CN109593203B - 一种线性多元嵌段共聚硅油及其制备方法 - Google Patents

一种线性多元嵌段共聚硅油及其制备方法 Download PDF

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CN109593203B
CN109593203B CN201811528594.8A CN201811528594A CN109593203B CN 109593203 B CN109593203 B CN 109593203B CN 201811528594 A CN201811528594 A CN 201811528594A CN 109593203 B CN109593203 B CN 109593203B
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傅人俊
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Suzhou Qitian New Materials Co ltd
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Abstract

本发明公开了一种线性多元嵌段共聚硅油及其制备方法,其合成步骤为:将二元胺与二元酸反应生成聚酰胺;将羟基羧酸酯化缩聚成聚酯;将上述步骤所得的聚酰胺和聚酯反应生成聚酯聚酰胺;将所得的聚酯聚酰胺与双端环氧聚醚硅油在有机溶剂中反应,得到所述线性多元嵌段共聚硅油。本发明的反应过程容易控制和实现,反应原料易得,成本低,易于工业化生产,所得的线性多元嵌段共聚硅油,具有普适性,并具有良好的柔软亲水性能和稳定性,可以使纺织品报纸耐久的亲水、优良的透湿、透气性和滑爽的手感,黄变低,能有效提高了纺织品的服用性能。

Description

一种线性多元嵌段共聚硅油及其制备方法
技术领域
本发明涉及织物整理剂合成技术领域,特别是涉及一种含有聚酯、聚酰胺、聚醚、氨基和羟基官能团的线性多元嵌段共聚硅油及其制备方法。
背景技术
随着生活水平的日益提高,人们对于穿着服饰的要求越来越向着美观、舒适和功能性的方向发展。而纤维在经过加工后手感会发生改变,如棉经过练漂和染色加工后,纤维受损,使得手感很差。为了满足广大消费者对纺织品柔软舒适性的需求,织物整理剂越来越受到人们的重视。
目前,市场上使用最多的纺织品柔软剂是改性有机硅类柔软剂,包括氨基改性有机硅柔软剂、环氧改性有机硅柔软剂和聚醚改性有机硅柔软剂等,其中氨基改性有机硅柔软剂应用最为广泛。但由于氨基改性或聚醚改性等单官能团有机硅柔软剂存在泛黄、稳定性差和柔软性差等缺陷,双官能团和多官能团改性的有机硅整理剂成为研究的热点。
但现有双官能团或多官能团改性的柔软剂仍存在问题,不能满足使用需求。如专利CN 105175734A公布了一种三元共聚硅油的制备方法,工艺简单且成本较低,但是织物会出现不同程度的变黄现象,并且手感较差。专利CN 103214676 B公布了一种三元共聚嵌段硅油的合成方法,使得织物具有蓬松感、爽滑感,且无变黄或低变黄,但织物耐洗性较差。专利CN 102031697B公布了一种聚酯、聚醚改性硅油三元共聚织物整理剂的制备方法,可以使得织物具有亲水、抗静电,同时兼具柔软手感,而且耐洗性好,但是应用针对性较强。
发明内容
本发明主要解决的技术问题是提供一种含有聚酯、聚酰胺、聚醚、氨基和羟基官能团的线性多元嵌段共聚硅油及其制备方法,能够解决现有纺织品柔软剂存在的上述缺陷。
为解决上述技术问题,本发明采用的一个技术方案是:提供一种线性多元嵌段共聚硅油,所述线性多元嵌段共聚硅油包含聚酯官能团、聚酰胺官能团、聚醚官能团、氨基官能团和羟基官能团;
所述线性多元嵌段共聚硅油的结构式为:
Figure RE-GDA0001936313830000021
其中,0≤x≤20,1≤y≤20,0≤z≤1000,0≤m≤30,0≤n≤30,x、y、z、 m、n均为整数;
R1、R2和R3为相同或不同结构的亚烃基。
本发明采用的另一个技术方案是:提供一种线性多元嵌段共聚硅油的制备方法,其合成步骤为:
(1)将二元胺与二元酸反应生成聚酰胺;
(2)将羟基羧酸缩聚成聚酯;
(3)将步骤(1)所得的聚酰胺和步骤(2)所得的聚酯反应生成聚酯聚酰胺;
(4)将步骤(3)所得的聚酯聚酰胺与双端环氧聚醚硅油在有机溶剂中反应,得到所述线性多元嵌段共聚硅油。
在本发明一个较佳实施例中,所述步骤(1)中,所述二元胺与二元酸的摩尔比为1:0.1~0.99;所述步骤(2)中,所述羟基羧酸的投料量相对应于步骤 (1)中的二元胺的摩尔比为0.1~20:1。
在本发明一个较佳实施例中,所述步骤(4)中,所述聚酯聚酰胺的氨基与双端环氧聚醚硅油的环氧基的摩尔比为1:0.5~2.0。
在本发明一个较佳实施例中,所述聚酯聚酰胺的氨基与双端环氧聚醚硅油的环氧基的摩尔比为1:1。
在本发明一个较佳实施例中,所述步骤(1)、步骤(2)和步骤(3)的反应条件均为:反应温度为50~250℃,反应时间为1~16h;所述步骤(4)的反应条件为:反应温度为20~150℃,反应时间为1~48h。
在本发明一个较佳实施例中,所述二元胺为乙二胺、丙二胺、丁二胺、己二胺、对苯二胺、辛二胺、癸二胺或4,4’-二氨基二苯醚。
在本发明一个较佳实施例中,所述二元酸为丁二酸、己二酸、辛二酸、癸二酸、对苯二甲酸、马来酸、富马酸、苹果酸、酒石酸或上述各酸对应的酸酐中的一种。
在本发明一个较佳实施例中,所述羟基羧酸为乳酸、β-羟基丁酸和12-羟基硬脂酸中的一种或两种以上以任意比例混合的混合物。
在本发明一个较佳实施例中,所述双端环氧聚醚硅油的结构为:
Figure RE-GDA0001936313830000041
式中,0≤m≤30,0≤n≤30,0≤z≤1000,m、n、z均为整数;
所述双端环氧聚醚硅油的分子量为1000~50000。
本发明的有益效果是:本发明一种线性多元嵌段共聚硅油及其制备方法,反应过程容易控制和实现,反应原料易得,成本低,易于工业化生产,所得的线性多元嵌段共聚硅油,具有普适性,并具有良好的柔软亲水性能和稳定性,可以使纺织品报纸耐久的亲水、优良的透湿、透气性和滑爽的手感,黄变低,能有效提高了纺织品的服用性能。
具体实施方式
下面对本发明的较佳实施例进行详细阐述,以使本发明的优点和特征能更易于被本领域技术人员理解,从而对本发明的保护范围做出更为清楚明确的界定。
本发明实施例包括:
本发明揭示了一种线性多元嵌段共聚硅油及其制备方法,所述线性多元嵌段共聚硅油包含聚酯官能团、聚酰胺官能团、聚醚官能团、氨基官能团和羟基官能团;其结构式为:
Figure RE-GDA0001936313830000051
其中,0≤x≤20,1≤y≤20,0≤z≤1000,0≤m≤30,0≤n≤30,x、y、z、 m、n均为整数;
R1、R2和R3为相同或不同结构的亚烃基。
所述线性多元嵌段共聚硅油的合成步骤为:
(1)二元胺与二元酸反应生成聚酰胺:将二元胺与二元酸按1:0.1~0.99 的摩尔比在反应瓶中,在反应温度为50~250℃的条件下反应1~16h,生成聚酰胺;
所得聚酰胺的结构式为:
Figure RE-GDA0001936313830000052
其中,所述二元胺为乙二胺、丙二胺、丁二胺、己二胺、对苯二胺、辛二胺、癸二胺或4,4’-二氨基二苯醚;
所述二元酸为丁二酸、己二酸、辛二酸、癸二酸、对苯二甲酸、马来酸、富马酸、苹果酸、酒石酸或上述各酸对应的酸酐中的一种;
(2)羟基羧酸缩聚成聚酯:在另一个反应瓶中加入相对应于步骤(1)中二元胺的摩尔比为0.1~20:1的羟基羧酸,在反应温度为50~250℃的条件下反应1~16h,生成聚羟基羧酸;
所述羟基羧酸为乳酸、β-羟基丁酸和12-羟基硬脂酸中的一种或两种以上以任意比例混合的混合物;
(3)生成聚酯聚酰胺:将步骤(1)所得的聚酰胺和步骤(2)所得的聚酯在温度为50~250℃的条件下反应1~16h,反应生成聚酯聚酰胺;
所得聚酯聚酰胺的结构式为:
Figure RE-GDA0001936313830000061
其中,0≤x≤20,1≤y≤20,x、y均为整数;
R1、R2和R3为相同或不同结构的亚烃基;
(4)按聚酯聚酰胺的氨基与双端环氧聚醚硅油的环氧基的摩尔比为 1:0.5~2.0的配比,优选为1:1的配比,将步骤(3)所得的聚酯聚酰胺与双端环氧聚醚硅油在有机溶剂中,在温度为20~150℃的条件下反应1~48h,得到所述线性多元嵌段共聚硅油;
其中,所述双端环氧聚醚硅油的结构为:
Figure RE-GDA0001936313830000062
式中,0≤z≤1000,0≤m≤30,0≤n≤30;m、n、z均为整数;R1、R2和R3为相同或不同结构的亚烃基;
所述双端环氧聚醚硅油的分子量为3000~30000。该双端环氧聚醚硅油中间体保证了纺织品的蓬松感。
所述溶剂为异丙醇、乙二醇单丁醚、二乙二醇单丁醚、异丙氧基乙醇或丙二醇单甲醚。
实施例1
(1)在反应瓶中投入乙二胺900g(15mol)、对苯二甲酸831g(5mol),缓慢升温至120℃反应4小时,再逐渐升温至180℃,蒸出过量的乙二胺和水分;
(2)向上述(1)制得的聚酰胺中加入12-羟基硬脂酸1500g(5mol),逐渐升温至200℃,反应15h;
(3)向上述(2)制得的聚酯聚酰胺中加入双端环氧基聚醚硅油(m=0, n=0,z=70)13.3kg,乙二醇单丁醚10.6kg,升温至85℃,反应16h,即得到含聚酯、聚酰胺、聚醚、氨基、羟基官能团的线性多元嵌段共聚硅油26.6kg,挥发分含量60.2%。
实施例2
(1)在反应瓶中投入对苯二胺324.42g(3mol)、丁二酸204.18g(2mol),缓慢升温至180℃,反应8h,制得聚酰胺;
在另一个反应瓶中投入β-羟基丁酸624.6g(3mol),升温至220℃,接收到约36g水后降温,得到聚酯;
(2)向上述(1)制得的聚酰胺和聚酯混合,升温至180℃反应10小时,制得聚酯聚酰胺;
(3)向上述(2)制得的聚酯聚酰胺中加入双端环氧基聚醚硅油(m=8,n=0,z=83)3658.2g,异丙醇11kg,升温至80℃,反应6h后蒸出异丙醇7800g,即得含聚酯、聚酰胺、聚醚、氨基、羟基官能团的线性多元嵌段共聚硅油7860g,含固量58.7%。
实施例3
(1)在反应瓶中投入己二胺581g(5mol)、己二酸584.56g(4mol),缓慢升温至180℃,反应10h,制得聚酰胺;
将L-乳酸450.4g(5mol)和300ml正己烷投入反应瓶中,升温至回流脱水,当水量脱至约72ml时,将正己烷蒸出,得到乳酸聚酯;
(2)向上述(1)制得的聚酰胺和乳酸聚酯混合,升温至180℃,反应8h,得到聚酯聚酰胺;
(3)向上述(2)制得的聚酯聚酰胺中加入双端环氧基聚醚硅油(m=18, n=13,z=200)8760g,异丙氧基乙醇10.16kg,升温至120℃,反应4h,即得到含聚酯、聚酰胺、聚醚、氨基、羟基官能团的线性多元嵌段共聚硅油20.3kg,含固量50.2%。
上述合成方法容易控制和实现,反应原料易得,成本低,易于工业化生产,所得的线性多元嵌段共聚硅油,因含有聚酯、聚酰胺、聚醚、氨基和羟基等官能团,具有良好的柔软亲水性能和稳定性,可以使纺织品报纸耐久的亲水、优良的透湿、透气性;本发明的线性多元嵌段共聚硅油具有普适性,且没有传统硅油的油腻感,由其整理后的纺织品具有滑爽的手感,且黄变低。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (8)

1.一种线性多元嵌段共聚硅油,其特征在于,所述线性多元嵌段共聚硅油包含聚酯官能团、聚酰胺官能团、聚醚官能团、氨基官能团和羟基官能团;
所述线性多元嵌段共聚硅油的结构式为:
Figure 546276DEST_PATH_IMAGE001
其中,0≤x≤20,1≤y≤20,0≤z≤1000,0≤m≤30,0≤n≤30,x、y、z、m、n均为整数;
R1、R2和R3为相同或不同结构的亚烃基;
所述线性多元嵌段共聚硅油的制备方法,其合成步骤为:
(1)将二元胺与二元酸反应生成聚酰胺;
(2)将羟基羧酸缩聚成聚酯;
(3)将步骤(1)所得的聚酰胺和步骤(2)所得的聚酯反应生成聚酯聚酰胺;
(4)将步骤(3)所得的聚酯聚酰胺与双端环氧聚醚硅油在有机溶剂中反应,得到所述线性多元嵌段共聚硅油;
所述双端环氧聚醚硅油的结构为:
Figure 626228DEST_PATH_IMAGE002
式中,0≤m≤30,0≤n≤30,0≤z≤1000,m、n、z均为整数;所述双端环氧聚醚硅油的分子量为1000~50000。
2.根据权利要求1所述的线性多元嵌段共聚硅油,其特征在于,所述步骤(1)中,所述二元胺与二元酸的摩尔比为1:0 .1~0 .99;所述步骤(2)中,所述羟基羧酸的投料量相对应于步骤(1)中的二元胺的摩尔比为0 .1~20:1。
3.根据权利要求1所述的线性多元嵌段共聚硅油,其特征在于,所述步骤(4)中,所述聚酯聚酰胺的氨基与双端环氧聚醚硅油的环氧基的摩尔比为1:0 .5~2 .0。
4.根据权利要求3所述的线性多元嵌段共聚硅油,其特征在于,所述聚酯聚酰胺的氨基与双端环氧聚醚硅油的环氧基的摩尔比为1:1。
5.根据权利要求1所述的线性多元嵌段共聚硅油,其特征在于,所述步骤(1)、步骤(2)和步骤(3)的反应条件均为:反应温度为50~250℃,反应时间为1~16h;所述步骤(4)的反应条件为:反应温度为20~150℃,反应时间为1~48h。
6.根据权利要求1或2所述的线性多元嵌段共聚硅油,其特征在于,所述二元胺为乙二胺、丙二胺、丁二胺、己二胺、对苯二胺、辛二胺、癸二胺或4 ,4’-二氨基二苯醚。
7.根据权利要求1或2所述的线性多元嵌段共聚硅油,其特征在于,所述二元酸为丁二酸、己二酸、辛二酸、癸二酸、对苯二甲酸、马来酸、富马酸、苹果酸、酒石酸或上述各酸对应的酸酐中的一种。
8.根据权利要求1或2所述的线性多元嵌段共聚硅油,其特征在于,所述羟基羧酸为乳酸、β-羟基丁酸和12-羟基硬脂酸中的一种或两种以上以任意比例混合的混合物。
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