CN112552515B - 一种含氟氨基硅油及其制备方法和应用 - Google Patents

一种含氟氨基硅油及其制备方法和应用 Download PDF

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CN112552515B
CN112552515B CN201910909598.9A CN201910909598A CN112552515B CN 112552515 B CN112552515 B CN 112552515B CN 201910909598 A CN201910909598 A CN 201910909598A CN 112552515 B CN112552515 B CN 112552515B
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张恒
张永明
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Shandong Dongyue Future Hydrogen Energy Materials Co Ltd
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Abstract

本发明属于高分子材料技术领域，具体涉及一种含氟氨基硅油及其制备方法。所述的含氟氨基硅油，其结构式为：

Description

一种含氟氨基硅油及其制备方法和应用
技术领域
本发明属于高分子材料技术领域，具体涉及一种含氟氨基硅油及其制备方法。
背景技术
氨基硅油是专门用于纺织品柔软整理剂的基本成份，由于氨基的极性极强，可以与纤维中的羟基、羧基等基团相互作用，产生极强的取向性和吸附性，使得硅氧烷在纤维上定向排列，即硅氧烷在纤维表面的成膜性极好。后期整理烘焙过程中，其极性基团易与纤维中的极性基团作用生成共价键，使得被处理织物有较好的耐洗性能。对氨基硅油进行酰化改性可以减少活泼氢的含量，抑制黄变，降低吸水性。氨基硅油拥有良好的表面性能，较低的表面能，交联后得到的网状树脂与压敏胶之间的离型力较低，可以作为离型剂使用。
以氨基硅油为主要原料作为离型、脱模及织物拨水拨油整理方面的应用，效果较好，但是也存在离型力较大，脱模不完全或脱模次数少，织物黄变和拒油性能差等问题。
发明内容
本发明要解决的技术问题是：克服现有技术的不足，提供一种含氟氨基硅油，其改性含氟片段为六氟环氧齐聚体，改性后的氨基硅油拥有6-7达因的低表面能，并且具有非常好的拨水拨油性能，较氨基硅油拒油性能有质的提升，用于离型、脱模和织物整理方面有着理想的结果。
本发明所述的含氟氨基硅油，其结构式为：
Figure BDA0002214320180000011
其中：R1为CH3或CH2CH3；
R2含有氨基或氟酰胺基团，具体为-(CH2)a-NH-(CH2)b-NHCORf、-(CH2)a-N(CORf)-(CH2)b-NH2或-(CH2)a-N(CORf)-(CH2)b-NHCORf中的一种或它们的任意比例的组合；
Rf为CF3CF2CF2O(CFCF3CF2O)n'CFCF3-，n'＝0-40；
R3为CF3CH2CH2-；
A为CH3、OH或-CH＝CH2；
m为0-20的整数，n为1-20的整数，p为0-5的整数；
a为1-10的整数，b为1-10的整数。
本发明所述的含氟氨基硅油的制备方法，包括以下步骤：
1)将氨基硅油加入到容器中，加入溶剂后开始搅拌，氮气保护下升温；
2)滴加CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2Me或五氟丙酸甲酯反应；
3)反应完毕，除去溶剂及低沸物，得含氟氨基硅油。
其中：
步骤1)中，所述的氨基硅油的氨值为0.3-2.0mmol/g。
步骤1)中，所述的溶剂为：沸点为40-120℃的氢氟醚、沸点为40-120℃的长链烷烃、甲苯、二甲苯、四氢呋喃或丁酮中的一种。
步骤1)中，所述的升温是指升温至25-120℃。
步骤2)中，所述的CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2Me或五氟丙酸甲酯的摩尔量为相对应氨值理论计算摩尔量的10-100％。
本发明所述的含氟氨基硅油的应用，用于离型剂、脱模剂或织物拨水拨油整理剂。
目前工业生产使用的离型材料向着绿色环保、耐高温、快速固化、涂布量低且均匀的方向发展。含氟氨基硅油作为离型材料的原料，在交联剂的存在下可以较好的解决快速固化问题，同时交联后的树脂具有耐高温的特点，既可以作为离型剂使用，也可以进行表面涂层处理，具有较好的低表面能，拥有良好的拨水拨油性能和耐刮擦性能，有效的降低涂层的涂布量。通过有机溶剂稀释含氟氨基硅油或在上述溶液中加入交联剂作为脱模剂喷涂于模具，拥有较好的脱模能力，脱模次数增加。含氟氨基硅油作为织物整理或纤维处理材料使用，其拨水拨油性能明显较氨基硅油提高，特别是拨油性能比氨基硅油有明显提高。
本发明的有益效果如下：
本发明采用六氟环氧齐聚体甲酯衍生物氟化改性原料，接枝到氨基硅油得到氟醚化的氨基硅油，经过接触角、表面能测试，发现效果优良，并对其进行了实际拨水拨油性能测试，发现含氟氨基硅油的拒油性能非常优良，并且在剥离效果上远远超出氨基硅油的效果。
附图说明
图1是氨基硅油改性前后拨水拨油性能对比图；
左图对应0.2％的氨基硅油溶液，右图对应0.2％的含氟氨基硅油溶液；
图中，从上向下依次为：水、咖啡、酱油、醋、花生油。
具体实施方式
以下结合具体实施例对本发明作进一步的描述。
实施例中采用的原料，除特殊说明外，均为市售。
实施例1
所述的含氟氨基硅油的制备方法，具体步骤如下：
1)在配有机械搅拌、氮气保护装置的2L三口瓶中，加入300g氨值为0.8的氨基硅油(单体为KH-602)和800mL四氢呋喃，开动搅拌，并于氮气保护下升温至回流；
2)滴加五氟丙酸甲酯30g，回流条件下反应8小时；
3)反应完毕，蒸除溶剂及反应副产物后，得到308g五氟乙酰基改性的氨基硅油产品，收率为95％，性状为无色粘稠油状物，氨值经测定为0.26。
实施例2
所述的含氟氨基硅油的制备方法，具体步骤如下：
1)在配有机械搅拌、氮气保护装置的3L三口瓶中，加入300g氨值为0.8的氨基硅油(氨基单体为KH-602)和800mL四氢呋喃，开动搅拌，并于氮气保护下升温至回流；
2)滴加CF3CF2CF2OCFCF3CF2OCFCF3COOMe 87g，回流条件下反应8小时；
3)反应完毕，蒸除溶剂及反应副产物后，得到321g氟醚改性的氨基硅油产品，收率为92％，性状为无色粘稠油状物，氨值经测定为0.23。
实施例3
所述的含氟氨基硅油的制备方法，具体步骤如下：
1)在配有机械搅拌、氮气保护装置的2L三口瓶中，加入300g氨值为0.5的氨基硅油(氨基单体为KH-602)和1500mL甲苯，开动搅拌，并于氮气保护下升温至回流；
2)滴加CF3CF2CF2O(CFCF3CF2O)n'CFCF3COOMe(平均分子量为1600)170g，回流条件下反应20小时；
3)反应完毕，蒸除溶剂及反应副产物后，得到455g氟醚改性的氨基硅油产品，收率为97％，性状为淡黄色极度粘稠油状物，氨值经测定为0.17。
实施例4
纤维处理及拨水拨油性能测试
纤维处理方法：将得到的含氟氨基硅油以氢氟醚为溶剂，配制成浓度为0.2％的溶液，将棉织物采用二浸二轧的工艺处理，得到浸凃后的棉织物，然后，经过80℃预烘，再经过130℃烘焙20min后，得到含氟氨基硅油整理的棉织物。
接触角测试结果见表1。
表1接触角测试结果
Figure BDA0002214320180000031
Figure BDA0002214320180000041
拨水拨油性能测试结果见附图1。
实施例5
薄膜表面涂层性能测试
将对应的氨基硅油配比为3％的氢氟醚溶液后，加入锚固剂和架桥剂涂布与清洗后的玻璃表面热固化后，测试接触角。
含氟氨基硅油 Water/° CH<sub>2</sub>I<sub>2</sub>/° Hexadecane/°
氨基硅油(N＝0.8) 117 79 35
实施例1 125 97 79
实施例2 131 115 106
实施例3 136 121 109

Claims (7)

1.一种含氟氨基硅油，其特征在于：其结构式为：
Figure FDA0003640146860000011
其中：R1为CH3或CH2CH3；
R2含有氨基或氟酰胺基团，具体为-(CH2)a-NH-(CH2)b-NHCORf、-(CH2)a-N(CORf)-(CH2)b-NH2或-(CH2)a-N(CORf)-(CH2)b-NHCORf中的一种或它们的任意比例的组合；
Rf为CF3CF2CF2O(CFCF3CF2O)n'CFCF3-，n'＝0-40；
R3为CF3CH2CH2-；
A为CH3、OH或-CH＝CH2；
m为0-20的整数，n为1-20的整数，p为0；
a为1-10的整数，b为1-10的整数。
2.一种权利要求1所述的含氟氨基硅油的制备方法，其特征在于：包括以下步骤：
1)将氨基硅油加入到容器中，加入溶剂后开始搅拌，氮气保护下升温；
2)滴加CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2Me反应；
3)反应完毕，除去溶剂及低沸物，得含氟氨基硅油。
3.根据权利要求2所述的含氟氨基硅油的制备方法，其特征在于：步骤1)中，所述的氨基硅油的氨值为0.3-2.0mmol/g。
4.根据权利要求2所述的含氟氨基硅油的制备方法，其特征在于：步骤1)中，所述的溶剂为：沸点为40-120℃的氢氟醚、沸点为40-120℃的长链烷烃、甲苯、二甲苯、四氢呋喃或丁酮中的一种。
5.根据权利要求2所述的含氟氨基硅油的制备方法，其特征在于：步骤1)中，所述的升温是指升温至25-120℃。
6.根据权利要求2所述的含氟氨基硅油的制备方法，其特征在于：步骤2)中，所述的CF3CF2CF2O(CFCF3CF2O)n'CFCF3CO2Me的摩尔量为相对应氨值理论计算摩尔量的10-100％。
7.一种权利要求1所述的含氟氨基硅油的应用，其特征在于：用于离型剂、脱模剂或织物拨水拨油整理剂。
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CN103881030A (zh) * 2012-12-19 2014-06-25 张家港市国泰华荣化工新材料有限公司 一种含氟氨基硅油乳液的制备方法
CN106750320A (zh) * 2016-12-07 2017-05-31 衢州学院 一种全氟烷基改性氨基硅油的制备方法

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