CN107082863B - 一种高强度腰果酚基水性聚氨酯的制备方法 - Google Patents

一种高强度腰果酚基水性聚氨酯的制备方法 Download PDF

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CN107082863B
CN107082863B CN201710362067.3A CN201710362067A CN107082863B CN 107082863 B CN107082863 B CN 107082863B CN 201710362067 A CN201710362067 A CN 201710362067A CN 107082863 B CN107082863 B CN 107082863B
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蒋平平
黄敏
张萍波
包燕敏
夏瑜
唐敏艳
俞晓琴
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KUNSHAN JIALIPU PLATE-MAKING TACKIFIER AND INK Co Ltd
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Abstract

一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：该制备方法依次包括下列步骤：将聚酯二元醇、二异氰酸酯、二羟甲基丙酸加入到反应釜中，升温至80~85℃，反应1.5~2.5h；加入催化剂辛酸亚锡和一半量的腰果酚二元醇反应1~1.5h，加入熊果苷，升温至90~100℃，反应1.5~2h，再加入另一半量的腰果酚二元醇，反应1~1.5h；将温度降低到45~50℃，加入三乙胺中和，反应30~35min；加入乙二胺扩链，加水乳化，在高速剪切力作用下，搅拌，减压蒸馏脱除丙酮得到产品。本发明的高强度腰果酚基水性聚氨酯产品力学性能好，拉伸强度高和断裂伸长率好，兼具刚性强和弹性好的优点，热稳定性好，保存时间长。

Description

一种高强度腰果酚基水性聚氨酯的制备方法
技术领域
本发明涉及水性聚氨酯制备技术领域，具体涉及一种高强度腰果酚基水性聚氨酯的制备方法。
背景技术
传统型聚氨酯含有机挥发物，污染环境，又危害人们身体健康。水性聚氨酯以水为分散介质，具有无毒、不燃、对环境友好等特点，广泛应用于涂料、油墨等领域。天然植物油来源广泛、价格低廉、品种繁多、可选择性强，含羟基的植物油、羟基化的植物油作为多元醇制备聚氨酯，符合环境保护的要求。腰果酚是从腰果壳液中得到的一种天然酚类化合物，它含有苯环结构和0-3个不饱和度长碳链烃基，由于其独特的结构，腰果酚及其衍生物被广泛的应用于酚醛树脂、环氧树脂、表面活性剂、增塑剂、聚氨酯等。中国专利CN106065061A公开了一种以植物油基腰果酚为原料制备水性聚氨酯的方法，腰果酚二元醇结构中含有不饱和长碳链，引入聚氨酯分子链中，形成悬挂链结构，悬挂链的存在能有效改善材料疏水性，但会增加体系自由体积，并且悬挂链之间相互缠绕，影响材料力学性能。因此，有必要寻求合适的方法弥补植物油基水性聚氨酯性能上的缺陷。
发明内容
本发明旨在提供一种高强度腰果酚基水性聚氨酯的制备方法，解决了现有的腰果酚基水性聚氨酯产品的力学性能和热稳定性差的问题。
为达到上述目的，本发明采用的技术方案是：一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：该制备方法依次包括下列步骤：
第一步，将聚酯二元醇、二异氰酸酯、二羟甲基丙酸加入到充满氮气的反应釜中，升温至80~85℃，反应1.5~2.5h；
第二步，加入催化剂辛酸亚锡和一半量的腰果酚二元醇反应1~1.5h，加入熊果苷，升温至90~100℃，反应1.5~2h，再加入另一半量的腰果酚二元醇，反应1~1.5h；
第三步，将温度降低到45~50℃，加入三乙胺中和，反应30~35min，反应过程中使用丙酮调节黏度；
第四步，加入乙二胺扩链，再加入水乳化，使得总反应体系的固含量为30%，在高速剪切力作用下，搅拌30~40min；其中，所述二异氰酸酯：聚酯二元醇：二羟甲基丙酸：腰果酚二元醇：熊果苷：三乙胺：乙二胺的摩尔比是100：15~35：15~35：15~60：5~30：15~35：5~30。
第五步，减压蒸馏脱除丙酮得到所述高强度腰果酚基水性聚氨酯。
上述技术方案中的有关内容解释如下：
1、上述方案中，所述聚酯二元醇选自聚碳酸酯二元醇、聚己二酸-1,4-丁二醇酯以及聚己二酸-1,3-丁二醇酯中的任意一种或任意两种以任意比例的混合物；所述聚酯二元醇的数均分子量的范围为1000~8000。
2、上述方案中，所述二异氰酸酯选自异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯以及甲苯二异氰酸酯中的任意一种或任意两种以任意比例的混合物。
3、上述方案中，在所述第四步中，在高速剪切力作用下，高速搅拌的转速为800~1500r/min，搅拌30~40min。
4、上述方案中，在所述第五步中，减压蒸馏的条件为40℃、-0.1MPa。
5、上述方案中，在所述第四步中，加入的水最好为去离子水；使得总反应体系的固含量为30%，意思是加水的质量占总反应体系总质量的70。
6、上述方案中，所述催化剂辛酸亚锡的加入量为反应物总质量的0.2~0.4%，反应物是指聚酯二元醇、二异氰酸酯、二羟甲基丙酸、腰果酚二元醇、熊果苷、三乙胺以及乙二胺。
7、上述方案中，所述腰果酚二元醇的化学结构式为：
Figure DEST_PATH_199134DEST_PATH_IMAGE001
。
8、上述方案中，所述熊果苷的化学结构式为：
Figure DEST_PATH_588659DEST_PATH_IMAGE002
。
本发明的设计原理以及有益效果是：现有的腰果酚基水性聚氨酯产品的力学性能和热稳定性差，这是因为腰果酚二元醇结构中含有不饱和长碳链，引入聚氨酯分子链中，形成悬挂链结构，悬挂链的存在能有效改善材料疏水性，但会增加体系自由体积，并且悬挂链之间相互缠绕，影响材料力学性能。
为了同时解决现有产品的力学性能和热稳定性差的问题，本发明的发明点之一是腰果酚二元醇与熊果苷联合使用。熊果苷是一种多羟基化合物，主要是作为美白成分运用在化妆品合成中。从它的分子结构式可以看出，它是具有多个羟基的小分子化合物，羟基能与异氰酸酯反应形成多交联结构，提高材料的力学性能和热稳定性。同时，熊果苷的分子结构中含有苯环，接入聚氨酯分子链中能进一步提高材料热稳定性。加入适量催化剂辛酸亚锡，并使反应温度保持在90~100℃，能够使熊果苷顺利与二异氰酸酯发生反应。
本发明的另一发明点是腰果酚二元醇与熊果苷的加入次序和加入时机的选择。将腰果酚二元醇分成两次加入，先在聚氨酯分子链中接入一半量的腰果酚二元醇1~1.5h，然后加入熊果苷，形成三维网状结构，再加入另一半量的腰果酚二元醇进行反应，由于三维网状结构的存在，使前后两次接入的悬挂链在空间上形成阻碍，悬挂链缠绕程度降低，并且形成的交联结构可以降低体系自由体积，胶膜内聚力增大，刚性增强，进一步加强了材料力学性能。
总之，本发明制备方法生产的高强度腰果酚基水性聚氨酯产品在保证了优异的耐水性能的同时，力学性能好，即拉伸强度高和断裂伸长率好，兼具刚性强和弹性好的优点；而且，产品的热稳定性好，保存时间长。本发明制备原料价廉易得，反应条件温和，工艺简单，合成步骤简单，目标产物绿色化学，实用性强。
具体实施方式
下面结合实施例对本发明作进一步描述：
实施例1：一种高强度腰果酚基水性聚氨酯的制备方法
按照以下步骤制备高强度腰果酚基水性聚氨酯：
将4.44g(0.02mol)异佛尔酮二异氰酸酯、10g(0.005mol)聚己二酸-1，4-丁二醇酯(Mn=2000)、0.798g(0.006mol)二羟甲基丙酸加入到充满氮气的反应瓶中，升温至80~85℃，反应2h；加入0.058g催化剂辛酸亚锡和1.134g(0.003mol)腰果酚二元醇反应1h，加入0.272g(0.001mol)熊果苷，升温至90~100℃，反应1.5h，再加入1.134g(0.003mol)腰果酚二元醇，反应1h；将温度降低到45~50℃，加入0.606g（0.006mol）三乙胺中和，反应30~35min，反应过程中使用15~20ml丙酮调节黏度；加入0.072g（0.001mol）乙二胺扩链、去离子水（固含量30%）乳化，在高速剪切力作用下，搅拌30~40min；在40℃、-0.1MPa条件下减压蒸馏脱除丙酮得到产品高强度腰果酚基水性聚氨酯。
实施例2：一种高强度腰果酚基水性聚氨酯的制备方法
按照以下步骤制备高强度腰果酚基水性聚氨酯：
将5.11g(0.023mol)异佛尔酮二异氰酸酯、10g(0.005mol)聚己二酸-1，4-丁二醇酯(Mn=2000)、0.798g(0.006mol)二羟甲基丙酸加入到充满氮气的反应瓶中，升温至80~85℃，反应2h；加入0.037g催化剂辛酸亚锡和1.134g(0.003mol)腰果酚二元醇反应1h，加入0.544g(0.002mol)熊果苷，升温至90~100℃，反应1.5h，再加入1.134g(0.003mol)腰果酚二元醇，反应1h；将温度降低到45~50℃，加入0.606g（0.006mol）三乙胺中和，反应30~35min，反应过程中使用丙酮调节黏度，15~20 ml；加入0.144g（0.002mol）乙二胺扩链、去离子水（固含量30%）乳化，在高速剪切力作用下，搅拌30~40min；在40℃、-0.1MPa条件下减压蒸馏脱除丙酮得到产品高强度腰果酚基水性聚氨酯。
实施例3：一种高强度腰果酚基水性聚氨酯的制备方法
按照以下步骤制备高强度腰果酚基水性聚氨酯：
将3.48g(0.02mol)甲苯二异氰酸酯、10g(0.005mol)聚己二酸-1，4-丁二醇酯(Mn=2000)、0.798g(0.006mol)二羟甲基丙酸加入到充满氮气的反应瓶中，升温至80~85℃，反应2h；加入0.069g催化剂辛酸亚锡和1.134g(0.003mol)腰果酚二元醇反应1h，加入0.272g(0.001mol)熊果苷，升温至90~100℃，反应1.5h，再加入1.134g(0.003mol)腰果酚二元醇，反应1h；将温度降低到45~50℃，加入0.606g（0.006mol）三乙胺中和，反应30~35min，反应过程中使用丙酮调节黏度，15~20 ml；加入0.072g（0.001mol）乙二胺扩链、去离子水（固含量30%）乳化，在高速剪切力作用下，搅拌30~40min；在40℃、-0.1MPa条件下减压蒸馏脱除丙酮得到产品高强度腰果酚基水性聚氨酯。
实施例4：一种高强度腰果酚基水性聚氨酯的制备方法
按照以下步骤制备高强度腰果酚基水性聚氨酯：
将1.74g(0.01mol)甲苯二异氰酸酯、1.68g(0.01mol) 六亚甲基二异氰酸酯、10g(0.005mol)聚己二酸-1，4-丁二醇酯(Mn=2000)、0.798g(0.006mol)二羟甲基丙酸加入到充满氮气的反应瓶中，升温至80~85℃，反应2h；加入0.061g催化剂辛酸亚锡和1.134g(0.003mol)腰果酚二元醇反应1h，加入0.272g(0.001mol)熊果苷，升温至90~100℃，反应1.5h，再加入1.134g(0.003mol)腰果酚二元醇，反应1h；将温度降低到45~50℃，加入0.606g（0.006mol）三乙胺中和，反应30~35min，反应过程中使用丙酮调节黏度，15~20 ml；加入0.072g（0.001mol）乙二胺扩链、去离子水（固含量30%）乳化，在高速剪切力作用下，搅拌30~40min；在40℃、-0.1MPa条件下减压蒸馏脱除丙酮得到产品高强度腰果酚基水性聚氨酯。
实施例5：一种高强度腰果酚基水性聚氨酯的制备方法
按照以下步骤制备高强度腰果酚基水性聚氨酯：
将5.11g(0.023mol)异佛尔酮二异氰酸酯、20g(0.005mol)聚己二酸-1，4-丁二醇酯(Mn=4000)、0.798g(0.006mol)二羟甲基丙酸加入到充满氮气的反应瓶中，升温至80~85℃，反应2h；加入0.088g催化剂辛酸亚锡和1.134g(0.003mol)腰果酚二元醇反应1h，加入0.544g(0.002mol)熊果苷，升温至90~100℃，反应1.5h，再加入1.134g(0.003mol)腰果酚二元醇，反应1h；将温度降低到45~50℃，加入0.606g（0.006mol）三乙胺中和，反应30~35min，反应过程中使用丙酮调节黏度，15~20 ml；加入0.144g（0.002mol）乙二胺扩链、去离子水（固含量30%）乳化，在高速剪切力作用下，搅拌30~40min；在40℃、-0.1MPa条件下减压蒸馏脱除丙酮得到产品高强度腰果酚基水性聚氨酯。
实施例6：一种高强度腰果酚基水性聚氨酯的制备方法
按照以下步骤制备高强度腰果酚基水性聚氨酯：
将3.48g(0.02mol)甲苯二异氰酸酯、5g(0.0025mol)聚己二酸-1，4-丁二醇酯(Mn=2000)、5g(0.0025mol)聚己二酸-1，3-丁二醇酯(Mn=2000)、0.798g(0.006mol)二羟甲基丙酸加入到充满氮气的反应瓶中，升温至80~85℃，反应2h；加入0.044g催化剂辛酸亚锡和1.134g(0.003mol)腰果酚二元醇反应1h，加入0.272g(0.001mol)熊果苷，升温至90~100℃，反应1.5h，再加入1.134g(0.003mol)腰果酚二元醇，反应1h；将温度降低到45~50℃，加入0.606g（0.006mol）三乙胺中和，反应30~35min，反应过程中使用丙酮调节黏度，15~20 ml；加入0.072g（0.001mol）乙二胺扩链、去离子水（固含量30%）乳化，在高速剪切力作用下，搅拌30~40min；在40℃、-0.1MPa条件下减压蒸馏脱除丙酮得到产品高强度腰果酚基水性聚氨酯。
其中，实施例1~实施例6所用的腰果酚二元醇是含有几种单体的混合物，具体的制备过程如下：在配有冷凝管、电动搅拌器的500mL三口烧瓶中加入119.4g的腰果酚，加热到95℃，加入0.12g ZnCl2，然后逐滴加入50mL的环氧氯丙烷，加入完毕后，在此条件下反应3h，然后逐滴加入定量的氢氧化钠（19.3g/100mL水），温度升高到100℃反应3h，将上述产物转移至分液漏斗，用去离子水洗涤至中性，分出有机层，加入无水硫酸钠干燥过滤，滤液真空旋转蒸出多余的环氧氯丙烷，即得腰果酚缩水甘油醚；在装有冷凝管、搅拌器的250mL三口烧瓶中加入40g腰果酚缩水甘油醚、80g10%的H2SO4，在105℃反应14h，冷却至室温，用去离子水洗涤至中性，分出有机层加入无水硫酸钠干燥过滤，即得腰果酚二元醇（CD）。
表1 高强度腰果酚基水性聚氨酯力学性能和热稳定性
样品 拉伸断裂强度/ MPa 断裂伸长率/% T<sub>5</sub>/℃
实施例1 39.5 1120 247
实施例2 43.1 1035 258
实施例3 40.8 1130 252
实施例4 37.9 1116 248
实施例5 41.3 1080 254
实施例6 39.8 1070 249
对比例1 17.5 650 215
对比例2 22.2 1050 238
注：T5为胶膜失重率为5%时的分解温度。，T5越大说明材料热稳定性越好。
对比例1为不加入腰果酚二元醇和熊果苷改性的水性聚氨酯（即空白样）。对比例2为不加入熊果苷，仅使用腰果酚二元醇改性的水性聚氨酯（即腰果酚基水性聚氨酯）。
上述实施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士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (7)

1.一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：该制备方法依次包括下列步骤：
第一步，将聚酯二元醇、二异氰酸酯、二羟甲基丙酸加入到充满氮气的反应釜中，升温至80~85℃，反应1.5~2.5h；
第二步，加入催化剂辛酸亚锡和一半量的腰果酚二元醇反应1~1.5h，加入熊果苷，升温至90~100℃，反应1.5~2h，再加入另一半量的腰果酚二元醇，反应1~1.5h；
第三步，将温度降低到45~50℃，加入三乙胺中和，反应30~35min，反应过程中使用丙酮调节黏度；
第四步，加入乙二胺扩链，再加入水乳化，使得总反应体系的固含量为30%，在高速剪切力作用下，搅拌30~40min；其中，所述二异氰酸酯：聚酯二元醇：二羟甲基丙酸：腰果酚二元醇：熊果苷：三乙胺：乙二胺的摩尔比是100：15~35：15~35：15~60：5~30：15~35：5~30；
第五步，减压蒸馏脱除丙酮得到所述高强度腰果酚基水性聚氨酯。
2.根据权利要求1所述的一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：所述聚酯二元醇选自聚碳酸酯二元醇、聚己二酸-1,4-丁二醇酯以及聚己二酸-1,3-丁二醇酯中的任意一种或任意两种以任意比例的混合物；所述聚酯二元醇的数均分子量的范围为1000~8000。
3.根据权利要求1所述的一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：所述二异氰酸酯选自异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯以及甲苯二异氰酸酯中的任意一种或任意两种以任意比例的混合物。
4.根据权利要求1所述的一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：所述催化剂辛酸亚锡的加入量为反应物总质量的0.2~0.4%。
5.根据权利要求1所述的一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：所述腰果酚二元醇的化学结构式为：
Figure DEST_PATH_RE-DEST_PATH_IMAGE001
。
6.根据权利要求1所述的一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：在所述第四步中，在高速剪切力作用下，高速搅拌的转速为800~1500r/min，搅拌30~40min。
7.根据权利要求1所述的一种高强度腰果酚基水性聚氨酯的制备方法，其特征在于：在所述第五步中，减压蒸馏的条件为40℃、-0.1MPa。
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