CN114369219B - 一种聚脲颗粒改性触变树脂及其制备方法 - Google Patents
一种聚脲颗粒改性触变树脂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚脲颗粒改性触变树脂，其特征在于，按重量份计算，包括如下组分：聚合物树脂60‑80份；溶剂5‑15份；二异氰酸酯1‑3份；小分子伯胺1‑2份。本发明还公开了其制备方法。本发明从触变树脂合成角度出发，对合成工艺进行改进，利用HMDI的分子内旋转，空间构象差异性，其硬段堆叠片段较短，生成的聚脲颗粒在储存过程中氢键解离与重构达到动态平衡，防止粘度增加。本发明的聚脲颗粒改性触变树脂具有优秀的储存稳定性，50℃储存30天，树脂粘度变化低于±10％，细度小于10μm，而且配置到汽车清漆中能显著提升清漆抗流挂性能。
Description
技术领域
本发明涉及触变树脂，具体涉及一种聚脲颗粒改性触变树脂及其制备方法。
背景技术
触变树脂广泛应用于涂料、油墨、胶粘剂等特种化学品领域，与人类的生产生活密切相关。本发明主要涉及汽车涂料领域，汽车涂料对漆膜外观、光泽要求较高。
本发明所述触变树脂的触变性来源于树脂基体中生成的聚脲棒状颗粒改性。聚脲颗粒为在树脂基体中通过多异氰酸酯与单胺的反应或单异氰酸酯与多胺的反应生成，使得到聚脲颗粒改性触变树脂具有较强的分子间氢键，具备假塑性。在静置等低剪切作用时，颗粒间脲基产生的强氢键作用，形成网络结构，树脂粘度较大，流动性较差；在施工喷涂等高剪切力作用时，强剪切力使氢键破坏，网络结构断裂，树脂粘度变小，具有较好的流动性。触变树脂应用于涂料中，假塑性行为可使附着在基材表面的漆膜迅速形成由脲基氢键交联的网络，降低漆膜流动性，可有效防止流挂、发花等影响漆膜外观的缺陷。
目前市面上传统的触变树脂都存在触变性随热储存时间延长而增强现象，主要原因是脲基结构在热储存过程中，氢键形成更优键合，网络结构强度升高，不易破坏，导致触变性增强。汽车涂料对涂料施工性要求较高，合适的触变性可以实现平整的涂层同时避免流挂，触变性过高会导致涂层流平不良，外观变差。
而涂料从生成到现场施工需要较长的存储时间，涂料施工时往往出现粘度和触变都升高的现象，现场需要加入溶剂来调整粘度和触变，但由于现场缺乏全面的涂料评估设备，调整粘度时经常会出现流挂问题，给生产效率及合格率造成较大影响。
使用聚脲结构改善树脂及涂料触变性的方法已有许多记载。专利CN 109923144 A公开了一种制备包含聚脲颗粒的触变性组合物的方法，其方法包括在液体介质中接触和反应以形成聚脲，并使聚脲沉淀以形成聚脲颗粒，其中将声波振动应用在反应物接触期间、作为后处理、或这二者中施加到形成的聚脲颗粒，特别是包含大量聚脲颗粒和任选的具有高触变功效的聚合物树脂的触变性组合物，可作为母料用于制备涂料组合物。专利CN101213230 A公开了一种触变流变改性剂的聚脲制品。其包含第一多聚异氰酸酯与第一胺的第一聚脲反应产物，和第一反应产物的胶体颗粒存在下沉淀的不同于第一聚脲反应产物的第二多聚异氰酸酯与第二胺的第二聚脲反应产物。而关于解决聚脲颗粒改性触变树脂储存(50℃静置储存)增粘问题的专利鲜有记载。
发明内容
为了克服现有技术的上述缺陷，本发明的目的在于提供一种聚脲颗粒改性触变树脂及其制备方法。
本发明从触变树脂合成角度出发，对合成工艺进行改进，利用HMDI的分子内旋转，空间构象差异性，其硬段堆叠片段较短，生成的聚脲颗粒在储存过程中氢键解离与重构达到动态平衡，防止粘度增加。
本发明的聚脲颗粒改性触变树脂具有优秀的储存稳定性，50℃储存30天，树脂粘度变化低于±10％，细度小于10μm，而且配置到汽车清漆中能显著提升清漆抗流挂性能。
一种聚脲颗粒改性触变树脂，按重量份计算，包括如下组分：
聚合物树脂 60-80份；
溶剂 5-15份；
二异氰酸酯 1-3份；
小分子伯胺 1-2份。
在本发明的一个优选实施例中，所述聚合物树脂为溶剂型丙烯酸树脂或溶剂型聚酯树脂。
在本发明的一个优选实施例中，所述溶剂为二甲苯、S-100A高沸点溶剂或S-150芳烃溶剂中的任意一种或多种。
在本发明的一个优选实施例中，所述二异氰酸酯为二环己基甲烷二异氰酸酯(HMDI)与1，4-丁二异氰酸酯、甲苯二异氰酸酯(TDI)、异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、1，4-环己基二异氰酸酯(CDHI)、环己烷二亚甲基二异氰酸酯(HXDI)、四亚甲基间苯二亚甲基二异氰酸酯(TMXDI)或甲基环己基二异氰酸酯(HTDI)当中的任意一种或多种的混合物。优选混合摩尔比为1:1。
在本发明的一个优选实施例中，所述小分子伯胺为异氰酸酯反应性单胺。优选苄胺、苯胺、乙胺、正丙胺、正丁胺、α-甲基丁胺、α-乙基丙胺、己胺、辛胺、癸胺或环己胺中的任意一种或多种。
一种聚脲颗粒改性触变树脂的制备方法，包括如下步骤：
将所述聚合物树脂、溶剂在反应釜当中混合均匀并持续搅拌后保持反应体系温度0-40℃，加入所述小分子伯胺后分散后加入所述二异氰酸酯后高速搅拌后分散得所述聚脲颗粒改性触变树脂。
优选体系温度为10-25℃。
将所述聚合物树脂、溶剂在反应釜当中混合均匀并持续搅拌的速度为1000rpm。
加入所述小分子伯胺后分散时间为1-5分钟。
加入所述二异氰酸酯后高速搅拌的速度为4000rpm，分散时间为40分钟。
本发明的有益效果在于：
制备聚脲颗粒改性触变树脂,其在涂料应用中表现出优异的施工性能，良好的储存稳定性，50℃储存1月剪切因子增加<±10％，满足汽车涂料领域的施工要求。
附图说明
图1为实施例1-3与对比例1-3热储前后的流变曲线对比示意图。
具体实施方式
为了使申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请及进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
一.制备耐储存聚脲颗粒改性触变树脂工艺：
1.溶剂型丙烯酸树脂PA合成
1)混合单体配制：往1000mL的烧杯中依次加入200.0g(甲基)丙烯酸丁酯、102.3g(甲基)丙烯酸羟丙酯、47.5g苯乙烯、10.5g(甲基)丙烯酸、80.7g甲基丙烯酸甲酯，然后用玻璃棒搅拌均匀，待用；
2)在装有搅拌装置、温度计的1000mL四口烧瓶中加入170.5g溶剂S-100A，通入氮气，升温至140℃出现回流后，快速加入二特戊基过氧化物22.0g，计时5min后，开始滴加混合单体，120分钟滴加完毕，滴加过程中温度控制在140-145℃之间。单体滴加完毕后，使用12.5g溶剂S-100A物料冲洗单体管线，并且保持回流120分钟。降温至110℃，并使用16.0gS-100A调整固体分至70％，最终降温出料。
2.溶剂型聚酯树脂PE合成
1)向聚酯反应釜中依次加入157.0g六氢苯酐、85.0g苯酐、48.7g己二酸、90.6g新戊二醇、140.3g三羟甲基丙烷，不开搅拌，先加热至160℃左右加热熔融。
2)物料融化后，开启搅拌，在160℃保温1小时。然后20度/小时逐步加热至235℃，观察出现回流的温度。
3)酸值达标后，加入49.5g二甲苯，保持在230℃回流脱水，目标固体酸值10-12mgKOH/g。
4)酸值合格后，降温到130℃，加入S-100A，调整固含至72％，并降温出料。
3.聚脲颗粒改性触变树脂工艺
1)实施例1：于PA树脂中苄胺+HDI+HMDI
在装有高速分散盘、温度计的1000mL分散罐中依次加入447.50g PA(固含量：70.00％)和87.83g的二甲苯，通入氮气，1000rpm转速搅拌均匀。在罐内温度为23℃时，将8.31g(77.55mmol)苄胺快速滴加至分散罐中，4000rpm搅拌分散1分钟。然后将HDI 3.19g(18.96mmol)加入分散罐中，提高搅拌速率至4000rpm，分散2分钟再加入HMDI 4.97g(18.96mmol),4000rpm分散40分钟,得到不透明的触变树脂R1，细度≤5μm。将部分R1树脂密封后放置50℃烘箱中储存30天，然后取出，标记为热储后树脂R1’，细度≤5μm。
通过旋转流变仪测定树脂R1及R1’热储(50℃)30天后的高剪切(1000s-1)和低剪切粘度(1s-1)变化，测定剪切因子。
2)实施例2：于PE树脂中HDI+HMDI
在装有高速分散盘、温度计的1000mL分散罐中依次加入423.30g的PE(固含量：72.00％)和112.16g的二甲苯，通入氮气，1000rpm转速搅拌均匀。在罐内温度为23℃时，将8.31g(77.55mmol)苄胺快速滴加至分散罐中，4000rpm搅拌分散1分钟。然后将HDI 3.19g(18.96mmol)加入分散罐中，提高搅拌速率至4000rpm，分散2分钟再加入HMDI 4.97g(18.96mmol),4000rpm分散40分钟,得到不透明的触变树脂R2，细度≤5μm。将部分R2树脂密封后放置50℃烘箱中储存30天，然后取出，标记为热储后树脂R2’，细度≤5μm。
通过旋转流变仪测定树脂R2及R2’热储(50℃)30天后的高剪切(1000s-1)和低剪切粘度(1s-1)变化，测定剪切因子。
3)实施例3：于PA中苄胺+TDI+HMDI
在装有高速分散盘、温度计的1000mL分散罐中依次加入447.50g的PA(固含量：70.00％)和87.83g的二甲苯，通入氮气，1000rpm转速搅拌均匀。在罐内温度为23℃时，将8.31g(77.55mmol)苄胺快速滴加至分散罐中，4000rpm搅拌分散1分钟。然后将TDI 3.19g(18.32mmol)加入分散罐中，提高搅拌速率至4000rpm，分散2分钟再加入HMDI 4.97g(18.96mmol),4000rpm分散40分钟,得到不透明的触变树脂R3，细度≤10μm。将部分R3树脂密封后放置50℃烘箱中储存30天，然后取出，标记为热储后树脂R3’，细度≤10μm。
通过旋转流变仪测定树脂R3及R3’热储(50℃)30天后的高剪切(1000s-1)和低剪切粘度(1s-1)变化，测定剪切因子。
4)对比例1：于PA中苄胺+HDI
在装有高速分散盘、温度计的1000mL分散罐中依次加入447.50g的PA(固含量：70.00％)和87.83g的二甲苯，通入氮气，1000rpm转速搅拌均匀。在罐内温度为23℃时，将8.31g(77.55mmol)苄胺快速滴加至分散罐中，4000rpm搅拌分散1分钟。然后将HDI 6.38g(37.93mmol)加入分散罐中，提高搅拌速率至4000rpm，分散40分钟,得到不透明的触变树脂R4，细度≤10μm，将部分R4树脂密封后放置50℃烘箱中储存30天，然后取出，标记为热储后树脂R4’，测得细度≤10μm。
通过旋转流变仪测定树脂R4及R4’热储(50℃)30天后的高剪切(1000s-1)和低剪切粘度(1s-1)变化，测定剪切因子。
5)对比例2：于PE中苄胺+HDI
在装有高速分散盘、温度计的1000mL分散罐中依次加入423.30g的PE(固含量：72.00％)和112.16g的二甲苯，通入氮气，1000rpm转速搅拌均匀。在罐内温度为23℃时，将8.31g(77.55mmol)苄胺快速滴加至分散罐中，4000rpm搅拌分散1分钟。然后将HDI 6.38g(37.93mmol)加入分散罐中，提高搅拌速率至4000rpm，分散40分钟,得到不透明的树脂R5，细度≤5μm，将部分R5树脂密封后放置50℃烘箱中储存30天，然后取出，标记为热储后树脂R5’，测得细度≤5μm。
通过旋转流变仪测定树脂R5及R5’热储(50℃)30天后的高剪切(1000s-1)和低剪切粘度(1s-1)变化，测定剪切因子。
6)对比例3：于PA中苄胺+TDI
在装有高速分散盘、温度计的1000mL分散罐中依次加入447.50g的PA(固含量：70.00％)和87.83g的二甲苯，通入氮气，1000rpm转速搅拌均匀。在罐内温度为23℃时，将8.31g(77.55mmol)苄胺快速滴加至分散罐中，4000rpm搅拌分散1分钟。然后将TDI 6.6g(37.93mmol)加入分散罐中，提高搅拌速率至4000rpm，4000rpm分散40分钟,得到不透明的触变树脂R6，细度≤10μm，将部分R6树脂密封后放置50℃烘箱中储存30天，然后取出，标记为热储后树脂R6’，测得细度≤10μm。
通过旋转流变仪测定树脂R6及R6’热储(50℃)30天后的高剪切(1000s-1)和低剪切粘度(1s-1)变化，测定剪切因子。
7)流变性能测试：
按照本领域常规的检测方法，将上述树脂实施流变行为测试
测试仪器型号：测试条件为：10#转子、温度：25℃、转速分为两段，第一段：1000s-1剪切时间5分钟；第二段：1s-1剪切时间9分钟。
剪切因子：按如下公式进行计算：X＝A0/A1。其中，A0为样品转速为1s-1时的粘度，A1为样品转速为1000s-1时的粘度。
实施例1-3与对比例1-3的触变树脂的流变性能测试结果如图1，表1所示。
如图1所示，实施例热储前后低剪切速率(1s-1)下粘度增加较小，而对比例都呈现明显的粘度增加。
表1.实施例1-3与对比例1-3热储前后粘度和剪切因子测试结果
通过比较热储前后低剪切粘度和剪切因子，可以看出热储后实施例1-3粘度增长较少，储存稳定性较好而对比例1-3粘度均增长明显，储存稳定性较差。
由图1及表1的实施例及对比例热储前后的流变结果可以看出，对比例低剪切粘度及剪切因子增幅明显，而实施例粘度增长较少，储存稳定性较好，50℃储存1月剪切因子增加<±10％。
尽管上述实施例对本发明做出了详尽的描述，但其只是本发明的一部分实例，只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人是能够了解本发明的内容并据以实施，并非是对本发明的实施方式的限定。人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明的保护范围。
Claims (3)
1.一种聚脲颗粒改性触变树脂，其特征在于，按重量份计算，为如下组分：
所述聚合物树脂为溶剂型丙烯酸树脂或溶剂型聚酯树脂；
所述溶剂为二甲苯、S-100A高沸点溶剂或S-150芳烃溶剂中的任意一种或多种；
所述二异氰酸酯为二环己基甲烷二异氰酸酯与1，4-丁二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、1，4-环己基二异氰酸酯、环己烷二亚甲基二异氰酸酯、四亚甲基间苯二亚甲基二异氰酸酯或甲基环己基二异氰酸酯当中的任意一种或多种的混合物；
所述小分子伯胺为异氰酸酯反应性单胺；
将所述聚合物树脂、溶剂在反应釜当中混合均匀并持续搅拌后保持反应体系温度0-40℃，加入所述小分子伯胺后分散后加入所述二异氰酸酯后搅拌后分散得所述聚脲颗粒改性触变树脂。
2.如权利要求1所述的一种聚脲颗粒改性触变树脂，其特征在于，所述二环己基甲烷二异氰酸酯与1，4-丁二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、1，4-环己基二异氰酸酯、环己烷二亚甲基二异氰酸酯、四亚甲基间苯二亚甲基二异氰酸酯或甲基环己基二异氰酸酯当中的任意一种或多种的混合摩尔比为1:1。
3.如权利要求1所述的一种聚脲颗粒改性触变树脂，其特征在于，
所述体系温度为10-25℃；
将所述聚合物树脂、溶剂在反应釜当中混合均匀并持续搅拌的速度为1000rpm；
加入所述小分子伯胺后分散时间为1-5分钟；
加入所述二异氰酸酯后高速搅拌的速度为4000rpm，分散时间为40分钟。
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| CN101213230A (zh) * | 2005-06-28 | 2008-07-02 | 树脂核动力工业有限公司 | 作为触变流变改进剂的聚脲制品 |
| WO2012076611A1 (de) * | 2010-12-09 | 2012-06-14 | Sika Technology Ag | Thixotrope polyharnstoffaddukte |
| CN104497684A (zh) * | 2014-12-16 | 2015-04-08 | 中国海洋石油总公司 | 一种聚脲型防沉剂 |
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| CN1396224A (zh) * | 2002-08-12 | 2003-02-12 | 中国化工建设总公司常州涂料化工研究院 | 含流变改性树脂的溶剂型高固体分涂料 |
| CN101103061A (zh) * | 2005-01-11 | 2008-01-09 | 树脂核动力工业有限公司 | 用于流变改进的混合物 |
| CN101213230A (zh) * | 2005-06-28 | 2008-07-02 | 树脂核动力工业有限公司 | 作为触变流变改进剂的聚脲制品 |
| WO2012076611A1 (de) * | 2010-12-09 | 2012-06-14 | Sika Technology Ag | Thixotrope polyharnstoffaddukte |
| CN104497684A (zh) * | 2014-12-16 | 2015-04-08 | 中国海洋石油总公司 | 一种聚脲型防沉剂 |
| CN109923144A (zh) * | 2016-11-07 | 2019-06-21 | 湛新荷兰有限公司 | 制备触变性组合物的方法 |
| CN111349370A (zh) * | 2020-04-24 | 2020-06-30 | 湖南湘江关西涂料有限公司 | 高触变性树脂及其制备方法与应用、涂料 |
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