CN109608643A - 一种有机硅原油、含硅硬挺剂及其制备方法 - Google Patents

一种有机硅原油、含硅硬挺剂及其制备方法 Download PDF

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CN109608643A
CN109608643A CN201811537059.9A CN201811537059A CN109608643A CN 109608643 A CN109608643 A CN 109608643A CN 201811537059 A CN201811537059 A CN 201811537059A CN 109608643 A CN109608643 A CN 109608643A
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siliceous
stiffening agent
parts
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袁金亮
杨中新
王胜鹏
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Guangdong Transfar Jzeng Fine Chemical Co
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Abstract

本发明公开一种含硅硬挺剂,属于纺织助剂领域,按重量份计,包括以下原料:中间体原油10‑30份,聚醋酸乙烯酯5‑10份,乙酸乙酯10‑20份,乳化剂4‑10份,去离子水30‑70份;其制备方法为,先将有机硅原油,聚醋酸乙烯酯、乙酸乙酯混合均匀,再加入乳化剂,然后用高速分散机、均质机分散乳化1~2h,然后多次分批加入水使其转相成乳液状。本发明的含硅硬挺剂,具有极佳的耐酸、碱、盐等化学稳定性,能赋予织物硬挺、平滑、厚实的手感,耐洗性能优异,经过含硅硬挺剂处理的织物,用水洗5次以上,依然可以保持硬挺、平滑、悬垂的手感风格。

Description

一种有机硅原油、含硅硬挺剂及其制备方法
技术领域
本发明涉及一种有机硅原油、含硅硬挺剂及其制备方法,属于纺织助剂领域。
背景技术
目前,在纺织后整理领域,硬挺整理能够赋予织物特殊的硬挺骨感和悬垂外观,是一种重要的织物整理方式。现有硬挺剂分类包括:聚乙烯醇、聚醋酸乙烯酯,聚丙烯酸树脂、脲醛树脂、三聚氰胺树脂等。其中,脲醛树脂和三聚氰胺树脂由于会缓慢释放游离甲醛,对人体健康会造成隐形伤害,使用时越来越受限制,因此无甲醛环保的织物硬挺剂更受市场欢迎。聚乙烯醇和聚醋酸乙烯酯及聚丙烯酸树脂类硬挺剂均符合环保要求,且挺刮度、回弹性都较好,深受市场欢迎。
如现有中国专利“一种硬挺剂及其制备方法”(申请号为201711320178.4),制备方法如下:(1)将甲基丙烯酸硬脂酸酯、甲基丙烯酸异丁酯、甲基丙烯酸正丙酯、顺丁烯二酸酐、丙烯酸月桂酯、硅氧烷三醇藻酸酯、月桂酸单甘油酯、改性大豆磷脂、香草醛、角黄质和去离子水混合搅拌得混合液A;(2)将过硫酸钾、硝酸银和去离子水混合搅拌得混合液B;(3)将一半混合液A和一半混合液B混合保温;(4)滴加剩余混合液A和剩余混合液B,反应得反应液C;(5)将反应液C降温至,加入氢氧化钠溶液搅拌;(6)加入聚乙烯吡咯烷酮、聚环氧乙烷、聚阴离子纤维素和聚乙烯醇搅拌;(7)冷却至室温出料即得。
但是织物经传统硬挺剂整理后,虽然挺刮度明显提高,但手感容易变得粗糙,无滑感,无厚实感,且不耐洗。
发明内容
针对上述现有技术存在的问题,本发明提供一种含有机硅原油的硬挺剂,能赋予织物硬挺、厚实、平滑的手感,尤其能耐洗5次以上,保持硬挺、平滑的手感风格。
本发明还同时提供了上述含硅硬挺剂的制备方法。
为了实现上述目的,本发明采用的一种有机硅原油,所述有机硅原油具有如下的结构式:
其中的R为胺基、多胺基、乙烯基、环氧基中的任一种。
一种所述有机硅原油的制备方法,先将线性硅烷与硅烷偶联剂在100-115℃下,反应1-3h,加入碱性催化剂,开启真空,升温至130-140℃,继续抽真空反应10-20h,得到在100℃下粘度大于100万mPa.s的有机硅原油。
作为改进,所述的线性硅烷采用道康宁的线性体PMX 0156或瓦克的线性体WS62M。
作为改进,所述的硅烷偶联剂的用量为线性硅烷重量的0.05~0.15%。
作为改进,所述的碱性催化剂的用量为线性硅烷重量的0.05~0.5%;
所述碱性催化剂为氢氧化钾、氢氧化钠、氢氧化锂中的任一种或几种的混合。
一种含硅硬挺剂,按重量份计,包括以下原料:有机硅原油10-30份,聚醋酸乙烯酯5-10份,乙酸乙酯10-20份,乳化剂4-10份,去离子水30-70份。
作为改进,使用时,所述的有机硅原油加调粘剂稀释,所述调粘剂为高沸点醇类,调粘剂的添加量为有机硅原油重量的1~5%。
作为改进,所述聚醋酸乙烯酯的分子量大于50万。
作为改进,所述乳化剂采用HLB值在11~13之间的乳化剂。
一种含硅硬挺剂的制备方法,先将有机硅原油,聚醋酸乙烯酯、乙酸乙酯混合均匀,再加入乳化剂,然后用高速分散机、均质机分散乳化1~2h,然后多次分批加入水使其转相成乳液状。
本发明的原理为:有机硅类产品由于硅油分子链高度卷曲,并具有螺旋形结构,分子链中甲基伸向外侧,硅氧键可以灵活旋转,使得有机硅产品都具有优越的平滑感和蓬松厚实感。结合硬挺整理的微观机理,实际上只要将织物中的纤维与纤维交织处固定好,在纤维交织处形成玻璃化结晶,就可以做出硬挺效果。将硅类产品做出相应硬挺效果来,兼顾织物在有机硅整理后具有相应的滑感、厚实感和耐洗性能,这类含硅硬挺剂将具有非常好的发展前景。
与现有技术相比,本发明的含硅硬挺剂,包括有机硅原油,而有机硅原油通过线性硅烷与硅烷偶联剂反应制得,因此具有极佳的耐酸、碱、盐等化学稳定性,能赋予织物硬挺、平滑、厚实的手感,耐洗性能优异,经过含硅硬挺剂处理的织物,用水洗5次以上,依然可以保持硬挺、平滑、悬垂的手感风格。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明了,下面对本发明进行进一步详细说明。但是应该理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限制本发明的范围。
除非另有定义,本文所使用的所有的技术术语和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同,本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明。
一种有机硅原油,所述有机硅原油具有如下的结构式:
其中的R为胺基、多胺基、乙烯基、环氧基中的任一种。
一种所述有机硅原油的制备方法,先将线性硅烷与硅烷偶联剂在100-115℃下,反应1-3h,加入碱性催化剂,开启真空,升温至130-140℃,继续抽真空反应10-20h,得到在100℃下粘度大于100万mPa.s的有机硅原油,常温为半透明固态。
作为改进,所述的线性硅烷采用道康宁的线性体PMX 0156或瓦克的线性体WS62M。
作为改进,所述的硅烷偶联剂的用量为线性硅烷重量的0.05~0.15%。
作为改进,所述的碱性催化剂的用量为线性硅烷重量的0.05~0.5%;
所述碱性催化剂为氢氧化钾、氢氧化钠、氢氧化锂中的任一种或几种的混合。
一种含硅硬挺剂,按重量份计,包括以下原料:有机硅原油10-30份,聚醋酸乙烯酯5-10份,乙酸乙酯10-20份,乳化剂4-10份,去离子水30-70份。
作为改进,使用时,所述的有机硅原油加调粘剂稀释,所述调粘剂为高沸点醇类,优选二乙二醇丁醚,调粘剂的添加量为有机硅原油重量的1~5%。
作为改进,所述聚醋酸乙烯酯的分子量大于50万。
作为改进,所述乳化剂采用HLB值在11~13之间的乳化剂,优选采用脂肪醇聚氧乙烯醚(9EO),C13异构醇聚氧乙烯醚(8EO)。
一种含硅硬挺剂的制备方法,先将有机硅原油,聚醋酸乙烯酯、乙酸乙酯混合均匀,再加入乳化剂,然后用高速分散机、均质机分散乳化1~2h,然后多次分批加入水使其转相成乳液状。
所述的含硅硬挺剂的制备方法中,高速分散转速需到达2000-3000转/分钟。另外,由于高速分散会发热,需要用冷却***冷却。
实施例1
一种含硅硬挺剂的制备方法,包括以下步骤:
1)在装有温度计、冷凝管以及电动搅拌器的1L四口烧瓶中,加入500g线性体PMX0156与0.4g3-(2-氨乙基)-氨丙基甲基二甲氧基硅烷,在110℃下反应2h,之后加入浓度为50%的氢氧化钾溶液1.0g,开真空并升温,至135℃反应12h,测粘度,在100-120℃间在线粘度计显示100万mPa.s以上,粘度合格(冷却常温为半透明固态),向烧瓶内加入15g丙二醇丁醚,继续搅拌1h,得中间体原油Ⅰ;
2)在装有冷凝***、分散机、均质机的2L烧杯中,加入聚醋酸乙烯酯(PVAC)100g、乙酸乙酯150g、中间体原油Ⅰ250g,开动分散机,先于1500转/分钟搅拌0.5h,再向烧杯中加入脂肪醇聚氧乙烯醚(3EO)20g、脂肪醇聚氧乙烯醚(9EO)30g,开动均质机,并将分散机转速调至2000转/分钟,开冷却水冷却物料,如此分散乳化2h,然后,向烧杯中加入去离子水50g,继续分散均质30分钟,再向烧杯加入去离子水100g,继续分散均质30分钟,如此操作3-4次,至水全部加完,烧杯中物料已成白色粘稠乳液,加入冰醋酸调整PH值6.5-7,得含硅硬挺剂YT-1。
实施例2
一种含硅硬挺剂的制备方法,包括以下步骤:
1)在装有温度计、冷凝管以及电动搅拌器的1L四口烧瓶中,加入500g线性体WS62M与0.3g y-缩水甘油醚丙基甲基二甲氧基硅烷,在110℃下反应1h,之后加入氢氧化锂1.0g,开真空并升温,至140℃反应16h,测粘度,在100~120℃间在线粘度计显示100万mPa.s以上,粘度合格(冷却常温为半透明固态),向烧瓶内加入10g二乙二醇丁醚,继续搅拌1h,得中间体原油Ⅱ;
2)在装有冷凝***、分散机、均质机的2L烧杯中,加入聚醋酸乙烯酯(PVAc)80g、乙酸乙酯100g、中间体原油Ⅱ300g,开动分散机,先在1500转/分钟搅拌0.5h,再向烧杯中加入C13异构醇聚氧乙烯醚(6EO)22g、C13异构醇聚氧乙烯醚(8EO)28g,开动均质机,并将分散机转速调至2000转/分钟,开冷却水冷却物料,如此分散乳化1.5h,然后向烧杯中加入去离子水50g,继续分散均质30分钟,再向烧杯加入去离子水100g,继续分散均质30分钟,如此操作3~4次,至水全部加完,烧杯中物料已成白色粘稠乳液,控制PH值6.5-7,得含硅硬挺剂YT-2。
实施例3
应用对比试验。
1)试验材料:实施例1制得含硅硬挺剂YT-1;实施例2制得含硅硬挺剂YT-2;聚醋酸乙烯硬挺剂TF-6350(对比);市售聚丙烯酸酯硬挺剂(对比);锦棉交织直弹布。
2)试验工艺:一浸一轧,160℃中焙烘2min定型,对比硬挺度和手感。
硬挺整理后的布样分别裁成4cm*10cm样条通过L&W BENDING TESTER进行挺度测试,具体测试结果如下表1-3所示。
表1硬挺度对比结果
硬挺度
YT-1 2.0
YT-2 2.2
聚醋酸乙烯硬挺剂TF-6350 2.1
市售聚丙烯酸酯硬挺剂 1.7
表2洗后5次硬挺度对比结果
硬挺度
YT-1 1.8
YT-2 1.9
聚醋酸乙烯硬挺剂TF-6350 1.0
市售聚丙烯酸酯硬挺剂 0.5
表3手感对比结果
洗前 洗后5次
YT-1 ★★★★ ★★★
YT-2 ★★★ ★★★
聚醋酸乙烯硬挺剂TF-6350
市售聚丙烯酸酯硬挺剂
注:★★★★★五星表示厚实滑感最佳。
分析上表可知,本发明的含硅硬挺剂,具有极佳的耐酸、碱、盐等化学稳定性,能赋予织物硬挺、平滑、厚实的手感,耐洗性能优异,经过含硅硬挺剂处理的织物,用水洗5次以上,依然可以保持硬挺、平滑、悬垂的手感风格,性能远优于现有的硬挺剂。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换或改进等,均应包含在本发明的保护范围之内。

Claims (10)

1.一种有机硅原油,其特征在于,所述有机硅原油具有如下的结构式:
其中的R为胺基、多胺基、乙烯基、环氧基中的任一种。
2.一种权利要求1所述有机硅原油的制备方法,其特征在于,先将线性硅烷与硅烷偶联剂在100-115℃下,反应1-3h,加入碱性催化剂,开启真空,升温至130-140℃,继续抽真空反应10-20h,得到在100℃下粘度大于100万mPa.s的有机硅原油。
3.根据权利要求2所述有机硅原油的制备方法,其特征在于,所述的线性硅烷采用道康宁的线性体PMX 0156或瓦克的线性体WS 62M。
4.根据权利要求2所述有机硅原油的制备方法,其特征在于,所述的硅烷偶联剂的用量为线性硅烷重量的0.05~0.15%。
5.根据权利要求2所述有机硅原油的制备方法,其特征在于,所述的碱性催化剂的用量为线性硅烷重量的0.05~0.5%;
所述碱性催化剂为氢氧化钾、氢氧化钠、氢氧化锂中的任一种或几种的混合。
6.一种含硅硬挺剂,其特征在于,按重量份计,包括以下原料:权利要求1-5任一项所述的有机硅原油10-30份,聚醋酸乙烯酯5-10份,乙酸乙酯10-20份,乳化剂4-10份,去离子水30-70份。
7.根据权利要求6所述的一种含硅硬挺剂,其特征在于,使用时,所述的有机硅原油加调粘剂稀释,所述调粘剂为高沸点醇类,调粘剂的添加量为有机硅原油重量的1~5%。
8.根据权利要求6所述的一种含硅硬挺剂,其特征在于,所述聚醋酸乙烯酯的分子量大于50万。
9.根据权利要求6所述的一种含硅硬挺剂,其特征在于,所述乳化剂采用HLB值在11~13之间的乳化剂。
10.一种权利要求6-9任一项所述含硅硬挺剂的制备方法,其特征在于,先将有机硅原油,聚醋酸乙烯酯、乙酸乙酯混合均匀,再加入乳化剂,然后用高速分散机、均质机分散乳化1~2h,然后多次分批加入水使其转相成乳液状。
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