CN107880270A - 一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法 - Google Patents
一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法 Download PDFInfo
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Abstract
本发明提供一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法，该固化剂组成物单元组成为：R3NHCONHXc R1 a(R2O)bSiO(4‑a‑b‑c)/2(Ia)。该方法包括加热单位组成为R1 a(R2O)bSiO(4‑a‑b‑c)/2Xc(Ib)的含氨基有机硅树脂和含有亲水基团的多异氰酸酯R3。其中，X为式(Ia)的SiOC‑键连接的基团：‑O‑Z‑NH2；本方法合成工艺简单，不需压力设备，无腐蚀性副产物产生，可制备含有有机硅链段的多异氰酸酯水性固化剂。该有机硅水性异氰酸酯固化剂组成物特别适合用于高性能水性双组分聚氨酯涂料，可常温或低温烘烤与水性羟基丙烯酸树脂反应固化。由于有机硅链节的导入，与水性羟基丙烯酸树脂的成膜物具有优异的耐热性、耐候性、耐水性和高附着力，可用于高耐性水性涂料。
Description
技术领域
本发明涉及一种含有有机硅链段的水性异氰酸酯型固化剂，尤其涉及其制备方法与组成物。
背景技术
随着政府限制VOC排放法律法规的不断推出及执法力度的不断加强，涂料行业的油转水趋势开始加速。众所周知，油性双组分聚氨酯体系占了整个涂料市场的60％以上，那么我们应该用何种环保体系来替换它呢？其中之一的解决方案就是双组份聚氨酯水性漆，其各方面性能俱佳，大部分性能已经达到甚至超过油性漆的水平，为水性漆中的高级产品。双组份聚氨酯水性漆靠-NCO基团和-OH基团的反应来交联固化得到优异的性能效果外，这从反应机理和结构上来说与油性聚氨酯体系基本一致，因此水性双组分聚氨酯体系是从结构和性能上最接近油性双组分聚氨酯体系的解决方案。此外，由于水性体系羟基树脂端选择的是耐候性极佳的羟基丙烯酸体系，固化剂端多采用的是脂肪族异氰酸酯固化剂，因此在耐候性上较油性有巨大优势，可使用于耐候性要求高的涂装体系。
水性异氰酸酯固化剂最早由拜尔公司发明，其通过在HDI或者IPDI 等脂肪族异氰酸酯三聚体上接入一定量的亲水基团，使得异氰酸酯三聚体具有一定的水分散性。其所采用的亲水基团主要分为聚醚型和磺酸盐基团两种类型，特别是使用磺酸盐类型亲水基团改性的多异氰酸酯三聚体具有水分散性好，最终漆膜性能优异的特点。
发明内容
针对现有技术存在的不足，本发明的目的是提供一种含有有机硅链段的水性异氰酸酯型固化剂R3NHCONHXc R1 a(R2O)bSiO(4-a-b-c)/2(Ia)的制备方法。
为了实现上述目的，本发明所采用的技术方案是：一种含有有机硅链段的水性异氰酸酯型固化剂R3NHCONHXc R1 a(R2O)bSiO(4-a-b-c)/2(Ia)的制备方法，该方法包括加热1至25质量份的含有氨基并由 R1 a(R2O)bSiO(4-a-b-c)/2Xc(Ib)的单元组成的有机硅树脂，75至99质量份的含有亲水基团的多异氰酸酯R3；其中，X为式(Ia)的SiOC-键连接的基团： -O-Z-NH2；R3为含有亲水基团的水性异氰酸酯固化剂，主结构为亲水基团改性多异氰酸酯三聚体，多异氰酸酯包含但不限于HDI、IPDI、HMDI等脂肪族多异氰酸酯；其亲水基团包含但不限于聚醚链段、磺酸盐基团，优选磺酸盐基团；NCO值(wt％)范围为9～21％。
进一步的技术方案中，该多异氰酸酯优选HDI和IPDI。
进一步的技术方案中，该亲水基团优选磺酸盐基团。
进一步的技术方案中，该方法中含有氨基并由R1 a(R2O)bSiO(4-a-b-c)/2Xc(Ib) 的单元组成的有机硅树脂的制备方法如下：加热30至99质量份的由 R1 a(R2O)b+cSiO(4-a-b-c)/2(Ic)的单元组成的含硅羟基或硅烷氧基的有机硅树脂、1至70质量份的含羟基的胺基化合物HO-X-NH2(Id)和0.001-1质量份的催化剂；
其中，含硅羟基或硅烷氧基的有机硅树脂的单位组成为 R1 a(R2O)b+cSiO(4-a-b-c)/2(Ic)，具有2至10重量％的硅羟基或4-20重量％的硅烷氧基；其中a与b的总和介于0至4之间；b大于0；条件是a+b+c≤4； R1选自芳香基、烷基、或烯基，其可由O、S、N或P间隔，R2选自氢或烷基；含羟基的胺基化合物的单位组成为HO-X-NH2(Id)；X为二价的、未取代的或经取代的芳香基、烷基、或烯基，其可由O、S、N或P间隔；在制备过程中，部分或全部的R2O基团被HO-X-NH2(Id)中的X基团所置换，并消除相应的R2OH分子；有机硅化合物优选由1至100个式(Ib)或(Ic) 的单元组成，特别为1至10个单；总和a+b+c＝4；换言之，有机硅化合物为硅烷；由(Ib)的单元组成的有机硅化合物优选含有1至50个，特别为2-10 个X基团。
进一步的技术方案中，催化剂包括但不限于金属盐类。
进一步的技术方案中，催化剂优选为二丁基二月桂酸锡、单丁基氧化锡、钛酸四丁酯、钛酸四异丙酯的一种或上述的组合。
本方法合成工艺简单，不需压力设备，无腐蚀性副产物产生，可制备含有有机硅链段的多异氰酸酯水性固化剂。该有机硅水性异氰酸酯固化剂组成物特别适合用于高性能水性双组分聚氨酯涂料，可常温或低温烘烤与水性羟基丙烯酸树脂反应固化。由于有机硅链节的导入，与水性羟基丙烯酸树脂的成膜物具有优异的耐热性、耐候性、耐水性和高附着力，可用于高耐性水性涂料。
具体实施方式
下面结合实施例对本发明作进一步描述。
第一实施例
在安装有搅拌、氮气和温度计的反应釜中投入DC-3074(DC-3074为道康宁有机硅中间体，硅甲氧基含量约为18％)900g、6-氨基-1-己醇510.36g、二月桂酸二丁基锡0.8g，加热至125±5℃，开始可以收集到甲醇馏出物，保持馏温≤65℃，缓慢升温至160-180℃，直到馏温≤50℃停反应，过滤得到淡黄色透明含氨基的有机硅化合物，室温下粘度为2500cps。
将该有机硅化合物与AQUALINKER 816(AQUALINKER 816采用广东拓普合成科技股份有限公司的产品，NCO值为16％)按0.1:1的比例混合均匀，升温到60℃反应2小时，测NCO值为13±0.5％时停止反应，得到有机硅水性异氰酸酯固化剂固化剂。
第二实施例
在安装有搅拌、氮气和温度计的反应釜中投入IC 232(瓦克有机硅中间体，硅甲氧基含量约为15％)900g、6-氨基-1-己醇425.3g、单丁基氧化锡0.8g，加热至125±5℃，开始可以收集到甲醇馏出物，保持馏温≤65℃，缓慢升温至160-180℃，直到馏温≤50℃停反应。过滤得到淡黄色透明含氨基的有机硅化合物，室温下粘度为1600cps。
将该有机硅化合物与AQUALINKER 816(AQUALINKER 816广东拓普合成科技股份有限公司产品，NCO值为16％)按0.3:1的比例混合均匀，升温到60℃反应2小时，测NCO值为7±0.5％时停止反应，得到有机硅水性异氰酸酯固化剂固化剂。
第三实施例
在安装有搅拌、氮气和温度计的反应釜中投入1,3-二甲氧基-1,1,3,3-四甲基二硅氧烷800g、1,3-二氨基-2-羟基丙烷741.80g、二月桂酸二丁基锡1.0g，加热至125±5℃，开始可以收集到甲醇馏出物，保持馏温≤65℃，缓慢升温至160-180℃，直到馏温≤50℃停反应。过滤得到淡黄色透明含氨基的有机硅化合物，室温下粘度为1500cps。
将该有机硅化合物与AQUALINKER 818(AQUALINKER 818为广东拓普合成科技股份有限公司产品，NCO值为20％)按0.01:1的比例混合均匀，升温到60℃反应2小时，测NCO值为18±0.5％时停止反应，得到有机硅水性异氰酸酯固化剂固化剂。
Claims (6)
1.一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法，该固化剂组成物单元组成为：R3NHCONHXcR1 a(R2O)bSiO(4-a-b-c)/2(Ia)，
该方法包括加热1至25质量份的含有氨基并由R1 a(R2O)bSiO(4-a-b-c)/2Xc(Ib)的单元组成的有机硅树脂，75至99质量份的含有亲水基团的多异氰酸酯R3；
其中，
X为式(Ia)的SiOC-键连接的基团：-O-Z-NH2；
R3为含有亲水基团的水性异氰酸酯固化剂，主结构为亲水基团改性多异氰酸酯三聚体，多异氰酸酯包含但不限于HDI、IPDI、HMDI等脂肪族多异氰酸酯；其亲水基团包含但不限于聚醚链段、磺酸盐基团，优选磺酸盐基团；NCO值(wt％)范围为9～21％。
2.根据权利要求1所述的一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法，该多异氰酸酯优选HDI和IPDI。
3.根据权利要求1所述的一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法，该亲水基团优选磺酸盐基团。
4.根据权利要求1所述的一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法，该方法中含有氨基并由R1 a(R2O)bSiO(4-a-b-c)/2Xc(Ib)的单元组成的有机硅树脂的制备方法如下：
该方法包括加热30至99质量份的由R1 a(R2O)b+cSiO(4-a-b-c)/2(Ic)的单元组成的含硅羟基或硅烷氧基的有机硅树脂、1至70质量份的含羟基的胺基化合物HO-X-NH2(Id)和0.001-1质量份的催化剂；
其中，
含硅羟基或硅烷氧基的有机硅树脂的单位组成为R1 a(R2O)b+cSiO(4-a-b-c)/2(Ic)，具有2至10重量％的硅羟基或4-20重量％的硅烷氧基；
其中a与b的总和介于0至4之间；
b大于0；
条件是a+b+c≤4；
R1选自芳香基、烷基、或烯基，其可由O、S、N或P间隔，
R2选自氢或烷基；
含羟基的胺基化合物的单位组成为HO-X-NH2(Id)；
X为二价的、未取代的或经取代的芳香基、烷基、或烯基，其可由O、S、N或P间隔；
在实施本方法的过程中，部分或全部的R2O基团被HO-X-NH2(Id)中的X基团所置换，并消除相应的R2OH分子；有机硅化合物优选由1至100个式(Ib)或(Ic)的单元组成，特别为1至10个单；总和a+b+c＝4；换言之，有机硅化合物为硅烷；
由(Ib)的单元组成的有机硅化合物优选含有1至50个，特别为2-10个X基团。
5.根据权利要求4所述的一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法，在制备含有氨基并由R1 a(R2O)bSiO(4-a-b-c)/2Xc(Ib)的单元组成的有机硅树脂时使用的催化剂包括但不限于金属盐类。
6.根据权利要求5所述的一种含有有机硅链段的水性异氰酸酯型固化剂的制备方法，催化剂优选为二丁基二月桂酸锡、单丁基氧化锡、钛酸四丁酯、钛酸四异丙酯的一种或上述的组合。
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| CN114605606A (zh) * | 2022-03-31 | 2022-06-10 | 安徽省金盾涂料有限责任公司 | 一种多重固化阴离子有机硅改性多异氰酸酯水性固化剂的制备方法及应用 |
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