CN101348571A - 一种分散高粘度有机硅组合物于水中的方法 - Google Patents
一种分散高粘度有机硅组合物于水中的方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Colloid Chemistry (AREA)
Abstract
一种分散高粘度有机硅组合物于水中的方法解决了高粘度有机硅组合物在水中乳化分散比较困难的问题，其特征在于向高粘度有机硅组合物中添加了低分子量聚硅氧烷和乳化剂组分，其中所述的低分子量聚硅氧烷粘度为5～3,000MPa·s，乳化剂为非离子表面活性剂。以所述的高粘度有机硅组合物按100份计，低分子量聚硅氧烷用量为5～50份，乳化剂用量为40～150份。该方法采用“剂在油中法”制备乳液，实现步骤为：A.将高粘度有机硅组合物和低分子量聚硅氧烷在强烈搅拌下充分混合拌20～40min；B.加入乳化剂，搅拌15～45min；C.将体系的温度升高至55～85℃，然后保持体系温度，缓慢地加水，提高搅拌速度使其由W/O型乳液变为O/W型乳液，初步达到质量浓度为20～60％；D.乳液通过胶体磨后，进一步乳化；E.最后用水稀释为所需浓度。
Description
技术领域
本发明涉及一种乳化高粘度有机硅组合物的方法，更准确地说本发明涉及到一种提高高粘度有机硅组合物乳状分散液稳定性的方法，它涉及精细化学品添加剂的制备，因此隶属于精细化工制剂技术领域。
技术背景
有机硅分散液，即乳液，有着很宽的应用范围，可以用于纺织后整理剂、织物柔软剂、抗汗剂、消泡剂、脱模剂等等。高粘度聚硅氧烷是洗发香波中的重要组分。白炭黑和高粘度聚硅氧烷的组合物在密封、润滑、绝缘、防锈上有着重要的应用，在泡沫控制上，它也有着优良的抑制泡沫产生的性能。
有机硅乳液的类型主要有两种，油包水型(W/O)和水包油型(O/W)。作为纺织品、化妆品等领域中用的有机硅乳液基本是O/W型的。O/W型有机硅乳液的制备不外乎以下两种方法制备，第一种是通过聚合的方法形成的，将有机硅单体在催化剂和引发剂以及表面活性剂等作用下聚合而成，如羟基硅油乳液；第二种是通过机械的方法制备，将制备乳液的各种组分，包括油相组分、乳化剂、水、稳定剂等等，通过加热搅拌、机械剪切、胶体磨、均质机等方式分散制得。
要将高粘度的有机硅组合物乳化分散在水中是比较困难的，这在专利CN1807512中也有说明。有机硅乳液的功能与乳液自身的许多性质有关，例如乳液的耐温稳定性、抗剪切性能、稀释稳定性和储存稳定性，专利US6001887也针对乳液的稳定性介绍了一些测试方法。就消泡剂而言，如果将稳定性不好的有机硅消泡剂乳液用在棉、化纤等染色上消除有害泡沫的话，就会在布匹上形成“硅斑”，严重影响到染色的效率和最终产品的质量。因此，有机硅乳液的稳定性是非常重要的。
美国专利US4853474通过交联的硅聚醚来提高乳液的耐低温性能，但是这种方法难以控制硅聚醚自身的交联程度，因此，乳液的稳定性很难保证一致性；US5451692介绍的烷基硅聚醚在油包水型乳液制备中的应用，通过烷基的引入，提高了与油相组分之间的相容性。EP-A-163541在研究消泡剂时介绍高粘度的聚硅氧烷的乳液制备比较困难，需要很高的成本，而且效果不佳。
本专利发明人经过大量的实验摸索，发现在分散高粘度有机硅组合物时向这种组合物中加入低分子量聚硅氧烷对制备稳定的乳液有很大的帮助。
发明内容
本发明的目的是提供一种乳化高粘度有机硅组合物的方法，解决高粘度的有机硅组合物在水中乳化分散比较困难的问题。
技术方案：
一种分散高粘度有机硅组合物于水中的方法，其特征在于向高粘度有机硅组合物中加入了低分子量聚硅氧烷和乳化剂组分，该方法很好的解决了高粘度有机硅组合物乳化困难的问题，本方法所述的高粘度有机硅的粘度为100,000m～1,000,000Pa·s。
前述的低分子量聚硅氧烷，其分子结构如下：
其中m、n和s为聚合度，m为1～1,000的整数，n为1～500的整数，s为1～1,000的整数。m、n和s的取值保证低分子量聚硅氧烷的粘度为50～3,000 mPa·s，优选100～1,000mPa·s。
R和R1为取代基。R为碳原子数为1～20的烷基，为直链或支链的，包括甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、异戊基、叔戊基、辛基、异辛基、仲辛基、十二碳烷基、十四碳烷基、十六碳烷基或十八碳烷基。出于成本和原材料易得的考虑，优选R为甲基。R1为烷基、含氨烃基、羟基或卤原子中的一种，烷基为碳原子数为1～18的烷基，它和R一样，也可以不一样；卤原子包括氟、氯、溴、碘原子，优选氯原子。含氨烃基包括-NH2、-NHCH2CH2NH2、-NHC2H4NHC2H4NH2及-OC6H4NH2。R1优选含氨烃基或甲基或羟基。
接通常质量份数计，所述的高粘度有机硅组合物为100份，则低分子量聚硅氧烷的份数选择为5～50份，优选10～30份。
前述的乳化剂属于表面活性剂，包括阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂。
非离子表面活性剂的例子是壬基酚聚氧乙烯醚、辛基酚聚氧乙烯醚、月桂酸聚氧乙烯醚、油酸聚氧乙烯醚、月桂醇聚氧乙烯醚、十六醇聚氧乙烯醚、十八醇聚氧乙烯醚、失水山梨醇单月桂酸酯、失水山梨醇单棕榈酸酯、失水山梨醇单硬脂酸酯、失水山梨醇单油酸酯、失水山梨醇三硬脂酸酯、失水山梨醇三油酸酯、聚氧乙烯失水山梨醇单月桂酸酯、聚氧乙烯失水山梨醇单棕榈酸酯、聚氧乙烯失水山梨醇单硬脂酸酯、聚氧乙烯失水山梨醇单油酸酯、聚氧乙烯失水山梨醇三硬脂酸酯、聚氧乙烯失水山梨醇三油酸酯、聚氧烷烯改性聚硅氧烷形成的硅聚醚以及诸如此类。
阴离子表面活性剂的例子为壬基酚聚氧乙烯醚硫酸盐、辛基酚聚氧乙烯醚硫酸盐、烷基磷酸盐以及诸如此类的表面活性剂。
阳离子表面活性剂的例子为烷基苄基铵盐、月桂酸咪唑啉、油酰基咪唑啉、十六烷基胺的盐以及诸如此类表面活性剂。
两性表面活性剂的例子为烷基三甲铵己内脂类型、磷酸酯类型的两性表面活性剂。
优选非离子表面活性剂，使用的非离子表面活性剂为一种或多种的混合物，优选多种混合物。
按通常质量份数计，所述的高粘度有机硅组合物为100份，则乳化剂的总量选择为40～150份，优选60～110份。
根据对乳液粘度的要求，可加入增稠剂，增稠剂包括聚丙烯酰胺、卡波姆、汉生胶、聚丙烯酸酯、纤维素醚类，增稠剂的加量根据乳液的粘度调整。长期储存时需要加入杀菌剂和防腐剂，如次氯酸钠、山梨酸钾、均三嗪、凯松等。
制备乳液的方法有“剂在油中法”、“剂在水中法”和“初生皂法”等等，本发明人选用“剂在油中法”制备高粘度有机硅组合物的水分散乳液，具体方法如下：
将高粘度有机硅组合物和低分子量聚硅氧烷在强烈搅拌下充分混合5～60min，使得高粘度有机硅组合物与低分子量聚硅氧烷充分混合浸润，优选搅拌时间20～40min，然后再加入乳化剂，再搅拌5～60min，优选15～45min；完成后将上述体系的温度升高至55～85℃，然后，保持体系温度，缓慢地加水，提高搅拌速度使其由W/O型乳液变为O/W型乳液转相，继续加水至所需要的质量浓度，一般为20-60％，优选30-50％；乳液通过胶体磨进一步乳化；最后用水稀释到所需要的乳液浓度。
本发明方法制备的高粘度有机硅组合物乳液的性能主要从以下几个方面进行评估：
(1)水稀释液的稳定性：
按照1份的有机硅乳液加入到99份的水中，分散均匀后，观察水稀释液的液面状况。
(2)水稀释液的高温稳定性：
按照1份的有机硅乳液加入到99份的水中，升温后观察水稀释液的液面状况。
(3)乳液的抗剪切性能：
常温下，将乳液原液放置在水平振荡器上以6cm的振幅，100次/min的频率振荡30min，按照(1)的方法，比较水稀释液的液面状况。
(4)乳液消抑泡性能：
配制0.5％十二烷基苯磺酸钠的水溶液做起泡液，用100mL摇瓶加入配制好的50mL起泡液加入3‰乳液，将体系升温至60℃，摇瓶10次测试消泡性能，继续摇瓶200次测试抑泡性能。
具体实施举例
实施例1：
低分子量聚硅氧烷(LPS)的具体结构如下：
LPS-1：R为CH3，R1为CH3，s＝10，m＝50，n＝10，该聚硅氧烷的粘度为70mPa·s；
LPS-2：R为CH3，R1为OH，s＝250，m＝300，n＝2，该聚硅氧烷的粘度为800mPa·s；
LPS-3：R为CH3，R1为OH，s＝10，m＝30，n＝2，该聚硅氧烷的粘度为50mPa·s；
LPS-4：R为CH3，R1为NH2，s＝15，m＝100，n＝50，该聚硅氧烷的粘度为350mPa·s。
实施例2：高粘度有机硅组合物制备
参考US4639489中例1的制备方法制备高粘度有机硅组合物：将378g粘度为100,000mPa·s的聚二甲基硅氧烷和180g粘度为10,000mPa·s的两端羟基的聚硅氧烷以及18g正硅酸乙酯投入到反应釜瓶中，加热到130～140℃，然后向其中加入3g催化剂(催化剂的制备：90g粘度为1,000mPa·s的聚二甲基硅氧烷和10gKOH在120℃反应15min)，搅拌，继续加热。然后，向其中加入30g比表面积为200m2/g的白炭黑用均质机均质化。反应组合物加热到180℃，并维持4h，冷却到室温得到粘稠液体为高粘度有机硅组合物，粘度为400,000mPa·s。
实施例3：
取50份例2中的高粘度有机硅组合物和5份LPS-1在高速分散机中分散20min，均匀后向其中加入15份辛基酚聚氧乙烯(10)醚、10份N-90(聚氧丙烯醚改性聚硅氧烷，南京四新科技应用研究所有限公司自产)壬基酚聚氧乙烯(3)醚、12份失水山梨醇单硬脂酸酯和8份聚氧乙烯(20)失水山梨醇单硬脂酸酯，升温至60℃，以50Hz的频率搅拌30min，使得有机硅组合物和乳化剂充分混合均匀。然后向其中缓慢加入50份水，在转相时提高转速为65Hz，使得W/O型乳液充分转变成O/W型乳液，然后继续加50份水，此时粗乳液浓度为50％，通过均质机，进一步乳化，直到乳液的粒径达到10～30μm。然后快速降温至常温，并用800份丙烯酸增稠水溶液稀释成浓度为10％的乳液，加入0.2％次氯酸钠防腐剂。性能评估如表1所示。
实施例4：
取50份的例2中的高粘度有机硅组合物和8份LPS-2在高速分散机中分散30min，然后向其中加入10份失水山梨醇单油酸酯、12份聚氧乙烯(20)失水山梨醇单油酸酯、10份N-90和10份N-28(聚氧乙烯醚改性聚硅氧烷，南京四新科技应用研究所有限公司自产)，以50Hz的频率搅拌35min，使得有机硅组合物和乳化剂充分混合均匀。然后将上述混合物温度升高到75℃，向其中缓慢加入40份水，在转相时提高转速为65Hz，使得W/O型乳液转变成O/W型乳液，然后继续加60份水，此时粗乳液浓度为50％，通过均质机，进一步乳化，直到乳液的粒径达到10～30μm。然后快速降温至常温，并用800份丙烯酸增稠水稀释成浓度为10％的乳液，加入0.2％次氯酸钠防腐剂。性能评估如表1所示。
实施例5：
取50份的例2中的高粘度有机硅组合物，然后向其中加入10份LPS-3在高速分散机中分散25min，15份辛基酚聚氧乙烯(10)醚、10份辛基酚聚氧乙烯(3)醚、12份N-23(聚氧乙烯聚氧丙烯醚改性聚硅氧烷，南京四新科技应用研究所有限公司自产)和8份N-28，以45Hz的频率搅拌35min，使得上述有机硅混合物和乳化剂充分混合均匀。然后升高体系温度到70℃，向其中缓慢加入50份水，在转相时提高转速为60Hz，使得W/O型乳液转变成O/W型乳液，然后继续加50份水，此时粗乳液浓度为50％，通过均质机进一步乳化，直到乳液的粒径达到10～30μm。然后快速降温至常温，并用800份丙烯酸增稠水稀释成浓度为10％的乳液，加入0.2％次氯酸钠防腐剂。性能评估如表1所示。
实施例6：
取50份例2中的高粘度有机硅组合物，然后向其中加入15份LPS-4在高速分散机中分散20min充分混合，然后向上述体系中加入5份辛基酚聚氧乙烯(10)醚、3份辛基酚聚氧乙烯(3)醚、12份N-23、6份N-90和9份N-28，并以50Hz的频率搅拌35min，使得体系混合均匀。然后升高体系的温度至65℃，并缓慢地向其中加入60份水，在转相时提高转速为65Hz，使得W/O型乳液转变成O/W型乳液，然后继续加40份水，此时粗乳液浓度为50％，通过均质机，进一步乳化，直到乳液的粒径达到10～30μm。然后快速降温至常温，并用800份丙烯酸增稠水稀释成浓度为10％的乳液，加入0.2％次氯酸钠防腐剂。性能评估如表1所示。
对比例1：
取50份例2中的高粘度有机硅组合物，然后向其中加入15份的乳化剂辛基酚聚氧乙烯(10)醚、15份N-90(聚氧丙烯醚改性聚硅氧烷，南京四新科技应用研究所有限公司自产)壬基酚聚氧乙烯(3)醚、12份失水山梨醇单硬脂酸酯和8份聚氧乙烯(20)失水山梨醇单硬脂酸酯，升温至60℃，以50Hz的频率搅拌30min，使得有机硅组合物和乳化剂充分混合均匀。然后向其中缓慢加入50份水，在转相时提高转速为65Hz，使得W/O型乳液转变成O/W型乳液，然后继续加50份水，此时粗乳液浓度为50％，通过均质机，进一步乳化，直到乳液的粒径达到10～30μm。然后快速降温至常温，并用800份丙烯酸增稠水稀释成浓度为10％的乳液，加入0.2％次氯酸钠防腐剂。性能评估如表1所示。
对比例2：
取50份例2中的高粘度有机硅组合物，然后向其中加入10份辛基酚聚氧乙烯(10)醚、8份辛基酚聚氧乙烯(3)醚、12份N-23、11份N-90和9份N-28，并以50Hz的频率搅拌35min，使得体系混合均匀。然后升高体系的温度至65℃，并缓慢地向其中加入60份水，在转相时提高转速为65Hz，使得W/O型乳液转变成O/W型乳液，然后继续加40份水，此时粗乳液的浓度为50％，通过均质机，进一步乳化，直到乳液的粒径达到10～30μm。然后快速降温至常温，并用800份丙烯酸增稠水稀释成浓度为10％的乳液，加入0.2％次氯酸钠做防腐剂。性能评估如表1所示。
通过低分子量聚硅氧烷的加入能明显改善高粘度有机硅组合物分散液的稳定性和抗剪切性能。相比较而言，还是氨基硅油的加入对乳液稳定性的贡献大些。
Claims (3)
1、一种分散高粘度有机硅组合物于水中的方法，其特征在于向高粘度有机硅组合物中添加了低分子量聚硅氧烷和乳化剂组分：
(1)低分子量聚硅氧烷，其分子结构为：
其中m、n和s为聚合度，m为1～1000的整数，n为1～500的整数，s为1～1000的整数；R为碳原子数为1～20的烷基；R1为碳原子数为1～18烷基或氨烃基或羟基或卤原子，其中所述的氨烃基为-NH2、-NHCH2CH2NH2、-NHC2H4NHC2H4NH2或-OC6H4NH2；高粘度有机硅组合物按100份计，低分子量聚硅氧烷用量为5～50份；
(2)乳化剂，包括阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂，高粘度有机硅组合物按100份计，乳化剂用量为40～150份；
所述的一种分散高粘度有机硅组合物于水中的方法，实现的特征步骤为：
A、将高粘度有机硅组合物和低分子量聚硅氧烷在强烈搅拌下充分混合20～40min，使得高粘度有机硅组合物与低分子量聚硅氧烷充分混合浸润；
B、加入乳化剂，搅拌15～45min；
C、将体系的温度升高至55～85℃，然后保持体系温度，缓慢地加水，提高搅拌速度使其由W/O型乳液变为O/W型乳液转相，初步达到质量浓度为20～60％；
D、乳液通过胶体磨后，进一步乳化；
E、最后用水稀释为所需浓度。
2、权利要求1所述的一种分散高粘度有机硅组合物于水中的方法，其特征在于其中所述的低分子量聚硅氧烷的粘度为50～3,000mPa·s。
3、权利要求1所述的一种分散高粘度有机硅组合物于水中的方法，其特征在于其中所述的乳化剂为非离子表面活性剂。
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| US (1) | US8258192B2 (zh) |
| CN (1) | CN101348571B (zh) |
| WO (1) | WO2010025618A1 (zh) |
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| WO2010025618A1 (zh) * | 2008-09-02 | 2010-03-11 | 南京四新科技应用研究所有限公司 | 一种有机硅组合物乳液及其制备方法 |
| CN102120159A (zh) * | 2010-11-19 | 2011-07-13 | 苏州博纳化学科技有限公司 | 一种乳化硅油消泡剂的制备方法 |
| CN102199352A (zh) * | 2010-03-25 | 2011-09-28 | 日照岚星化工工业有限公司 | 一种水溶性有机硅乳液脱模剂的制备方法 |
| CN109912814A (zh) * | 2019-03-27 | 2019-06-21 | 江西蓝星星火有机硅有限公司 | 一种高粘度硅生胶乳液的制备方法和应用 |
| CN110564293A (zh) * | 2019-08-23 | 2019-12-13 | 山东易石环保新材料有限公司 | 一种高粘度有机硅乳液型烘缸/干网保洁剂的制备方法 |
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| RU2545274C2 (ru) * | 2009-11-11 | 2015-03-27 | БАСФ Констракшн Полимерс ГмбХ | Порошкообразная композиция |
| US9282772B2 (en) | 2012-01-31 | 2016-03-15 | Altria Client Services Llc | Electronic vaping device |
| ES2644316T3 (es) | 2012-02-22 | 2017-11-28 | Altria Client Services Llc | Artículo electrónico para fumar |
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| CN113355127A (zh) * | 2020-03-06 | 2021-09-07 | 成都华阳兴华化工有限公司 | 天然气井凝析油净化剂及其制备方法 |
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| JPS60251906A (ja) * | 1984-05-30 | 1985-12-12 | Dow Corning Kk | シリコ−ン消泡剤組成物の製造方法 |
| US4853474A (en) * | 1987-07-08 | 1989-08-01 | Dow Corning Corporation | Cross-linked organopolysiloxanes and emulsions based thereon |
| CA2077828A1 (en) * | 1991-10-10 | 1993-04-11 | William J. Raleigh | Silicone polyether alkyl copolymer synthesis |
| US5895794A (en) * | 1993-08-30 | 1999-04-20 | Dow Corning Corporation | Shelf stable cross-linked emulsions with optimum consistency and handling without the use of thickeners |
| US6001887A (en) * | 1993-12-17 | 1999-12-14 | Th. Goldschmidt Ag | Defoamer emulsion based on organofunctionally modified polysiloxanes |
| DE69803740T2 (de) * | 1997-11-17 | 2003-03-13 | Shinetsu Chemical Co | Wasser-in-Öl Polysiloxanemulsion und Verfahren zu ihrer Herstellung |
| GB9911840D0 (en) * | 1999-05-21 | 1999-07-21 | Dow Corning Sa | Siloxane emulsions |
| US6737444B1 (en) * | 2003-01-16 | 2004-05-18 | Dow Corning Corporation | Method of making silicone resin emulsions |
| DE102005002163A1 (de) * | 2005-01-17 | 2006-07-27 | Wacker Chemie Ag | Entschäumerzusammensetzungen |
| CN101652164A (zh) * | 2006-10-10 | 2010-02-17 | 陶氏康宁公司 | 硅氧烷泡沫控制剂 |
| CN101348571B (zh) * | 2008-09-02 | 2011-08-03 | 南京四新科技应用研究所有限公司 | 一种分散高粘度有机硅组合物于水中的方法 |
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- 2009-08-10 US US12/733,905 patent/US8258192B2/en active Active
- 2009-08-10 WO PCT/CN2009/000908 patent/WO2010025618A1/zh active Application Filing
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010025618A1 (zh) * | 2008-09-02 | 2010-03-11 | 南京四新科技应用研究所有限公司 | 一种有机硅组合物乳液及其制备方法 |
| US8258192B2 (en) | 2008-09-02 | 2012-09-04 | Zhiping Cao | Silicone composition emulsion and method for preparing the same |
| CN102199352A (zh) * | 2010-03-25 | 2011-09-28 | 日照岚星化工工业有限公司 | 一种水溶性有机硅乳液脱模剂的制备方法 |
| CN102120159A (zh) * | 2010-11-19 | 2011-07-13 | 苏州博纳化学科技有限公司 | 一种乳化硅油消泡剂的制备方法 |
| CN109912814A (zh) * | 2019-03-27 | 2019-06-21 | 江西蓝星星火有机硅有限公司 | 一种高粘度硅生胶乳液的制备方法和应用 |
| CN109912814B (zh) * | 2019-03-27 | 2021-09-10 | 江西蓝星星火有机硅有限公司 | 一种高粘度硅生胶乳液的制备方法和应用 |
| CN110564293A (zh) * | 2019-08-23 | 2019-12-13 | 山东易石环保新材料有限公司 | 一种高粘度有机硅乳液型烘缸/干网保洁剂的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20100249275A1 (en) | 2010-09-30 |
| US8258192B2 (en) | 2012-09-04 |
| CN101348571B (zh) | 2011-08-03 |
| WO2010025618A1 (zh) | 2010-03-11 |
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