CN114846054B - 包含支链硅氧烷的止泡剂组合物 - Google Patents
包含支链硅氧烷的止泡剂组合物 Download PDFInfo
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- CN114846054B CN114846054B CN201980103107.XA CN201980103107A CN114846054B CN 114846054 B CN114846054 B CN 114846054B CN 201980103107 A CN201980103107 A CN 201980103107A CN 114846054 B CN114846054 B CN 114846054B
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- organopolysiloxane
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- 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
- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08G77/32—Post-polymerisation treatment
-
- 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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- 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
- C08J3/28—Treatment by wave energy or particle radiation
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Abstract
通过用高能辐射照射式(1)的有机聚硅氧烷(X)来制备在消泡剂中使用的支链有机聚硅氧烷(A)，其中，R1和R2独立地是一价未取代的或卤化的饱和C1‑30或不饱和烃基、或氢，R3是氢或一价C1‑9烃基，a是0或1，n是整数，使得在25℃和1013hPa下，有机聚硅氧烷(X)的粘度是350‑20,000mPa sec，条件是在式(1)中，至多0.22mol％的a是1并且R2是H，使得在照射之后有机聚硅氧烷(A)的粘度比有机聚硅氧烷(X)的粘度高至少40％。R1 3‑a(R2O)aSi‑[OSiR3 2]n‑OSi(OR2)aR1 3‑a (1)。
Description
技术领域
本发明涉及通过用高能辐射处理直链聚合物制备支链有机聚硅氧烷(A)的方法，涉及支链有机聚硅氧烷(A)，涉及用于制备包含支链有机聚硅氧烷(A)的消泡剂制剂的方法和包含支链有机聚硅氧烷(A)的消泡剂制剂。
背景技术
在许多液体体系，更具体地水性体系(包括作为所希望的亦或不希望的组分的表面活性化合物)中，如果使这些体系与气态物质或多或少地强烈接触，例如当使废水气化时，当密集搅拌液体时，在蒸馏、洗涤、或着色操作中，或在分配程序期间，可能出现由于发泡引起的问题。
可以使用消泡剂机械地或化学地实现对这种泡沫的控制。在这种背景下，已经证明基于硅氧烷的消泡剂本身特别有用，更具体地，使用部分交联的聚二甲基硅氧烷。
支链有机聚硅氧烷流体的合成广泛地使用昂贵的贵金属催化剂(Rh、Pd、Pt)制备。EP0434060描述了包含交联的聚二有机硅氧烷流体的止泡剂化合物，该交联的聚二有机硅氧烷流体使用乙烯基封端的聚二有机硅氧烷和侧位官能化的有机氢聚硅氧烷(Si-H)通过铂催化的氢化硅烷化制备以产生交联的流体。这种方法需要去除催化剂并且可以导致含有溶解的催化剂种类的硅氧烷流体赋予硅氧烷流体颜色。此外，氢化硅烷化可能不能实现乙烯基官能化的二有机硅氧烷聚合物的完全转化，并且需要使用过量的有机氢聚硅氧烷聚合物。有机聚硅氧烷流体中残留的Si-H可能是有问题的并且对合成泡沫控制化合物提出挑战。US8053480要求仔细地选择乙烯基聚二有机硅氧烷和聚有机氢硅氧烷以确保氢化硅烷化良好地进行和控制。使用过量的不饱和脂族烃基产生最终交联的有机聚硅氧烷。
官能化的聚合物通常比非官能化的聚二有机硅氧烷聚合物诸如聚二甲基硅氧烷更昂贵。
US5531920描述了一种有机硅氧烷聚合物，其中主链由亚烯基组成并且需要使用铂催化剂与乙烯基和Si-H官能化的有机聚硅氧烷以产生适合于泡沫控制应用的化合物。
过渡金属络合物通常被认为是毒理学上不安全的，尤其是在高浓度下；因此，形成支链单元的无过渡金属途径将是高度令人期望的。此外，含Si-H硅氧烷的处理对湿气敏感，并且可以容易地进行水解并且导致形成凝胶状固体。
US7829647描述了一种使用铵或金属羧酸盐以及含Si-H的硅氧烷制备支链硅氧烷的方法。
残留的Si-H是有问题的。EP1678335描述了使用氢化硅烷化和与醇(ROH)脱氢偶联两者以从支链聚合物除去非反应性Si-H的方法。
US6573355描述了一种通过共水解使用碱性化合物诸如氢氧化钾以引起具有OH或烷氧基(Si-OR)官能度的聚二有机硅氧烷、聚二有机硅氧烷和环状二烷基硅氧烷低聚物的重排来制备支链有机聚硅氧烷的方法。该方法需要中和催化剂以停止直链和环状硅氧烷的平衡，并且必须进一步除去挥发性材料。大量(>0.1wt％)的环状硅氧烷是不期望的，并且这种方法可能对生产具有低环状硅氧烷含量的支链流体提出挑战。
可替换地，已经描述了产生支链流体结构的自由基方法。EP273448描述了在敏化剂的存在下使用辐射引发的聚合。DE 3805661描述了在高温下在有机过氧化物的存在下使用大气氧。
然而，在富含表面活性剂的强烈发泡体系中，根据现有技术生产的消泡剂制剂并不总是表现出足够的活性或由于所实现的高粘度和/或交联度而难以处理。
众所周知的硅酮可以使用高能辐射源诸如X射线、电子束和γ射线来辐射以引发交联和凝胶形成。(Palsule,AS,Clarson SJ,Widenhouse CW；J.Inorg.Organomet.Polym.2008,18,207-221)。用高能电子的辐射随机地产生辐射，该辐射在某个水平以上可以引起凝胶形成(由电子辐射生产的随机交联的聚(二甲基硅氧烷)网络的结构，大分子1993，26，20，5350-5364)。
US8541481描述了使用非官能化的有机聚硅氧烷的辐射来产生交联网络，这些交联网络被要求适合于硅酮凝胶粘合剂。硅酮凝胶的分子量更高并且表现出耐流动的特性。这种性能在通常需要在室温下具有流体特性的有机硅氧烷的泡沫控制化合物中是不期望的。
US9359529描述了使用电子束辐射以产生用于压敏粘合剂应用的交联的非官能化的有机聚硅氧烷，但没有描述使用官能化的有机聚硅氧烷，也没有描述产生在25℃下具有低于50,000mPa sec粘度范围的支链流体的方法。对于泡沫控制应用，在25℃下，期望具有粘度小于50,000mPa sec的有机聚硅氧烷流体，因为现有技术的泡沫控制化合物需要结合导致粘度增加的填料。由于加工时间和设备限制，太粘的经辐射的聚有机硅氧烷聚合物是不经济的。
发明内容
本发明提供了一种用于制备支链有机聚硅氧烷(A)的方法，其中，
通式(1)的有机聚硅氧烷(X)
R1 3-a(R2O)aSi-[OSiR3 2]n-OSi(OR2)aR1 3-a (1)，
其中，
R1和R2独立地是具有1-30个碳原子的一价未取代的或卤化的、饱和的或不饱和的烃基、或氢原子，
R3是氢原子或具有1-9个碳原子的一价烃基，
a是0或1，
n是整数，并且具有的值使得有机聚硅氧烷(X)的粘度在25℃和1013hPa下为350-20,000mPa sec，
条件是在通式(1)中，至多0.22mol％的a是1并且R2是H，
以有机聚硅氧烷(A)的粘度比有机聚硅氧烷(X)的粘度高至少40％的方式用高能辐射处理。
具体实施方式
支链有机聚硅氧烷(A)可以由直链有机聚硅氧烷(X)经济地制备，而无需使用催化剂，特别是Pt，并且避免了对环烷基硅氧烷和湿气敏感的Si-H官能化的有机聚硅氧烷聚合物的需要。
所得到的更粘的有机聚硅氧烷(A)具有交联，但是在常温下，诸如在25℃下，仍然可以具有液体特性。可以容易地监测该过程以避免不期望的凝胶形成。在不使用催化剂的情况下产生支链有机聚硅氧烷流体的能力对于环境问题和可持续性是高度有利的。有机聚硅氧烷(A)作为泡沫控制剂的成分是非常有用的。
高能辐射优选选自γ、X射线或电子束。优选的高能辐射源是电子束。
优选的剂量是10至150kGy、更优选20至100kGy每kg有机聚硅氧烷(X)。
在该方法中优选的温度是0至100℃、更优选10至50℃。
辐射的有机聚硅氧烷(A)具有无规支化并且具有在25℃下1000至80,000mPa sec范围内的优选粘度；更优选在25℃下1000至50,000mPa sec。
基团R1和R2可以是烷基、环烷基、烯基、芳基或芳烷基。优选地，R1和R2具有1-18个碳原子、更优选1-9个碳原子。基团R1和R2的实例是甲基乙基、乙烯基、辛基、2-丙烯基苯基和苯基。卤素取代的基团R1和R2的实例是卤代烃基，诸如3,3,3-三氟丙基。特别优选地，基团R1是甲基或乙烯基并且R2是甲基。
基团R3的实例是甲基、乙基、乙烯基、辛基、2-丙烯基苯基或苯基。特别优选地，基团R3是甲基。
在优选的实施方式中，R1的基团是甲基或乙烯基，但是出于经济考虑，甲基是最优选的。在一个优选的实施方式中，基团R1和R3是甲基并且基团R2选自甲基、乙基或氢基。
本发明进一步提供了通过上述方法可制备的支链有机聚硅氧烷(A)。
本发明进一步提供了一种用于制备消泡剂制剂的方法，其中，第一步骤是如以上描述的制备支链有机聚硅氧烷(A)，并且在第二步骤中，用填料(B)处理支链有机聚硅氧烷(A)，填料(B)选自沉淀二氧化硅或气相二氧化硅和有机聚硅氧烷树脂(C)。
本发明进一步提供可通过上述方法制备的消泡剂制剂。
在本发明的消泡剂制剂中使用的填料(B)优选具有20至1000m2/g的BET表面积。填料(B)优选具有小于10μm的粒径和小于100μm的团聚尺寸。
填料(B)的实例是二氧化硅(silicon dioxide(silicas))、二氧化钛、氧化铝、金属皂、精细研磨的石英、PTFE粉末、脂肪酸酰胺，例如亚乙基双硬脂酰胺以及精细分散的疏水聚氨酯。
优选使用的填充剂(B)是具有20至1000m2/g的BET表面积的二氧化硅、二氧化钛或氧化铝。这些填料优选具有小于10μm的粒径和小于100μm的团聚尺寸。
优选的填料(B)是二氧化硅，更具体地具有50至800m2/g的BET表面积的那些。这些二氧化硅可以是气相二氧化硅或沉淀二氧化硅。填料(B)可以是未处理的亲水性二氧化硅酶或预处理的。
根据本发明可以使用的商业疏水性二氧化硅的实例是
H2000，用六甲基二硅氮烷处理的并且具有140m2/g的BET表面积的气相二氧化硅(可以商购自德国的Wacker-Chemie GmbH)，以及沉淀的、聚二甲基硅氧烷处理的具有90m2/g的BET表面积的二氧化硅(可以以名称“Sipernat D10”商购自德国的Degussa AG)。
如果这有利于消泡剂制剂的期望活性，亲水性二氧化硅也可以原位疏水化。用于原位疏水化亲水性二氧化硅的方法是众所周知的。例如，在100至200℃的温度下，通过加热分散在如下所述的组分(A)或(C)中，或者分散在如下所述的组分(A)、(C)和任选地(E)的混合物中的二氧化硅，可以实现亲水性二氧化硅的原位疏水化，持续若干小时。可以通过添加催化剂诸如KOH、疏水化剂诸如短链、OH-封端的聚二甲基硅氧烷、硅烷或硅氮烷支持该反应。
在各种情况下，基于100重量份的组分(A)，消泡剂制剂以优选0.1至20重量份、更优选1至10重量份的量包含填料(B)。
有机聚硅氧烷树脂(C)优选是由下式的单元组成的MQ树脂：
SiO2(Q单元)和
R4 3SiO1/2(M单元)，
其中R4具有以上指定的R1的定义，优选C1-C4烷基并且最优选甲基。
在此，M与Q单元的摩尔比优选在0.5至2.0的范围内、更优选在0.6至1.0的范围内。除了M和Q单元之外，基于所有硅氧烷单元的总和，MQ树脂还可以以优选0.01至20mol％、更优选0.01至5mol％的量任选地包含少量的R4SiO3/2(T)单元或R4 2SiO2/2(D)单元。R4如以上所定义。这些有机聚硅氧烷可以进一步包括至多10wt％的游离、Si-键合的羟基或烷氧基，诸如甲氧基或乙氧基。
在25℃和1014.25hPa下，这些有机聚硅氧烷树脂(C)优选具有大于1000mPa·s的粘度或是固体。对于这些树脂通过凝胶渗透色谱法(相对于聚苯乙烯标准)确定的重均分子量优选是200至200,000g/mol、更具体地1000至20,000g/mol。
组分(B)与组分(C)的重量比优选为95:5至5:95，更具体地为80:20至20:80。
任选使用的组分(D)优选包含在周围大气压力下，即在900至1100hPa、具体地1014.25hPa下，具有大于100℃的沸点的水不溶性有机化合物，更具体地选自矿物油、天然油、异链烷烃、聚异丁烯、来自氧化合成法醇合成的残余物(来自羰基合成醇合成的残余物，residues from the oxo-process alcohol synthesis)、低分子量合成羧酸的酯的那些，诸如戊烷-1,3-二醇二异丁酸酯，脂肪酸酯，诸如硬脂酸辛酯、棕榈酸十二烷基酯、或肉豆蔻酸异丙酯、脂肪醇，低分子量醇的醚，邻苯二甲酸酯，磷酸的酯以及蜡。
组分(E)是碱金属和碱土金属氢氧化物，诸如NaOH、KOH、CsOH、LiOH和Ca(OH)2，或酸性组分(E)，诸如盐酸、硫酸和氮化磷氯化物。
(E)与组分(A)至(D)的反应产物包含例如优选作为填料(B)的二氧化硅与碱金属氢氧化物(诸如硅酸钾或硅酸钠)的产物。
组分(E)的计量可以在典型的有机溶剂诸如醇类(诸如甲醇、乙醇、异丙醇)或酯类(诸如乙酸乙酯)中进行。
在消泡剂制剂中使用的组分(B)至(E)在每种情况下可以是一种这样的组分或至少两种相应组分的混合物。
在每种情况下，在25℃和1014.25hPa下，消泡剂制剂具有优选100至2,000,000mPa·s、更优选10,000至80,000mPa·s的粘度。
消泡剂制剂可以通过已知的方法制备，诸如通过混合所有组分，诸如在胶体磨、溶解器、或转子-定子均化器中施加高剪切力。在这种情况下，混合操作可以在减压下进行，以便防止混入存在于精细分散的填料中的空气。例如，在需要的情况下，这可以通过原位疏水化填料来进行。
还可以首先引入并可能加热辐射的组分(A)，然后依次加入组分(B)、(C)、任选的(D)和任选的(E)。在一个优选的实施方式中，以溶解的形式将组分(C)作为溶液加入到组分(D)或组分(D)的部分中。
本发明还提供了包含消泡剂制剂的洗涤剂和清洁组合物，对于本领域技术人员而言，本发明可以进一步与介质配制成其乳液或粉末。消泡剂制剂可以在迄今还有可能使用消泡剂制剂的任何地方使用，即作为基于有机硅化合物的消泡剂和/或止泡剂。
消泡剂制剂可以在要抑制破坏性泡沫的任何地方使用。消泡剂制剂特别适合于在水性表面活性剂体系中控制泡沫，在洗涤剂中使用，在废水工厂中、在纺织品染色过程中、在天然气的洗涤中、在聚合物分散体中控制泡沫，和在纸浆生产中产生的水性介质消泡。
本发明进一步提供了通过混合消泡剂制剂使介质消泡和/或防止介质发泡的方法，对于本领域技术人员来说，可以将消泡剂制剂与介质进一步配制成其乳液或粉末。当消泡剂制剂是乳液时，可以使用技术人员已知的任何乳化剂用于制备硅酮乳液，诸如阴离子、阳离子或非离子乳化剂。例如，优选使用乳化剂混合物，在这种情况下应该存在至少一种非离子乳化剂，诸如脱水山梨醇脂肪酸酯、乙氧基化脱水山梨醇脂肪酸酯、乙氧基化脂肪酸、具有10至20个碳原子的乙氧基化直链或支链醇和/或甘油酯。此外，作为增稠剂，可以加入已知化合物诸如聚丙烯酸、聚丙烯酸酯，纤维素醚诸如羧甲基纤维素和羟乙基纤维素，天然增稠剂诸如黄原胶，例如聚氨酯，以及防腐剂和本领域技术人员已知的其他常规添加剂。本发明的乳液的连续相优选是水。然而，消泡剂制剂也可以以乳液的形式制备，其中，连续相由组分(A)至(E)形成或由水不溶性有机化合物(D)形成。例如，粉末在应用于衣物粉末洗涤剂的上下文中是优选的。从包含组分(A)至(C)和任选地(D)和任选地(E)的本发明的消泡剂制剂开始，通过本领域技术人员已知的方法，诸如喷雾干燥或凝聚造粒，以及用本领域技术人员已知的添加剂完成这些粉末的生产。本发明的粉末优选包含2至20重量％的包含组分(A)至(C)和任选地(D)和任选地(E)的消泡剂制剂。所用的载体可以是例如沸石、硫酸钠、碳酸氢钠、碳酸钠、纤维素衍生物、脲(衍生物)和糖。本发明的粉末包含80至98wt％的载体材料。本发明的粉末的另外的组分可以是例如蜡或有机聚合物。
在以下实施例中，除非另外指明，所有份数和百分比均涉及重量。除非另外指明，在周围大气压力下，即在1014.25hPa下，以及在室温下，即20℃下，或在当反应物在室温下合并而没有另外的加热或冷却时产生的温度下进行以下实施例。
在实施例中引用的所有粘度数字旨在基于25℃的温度和1014.25hPa的压力。使用布氏粘度计(用转子S64以10至100的RPM速度测量实施例的粘度。
实例1-6-辐射有机聚硅氧烷(X)以制备有机聚硅氧烷(A)
如在组分(X)中描述的有机聚硅氧烷流体(AK1000和AK2000是聚二甲基硅氧烷，ViPo1000是乙烯基封端的聚二甲基硅氧烷，可商购自德国的Wacker-Chemie GmbH)并且按接收时的状态使用，任选地，在辐射之前，使组分X经受脱气处理，称为“脱气”。流程如下：将1kg的有机聚硅氧烷流体放置在具有搅拌器的反应器中，并且放置在动态真空(500hPa)下，直到观察不到另外的气泡，持续10分钟，重新填充氮气(1014.25hPa)，并且重复3次。将所有样品密封在适合于辐射测试的容器中。γ辐射试验在位于Albuquerque,NM的圣地亚国家实验室进行。X射线辐射试验在位于Edgewood,NY的IBA工业中进行。电子束试验在位于Lebanon,OH的电子束集团进行。
表1
实施例1-6举例说明了辐射在有机聚硅氧烷流体(X)中诱导交联的能力。非官能化的有机聚硅氧烷(X)的用途在实施例1、2、3和5中展示。在实施例4和6中说明了官能化的有机聚硅氧烷(X)的用途。两种流体都适于辐射并且当暴露于高能辐射时显示出粘度增加。
液体洗涤剂中的消泡剂有效性的测试
实施例7和对比实验V1-使用辐射的实施例1、5和6生产本发明的消泡剂制剂。
为了生产消泡剂制剂，使用溶解器混合表2中描述的物质并且在1500ppm的KOH(在甲醇中浓度为20％的溶液形式的组分E)存在下在150℃下加热4h；冷却之后，用溶解器再次进行均化。
表2
A1：具有300m2/g的BET表面积的亲水性气相二氧化硅(可以以名称
T30从德国的Wacker Chemie AG获得)
B1：一种硅酮树脂，在室温下是固体并且由(根据29Si-NMR和IR分析)40mol％的CH3SiO1/2、50mol％的SiO4/2、8mol％的C2H5OSiO3/2和2mol％的HOSiO3/2单元组成，具有7900g/mol的重均摩尔质量(相对于聚苯乙烯标准)
C1：一种具有235-270℃沸程的烃混合物。
D1：用三甲基硅氧烷基团封端并且具有8000mPa sec粘度的非官能直链聚二甲基硅氧烷)
洗涤剂体系中的测试
用于测试消泡剂活性的测量系统：使用以下条件，使用旋转圆筒测试来测试实施例7a-i和比较C1：将实施例制备为在甲基乙基酮中的10wt％溶液，然后添加(100μL)到包含在300份蒸馏水中的1.8份洗涤剂(如表3中所述)的圆筒中。将这些圆筒密封并且以30rpm旋转12min。在循环结束时立即记录泡沫高度(mm)。较低的高度表明更有效的消泡剂，即更好的性能。
衣物洗涤剂制剂W1的生产：
在剧烈搅拌下，向65.09g的完全脱矿质水中加入16.80g的烷氧基化的脂肪醇(可以以名称
TO 8从BASF SE获得)。加入5.70g十二烷基苯磺酸钠(作为工业产品从Aldrich获得)和5.70g十二烷基硫酸钠(作为90％产品从Aldrich获得)，随后一起短暂搅拌。将5.61g的1,2-丙二醇(可从Merck获得)混合于其中。最后，在搅拌下加入1.00g的柠檬酸三钠二水合物(可从Aldrich可获得)直到所有成分都在溶液中。对于本领域技术人员而言，水性液体洗涤剂组合物还可以如EP3310451中所述制备。
表3
在黑液(black liquor)中测试
在恒温80℃的1000ml循环泵送装置中，以83.6L/h的泵送速率在循环中泵送400ml合成黑液。对于本领域的技术人员来说，制备合成黑液以代表来自如US6207722中所述的商业纸浆工艺的商业黑液。
一旦泡沫水平达到75mm的高度，计量加入消泡剂(在消泡剂制剂中10mg，基于组分(A)至(C)，任选地(D)和任选地(E))，并记录泡沫坍缩时间和加入消泡剂和随后泡沫坍缩之后达到的最低泡沫水平。泡沫坍缩时间t1越小并且泡沫水平h1越低，消泡剂的快速效果越好。之后，确定消泡剂的长期效果，表示从最低泡沫水平至初始泡沫水平(50mm)所需的时间间隔t2。
实施例8a-g和对比实验V2-使用辐射的实施例1、5和6生产本发明的消泡剂制剂。
为了生产消泡剂制剂，使用溶解器混合表4中描述的物质并且在1500ppm的KOH(在甲醇中以20％浓度的溶液的形式)存在下在150℃加热3h；冷却之后，用溶解器再次进行均化。实施例8a-g被制备为在矿物油中的40wt％溶液，并且然后添加(10μL)
表4
表5
本发明的实施例显示它们本身在黑液的消泡中是高效的。实施例8a-g举例说明了与对比制剂V2相比，使用支链有机聚硅氧烷流体消泡化合物的有效性。本发明的实施例8a-g在泡沫坍缩时间(t1)上是优越的，并且实施例8a、b、d、f和g显示出在长期效应(t2)方面的有效性。
Claims (7)
1.一种用于制备消泡剂制剂的方法，包括：在第一步骤中，通过辐照式(1)的有机聚硅氧烷(X)制备支链有机聚硅氧烷(A)
R1 3-a(R2O)aSi-[OSiR3 2]n-OSi(OR2)aR1 3-a(1)，
其中，
R1和R2独立地是具有至多30个碳原子的一价未取代的或卤化的、烷基或环烷基、或氢，
R3是甲基、乙基、乙烯基、辛基或、2-丙烯基苯基，
a是0或1，
n是整数，并且具有的值使得所述有机聚硅氧烷(X)的粘度在25℃和1013hPa下为350-4800mPa sec；
条件是在式(1)中，至多0.22mol％的a是1并且R2是H，
以高能辐射的方式，使得所述有机聚硅氧烷(A)的粘度比所述有机聚硅氧烷(X)的粘度高至少40％，以及
在第二步骤中，用填料(B)处理所述支链有机聚硅氧烷(A)，所述填料(B)选自沉淀二氧化硅、气相二氧化硅和有机聚硅氧烷树脂(C)。
2.根据权利要求1所述的方法，其中，所述填料(B)具有20至1000m2/g的BET表面积。
3.根据权利要求1或2所述的方法，其中，所述填料(B)选自气相二氧化硅或沉淀二氧化硅。
4.根据权利要求1或2所述的方法，其中，所述有机聚硅氧烷树脂(C)是由下式的单元组成的MQ树脂
SiO2(Q单元)和
R4 3SiO1/2(M单元)，其中
R4是具有1-30个碳原子的一价未取代的或卤代的、饱和烃基、或氢原子。
5.根据权利要求1或2所述的方法，其中，存在水不溶性有机化合物组分(D)，所述水不溶性有机化合物组分(D)在1013hPa下具有大于100℃的沸点，所述水不溶性有机化合物组分(D)选自矿物油、天然油、异链烷烃、聚异丁烯、来自氧化合成法醇合成的残余物、低分子量合成羧酸的酯、脂肪酸酯、脂肪醇、低分子量醇的醚、邻苯二甲酸酯、磷酸的酯以及蜡。
6.根据权利要求1或2所述的方法，其中，存在组分(E)，所述组分(E)选自碱金属和碱土金属氢氧化物或酸性组分。
7.根据权利要求1至6中任一项所述的方法制备的消泡剂制剂。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0184598A1 (en) * | 1984-12-06 | 1986-06-18 | Toray Silicone Company Limited | Ultraviolet and electron-beam curable polyorganosiloxane composition |
| JPS61255934A (ja) * | 1985-05-08 | 1986-11-13 | Sumitomo Electric Ind Ltd | シリコンポリマ−の製造方法 |
| EP0233752A2 (en) * | 1986-02-14 | 1987-08-26 | Shin-Etsu Chemical Co., Ltd. | A method for the preparation of a cured organopolysiloxane composition |
| WO2010056544A1 (en) * | 2008-10-29 | 2010-05-20 | 3M Innovative Properties Company | Gentle to skin adhesive |
| WO2012069794A1 (en) * | 2010-11-25 | 2012-05-31 | Smith & Nephew Plc | Composition i-ii and products and uses thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63185411A (ja) | 1986-12-30 | 1988-08-01 | ユニオン・カーバイド・コーポレーシヨン | シリコーン消泡剤 |
| DE3805661A1 (de) | 1988-02-24 | 1989-09-07 | Henkel Kgaa | Verfahren zur herstellung von schauminhibitoren |
| JPH0779930B2 (ja) | 1989-12-20 | 1995-08-30 | ダウコーニングアジア株式会社 | シリコーン消泡剤組成物 |
| US5531920A (en) | 1994-10-03 | 1996-07-02 | Motorola, Inc. | Method of synthesizing alkaline metal intercalation materials for electrochemical cells |
| US6207722B1 (en) | 1998-12-31 | 2001-03-27 | Dow Corning Corporation | Foam control compositions having resin-fillers |
| JP3724782B2 (ja) | 2000-07-11 | 2005-12-07 | 信越化学工業株式会社 | 分岐型オルガノポリシロキサンの製造方法 |
| US20050076975A1 (en) | 2003-10-10 | 2005-04-14 | Tenaris Connections A.G. | Low carbon alloy steel tube having ultra high strength and excellent toughness at low temperature and method of manufacturing the same |
| DE102004040263A1 (de) * | 2004-08-19 | 2006-02-23 | Wacker-Chemie Gmbh | Entschäumerzusammensetzungen |
| DE102005007313A1 (de) * | 2005-02-17 | 2006-08-24 | Wacker Chemie Ag | Verfahren zur Herstellung von Entschäumerformulierungen |
| GB0610622D0 (en) | 2006-05-31 | 2006-07-05 | Dow Corning | Process for making and using foam control compositions |
| US7768605B2 (en) | 2006-06-30 | 2010-08-03 | Motorola, Inc. | Display stack-up for a mobile electronic device having internal and external displays |
| DE102007037292A1 (de) | 2007-08-07 | 2009-02-12 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung von verzweigten Polyorganosiloxanen |
| BRPI0919627A8 (pt) | 2008-10-29 | 2018-12-18 | 3M Innovative Properties Co | materiais de silicone curados com feixe de elétrons |
| DE102016203346A1 (de) | 2016-03-01 | 2017-09-07 | Wacker Chemie Ag | Entschäumerzusammensetzungen für Waschmittel |
| JP7280220B2 (ja) | 2020-06-05 | 2023-05-23 | 花王株式会社 | 脱泡促進用組成物 |
| CN114712899A (zh) | 2022-03-15 | 2022-07-08 | 广州崃克保新材料科技有限公司 | 一种水性纳米环保消泡剂及其制备方法 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0184598A1 (en) * | 1984-12-06 | 1986-06-18 | Toray Silicone Company Limited | Ultraviolet and electron-beam curable polyorganosiloxane composition |
| JPS61255934A (ja) * | 1985-05-08 | 1986-11-13 | Sumitomo Electric Ind Ltd | シリコンポリマ−の製造方法 |
| EP0233752A2 (en) * | 1986-02-14 | 1987-08-26 | Shin-Etsu Chemical Co., Ltd. | A method for the preparation of a cured organopolysiloxane composition |
| WO2010056544A1 (en) * | 2008-10-29 | 2010-05-20 | 3M Innovative Properties Company | Gentle to skin adhesive |
| WO2012069794A1 (en) * | 2010-11-25 | 2012-05-31 | Smith & Nephew Plc | Composition i-ii and products and uses thereof |
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