氨基硅油的膜形貌、表面性能及成膜机理研究
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摘要
氨基硅油作为功能性有机硅柔软整理剂,能赋予织物舒适的柔软感和丝滑感。氨基硅油对织物的功能性修饰作用与其在纤维表面的定向排列成膜方式、膜形貌及其表面性能有密切关系。
本文以α,ω-二羟基聚二甲基硅氧烷和五种不同的氨基硅烷偶联剂为原料,在碱溶液催化下,通过本体聚合法合成了不同氨值、不同分子量和不同氨基类型的氨基硅油。产物经衍生化后,利用GPC测定了氨基硅油分子量。
利用接触角测量仪、椭偏仪、场发射电子扫描电镜、原子力显微镜、衰减全反射红外和X-光电子能谱等方法分析表征了氨基硅油在纤维素膜基质表面组装成膜的膜形貌及其表面性能,提出了氨基硅油在纤维素膜基质表面的多分子层吸附模型,即靠近纤维素膜基质表面的是通过端羟基与基质表面羟基共价结合的氨基硅油,最外层是能溶解于25℃异丙醇、通过物理吸附的氨基硅油,中间区域是能溶解于50℃异丙醇、通过氢键结合的氨基硅油。
将氨基硅油以乳液形式在纤维素膜基质表面组装成膜时,氨基硅油膜相对粗糙、亲水,表明乳化剂参与成膜,并主要存在于氨基硅油膜表面。
氨基硅油氨基与纤维素膜基质间氢键作用力和氨基硅油中极性氨基间斥力的共同作用使得适中氨值的氨基硅油的柔软效果最佳。氨基硅油聚硅氧烷链段的柔软性和它会包裹羟基阻碍共价结合成膜的作用使得适中分子量的氨基硅油的柔软效果最佳。相对于单氨基硅油,双氨基硅油的结合力更强,织物表面的氨基硅油聚硅氧烷链段增加,赋予织物更佳的柔软效果。
Amino silicone oils are special materials that impart desired mechanical performance properties such as softness, bounciness and anti-wrinkle properties to fabrics and related materials, possibly owing to their excellent film forming ability and morphology. It has been proposed that a film of amino silicone forming on the cellulose not only lowers the friction coefficient of the cellulose surface, but also minimizes the clearance between the wool squamae, and thus makes the surface smoother.
Amino silicone oils of different amino values, molecular weights and amino types were synthesized byα,ω-dihydroxypolydimethylsiloxane and different kinds of amino silane coupling agents under alkaline catalysts. A method of measuring molecular weight of amino silicone oils was proposed by grafted phenyl isocyanate before GPC analysis.
The assembled films morphological features were characterized by ellipsometer, contact angle measurement, filed emission scanning electron microscope (FESEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The orientation of assembled films was proposed. At the cellulose substrate surface a chemically bound molecular layer could be identified, a layer of 25℃isopropanol soluble amino silicone oils existed at the air interface and a layer of 50℃isopropanol soluble amino silicone oils existed between them.
It was discovered that the films assembled from the emulsion were rougher and hydrophilic than the films assembled from diluted amino silicone oils in isopropanol solution, which possibly resulted from some emulsifier participating films formation and residual on the assembled films surface.
The effect mechanism of amino value, molecular weight and amino type on softening property was studied by investigating the surface properties of cellulose substrates treated with amino silicone oils of different amino values, different molecular weights and different amino types combined with their application performances. Amino silicone oils with moderate amino values and molecular weights exhibit excellent softening property. Amino silicone oils with two amino groups on each aminosilane coupling agent exhibit superior softening property than those with one amino group on each aminosilane coupling agent.
本文以α,ω-二羟基聚二甲基硅氧烷和五种不同的氨基硅烷偶联剂为原料,在碱溶液催化下,通过本体聚合法合成了不同氨值、不同分子量和不同氨基类型的氨基硅油。产物经衍生化后,利用GPC测定了氨基硅油分子量。
利用接触角测量仪、椭偏仪、场发射电子扫描电镜、原子力显微镜、衰减全反射红外和X-光电子能谱等方法分析表征了氨基硅油在纤维素膜基质表面组装成膜的膜形貌及其表面性能,提出了氨基硅油在纤维素膜基质表面的多分子层吸附模型,即靠近纤维素膜基质表面的是通过端羟基与基质表面羟基共价结合的氨基硅油,最外层是能溶解于25℃异丙醇、通过物理吸附的氨基硅油,中间区域是能溶解于50℃异丙醇、通过氢键结合的氨基硅油。
将氨基硅油以乳液形式在纤维素膜基质表面组装成膜时,氨基硅油膜相对粗糙、亲水,表明乳化剂参与成膜,并主要存在于氨基硅油膜表面。
氨基硅油氨基与纤维素膜基质间氢键作用力和氨基硅油中极性氨基间斥力的共同作用使得适中氨值的氨基硅油的柔软效果最佳。氨基硅油聚硅氧烷链段的柔软性和它会包裹羟基阻碍共价结合成膜的作用使得适中分子量的氨基硅油的柔软效果最佳。相对于单氨基硅油,双氨基硅油的结合力更强,织物表面的氨基硅油聚硅氧烷链段增加,赋予织物更佳的柔软效果。
Amino silicone oils are special materials that impart desired mechanical performance properties such as softness, bounciness and anti-wrinkle properties to fabrics and related materials, possibly owing to their excellent film forming ability and morphology. It has been proposed that a film of amino silicone forming on the cellulose not only lowers the friction coefficient of the cellulose surface, but also minimizes the clearance between the wool squamae, and thus makes the surface smoother.
Amino silicone oils of different amino values, molecular weights and amino types were synthesized byα,ω-dihydroxypolydimethylsiloxane and different kinds of amino silane coupling agents under alkaline catalysts. A method of measuring molecular weight of amino silicone oils was proposed by grafted phenyl isocyanate before GPC analysis.
The assembled films morphological features were characterized by ellipsometer, contact angle measurement, filed emission scanning electron microscope (FESEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The orientation of assembled films was proposed. At the cellulose substrate surface a chemically bound molecular layer could be identified, a layer of 25℃isopropanol soluble amino silicone oils existed at the air interface and a layer of 50℃isopropanol soluble amino silicone oils existed between them.
It was discovered that the films assembled from the emulsion were rougher and hydrophilic than the films assembled from diluted amino silicone oils in isopropanol solution, which possibly resulted from some emulsifier participating films formation and residual on the assembled films surface.
The effect mechanism of amino value, molecular weight and amino type on softening property was studied by investigating the surface properties of cellulose substrates treated with amino silicone oils of different amino values, different molecular weights and different amino types combined with their application performances. Amino silicone oils with moderate amino values and molecular weights exhibit excellent softening property. Amino silicone oils with two amino groups on each aminosilane coupling agent exhibit superior softening property than those with one amino group on each aminosilane coupling agent.
引文
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