CN1169515C - 制备硅氧烷弹性体的方法 - Google Patents

制备硅氧烷弹性体的方法 Download PDF

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CN1169515C
CN1169515C CNB971255156A CN97125515A CN1169515C CN 1169515 C CN1169515 C CN 1169515C CN B971255156 A CNB971255156 A CN B971255156A CN 97125515 A CN97125515 A CN 97125515A CN 1169515 C CN1169515 C CN 1169515C
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W・J・小舒尔茨
W·J·小舒尔茨
张世中
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Abstract

用硅氧烷弹性体增粘低分子量的硅氧烷流体。通过含≡Si-H的聚硅氧烷和诸如α，ω-二烯的不饱和烃在低分子量硅氧烷流体存在下的交联反应制备硅氧烷弹性体。含≡Si-H的聚硅氧烷首先部分地与单烯官能的聚醚反应。然后，在低分子量硅氧烷流体存在下通过α，ω-二烯交联。生成一种有聚醚基的弹性体，即凝胶。硅氧烷弹性体可在剪切力下用低分子量硅氧烷流体溶胀，得到均匀的硅氧烷浆料。硅氧烷浆料有极好研磨延展性并且由于是触变的和剪切稀化的而表现出独特的流变性质。不使用能将一般不可混合的材料变得紧密混合的表面活性剂，硅氧烷浆料可容易地用水乳化生成稳定均匀的乳液。

Description

制备硅氧烷弹性体的方法
本发明涉及增粘的低分子量硅氧烷流体或溶剂，是聚硅氧烷弹性体在聚硅氧烷凝胶和聚硅氧烷浆液中溶胀的形式，可形成聚硅氧烷乳液。
交联是聚合物纤维三维网状地结合。可看成长链分支，其为数众多以致形成连续不可溶的网络或凝胶。
铂催化的氢化甲硅烷化反应越来越多地被用于网络的形成。其一般包括在含若干≡Si-H基的低分子量硅氧烷和含若干≡Si-乙烯基的高分子量硅氧烷(反之亦然)之间进行的反应。
这个机理引人注意的特性是(1)不形成副产物；(2)交联点和因此形成的网络结构可被精确规定；(3)甚至可在室温进行氢化甲硅烷化反应形成网络。在这个机理中，交联涉及在双键两端的≡SiH加成，即
；
或交联涉及在三键两端的≡SiH加成，即
。
我们已经使用了这个机理，但通过使用一些非显而易见的和独特的对该机理的改进，我们已经能构造具有新的独特性质的产品形式的新范围和应用范围。特别是，一个独特的方面是我们的硅氧烷浆料无需表面活性剂就可用来形成乳液。这在私人护理方面会有重要的价值，因为一定的表面活性剂的存在会导致皮肤过敏。
我们的发明涉及一种制备硅氧烷弹性体的方法，在第一步将(A)含≡Si-H的聚硅氧烷和(B)单烯聚醚在铂催化剂存在下反应，直到生成有聚醚基团的含≡Si-H的硅氧烷。在第二步中，将(C)有聚醚基团的含≡Si-H硅氧烷和(D)诸如α，ω-二烯的不饱和烃在(E)一种溶剂和铂催化剂存在下反应，直到通过交联和≡SiH在α，ω-二烯的双键两端的加成生成硅氧烷弹性体。
作为我们的发明的另一个特性，在硅氧烷弹性体中加入另外的溶剂，并且搅拌溶剂和硅氧烷弹性体直至形成硅氧烷浆料。
作为我们的发明的再一个特性，在硅氧烷浆料中加入水，并且搅拌水和硅氧烷浆料直到形成硅氧烷乳液。在没有表面活性剂存在下形成硅氧烷乳液。
根据这些方法制备的硅氧烷弹性体、硅氧烷浆料和硅氧烷乳液在人体毛发、皮肤或腋下区域的处理方面有特殊价值和效用。此外，在蒸发任何溶剂或挥发成分后，硅氧烷弹性体，硅氧烷浆料和硅氧烷乳液可形成阻隔薄膜。
我们的发明和进行根据我们的方法的各个步骤可参照如下所述的过程详细说明。
步骤1：聚醚的连接
≡SiH硅氧烷+单烯基聚醚+铂催化剂→有聚醚基的≡SiH硅氧烷
步骤2：凝胶化
有聚醚基的≡SiH硅氧烷+≡SiH硅氧烷(任选)+α，ω-二烯+低分子量硅氧烷液体+铂催化剂→凝胶(弹性体)
步骤3：搅拌和溶胀
凝胶/弹性体+低分子量硅氧烷流体→浆料
步骤4：乳化
硅氧烷浆料+水+搅拌→硅氧烷乳液
在步骤1中，聚醚与在≡SiH硅氧烷中的≡SiH的摩尔比应在0和1之间。
在步骤2中，低分子量硅氧烷流体与有聚醚基团和α，ω-双烯的≡SiH硅氧烷的重量比可以是1-98，但优选3-10。有聚醚基团的≡SiH硅氧烷和α，ω-二烯的摩尔比可以是20∶1-1∶20，但优选1∶1。同时步骤2可包括不同类型的化合物的混合物，至少一种含≡SiH的硅氧烷必须包括一个聚醚基团。
例如，发现了一个特别适合步骤2的配方，是含有下列化合物的混合物：Me3SiO(Me2SiO)50[MeQSiO]4(MeHSiO)5SiMe3、HSiMe2O(Me2SiO)10SiHMe2、Me3SiO(Me2SiO)8(MeHSiO)4SiMe3、1，5-己二烯和十甲基环戊硅氧烷。在这些分子式中，Me是甲基，Q是-CH2CH2CH2(CH2CH2O)10H。
在步骤3，硅氧烷浆料应含80-98％wt的低分子量硅氧烷流体或其它流体或溶剂用以增粘。
在步骤4，水与硅氧烷浆料的重量比可以是95∶5-5∶95。
代表性的含≡SiH聚硅氧烷是称为A1型的式R3SiO(R′2SiO)a(R″HSiO)bSiR3化合物和称为A2型的式HR2SiO(R′2SiO)cSiR2H化合物或式HR2SiO(R′2SiO)a(R″HSiO)bSiR2H化合物。在这三分子式中，R、R′和R”是1-6个碳原子的烷基；a是0-250；b是1-250；c是0-250。化合物A2∶A1的摩尔比是0-20，优选0-5。在一个优选的实施方案中，在反应中使用A1和A2型化合物，但能够只用A1型化合物成功地进行反应。
含≡Si-H的聚硅氧烷A1还可含有式(R′2SiO)a(R″HSiO)b表示的烷基氢环硅氧烷或烷基氢二烷基环硅氧烷共聚物，其中R′、R″、a和b的定义如上文。优选a是0-7；b是3-10。一些代表性的化合物是(OSiMeH)4、(OSiMeH)3(OSiMeC6H13)、(OSiMeH)2(OSiMeC6H13)2、(OSiMeH)(OSiMeC6H13)3，其中Me是-CH3。
最优选的不饱和烃是式CH2＝CH(CH2)XCH＝CH2的α，ω-二烯，其中X是1-20。适用的α，ω-二烯的一些代表性例子是1，4-戊二烯、1，5-己二烯、1，6-庚二烯、1，7-辛二烯、1，8-壬二烯、1，9-癸二烯、1，11-十二双烯、1，13-十四双烯和1，19-二十双烯。
但是，也可以使用其它不饱和烃，诸如，式CH≡C(CH2)XC≡CH的α，ω-二炔；或式CH2＝CH(CH2)XC≡CH的α，ω-烯炔，其中X是1-20。可在此使用的适合的一些代表性α，ω-二炔的例子是1，3-丁二炔HC≡C-C≡CH和1，5-己二炔(联炔丙基dipropargyl)HC≡C-CH2CH2-C≡CH。可在此使用的合适的一个代表性α，ω-烯炔的例子是己烯-5-炔-1 CH2＝CHCH2CH2C≡CH。
在步骤1和2的反应需要一种催化剂来影响含≡SiH硅氧烷、单烯基聚醚和α，ω-二烯之间的反应。适合的催化剂是VIII族过渡金属，即贵金属。在US3923705中描述了这类贵金属催化剂。一种优选的铂催化剂是Karstedt催化剂，在US3715334和3814730中描述了这种催化剂。Karstedt催化剂是铂二乙烯基四甲基二硅氧烷配合物，一般含有约1％wt的铂，附载在聚二甲基硅氧烷流体中或在诸如甲苯的一种溶剂中。在我们的实施例中使用的特别的催化剂是附载在2厘斯(mm2/s)的聚二甲基硅氧烷流体中的1％wt铂的20μl和200μl级的Karstedt催化剂。另一个优选的铂催化剂是在US3419593中描述的端基脂族不饱和的有机硅化合物与氯铂酸的反应产物。贵金属催化剂的用量为每100重量份含≡SiH的聚硅氧烷用0.00001-0.5份，优选0.00001-0.02份，最优选0.00001-0.002份。
单烯聚醚是式CH2＝CH(CH2)XO(CH2CH2O)Y(CH2CH3CHO)ZT化合物或式CH2-CH-Q-O(CH2CH2O)Y(CH2CH3CHO)ZT化合物。式中T表示端基，可以是H；C1-C10烷基，诸如甲基、乙基、丙基、丁基和癸基；芳基，诸如苯基；或C1-C20酰基，诸如乙酰基、丙酰基、丁酰基、月桂酰基、肉豆寇酰基和硬脂酰基。Q是二价不饱和连接基团，诸如亚苯基-C6H4-。x的值是1-6；y可以是0或1-100的值；z可以是0或1-100的值；条件是y和z不能同时为0。
低分子量的硅氧烷流体可以是(1)低分子量线形或环状挥发性甲基硅氧烷；(2)低分子量线形或环状挥发性或非挥发性烷基或芳基硅氧烷；或(3)低分子量线形或环状官能硅氧烷，但最优选的是低分子量线形或环状挥发性甲基硅氧烷(VMS)。
VMS化合物具有式(CH3)aSiO(4-a)/2的平均单元，平均值为2-3。含硅氧烷单元的化合物通过≡Si-O-Si≡键相连。代表性的单元是单官能的“M”单元(CH3)3SiO1/2和双官能的“D”单元(CH3)2SiO2/2。
三官能“T”单元CH3SiO3/2的存在导致支化线型或环状挥发性甲基硅氧烷的生成。四官能的“Q”单元SiO4/2的存在导致支链或环状挥发性甲基硅氧烷生成。
线形VMS具有式(CH3)3SiO{(CH3)2SiO}YSi(CH3)3。y值为0-5。环状VMS具有式{(CH3)2SiO}z。z值为3-8，优选3-6。这些挥发性甲基硅氧烷的沸点一般低于250℃，粘度为0.65-5.0厘斯(mm2/s)。
这些挥发性甲基硅氧烷可表示为：
(I)线形
(II)环形
(III)支化线形
(IV)带支链的环形
一些代表性的线形挥发性甲基硅氧烷(I)是沸点100℃、粘度0.65mm2/s的式Me3SiOSiMe3的六甲基二硅氧烷(MM)；沸点152℃、粘度1.04mm2/s的式Me3SiOMe2SiOSiMe3的八甲基三硅氧烷(MDM)；沸点194℃、粘度1.53mm2/s的式Me3SiO(Me2SiO)2SiMe3的十甲基四硅氧烷(MD2M)；沸点229℃、粘度2.06mm2/s的式Me3SiO(Me2SiO)3SiMe3的十二甲基五硅氧烷(MD3M)；沸点245℃、粘度2.63mm2/s的式Me3SiO(Me2SiO)4SiMe3的十四甲基六硅氧烷(MD4M)；沸点270℃、粘度3.24mm2/s的式Me3SiO(Me2SiO)5SiMe3的十六甲基七硅氧烷(MD5M)。
一些代表性的环状挥发性甲基硅氧烷(II)是沸点为134℃式{(Me)2SiO}3的六甲基环三硅氧烷(D3)固体；沸点176℃，粘度2.3mm2/s的式{(Me1)SiO}4的八甲基环四硅氧烷(D4)；沸点210℃，粘度3.87mm2/s的式{(Me2)SiO}5的十甲基环五硅氧烷(D5)；沸点245℃，粘度6.62mm2/s的式{(Me2)SiO}6的十二甲基环六硅氧烷(D6)。
一些代表性的支化挥发性甲基硅氧烷(III)和(IV)是沸点192℃、粘度1.57mm2/s的式C10H30O3Si4的七甲基-3-{(三甲基甲硅烷基)氧基}三硅氧烷(M3T)；沸点222℃、粘度2.86mm2/s的式C12H36O4Si5的六甲基-3，3-双{(三甲基甲硅烷基)氧基}三硅氧烷(M4Q)；式C8H24O4Si4的五甲基{(三甲基甲硅烷基)氧基}环三硅氧烷(MD3)。
我们的方法还可以包括使用低分子量的线形或环状、挥发性或非挥发性、烷基和芳基硅氧烷。代表性的线形硅氧烷是式R3SiO(R2SiO)ySiR3的化合物，代表性的环状硅氧烷是式(R2SiO)Z的化合物。R是2-6个碳原子的烷基或诸如苯基的芳基。Y值是0-80，优选0-20。Z值是0-9，优选4-6。这些硅氧烷的粘度一般在约1-100厘斯(mm2/s)范围内。
其它代表性的低分子量非挥发性硅氧烷具有通式：
Figure C9712551500091
其中n是使聚合物粘度在约100-1000厘斯(mm2/s)范围内的值。
R1和R2是2-20个碳原子的烷基，芳基，如苯基，或-官能基。n值一般是约80-375。具体的硅氧烷是聚二乙基硅氧烷、聚甲基乙基硅氧烷、聚甲基苯基硅氧烷和聚二苯基硅氧烷。
代表性的低分子量的官能硅氧烷可以是丙烯酰胺官能硅氧烷流体、丙烯酸酯官能的硅氧烷流体、酰胺官能的硅氧烷流体、氨基官能的硅氧烷流体、甲醇官能的硅氧烷流体、羧基官能的硅氧烷流体、氯烷基官能的硅氧烷流体、环氧官能的硅氧烷流体、二醇官能的硅氧烷流体、缩酮官能的硅氧烷流体、缩硫醇官能的硅氧烷流体、甲酯官能的硅氧烷流体、全氟官能的硅氧烷流体和硅烷醇官能的硅氧烷。
我们的发明不局限于仅用低分子量硅氧烷流体溶胀硅氧烷弹性体。其它类型的溶剂也可用于溶胀硅氧烷弹性体，并且可以用一种溶剂或各种溶剂的混合物。
因此，我们所指的溶剂是(1)有机化合物、(2)含硅原子的化合物、(3)有机化合物的混合物、(4)含硅原子的化合物的混合物或(5)有机化合物与含硅原子的化合物的混合物。这些定义预计化合物以工业规模用于其它材料的溶解、悬浮或物理性质的改变。
通常，有机化合物可以是芳烃类、脂族烃类、醇类、醛类、酮类、胺类、酯类、醚类、二醇类、二醇醚类、卤代烷或卤代芳烃。一些代表性的更常用的有机溶剂是醇类，诸如甲醇、乙醇、1-丙醇、环己醇、苄基醇、2-辛醇、-乙二醇、丙二醇和丙三醇；脂族烃类，诸如戊烷、己烷、环己烷、庚烷、Varnish Makers & Painters溶剂(naptha)和石油溶剂油；卤代烷类，诸如氯仿、四氯化碳、全氯乙烯、氯乙烷和氯苯；胺类，诸如异丙胺、环己胺、乙醇胺和二乙醇胺；芳烃类，诸如苯、甲苯、乙苯和二甲苯；酯类，诸如乙酸乙酯、乙酸异丙酯、乙酰乙酸乙酯、乙酸戊酯、异丁酸异丁酯和乙酸苄酯；醚类，诸如乙醚、正丁醚、四氢呋喃和1，4-二噁烷；二醇醚类，诸如乙二醇单甲醚、乙醇酸乙二醇单甲醚酯、二甘醇单丁基醚和丙二醇单苯基醚；酮类，诸如丙酮、甲基乙基酮、环己酮、双丙酮醇、甲基戊基酮和二异丁基酮；石油烃类，诸如矿物油、汽油、石脑油、煤油、粗柴油、重油和原油；润滑油类，诸如锭子油和汽轮机油；脂油类，诸如玉米油、豆油、橄榄油、菜子油、棉子油、沙丁鱼油、鲱鱼油和鲸油。
还可以使用其它各种有机溶剂，诸如乙腈、硝基甲烷、二甲基甲酰胺、1，2-环氧丙烷、三辛基磷酸酯、丁内酯、糠醛、松油、松节油和间-甲氧甲酚。
我们还要在溶剂的定义中包括挥发性调味剂，诸如冬青油；薄荷油；薄荷醇；香草属；肉桂油；丁子香油；月桂油；茴香油；桉树油；百里香油；雪松叶油；肉豆蔻油；鼠尾草油；肉桂油；可可；甘草；高果糖玉米糖浆；柑橘油，诸如柠檬、橙子、白柠檬和柚子；水果香精，诸如苹果、梨、桃、葡萄、草莓、覆盆子、樱桃、柚、菠萝和杏；其它有用的调味剂，包括醛类和酯类，诸如乙酸肉桂酯、肉桂醛、富马酸丁子香酯、对甲基茴香醚、乙醛、苯甲醛、茴香醛、柠檬醛、橙花醛、癸醛、香草醛、甲苯基醛、2，6-二甲基辛醛和2-乙基丁醛。
另外，我们要在溶剂的定义中包括挥发性芳香物质，诸如天然产物和芳香油。一些代表性的天然产物和芳香油是龙涎香、安息香、灵猫香、丁子香、叶油、茉莉、冬青茶、含羞草、麝香、没药、鸢尾油、檀香油、须芒草油；合成香料，诸如水杨酸戊酯、戊基肉桂醛、乙酸苄酯、香茅醇、香豆素、香叶醇、乙酸异冰片酯、黄葵和乙酸松油酯；不同类族的香料油，诸如花香型族、东方香型族、素心兰族、木香族、柑橘香型族、canoe族、皮革香型族、辛香型族和草药香族。
分步进行本方法，结合含≡SiH的硅氧烷、单烯基聚醚、α，ω-二烯、低分子量硅氧烷或溶剂以及铂催化剂；在室温混合这些成分直至生成凝胶、弹性体、浆料或乳液。如果需要，凝胶、弹性体、浆料或乳液可用另外的相同或不同的溶剂稀释成最终的组合物。可以使用的稀释剂的例子是己烷和四氢呋喃的混合物、香料物质、油或另一种低分子量硅氧烷。可用较高的温度加快反应。
在凝胶中加入额外量的低分子量硅氧烷或溶剂，即步骤3，生成的混合物在剪切力作用下形成浆料。在步骤4，在向浆料加入水形成乳液期间或之后，再次使用剪切力。可以用任何类型的混合和搅拌设备进行这些步骤，诸如分批混合器、行星式混合器、单或多螺杆挤压机、动态或静态混合器、胶体磨、均化器、声谱显示仪或它们的结合。
一般地，我们进行本方法时，使用的有聚醚基团的含≡SiH硅氧烷与α，ω-二烯的摩尔比约为1∶1，预计用过量的含≡SiH的硅氧烷或α，ω-二烯进行本方法也可制备有用的材料，但认为这样做材料的利用效率较低。组合物的剩余物含有低分子量硅氧烷或溶剂，一般在组合物重量的65-98％范围内，但优选80-98％wt。
下列实施例更详细地说明我们的发明。
实施例1
在三颈圆底烧瓶中，将100g平均结构为
Me3SiO(Me2SiO)93(MeHSiO)6SiMe3的有机聚硅氧烷和6.07gCH2＝CHCH2O(CH2CH2O)7H与100g 2-丙醇混合。在该溶液中加入200μlKarstedt催化剂(即，1％重量铂在2厘斯(mm2/s)聚二甲基硅氧烷流体中)。搅拌并加热该溶液，将其保持在近似70℃。1小时后，三颈瓶与真空泵相接，蒸馏除去2-丙醇。几乎以定量得到聚醚支化的≡SiH硅氧烷聚合物。
在一个反应容器中，将16g聚醚支化的≡SiH硅氧烷聚合物和0.411g 1，5-己二烯与65.64g十甲基环戊硅氧烷混合。一边搅拌溶液，一边加入20μlKarstedt催化剂。在几小时内发生胶凝。凝胶置于反应器中过夜，随后在剪切力下用50重量份十甲基环戊硅氧烷溶胀50重量份的凝胶。得到均匀的浆料，在0.02S-1的剪切速率的粘度为1.82×106cP/mPa s。
在有机械搅拌器的玻璃缸中将该均匀的浆料和去离子水以1∶1的重量比混合，形成完美稳定的白色乳液。形成该乳液无需表面活性剂。
实施例2
在三颈圆底烧瓶中，将100g平均结构为Me3SiO(Me2SiO)108(MeHSiO)10SiMe3的有机聚硅氧烷和12.42g CH2＝CHCH2O(CH2CH2O)10[CH(CH3)CH2O]4H与100g 2-丙醇混合。在该溶液中加入200μl Karstedt催化剂。搅拌并加热该溶液，将其保持在近似70℃。1小时后，三颈瓶与真空泵相接，蒸馏除去2-丙醇。几乎以定量得到聚醚支化的≡SiH硅氧烷聚合物。
在一个反应容器中，将12g聚醚支化的≡SiH硅氧烷聚合物和0.72g 1，9-癸二烯与65.64g十甲基环戊硅氧烷混合。一边搅拌溶液，一边加入20μlKarstedt催化剂。在几小时内发生胶凝。凝胶置于反应器中过夜，随后在剪切力下用26重量份十甲基环戊硅氧烷溶胀50重量份的凝胶。得到均匀的浆料，在0.02S-1的剪切速率下粘度为2.66×106cP/mPa·s。
在有机械搅拌器的玻璃缸中将该均匀的浆料和去离子水以1∶1的重量比混合，形成完美稳定的白色乳液。乳液的粘度在0.02S-1的剪切速率下粘度为4.93×106cP/mPa·s。并且，形成该乳液无需表面活性剂。
实施例3
在三颈圆底烧瓶中，将100g平均结构为Me3SiO(Me2SiO)93(MeHSiO)6SiMe3的有机聚硅氧烷和7.99gCH2＝CHCH2O(CH2CH2O)7H与100g 2-丙醇混合。在该溶液中加入200μlKarstedt催化剂。搅拌并加热该溶液，将其保持在近似70℃。1小时后，三颈瓶与真空泵相接，蒸馏除去2-丙醇。几乎以定量得到聚醚支化的≡SiH硅氧烷聚合物。
在一个反应容器中，将12g聚醚支化的≡SiH硅氧烷聚合物、1.5g平均结构为Me3SiO(Me2SiO)16(MeHSiO)39SiMe3的硅氧烷和0.925g 1，5-己二烯与84.8g十甲基环戊硅氧烷混合。一边搅拌溶液，一边加入20μl Karstedt催化剂。在几小时内发生胶凝。凝胶置于反应器中过夜，随后在剪切力下用50重量份十甲基环戊硅氧烷溶胀75重量份的凝胶。得到均匀的浆料，在0.02S-1的剪切速率下粘度为6.6×105cP/mPa·s。
在有机械搅拌器的玻璃缸中将该均匀的浆料和去离子水以1∶1的重量比混合，形成完美稳定的白色乳液。乳液的粘度在0.02S-1的剪切速率下粘度为2.7×106cP/mPa·s。并且，形成该乳液无需表面活性剂。
这个实施例描述了上述步骤2中的替代实施方案，其中包括“任意”≡SiH硅氧烷作为一个成分。
实施例4  第一个比较实施例
以实施例1中的比例和工艺将含≡SiH的硅氧烷Me3SiO(Me2SiO)93(MeHSiO)6SiMe3与1，5-己二烯在十甲基环戊硅氧烷中交联。生成凝胶，随后用另外的十甲基环戊硅氧烷溶胀凝胶。所得到的是光滑、透明的浆料。但是，当该浆料与水混合后，水不能被分散。这个实施例表明，不使用单烯基官能的聚醚所产生的影响。
实施例5  第二个对比实施例
用实施例1的工艺，从100g Me3SiO(Me2SiO)93(MeHSiO)6SiMe3和6.07gCH2＝CHCH2O(CH2CH2O)7H制备聚醚支化的≡SiH硅氧烷聚合物。然后将1g上述聚醚支化的≡ SiH硅氧烷聚合物、10g十甲基环戊硅氧烷和11g去离子水混合。在使用机械搅拌器强力混合下，混合物表现出乳化，并且表现出形成了牛奶状的乳液。但是，在约2小时内，乳液分为两相。这表示没有进行α，ω-二烯变联反应产生的影响。
我们的发明的硅氧烷弹性体、硅氧烷凝胶、硅氧烷浆料和硅氧烷乳液在个人护理领域有特别的价值。由于这些组合物的VMS成分有极好的挥发性，它们可以单独地或与其它化妆品流体结合，形成多种无需处方可出售的(OTC)身体护理产品。
因此，它们可用作防汗剂和除臭剂的载体，因为它们使人有干爽感并且在蒸发过程中不使皮肤变凉。它们是滑的，这改进了皮肤霜剂、皮肤护理洗液、增湿剂、面部处理剂-诸如痤疮或皱纹消除剂、身体和面部清洗剂、浴油、香水、古龙水、香囊、防晒霜、剃须前和剃须后洗液、液体皂、剃须皂和剃须泡的性能。它们可用于洗发香波、头发调理剂、头发喷雾剂、摩丝、定型剂、脱毛剂、指甲油，增加光泽和干燥时间并改进调理的益处。
在化妆品中，它们作为均化和扩展剂，用于化妆品的色料、彩妆化妆品、粉底、胭脂、口红、唇油、眼线液、睫毛油、去油剂、彩妆卸妆剂和粉。它们可用作诸如维生素的油和水可溶物质的输送体系。当掺入条状物、凝胶、洗液、气溶胶和roll-on时，组合物被赋予干爽、丝滑的感觉。
另外，组合物还表现出其它有益的性能，诸如透明度、储存稳定性和易于制备。因此，它们有广泛的用途，但特别用于防汗剂、除臭剂、香水的载体和用于头发调理剂。
我们的硅氧烷弹性体、凝胶、浆料和乳液除了身体护理方面还有其它应用，包括作为填料或绝缘材料用于电缆，作为土壤或水分阻挡物用于地下(in-ground)稳定作用，或作为在电子工业中在coil-on-plug设计中使用的环氧树脂材料的替代物。
它们还可作为载体用于交联的硅氧烷橡胶颗粒。在这个应用中，(1)它们可以允许颗粒容易地掺入这类硅氧烷或有机相中，作为密封剂、颜料、涂料、润滑油、粘合剂、消泡剂和铸封化合物；和(2)它们提供了在它们的纯净或成品条件下的改进的流变学、物理学或能量吸收性质。
另外我们的硅氧烷弹性体、凝胶、浆料、和乳液可作为载体用于药物、生物杀伤剂、除草剂、农药和其它生物活性物质；它们可用于把水和水溶性成分引入疏水体系。一些水溶性物质的例子是水杨酸、甘油、酶和乙醇酸(glycolic acid)。
当需要阻隔薄膜时，可将硅氧烷弹性体、凝胶、浆料和乳液施加到基片的表面上，从而当溶剂或低分子量硅氧烷蒸发时，在基片表面上留下了细粉状颗粒薄膜。
可用在此描述的化合物、组合物和方法进行其它变化，而不脱离我们的发明的基本特征。我们的发明的形式只是典型的，并且不对所附权利要求定义的发明范围构成限制。

Claims (8)

1一种制备硅氧烷弹性体的方法，包括使：
(A)式R3SiO(R′2SiO)a(R″HSiO)bSiR3或式(R′2SiO)a(R″HSiO)b含≡Si-H的聚硅氧烷和任意的式HR2SiO(R′2SiO)cSiR2H含≡SiH聚硅氧烷或式HR2SiO(R′2SiO)a(R″HSiO)bSiR2H含≡Si-H的聚硅氧烷，其中R、R′和R”是1-6个碳原子的烷基，a是0-250，b是1-250，c是0-250；和
(B)式CH2＝CH(CH2)XO(CH2CH2O)Y(CH2CH3CHO)ZT或式CH2＝CH-Q-O(CH2CH2O)Y(CH2CH3CHO)ZT的一种单烯聚醚，其中T是H、C1-C10烷基、芳基或C1-C20酰基；Q是二价不饱和连接基团；x的值是1-6；y是0或1-100的值；z是0或1-100的值；条件是y和z不能同时为0；在铂催化剂存在下反应，直到生成有聚醚基团的含≡Si-H的聚硅氧烷；和使
(C)有聚醚基团的含≡ Si-H的聚硅氧烷；
(D)不饱和烃，选自式CH2＝CH(CH2)xCH＝CH2的α，ω-二烯、式CH≡C(CH2)xC≡CH的α，ω-二炔和式CH2＝CH(CH2)xC≡CH的α，ω-烯炔，其中x是1-20；在
(E)一种选自(1)有机化合物、(2)含硅原子的化合物、(3)有机化合物的混合物、(4)含硅原子的化合物的混合物和(5)有机化合物与含硅原子的化合物的混合物的溶剂存在下；和铂催化剂存在下反应，直到通过交联和≡SiH在不饱和烃的双键或三键两端的加成生成硅氧烷弹性体。
2根据权利要求1的方法，包括附加的步骤，即在硅氧烷弹性体中加入另外量的溶剂，搅拌溶剂和硅氧烷弹性体，直到生成硅氧烷浆料。
3根据权利要求2的方法，包括附加的步骤，即在硅氧烷浆料中加入水，搅拌水和硅氧烷浆料，直到生成硅氧烷乳液。
4根据权利要求1的方法，其中第二步包括作为附加反应剂的(F)式R3SiO(R′2SiO)a(R″HSiO)bSiR3或式(R′2SiO)a(R″HSiO)b的含≡Si-H的聚硅氧烷和任意的式HR2SiO(R′2SiO)cSiR2H的含≡SiH的聚硅氧烷或式HR2SiO(R′2SiO)a(R″HSiO)bSiR2H的含≡Si-H的聚硅氧烷，其中R、R’和R”是1-6个碳原子的烷基，a是0-250，b是1-250，c是0-250。
5按照权利要求1的方法制备的硅氧烷弹性体在用作防汗剂、防臭剂、香水和头发调理剂中的载体的用途。
6按照权利要求2的方法制备的硅氧烷浆料在用作防汗剂、防臭剂、香水和头发调理剂中的载体的用途。
7按照权利要求3的方法制备的硅氧烷乳液在用作防汗剂、防臭剂、香水和头发调理剂中的载体的用途。
8一种在基片表面提供阻隔薄膜的方法，包括将通过权利要求1的方法获得的硅氧烷弹性体施加给基片并将溶剂蒸发。
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CN1185314A (zh) 1998-06-24
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EP0848029A3 (en) 1998-09-16
US5811487A (en) 1998-09-22
TW508244B (en) 2002-11-01
KR100545456B1 (ko) 2006-06-07
JPH10176059A (ja) 1998-06-30
DE69712026T2 (de) 2002-11-14
DE69712026D1 (de) 2002-05-23
JP4037499B2 (ja) 2008-01-23
KR19980064149A (ko) 1998-10-07

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