CN109280171B - 小粒径氨基硅油微乳液及其制备方法和应用 - Google Patents
小粒径氨基硅油微乳液及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种小粒径氨基硅油微乳液及其制备方法和应用，所述的小粒径氨基硅油微乳液，粒径为26nm以下，粒径分散指数(PDI)为0.29～0.42，透过率为95～98。本发明的微乳液透明性高，粒径小且分布均匀，不挥发物含量较高，稳定性好，粘度可控，作为柔软整理剂，用于织物后处理，个人护理用品添加剂等，具有较好地应用效果。
Description
技术领域
本发明涉及一种氨基硅油微乳液及其制备方法。
背景技术
氨基硅油是近年来纺织助剂领域中最受欢迎的柔软整理剂。氨基硅油大多以乳液状态使用，由于普通乳液粒径大，颗粒表面的双电层较弱，颗粒间易相互作用而凝聚，导致乳化状态破坏，水与油相分离。而微乳液粒径小，乳液呈热力学稳定的分散状态，粘度低且结构稳定，从而减少了聚结或破乳的危险，其贮藏性、耐热及抗剪切稳定性均很优越；氨基硅油微乳液乳胶粒径小，能够渗透到纤维内部，为织物提供内在的柔软性和出色的表面平滑性，故使用效果优异。
因而，工业应用力图将氨基硅油进行微乳化。通常制备的氨基硅油微乳液粒径大多在40nm以上，且分布不均匀；少数粒径小的产品不挥发物含量甚低，性价比小。
发明内容
本发明的目的是公开一种小粒径氨基硅油微乳液及其制备方法和应用，以克服现有技术存在的缺陷。
所述的小粒径氨基硅油微乳液，氨基硅油微乳液粒径为26nm以下，优选的为8～24nm，粒径分散指数(PDI)为0.29～0.42，透过率为95～98；
术语“粒径分散指数(PDI)”的定义如下：
也叫多分散系数，表示粒径分布的均一程度，数值越小表示体系中的颗粒粒度分布越集中。
所述的小粒径氨基硅油微乳液的制备方法，包括如下步骤：
所述的小粒径氨基硅油微乳液氨基硅油微乳液的制备方法，包括如下步骤：
将氨基硅油、乳化剂聚乙二醇十三烷基醚和助乳化剂乙二醇单丁醚混合，然后将冰醋酸水溶液以2.5～3.5份/min的速度滴加，滴加25～35min后，调整滴加速度为1～2份/min；5～10min后，降低搅拌速度至500～600rpm，当所有酸化水滴加完毕后，再搅拌5～10min；静置即可得所述的小粒径氨基硅油微乳液；
按质量份数计算：
优选的，所述的氨基硅油为一种高透过率氨基硅油，制备方法，包括以下步骤：
(1)将氨基硅烷偶联剂与水混合水解，温度为10～15℃，水解时间为1～2h；然后在-0.09MPa下维持0.5～2h，静置，即得在25℃时，粘度为100～300mPa·s的氨基硅烷偶联剂水解物；
(2)将八甲基环四硅氧烷在45～55℃下脱水，然后在常压下，以氮气作为保护气体，加入催化剂四甲基氢氧化铵溶解，再减压至-0.09MPa，维持20～30min；再滴加步骤(1)的氨基硅烷偶联剂水解物，再减压至-0.09MPa，20～30min后升温至90℃，反应10～30min后，加入封端剂六甲基二硅氧烷，反应1～2h；再升温至150℃，保温使得催化剂失活；然后升温至180℃，去除低分子化合物；静置冷却，即可制得所述的高透过率氨基硅油，所述的高透过率氨基硅油在25℃时的粘度为1000～2000mPa·s，氨值在0.2～0.6mmol/g，在波长为550nm时的透过率为94％以上。
进一步的，所述的氨基硅烷偶联剂为KH602，所述的氨基硅烷偶联剂和水的质量比为17～20：9～18。
进一步的，所述的八甲基环四硅氧烷、催化剂、封端剂和氨基硅烷偶联剂水解物的质量比为95～190：0.97～2.02：0.45～1.90：2.05～10.24；
通过上述方法获得的高透过率氨基硅油的结构式如下所示：
其中：
R1代表：
CH2CH2CH2NH2、-CH2CH2CH2NHCH2CH2NH2、-CH2CH2CH2NHCH2CH2CH2N(CH3)2、
R1中的氨基可被伯胺、仲胺、叔胺、芳香胺或者季胺盐代替。
上述的结构式为无规共聚物，是以x、y的随意数值连接后以聚合度n的形式重复交替而成，即x、y是变量。
本发明所述的小粒径氨基硅油微乳液，可作为柔软整理剂，用于织物后处理。
本发明的有益效果是：
得到的微乳液透明性高，氨基硅油微乳液粒径在26nm以下，粒径小且分布均匀，不挥发物含量较高，稳定性好，粘度可控，作为织物处理剂、个人护理用品添加剂等具有较好地应用效果。
附图说明
图1是实施例2制备的氨基硅油的透过率图；
图2是实施例2制备的氨基硅油的核磁共振氢谱图；
图3是实施例4制备的氨基硅油微乳液粒径图；
图4是实施例4制备的氨基硅油微乳液的透过率图。
具体实施方式
下面通过具体实施例，对本发明的技术方案作进一步的具体发明。应当理解，本发明的实施并不局限于下面的实施例。
不挥发物含量按照HG/T 4266-2011“纺织染整助剂含固量的测定”标准进行测定。
粘度采用上海精密科学仪器有限公司生产的NDJ-1型旋转粘度计按照GB/T22235-2008“液体黏度的测定”标准进行测定；
粒径采用Y571B型马尔文激光粒度仪，对氨基硅油微乳液的粒径大小及分布情况进行测定；
透过率采用德国安捷伦仪器有限公司生产的Cary5000紫外可见近红外分光光度计，在25℃下对样品的透过率进行测定。
PH值采用PHS-25数显PH计进行测定；静置稳定性：在正常条件下，将乳液倒入一定高度、一定直径的试管中，静置一段时间，考察乳液分层状况；离心稳定性：将硅油乳液置于离心试管中，在3000r/min条件下离心半个小时，观察乳液分层情况。稀释稳定性：加入去离子水，将微乳液稀释为硅油含量为2％的溶液，静置24小时，目测微乳液分层情况；耐热稳定性：移取一定量微乳液到玻璃瓶中(乳液体积不能超过玻璃瓶2/3)，加盖，将玻璃瓶置于烘箱中，在120℃条件下烘30min，然后将其取出，自然冷却，观察其分层情况；耐冻稳定性：移取一定量微乳液到烧瓶中，将烧杯置于冰箱中冷冻12h，取出自然解冻，观察微乳液的分层情况；耐电解质稳定性：向4％氯化镁溶液中加入1％的微乳液，静置观察微乳液的分层情况。本发明中使用的各种原料均为市售的有机硅产品制备常用原料，对本发明所做的任何形式上的变通和/或改变都将落入本发明保护范围。
在本发明中，若非特指，所有的份、百分比均为重量单位，所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法，如无特别说明，均为本领域的常规方法。
具体实施方式
实施例中，如无特别说明，均为重量份。
实施例1
(a)偶联剂水解物的制备
将20份KH602与18份水混合于封闭的四口烧瓶中匀速搅拌水解，水解温度为10℃，水解时间为2h；然后在-0.09MPa下维持1h去除低分子化合物；静置即得粘度为300mPa·s(25℃)的以硅二醇为主的KH602水解物。
(b)氨基硅油的制备
将95份八甲基环四硅氧烷在50℃下脱水1h后；常压时以高纯氮气保护，加入0.97份催化剂四甲基氢氧化铵溶解5min；然后减压至-0.09MPa维持20min；再逐步滴加2.05份上述实施例1制备的粘度为300mPa·s(25℃)的以硅二醇为主的KH602水解物，1min滴完，混合5min；然后减压至-0.09MPa维持20min；然后升温至90℃，反应10min后；加入0.45份封端剂六甲基二硅氧烷(MM)，反应1.5h；再升温至150℃催化剂失活30min；然后升温至180℃去除低分子化合物1h；静置冷却即可制得相应的氨基硅油。
实施例2
(a)偶联剂水解物的制备
将18份KH602与13.5份水混合于封闭的四口烧瓶中匀速搅拌水解，水解温度为15℃，水解时间为1h；然后在-0.09MPa下维持1h去除低分子化合物；静置即得粘度为200mPa·s(25℃)的以硅二醇为主的KH602水解物。
(b)氨基硅油的制备
将95份八甲基环四硅氧烷在50℃下脱水1h后；常压时以高纯氮气保护，加入1.02份催化剂四甲基氢氧化铵溶解5min；然后减压至-0.09MPa维持30min；再逐步滴加6.15份步骤(a)的KH602水解物，2min滴完，混合5min；然后减压至-0.09MPa维持25min；然后升温至90℃，反应30min后；加入0.90份封端剂六甲基二硅氧烷(MM)，反应1.5h；再升温至150℃催化剂失活30min；然后升温至180℃去除低分子化合物1h；静置冷却即可制得相应的氨基硅油。
采用美国Thermo Nicolet公司生产的Nexus型傅里叶变换红外光谱仪对其氨基硅油化学结构进行表征，如图1所示；还采用德国Bruker公司生产的AVANCE-III 500MHZ核磁共振氢谱分析产物的结构，如图2所示。
从图1的氨基硅油的红外光谱图，可以得出：在1045.97cm-1和1129.62cm-1处，具有两个强度相似的强峰，这是由于聚硅氧烷在链增长过程中产生的Si-O-Si的伸缩振动峰；在1259.33cm-1和1410.50cm-1处，具有明显的Si-CH3的特征峰；1452.82cm-1处有较强的N-H弯曲振动吸收峰；在3479.06cm-1处出现氨基伸缩振动吸收峰；因此，得出在以Si-O-Si为主连的分子链中引入了氨基基团，即反应所得产物为氨基硅油。
从图2的氨基硅油的核磁共振氢谱图分析，化学位移0.01ppm处的峰是氨基硅油中Si-CH3上的质子峰；化学位移为0.55ppm处的峰是Si-CH2中的氢原子引起的；化学位移为1.58ppm处的峰是CH2-CH2上的氢原子引起的；化学位移为2.61ppm和2.78ppm处的峰，它们的积分面积几乎为1：1，分别是NH-CH2和CH2-NH2的质子峰；化学位移7.34ppm是CDCl3溶剂峰。
结合氨基硅油的红外光谱图及核磁共振氢谱图的分析，得出偶联剂水解物已经成功接入硅氧烷中，该化合物的结构式如下(结构式)：
实施例3
(a)偶联剂水解物的制备
将17份KH602与9份水混合于封闭的四口烧瓶中匀速搅拌水解，水解温度为12℃，水解时间为1.5h；然后在-0.09MPa下维持1h去除低分子化合物；静置即得粘度为100mPa·s(25℃)的以硅二醇为主的KH602水解物。
(b)氨基硅油的制备
将95份八甲基环四硅氧烷D4在50℃下脱水1h后；常压时以高纯氮气保护，加入1.00份催化剂四甲基氢氧化铵溶解5min；然后减压至-0.09MPa维持25min；再逐步滴加4.10份步骤(a)的KH602水解物，1min滴完，混合5min；然后减压至-0.09MPa维持20min；然后升温至90℃，反应20min后；加入0.90份封端剂六甲基二硅氧烷(MM)，反应1.5h；再升温至150℃催化剂失活30min；然后升温至180℃去除低分子化合物1h；静置冷却即可制得相应的氨基硅油。
实施例4
氨基硅油微乳液的制备：
先将20份实施例1氨基硅油、5份乳化剂聚乙二醇十三烷基醚、7份助乳化剂乙二醇单丁醚放进搅拌器；在800rpm速度下搅拌20min直至完全混合，然后将0.25份冰醋酸与92.25份去离子水混合预制的酸化水，以3份/min速度滴加，30min后，调整酸化水的滴加速度为2份/min；10min后，降低搅拌速度至500rpm，当所有酸化水滴加完毕后，再搅拌5min；静置即得小粒径氨基硅油微乳液。
采用Y571B型马尔文激光粒度仪，对氨基硅油微乳液的粒径大小及分布情况进行测定，如图3所示，粒径为8nm，粒径分散指数(PDI)为0.291；采用德国安捷伦仪器有限公司生产的Cary5000紫外可见近红外分光光度计，在25℃下对氨基硅油微乳液的透过率进行测定，如图4所示，在波长(λ)为550nm，透过率为98％。
实施例5
氨基硅油微乳液的制备
先将18份实施例2的高透过率氨基硅油、6份乳化剂聚乙二醇十三烷基醚、7份助乳化剂乙二醇单丁醚放进搅拌器；在700rpm速度下搅拌18min直至完全混合；
然后将0.2份冰醋酸与79.8份去离子水混合预制的酸化水以3份/min速度滴加，30min后，调整酸化水的滴加速度为2份/min；10min后，降低搅拌速度至500rpm，当所有酸化水滴加完毕后，再搅拌5min；静置即得小粒径氨基硅油微乳液。
实施例6
氨基硅油微乳液的制备：
先将18份实施例3的高透过率氨基硅油、6份乳化剂聚乙二醇十三烷基醚、6份助乳化剂乙二醇单丁醚放进搅拌器；在800rpm速度下搅拌15min直至完全混合；然后将0.23份冰醋酸与81.77份去离子水混合预制的酸化水以3份/min速度滴加，30min后，调整酸化水的滴加速度为2份/min；10min后，降低搅拌速度至600rpm，当所有酸化水滴加完毕后，再搅拌5min；静置即得小粒径氨基硅油微乳液。
实施例7
氨基硅油微乳液的制备：
先将15份实施例3的高透过率氨基硅油、5份乳化剂聚乙二醇十三烷基醚、6份助乳化剂乙二醇单丁醚放进搅拌器；在700rpm速度下搅拌18min直至完全混合；
然后将0.2份冰醋酸与73.75份去离子水混合预制的酸化水以3份/min速度滴加，30min后，调整酸化水的滴加速度为2份/min；10min后，降低搅拌速度至600rpm，当所有酸化水滴加完毕后，再搅拌5min；静置即得小粒径氨基硅油微乳液。
对上述实施例所得到的氨基硅油微乳液进行性能测试，主要测试其不挥发物含量、粘度、粒径、PH值、透过率、还有静置稳定性、离心稳定性、耐热稳定性、稀释稳定性、耐冻稳定性、耐剪切稳定性。
表1：实施例中所得到的氨基硅油微乳液的性能
表2：氨基硅油微乳液稳定性能评价表
从以上测试数据可以看出依据本发明技术路线制备的氨基硅油微乳液，粒径小且分布窄，粘度小，且透过率也高，各种稳定性也好。
Claims (4)
1.制备小粒径氨基硅油微乳液的制备方法，其特征在于，包括如下步骤：将氨基硅油、乳化剂聚乙二醇十三烷基醚和助乳化剂乙二醇单丁醚混合，然后将冰醋酸水溶液以2.5～3.5份/min的速度滴加，滴加25～35min后，调整滴加速度为1～2份/min；5～10min后，降低搅拌速度至500～600rpm，当所有酸化水滴加完毕后，再搅拌5～10min；静置即可得所述的小粒径氨基硅油微乳液；
粒径为8～24nm，粒径分散指数(PDI)为0.29～0.42，透过率为95～98；
所述的氨基硅油为一种高透过率氨基硅油，制备方法，包括以下步骤：
(1)将氨基硅烷偶联剂KH602与水混合水解，然后在-0.09MPa下维持0.5～2h，静置，即得氨基硅烷偶联剂水解物；
(2)将八甲基环四硅氧烷在45～55℃下脱水，然后在常压下，以氮气作为保护气体，加入催化剂四甲基氢氧化铵溶解，再减压至-0.09MPa，维持20～30min；再滴加步骤(1)的氨基硅烷偶联剂水解物，再减压至-0.09MPa，20～30min后升温反应，加入封端剂六甲基二硅氧烷，反应1～2h；然后从反应产物中收集所述的高透过率氨基硅油；
所述的八甲基环四硅氧烷、催化剂、封端剂和氨基硅烷偶联剂水解物的质量比为95～190：0.97～2.02：0.45～1.90：2.05～10.24。
2.根据权利要求1所述的方法，其特征在于，按质量份数计算：
3.根据权利要求2所述的方法，其特征在于，按质量份数计算：水为73.75～92.25份。
4.权利要求1～3任一项所述的方法制备的小粒径氨基硅油微乳液的应用，其特征在于，作为柔软整理剂，用于织物后处理。
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