CN108752564B - 原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法 - Google Patents

原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法 Download PDF

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CN108752564B
CN108752564B CN201810420956.5A CN201810420956A CN108752564B CN 108752564 B CN108752564 B CN 108752564B CN 201810420956 A CN201810420956 A CN 201810420956A CN 108752564 B CN108752564 B CN 108752564B
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nano
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chain extender
cellulose
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周建华
戴仲玉
马建中
罗宗武
陈志轩
金迪娜
朱小春
张凯强
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Jiangsu Huasheng Guolian Technology Co.,Ltd.
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Abstract

本发明公开了一种原位聚合制备ZnO/纳米纤维素复合粒子改性水性聚氨酯的合成方法，旨在提供一种力学性能、抗菌性和热稳定性能优异的复合材料，其技术要点依次包括下述步骤：多元醇、ZnO/纳米纤维素复合粒子、催化剂、三乙胺、含亲水基团的小分子扩链剂和异氰酸酯等保温反应一段时间，得到水性聚氨酯预聚体；继续加入小分子扩链剂，保温反应一段时间，得到水性聚氨酯扩链后的预聚体；最后加水高速剪切乳化得到ZnO/纳米纤维素复合粒子改性水性聚氨酯，本发明解决了现有技术中存在的ZnO/纳米纤维素和水性聚氨酯基体相容性差的问题。

Description

原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法
技术领域
本发明属于高性能新型材料合成技术领域，具体涉及一种原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法。
背景技术
纳米材料作为一种方兴正艾的功能材料，逐渐获得人们的青睐。纳米氧化锌(ZnO)是一种禁带宽度在3.37ev，颗粒尺寸在1-100nm左右的无机纳米材料，具有表界面效应、小尺寸效应、宏观量子隧道效应和抗菌性等。纳米纤维素(NCC)是近几年兴起的绿色高分子纳米材料，除了具有一般纳米材料优异的性能外，还具有良好的力学性能、高长径比和生物可降解性等。在以NCC为模板的基础上，通过水热法，制备出ZnO/纳米纤维素。目前将ZnO/纳米纤维素加入到水性聚氨酯中的制备方法，主要有物理共混和原位聚合法。物理共混法操作简单，但其与聚氨酯链间只有氢键作用相容性差，复合乳液储存稳定性低，材料综合性能稍弱。将其通过原位聚合的方式，加入到聚氨酯制备中，提高复合材料的力学性能、抗菌性和热稳定性等。
发明内容
本发明的目的是提供一种原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，解决了现有技术中存在的ZnO/纳米纤维素和水性聚氨酯基体相容性差的问题。
本发明所采用的技术方案是，原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，具体按照以下步骤实施：
步骤1、按照质量百分比称取多元醇15％～25％、ZnO/纳米纤维素0.1％～3％、催化剂0.01％～0.1％、三乙胺0.5％～1.5％、含亲水基团的小分子扩链剂0.5％～2％、异氰酸酯5％～15％、小分子扩链剂0.1％～1％、水60％～80％，以上组份质量百分比之和为100％；
步骤2、取多元醇、ZnO/纳米纤维素、催化剂、三乙胺和含亲水基团的小分子扩链剂以及异氰酸酯反应一段时间，得到水性聚氨酯预聚体；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入小分子扩链剂反应一段时间得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素复合粒子改性水性聚氨酯。
本发明的特点还在于，
步骤1中的多元醇为聚醚多元醇、聚酯多元醇的一种或其组分的混合物。
步骤1中的含亲水基团的小分子扩链剂为二羟甲基丁酸、二羟甲基丙酸的一种。
步骤1中异氰酸酯可能为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六次亚甲基二异氰酸酯的一种。
步骤1中催化剂为二丁基二月桂酸锡或二醋酸二丁基锡的一种。
步骤1中小分子扩链剂为1,4-丁二醇、乙二胺的一种。
步骤2中多元醇、ZnO/纳米纤维素复合粒子、催化剂、三乙胺和含亲水基团的小分子扩链剂以及异氰酸酯的反应时间为0.5～3h，反应温度为40℃～90℃。
步骤3中水性聚氨酯预聚体与小分子扩链剂反应的反应时间为0.5～2h，反应温度为30℃～70℃。
本发明的有益效果是，原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，将ZnO/纳米纤维素通过原位聚合的方式引入到水性聚氨酯中，得到了ZnO/纳米纤维素改性水性聚氨酯，改性后的水性聚氨酯产品，具有更加优异的力学性能、抗菌性。
附图说明
图1(a)是本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法中未改性的水性聚氨酯抗菌图；
图1(b)是本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法中ZnO/纳米纤维素改性的水性聚氨酯抗菌图；
图2是本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法未改性水性聚氨酯和ZnO/纳米纤维素改性的水性聚氨酯力学性能图。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，具体按照以下步骤实施：
步骤1、按照质量百分比称取多元醇15％～25％、ZnO/纳米纤维素0.1％～3％、催化剂0.01％～0.1％、三乙胺0.5％～1.5％、含亲水基团的小分子扩链剂0.5％～2％、异氰酸酯5％～15％、小分子扩链剂0.1％～1％，水60％～80％，以上组份质量百分比之和为100％，其中，多元醇为聚醚多元醇、聚酯多元醇的一种或其组分的混合物；含亲水基团的小分子扩链剂为二羟甲基丁酸、二羟甲基丙酸的一种；异氰酸酯可能为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六次亚甲基二异氰酸酯的一种；催化剂为二丁基二月桂酸锡或二醋酸二丁基锡的一种；小分子扩链剂为1,4-丁二醇、乙二胺的一种；
步骤2、取多元醇、ZnO/纳米纤维素、催化剂、三乙胺和含亲水基团的小分子扩链剂以及异氰酸酯反应0.5～3h，反应温度为40℃～90℃，得到水性聚氨酯预聚体；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入小分子扩链剂反应0.5～2h，反应温度为30℃～70℃，得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素改性水性聚氨酯。
本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，如图1(a)、图1(b)所示，其中，图1(a)是未改性水性聚氨酯抗菌图，图1(b)是ZnO/纳米纤维素改性的水性聚氨酯抗菌图。相比于图1(a)的结果，图1(b)中在浸有乳液的纸片周围，有2mm左右抑菌圈，这主要是因为，ZnO/纳米纤维素引入聚氨酯材料后，由于ZnO中锌离子溶出，破坏细菌结构，抑制细菌生长，从而使改性水性聚氨酯材料表现出一定的抗菌性。图2是未改性水性聚氨酯和ZnO/纳米纤维素改性的水性聚氨酯力学性能，从图2可以看出，加入ZnO/纳米纤维素后，由于ZnO/纳米纤维素和水性聚氨酯之间产生氨基甲酸酯键的交联，胶膜力学性能增加，相对于未改性水性聚氨酯提高了34％。
实施例1
本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，具体按照以下步骤实施：
步骤1、按照质量百分比称取聚酯多元醇15％、ZnO/纳米纤维素0.2％、催化剂选用二丁基二月桂酸锡0.05％、三乙胺0.6％、含亲水基团的小分子扩链剂选用二羟甲基丙酸1％、异氰酸酯选用异佛尔酮二异氰酸酯6％、小分子扩链剂选用1,4-丁二醇0.06％，水77.09％，以上组份质量百分比之和为100％；
步骤2、取聚酯多元醇、ZnO/纳米纤维素、二丁基二月桂酸锡、三乙胺和二羟甲基丙酸以及异佛尔酮二异氰酸酯反应2.5h，反应温度为70℃，得到水性聚氨酯预聚体；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入1,4-丁二醇反应1h，反应温度为40℃，得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素改性水性聚氨酯。
实施例2
本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，具体按照以下步骤实施：
步骤1、按照质量百分比称取聚醚多元醇18％、ZnO/纳米纤维素0.6％、催化剂选用二醋酸二丁基锡0.05％、三乙胺0.6％、含亲水基团的小分子扩链剂选用二羟甲基丁酸1％、异氰酸酯选用六次亚甲基二异氰酸酯7％、小分子扩链剂选用1,4-丁二醇0.06％，水72.69％，以上组份质量百分比之和为100％；
步骤2、取聚醚多元醇、ZnO/纳米纤维素、二醋酸二丁基锡、三乙胺和二羟甲基丁酸以及六次亚甲基二异氰酸酯反应1h，反应温度为75℃，得到水性聚氨酯预聚体；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入1,4-丁二醇反应0.5h，反应温度为45℃，得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素改性水性聚氨酯。
实施例3
本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，具体按照以下步骤实施：
步骤1、按照质量百分比称聚酯多元醇和聚醚多元醇21％、ZnO/纳米纤维素0.4％、催化剂选用二醋酸二丁基锡0.08％、三乙胺1％、含亲水基团的小分子扩链剂选用二羟甲基丁酸1.5％、异氰酸酯选用甲苯二异氰酸酯8％、小分子扩链剂选用1,4-丁二醇0.06％，水67.96％，以上组份质量百分比之和为100％；
步骤2、取聚酯多元醇和聚醚多元醇、ZnO/纳米纤维素、二醋酸二丁基锡、三乙胺和二羟甲基丁酸以及异氰酸酯反应3h，反应温度为85℃，得到水性聚氨酯预聚体；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入小分子扩链剂反应1h，反应温度为50℃，得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素改性水性聚氨酯。
实施例4
本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，具体按照以下步骤实施：
步骤1、按照质量百分比称聚酯多元醇和聚醚多元醇23％、ZnO/纳米纤维素2％、催化剂选用二醋酸二丁基锡0.1％、三乙胺1.5％、含亲水基团的小分子扩链剂选用二羟甲基丁酸2％、异氰酸酯选用甲苯二异氰酸酯13％、小分子扩链剂选用1,4-丁二醇0.08％，水58.32％，以上组份质量百分比之和为100％；
步骤2、取聚酯多元醇和聚醚多元醇、ZnO/纳米纤维素、二醋酸二丁基锡、三乙胺和二羟甲基丁酸以及异氰酸酯反应3h，反应温度为75℃，得到水性聚氨酯预聚体；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入小分子扩链剂反应1.5h，反应温度为60℃，得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素改性水性聚氨酯。
实施例5
本发明原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，具体按照以下步骤实施：
步骤1、按照质量百分比称聚酯多元醇和聚醚多元醇25％、ZnO/纳米纤维素3％、催化剂选用二醋酸二丁基锡0.08％、三乙胺1％、含亲水基团的小分子扩链剂选用二羟甲基丁酸1.5％、异氰酸酯选用甲苯二异氰酸酯8％、小分子扩链剂选用1,4-丁二醇1％，水60.42％，以上组份质量百分比之和为100％；
步骤2、取聚酯多元醇和聚醚多元醇、ZnO/纳米纤维素、二醋酸二丁基锡、三乙胺和二羟甲基丁酸以及异氰酸酯反应3h，反应温度为90℃，得到水性聚氨酯预聚体；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入小分子扩链剂反应2h，反应温度为70℃，得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素改性水性聚氨酯。

Claims (2)

1.原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，其特征在于，具体按照以下步骤实施：
步骤1、按照质量百分比称取多元醇15％～25％、ZnO/纳米纤维素0.1％～3％、催化剂0.01％～0.1％、三乙胺0.5％～1.5％、含亲水基团的小分子扩链剂0.5％～2％、异氰酸酯5％～10％、小分子扩链剂0.1％～1％，水60％～80％，以上组份质量百分比之和为100％；
所述步骤1中的多元醇为聚醚多元醇、聚酯多元醇的一种或其混合物，含亲水基团的小分子扩链剂为二羟甲基丁酸、二羟甲基丙酸的一种，异氰酸酯可能为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六次亚甲基二异氰酸酯的一种，催化剂为二丁基二月桂酸锡或二醋酸二丁基锡的一种，小分子扩链剂为1,4-丁二醇、乙二胺的一种；
步骤2、取多元醇、ZnO/纳米纤维素、催化剂、三乙胺和含亲水基团的小分子扩链剂以及异氰酸酯反应一段时间，得到水性聚氨酯预聚体；
所述步骤2中多元醇、ZnO/纳米纤维素、催化剂、三乙胺和含亲水基团的小分子扩链剂以及异氰酸酯的反应时间为0.5～3h，反应温度为40℃～90℃；
步骤3、在步骤2得到的水性聚氨酯预聚体中加入小分子扩链剂反应一段时间得到水性聚氨酯扩链后的预聚体；
步骤4、将步骤3得到的水性聚氨酯扩链后的预聚体加水乳化得到ZnO/纳米纤维素改性水性聚氨酯。
2.根据权利要求1所述的原位聚合制备ZnO/纳米纤维素改性水性聚氨酯的合成方法，其特征在于，所述步骤3中水性聚氨酯预聚体与小分子扩链剂反应的反应时间为0.5～2h，反应温度为30℃～70℃。
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