为基准计，过氧化物酶的浓度通常为0.1-1.1重量％(以粘结剂的重量为基准计，通常为0.05-0.5重量％)。
如本文中所用，术语“疏水性的氢过氧化物”是指具有EPI-Suite计算的LogP为0.5-5的氢过氧化物，更优选为0.75-4。所述氢过氧化物也是热稳定的，其具有至少100℃的10小时半衰期温度(参见阿克苏诺贝尔(AkzoNobel)、LUPEROX、广州渤龙化工有限公司的过氧化物的技术信息；《聚合物手册(Polymer Handbook)》，Eds.Brandrup,J；和Immergut,E.H.；Grulke,E.A，第4版，纽约约翰威利出版社，1999,II/2-69)。以胶乳的重量为基准计，疏水性氢过氧化物的浓度通常为0.02-1重量％(以粘结剂的重量为基准计，通常为0.01-0.5重量％)。
在活化剂的存在下，有机氢过氧化物在环境温度下反应；相反，不在本发明范围内的有机过氧化物，需要热活化或在室温下太不温度而不能使用。
合适的热稳定的氢过氧化物(它们的LogP和10小时半衰期温度)的例子是氢过氧化枯烯(LogP＝2.16,10小时T1/2＝140℃)、叔戊基过氧化氢(LogP＝1.43,10小时T1/2＝153℃)、叔丁基过氧化氢(LogP＝0.94,10小时T1/2＝163℃)、对薄荷烷过氧化氢(LogP＝3.63,10小时T1/2＝130℃)、异丙基枯基过氧化氢(LogP＝3.61,10小时T1/2＝129℃)和1,1,3,3-四甲基丁基过氧化氢(LogP＝2.30,10小时T1/2＝140℃)。
其他合适的疏水性氢过氧化物的例子包括正丁基过氧化氢、对甲基异丙基苯过氧化氢、月桂基过氧化氢、苄基过氧化氢、环己基过氧化氢、环己烯过氧化氢、溴-叔丁基过氧化氢、二十烷基过氧化氢、1,1-二氯甲基丙基过氧化氢、异丙基过氧化氢、仲丁基过氧化氢、α,α-二甲基苄基过氧化氢、氯叔丁基过氧化氢、1-氯甲基-1-溴甲基丙基过氧化氢、1-甲基环己基过氧化氢、环己醇过氧化氢、α,α-二甲基-对硝基苄基过氧化氢、2-氯-1-羟基环己基过氧化氢、2-羟基乙基过氧化氢和α,α-对硝基苄基过氧化氢。氢过氧化枯烯是优选的氢过氧化物。
因为过氧化物酶的水溶性，其优选分配进入胶乳的水相；另一方面，疏水性氢过氧化物优选分配进入胶乳颗粒，从而在将胶乳浇铸在基材上之前保证制剂的稳定性。一旦将该制剂施涂在基材上，水蒸发诱发了疏水性氢过氧化物和过氧化物酶之间的接触，从而在环境温度下引发固化。
第二方面，本发明是一种用于制备本发明组合物的方法。第一步中，可交联的聚合物颗粒的稳定的水性分散体、过氧化物酶、疏水性氢过氧化物一起接触以形成对于反应性交联稳定的组合物。优选包含在该步骤中的其他材料包括一种或多种颜料和流变改性剂，以及一种或多种选自填料、杀生物剂、表面活性剂、聚结剂和分散剂的添加剂。在第二步中，将该组合物涂覆在基材上以形成能相对快速固化的涂层。相信该过氧化物酶扩散到疏水性聚合物颗粒中，从而将该疏水性氢过氧化物分解成反应性过氧自由基，其在环境温度下引发功能性聚合物的交联。施涂到基材上之前胶乳组合物的稳定性可通过测量制剂的KU粘度证实。如以下实施例所示，当过氧化物酶和疏水性氢过氧化物相分离时，制剂显示了优异的储存稳定性(pot stability)。该实施例还表明了同时包含过氧化物酶和疏水性氢过氧化物以获得提高的后固化性能的必要性。
过氧化物酶和稳定的疏水性氢过氧化物的组合作为具有很多实际应用需要的加速的初始固化速率的有效的一锅式固化包。该固化包在与带有各种可聚合的官能团的水性(WB)胶乳粘结剂一起配制的涂料中具有广泛的应用。
实施例
材料
过氧化物酶以液体制剂提供(约10mg/mL)。丙烯酸和醇酸树脂母漆分别根据常用基于水的丙烯酸和醇酸树脂漆制剂制备。在该漆中加入氢过氧化枯烯，并在下一天加入过氧化物酶。
基于水的醇酸树脂漆应用测试
母料醇酸树脂漆制剂如表1所示。
表1–母料醇酸树脂漆配方
(AMP-95、TRITON和ACRYSOL都是是陶氏化学公司或其附属公司(The DowChemical Company or Its Affiliates)的商标。)
制备漆的刮涂膜(drawdown)(铝板上5密耳湿膜)用于测试和抗印痕性(print resistance)测试。所有刮涂膜储存在温控室(CTR)内直到使用，并在用于测试之间重新放入CTR中。使用Byk Mallinckrodt摆杆硬度测试机进行测试。测试前，用带手套的手指触碰来评估每个刮涂膜。如果该刮涂膜被评判为太粘，则不测量值。每一个记录的值是两次测量的平均值。根据改进的耐受性测试方法614进行抗印痕性测试，在该测试中用一片平织布(aida cloth)和4个#8橡胶塞覆盖每个刮涂膜。然后将砝码放在橡胶塞上并将板在60℃放置1小时。之后去除砝码和橡胶塞，在去除布之前将板冷却至室温。抗印痕性的程度根据之前报道的尺度进行评分。
所述干燥剂包如表2所示。
表2－干燥剂包和醇酸树脂漆的粘度调整
基于水的醇酸树脂粘结剂固化的化学测试
用红外光谱研究醇酸树脂固化速率。烯丙基烯烃的C-H伸缩在3007cm-1处具有区别吸收峰。随着C-H伸缩的功能消失监测固化的进程。C-H伸缩峰强度随着时间变化的曲线与起始、延伸和终止的动力学相关。选择醇酸树脂粘结剂BF28-RC2作为测试体系。该粘结剂与各种干燥剂包一起配制。用5密耳的刮棒将该醇酸树脂膜直接浇铸在金刚石ATR上。用自定义OMNIC macro(custom OMNIC macro)“cont2stginputdelay.mac.”连续测量光谱。分析在3007cm-1处不饱和的C-H伸缩强度随时间的变化。300小时后，不含干燥剂的对照样品没有显示显著的固化。醇酸树脂固化的动力学数据罗列在表4中；t1/2表示膜达到一半反应的时间(小时)。
表3－应用测试结果(水性醇酸树脂漆的硬度和抗印痕性)。
表4－在各种干燥剂存在下醇酸树脂膜固化的动力学
基于水的丙烯酸树脂漆应用测试
根据常用基于水的乙酰乙酰氧基官能化的丙烯酸漆制剂以表5中所示的配方表制备基于水的丙烯酸漆母料。将干燥剂包加入母漆中，并用ACRYSOLTMRM-2020NPR增稠剂调节最终KU和ICI。制备漆的刮涂膜(铝板上5密耳湿膜)用于测试。所有刮涂膜储存在温控室(CTR)内直到使用，并在测试的情况下在使用之间重新放入CTR中。使用BykMallinckrodt摆杆硬度测试机进行测试。每一个记录的值是两次测量的平均值。比较例4-6和实施例2的油漆配方如表6所示，其应用测试结果如表7所示。
表5–母料丙烯酸树脂漆配方
(TAMOL、KATHON和ACRYSOL是陶氏化学公司或其附属公司的商标。)
RHOPLEXTMHG-95P乳液聚合物的组成是40％(45％丙烯酸丁酯/53.5％甲基丙烯酸甲酯/0.5％甲基丙烯酸/1.0％甲基丙烯酸烯丙酯)//60％(35％丙烯酸丁酯/47.5％甲基丙烯酸甲酯/2.5％甲基丙烯酸/15％甲基丙烯酸乙酰乙酰氧基乙酯)
表6－干燥剂包和丙烯酸漆的粘度调节
表7－基于水的丙烯酸漆的应用测试结果(硬度)
水性乙烯基官能化的硅酮乳液的固化化学性。
照原样采用水性乙烯基官能化的硅酮乳液。研究与氢过氧化枯烯和过氧化物酶一起制剂的硅酮乳液的固化性能随被俘获在固化膜中的可提取的未反应的大分子单体的变化(通过FTIR光谱)。结果见表8。
表8－乙烯基官能化的水性硅酮乳液固化化学性随可提取的百分数以及拉伸强度的变化
干燥剂包 可提取的百分数 拉伸强度
无干燥剂 25 没有固化可用于测量
过氧化物酶 28 没有固化可用于测量
过氧化物酶+CHP 1.6 4.7MP
在水性硅酮乳液中，通常通过提取被俘获在膜中的未反应的大分子单体研究固化性能。当CHP和过氧化物酶都存在于制剂中时，从室温固化的膜中可提取的物质低于2％。采用氢过氧化物-过氧化物酶的干燥剂包的固化膜的拉伸强度相当于那些在较高温度下通过过氧化物固化的膜的拉伸强度。
储存期稳定性的测量
室温下以及热老化温度(45℃)下醇酸树脂漆和丙烯酸漆的储存期通过KU粘度测量监测，发现其至少稳定6周。在任何该体系中均没有观察到可见的胶凝。表9显示了醇酸树脂漆和丙烯酸漆以及乙烯基官能化的硅酮乳液的存储期稳定性。KUo是初始KU粘度，单位为克雷布斯(Krebs)；KURT(f)是在室温下储存6周后的KU粘度；KUΔ(f)的在6周热老化后的KU热老化粘度(45℃)。
表9－储存期稳定性
干燥剂包 KUo KURT(f) KUΔ(f)
醇酸树脂漆(实施例1) 104.5 105.1 103.5
丙烯酸漆(实施例2) 92 95 94
硅酮乳液(实施例3) 58 60 60

Claims (5)

1.一种组合物，其含有可交联的聚合物颗粒的稳定的水性分散体、过氧化物酶、以及具有至少100℃的10小时半衰期温度的疏水性氢过氧化物，所述可交联的聚合物颗粒的分散体是基于醇酸树脂的胶乳、乙酰乙酰氧基官能化的丙烯酸的胶乳、基于乙酸乙烯酯的胶乳或基于乙烯基硅氧烷的胶乳，其中以胶乳的重量为基准计，所述过氧化物酶的浓度为0.1-1.1重量％；以胶乳的重量为基准计，所述疏水性氢过氧化物的浓度为0.02-1重量％；由EPI-Suite计算的疏水性氢过氧化物的logP为0.75-4。
2.如权利要求1所述的组合物，其特征在于，所述疏水性氢过氧化物是氢过氧化枯烯、叔戊基过氧化氢、叔丁基过氧化氢、对薄荷烷过氧化氢、异丙基枯基过氧化氢或1,1,3,3-四甲基丁基过氧化氢或它们的组合。
3.如权利要求2所述的组合物，其特征在于，所述疏水性氢过氧化物是氢过氧化枯烯。
4.一种方法，该方法包括以下步骤：1)将可交联的聚合物颗粒的稳定的水性分散体、过氧化物酶、具有至少100℃的10小时半衰期温度的疏水性氢过氧化物、颜料和流变改性剂一起接触；和2)将步骤1)得到的混合物施涂在基材上以形成固化的涂层，所述可交联的聚合物颗粒的分散体是基于醇酸树脂的胶乳、乙酰乙酰氧基官能化的丙烯酸的胶乳、基于乙酸乙烯酯的胶乳或基于乙烯基硅氧烷的胶乳，其中以胶乳的重量为基准计，所述过氧化物酶的浓度为0.1-1.1重量％；以胶乳的重量为基准计，所述疏水性氢过氧化物的浓度为0.02-1重量％；由EPI-Suite计算的疏水性氢过氧化物的logP为0.75-4。
5.如权利要求4所述的方法，其特征在于，所述交联的涂层在环境温度下固化。
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