CN112189029A - 硅酮聚合物 - Google Patents
硅酮聚合物 Download PDFInfo
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- CN112189029A CN112189029A CN201980034728.7A CN201980034728A CN112189029A CN 112189029 A CN112189029 A CN 112189029A CN 201980034728 A CN201980034728 A CN 201980034728A CN 112189029 A CN112189029 A CN 112189029A
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- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- SRPFBWXLOGEXJT-UHFFFAOYSA-N trimethyl-(methyl-pentyl-trimethylsilyloxysilyl)oxysilane Chemical compound CCCCC[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C SRPFBWXLOGEXJT-UHFFFAOYSA-N 0.000 description 1
- PGRZLADNCDNGTC-UHFFFAOYSA-N trimethyl-(methyl-propyl-trimethylsilyloxysilyl)oxysilane Chemical compound CCC[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C PGRZLADNCDNGTC-UHFFFAOYSA-N 0.000 description 1
- IIPLONCQUDDCAY-UHFFFAOYSA-N trimethyl-[methyl-(2-methylbutan-2-yl)-trimethylsilyloxysilyl]oxysilane Chemical compound CCC(C)(C)[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C IIPLONCQUDDCAY-UHFFFAOYSA-N 0.000 description 1
- YTEFCOWNTDERNN-UHFFFAOYSA-N trimethyl-[methyl-(2-methylpropyl)-trimethylsilyloxysilyl]oxysilane Chemical compound CC(C)C[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C YTEFCOWNTDERNN-UHFFFAOYSA-N 0.000 description 1
- GQRUIQOFMCJKJP-UHFFFAOYSA-N trimethyl-[methyl-(3-methylbutyl)-trimethylsilyloxysilyl]oxysilane Chemical compound CC(C)CC[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C GQRUIQOFMCJKJP-UHFFFAOYSA-N 0.000 description 1
- JGSGMDRRTNHCKH-UHFFFAOYSA-N trimethyl-[methyl-(3-methylpentyl)-trimethylsilyloxysilyl]oxysilane Chemical compound CCC(C)CC[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C JGSGMDRRTNHCKH-UHFFFAOYSA-N 0.000 description 1
- FMIMVQOAKBPLEJ-UHFFFAOYSA-N trimethyl-[methyl-(4-methylpentyl)-trimethylsilyloxysilyl]oxysilane Chemical compound CC(C)CCC[Si](C)(O[Si](C)(C)C)O[Si](C)(C)C FMIMVQOAKBPLEJ-UHFFFAOYSA-N 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 239000001717 vitis vinifera seed extract Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 235000020334 white tea Nutrition 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
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- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
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- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
- C08G77/52—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
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Abstract
本发明提供了具有硅氧烷聚合物主链的聚合物和包含其的组合物。所述聚合物在硅氧烷聚合物主链内包含环状不饱和基团(Z3)。已经发现所述聚合物表现出良好的导热性，并且可以在多种应用中使用。
Description
技术领域
本发明涉及一种硅酮聚合物。特别地，本发明涉及一种包含不饱和环状部分的官能化的硅氧烷聚合物，其在宽温度范围内表现出弹性体性质。
背景技术
聚亚芳基醚是独特的工程热塑性材料，具有由沿聚亚芳基醚主链的互补化学连接引起的无定形和半结晶形态。表现出高热转变(或熔点)和稳定性、断裂和冲击韧性以及出色的抗氧化和抗水解性的能力近许多年已经使它们能够用于许多商业应用中。
多年来，聚亚芳基醚树脂已经以各种形式与聚硅氧烷共混以开发多相材料，以将其应用扩展到多个行业，例如美国专利号5,916,952和4,226,761中所述。这些组合物倾向于表现出相分离和差的柔性。
随着人们对尺寸稳定性、低吸湿性以及高机械和介电强度的兴趣不断增长，对定义明确的热塑性硅酮-聚苯醚嵌段共聚物的研究仍在继续。开发了例如美国专利号5,204,438、3,668,273和4,814,392中所述的聚合物。在聚亚芳基醚树脂中，具有一个或多个二芳基砜基团的循环或重复单元的聚亚芳基醚砜已经是与分段型嵌段共聚物形式的聚硅氧烷结合的最广泛研究的热塑性塑料之一。然而，这些通常在高温下通过熔融加工进行加工，这限制了它们在某些行业中的应用。试图掺入聚亚芳基醚部分的聚合物的其他实例在美国专利号5,596,048和美国公开号2007/0208144中示出。许多这些产品需要敏感而昂贵的试剂来生产。另外，所述产品可能具有不希望的低分子量并且表现出差的热稳定性和水解稳定性。
发明内容
提供了一种包含不饱和环状基团的有机硅氧烷聚合物。所述聚合物表现出可逆的热塑性行为。在不同条件下，聚合物可以是固体、流体、胶或蜡状液体。所述聚合物表现出增强的导热性，而没有掺入较少量的热填料，使得由所述聚合物形成的材料的后固化性质不受到显著影响。还公开了制备改性硅酮聚合物的方法以及制备导热组合物的方法。
在一个方面，提供了下式的聚合物：
其中R1-R12独立地选自氢、任选地含有杂原子的C1-C10一价烃基、任选地含有杂原子的C6-C20一价芳族基团、和任选地含有杂原子的C4-C30一价饱和或不饱和环烷基团、含1-20个硅原子的硅烷氧基团、Z1或Z2；
Z1和Z2独立地选自氢、任选地含有杂原子的C1-C10烃基、-OH、-NH2、-COOH或R16-A-R17-，其中A选自包含不饱和环状基团的基团，其选自的芳族基团、官能化芳族基团、任选地包含杂原子稠合芳族基团、不饱和脂环族基团、不饱和杂环基团或其两种或更多种的组合；R16和R17独立地选自无、任选地含有杂原子的C1-C10烃基、任选地含有杂原子的C6-C20芳族基团、和任选地含有杂原子的C4-C30饱和或不饱和环烷基团；
Z3选自–R19-A-R19-，其中A选自包含不饱和环状部分的基团，其选自芳族基团、稠合芳族基团、不饱和脂环族基团、不饱和杂环基团，或其两种或更多种的组合；且R19选自无、任选地含有杂原子的C1-C10烃基、任选地含有杂原子的C6-C20芳族基团、和任选地含有杂原子的C4-C30饱和或不饱和环烷基团；
m是1-100；x是0-200；且y是0-200，其中x+y≥1；且
(B)(i)第一填料，和(ii)第二填料，其中第一填料和/或第二填料中的至少一种包含在粒度和/或形态方面彼此不同的多种填料类型。
在一个实施方案中，A独立地选自：C6至C12芳族基团；C10至C36稠合芳族环基团；C4-C36不饱和脂环族基团；和C4-C36不饱和杂环基团。
在一个实施方案中，Z1、Z2和Z3中的一个或多个中的A选自式–A1-R18-A2-的基团，其中A1和A2独立地选自C6至C12芳基、C12-C36稠合芳族环基团、C5-C36不饱和脂环族基团，和C5-C36不饱和杂环基团；且R18选自直接键、–(CH2)n-、-C(CH3)2-、-O-、-S-、-S(O)2-、-C(O)-、C(O)-NH-、-NH-C(O)-NH-、C(O)-O-、-CH＝N-或-CH＝N-N＝CH-，其中n是1-10。
在一个实施方案中，A独立地选自
在一个实施方案中，其中Z1、Z2和Z3中的A是
在一个实施方案中，Z1、Z2和Z3中的A是
在一个实施方案中，Z1和Z2中的R16选自CH2＝CH2-(CH2)a-、CH2＝CH2-(CH2)a-O-，其中a是0-10；且R17选自C2-C10二价烷基、-O-(CH2)b-或–O-C(O)-(CH2)b-，其中b是2-10；且Z3中的R19选自R17。
在一个实施方案中，根据任一前述实施方案的聚合物的数均分子量为约1000g/mol至约50000g/mol。
另一方面，提供了一种包含如任一前述实施方案所述聚合物的汽车产品、家用产品、油漆、涂料、衣物洗涤剂、纺织品处理剂、石油或天然气产品、燃料电池、电子产品、农产品、航空航天产品、医疗或保健产品、膜、建筑产品、粘合剂、密封剂、可注塑和可压塑的橡胶或塑料、或硅酮基橡胶。
在一个实施方案中，所述产品选自：发光设备，计算机设备，叠层裸片，移动电话，平板电脑，倒装芯片封装，混合内存立方体，触摸屏，Wi-Fi设备，汽车技术hifi***，硅通孔设备，和音频***，在太阳能加热的供暖中的热管和水箱之间的连接中，在燃料电池和风力涡轮机中，在制造计算机芯片、游戏机、数据传输设备中，在照明设备中，电池，在外壳中，冷却器，热交换设备，电线，电缆，加热电线，冰箱，洗碗机，空调，蓄能器，变压器，激光器，功能性服装，汽车座椅，医疗设备，消防，电动机，飞机，和火车，作为用于3D打印材料的细丝，药物输送***，透皮贴剂，伤口愈合贴剂，伤口敷料贴剂，减疤贴剂，透皮离子电渗疗法，组织工程支架，抗微生物装置，伤口处理装置，眼科设备，生物***物，假体，身体植入物，油漆，结构涂料，砖石涂料，或船舶涂料，种子涂料，超级散播剂或控释肥料。
在另一方面，提供了包含任一前述实施方案的聚合物的个人护理产品。
在一个实施方案中，个人护理产品的形式为：止汗剂/除臭剂，剃刮产品，皮肤乳液，保湿剂，调色剂，沐浴产品，清洁产品，洗发剂，护发素，组合洗发剂/护发素，摩丝，定型凝胶，喷发剂，染发剂，头发着色剂，漂发剂，卷发剂，直发剂，指甲油，指甲油去除剂，护甲霜或乳液，角质层软化剂，防晒剂，驱虫剂，抗衰老产品，口红，粉底，扑面粉，眼线产品，眼影，腮红，彩妆，睫毛膏，保湿制剂，粉底，身体和手部制剂，皮肤护理制剂，面部和颈部制剂，滋补品，敷料，头发梳理助剂，气溶胶固定剂，香味制剂，须后水，彩妆制剂，柔焦应用，夜间和日间护肤制剂，无着色头发制剂，晒黑制剂，合成的和非合成的皂条，洗手液，鼻贴(nosestrip)，个人护理用无纺布应用，婴儿乳液，婴儿洗发剂，婴儿护发素，剃须制剂，黄瓜片，皮肤护垫，卸妆剂，面部清洁产品，冷霜，防晒产品，喷雾(spritzer)，糊剂面膜和泥，面膜，古龙水和淡香水，毛外皮凃剂(hair cuticle coat)，沐浴露，面部和身体洗涤剂，个人护理冲洗产品，凝胶，泡沫浴，擦洗清洁剂，收敛剂，指甲调理剂，眼影棒，用于脸部或眼睛的粉剂，润唇膏，唇彩，护发泵喷雾剂，毛发卷曲控制凝胶，免洗护发素，润发油，头发去缠结产品，头发固定剂，头发漂白剂，皮肤乳液，剃须前和电动剃须前产品，无水霜和乳液，油/水乳液，水/油乳液，抗水霜或乳液，抗粉刺制剂，漱口水，按摩油，牙膏，透明凝胶或棒，软膏基质，局部伤口愈合产品，气溶胶滑石，屏障喷雾剂，维生素和抗衰老制剂，草药提取制剂，沐浴盐，沐浴乳和身体乳，头发造型助剂，头发、眼部、指甲和皮肤柔软固体应用，控释个人护理产品，护发雾，护肤保湿雾，皮肤擦拭剂，毛孔皮肤擦拭剂，毛孔清洁剂，淡斑剂，皮肤去角质剂，皮肤脱屑强化剂，皮肤湿巾纸或布，脱毛制剂，或个人护理润滑剂。
具体实施方式
现在将参考示例性实施方案，其实例在附图中示出。应理解，可以使用其它实施方案，并且可以进行结构和功能的改变。此外，各实施方案的特征可以组合或改变。这样，以下描述仅以说明的方式呈现，且不应以任何方式限制可对所说明的实施方案作出的各种替代和修改。在本公开内容中，许多具体细节提供了对本公开内容的全面理解。应理解，本公开内容的各方面可以用不必包括本文所述的所有方面等的其它实施方案来实践。
如本文所使用的，词语“实例”和“示例性”意指例子或示例性说明。词语“实例”或“示例性”不指示关键或优选方面或实施方案。除非上下文另外暗示，否则词语“或”旨在是包括性的而非排他性的。作为实例，短语“A采用B或C”包括任何包含性的排列(例如，A采用B；A采用C；或A采用B和C二者)。作为另一个问题，冠词“一(a)”和“一(an)”通常旨在表示“一个或多个”，除非上下文另有说明。
本发明提供一种官能化硅酮聚合物和包含其的组合物。特别地，提供了一种官能化硅氧烷聚合物。所述官能化硅氧烷聚合物是在硅氧烷链内包含有机基团的(AB)n型硅氧烷聚合物。所述硅氧烷聚合物包含含不饱和环状部分的有机基团。
提供了一种具有下式的硅酮聚合物：
其中R1-R12独立地选自氢、任选地含有杂原子的C1-C10一价烃基、任选地含有杂原子的C6-C20一价芳族基团、和任选地含有杂原子的C4-C30一价饱和或不饱和环烷基团、含1-20个硅原子的硅烷氧基团、Z1或Z2；
Z1和Z2独立地选自氢、任选地含有杂原子的C1-C10烃基、-OH、-NH2、-COOH或R16-A-R17-，其中A选自包含不饱和环状基团的基团，其选自芳族基团、稠合芳族基团、不饱和脂环族基团、不饱和杂环基团或其两种或更多种的组合；R16和R17独立地选自无、任选地含有杂原子的C1-C10烃基、任选地含有杂原子的C6-C20芳族基团、和任选地含有杂原子的C4-C30饱和或不饱和环烷基团；
Z3选自–R19-A-R19-，其中A选自包含不饱和环状部分的基团，其选自芳族基团、稠合芳族基团、不饱和脂环族基团、不饱和杂环基团，或其两种或更多种的组合；且R19选自无、任选地含有杂原子的C1-C10烃基、任选地含有杂原子的C6-C20芳族基团、和任选地含有杂原子的C4-C30饱和或不饱和环烷基团；m是1-100；x是0-200；且y是0-200。
如本文所用，不饱和脂环族基团是指包含一个或多个不饱和键的脂族环状基团。在实施方案中，不饱和脂环族基团包含至少一个C＝C键。在实施方案中，不饱和脂环族基团选自包含一个或多个C＝C键的C4-C36脂环族基团。不饱和脂环族基团可以包含单环、稠环体系或双环环体系。不饱和脂环族化合物的非限制性实例包括但不限于环戊烯、环己烯、环戊二烯、二环戊二烯等。
如本文所用，不饱和杂环基团是指在环结构内包含至少一个不饱和键和至少一个杂原子的环状基团。不饱和基团可以是C＝C或在碳原子与杂原子之间的不饱和键。
在实施方案中，所述硅氧烷聚合物包含可固化的官能团。在这样的实施方案中，硅氧烷包含至少一个具有可固化官能团的Z1或Z2基团，所述可固化官能团例如是烯丙基、乙烯基、烯丙氧基、乙烯氧基、丙烯酸酯、甲基丙烯酸酯等。在一个实施方案中，Z1或Z2基团中的R16选自CH2＝CH2-(CH2)a-、CH2＝CH2-(CH2)a-O-、CH2＝CH2-(CH2)a-C(O)-O-，其中a是0-10。在一个实施方案中，R16是CH2＝CH2-(CH2)a-O-，其中a是0。在一个实施方案中，R16是CH2＝CH2-(CH2)a-O-，其中a是1。
Z1和Z2中的R17(和Z3中的R19)选自C2-C10二价烷基、-O-(CH2)b-或–O-C(O)-(CH2)b-，其中b是2-10。
在实施方案中，Z1、Z2和Z3中的A独立地选自C6至C12芳基、C10至C36稠合芳族基团、C4-C36不饱和脂环族基团和C4-C36不饱和杂环基团。
在一个实施方案中，Z1、Z2或Z3中的一个或多个的A选自式–A1-R18-A2-的基团，其中A1和A2独立地选自C6至C12芳基、C12-C36稠合芳族环、C5-C36不饱和脂环族基团，和C5-C36不饱和杂环基团；且R18选自直接键、–(CH2)n-、-C(CH3)2-、-O-、-S-、-S(O)2-、-C(O)-、C(O)-NH-、-NH-C(O)-NH-、C(O)-O-、-CH＝N-或-CH＝N-N＝CH-，其中n是1-10。在实施方案中，n是1-6、1-4或1-2。
对于A基团的合适基团的实例包括但不限于：
合适的Z3基团的实例包括但不限于苯二基、萘二基、联苯二基、萘嵌戊烯-5,6-二基、吡啶-2,3-二基、吡啶-2,6-二基、H-咪唑-4,5-二基，lH-吡咯-2,4-二基、呋喃-2,5-二基和噻吩-2,5-二基。苯二基(benzidyl)的实例包括1,2-苯二基、1,3-苯二基和1,4-苯二基。萘二基实例包括1,2-萘二基、1,3-萘二基、1,4-萘二基、1,5-萘二基、1,6-萘二基、1,7-萘二基、1,8-萘二基、2,3-萘二基、2,6-萘二基和2,7-萘二基。联苯二基的实例包括联苯-4,4'-二基。
联苯二基的实例包括4,4'-联苯二基、3,3'-联苯二基、4,4'-(2,2'-二苯基丙烷)二基、3,3'-(2,2'-二苯基丙烷)二基、4,4'-(二苯基砜)二基、3,3'-(二苯基砜)二基、4,4'-(3,3-二苯基六氟丙烷)二基、3,3'-(3,3-二苯基六氟丙烷)二基、4,4'-(二苯基醚)二基、3,3'-(二苯基醚)二基、4,4'-(二苯基酮)二基、3,3'-(二苯基酮)二基、4,4'-(2,2'-二甲基联苯)二基、4,4'-(2,2'-二(三氟甲基)联苯)联苯)二基和4,4'-(2,6,2',6'-四甲基联苯)二基。
在一个实施方案中，R1-R12是C1-C4烷基，Z1、Z2和Z3中的A是
Z1和Z2中的R16选自CH2＝CH2-(CH2)a-、CH2＝CH2-(CH2)a-O-，其中a是0-10；且R17选自C2-C10二价烷基、-O-(CH2)b-或–O-C(O)-(CH2)b-，其中b是2-10；且Z3中的R19选自R17。在一个实施方案中，R16是CH2＝CH2-(CH2)a-O-，其中a是0。在一个实施方案中，R16是CH2＝CH2-(CH2)a-O-，其中a是1。
在一个实施方案中，R1-R12是C1-C4烷基，Z1、Z2和Z3中的A是
Z1和Z2中的R16选自CH2＝CH2-(CH2)a-或CH2＝CH2-(CH2)a-O-，其中a是0-10；且R17选自C2-C10二价烷基、-O-(CH2)b-或–O-C(O)-(CH2)b-，其中b是2-10；且Z3中的R19选自R17。在一个实施方案中，R16是CH2＝CH2-(CH2)a-O-，其中a是0。在一个实施方案中，R16是CH2＝CH2-(CH2)a-O-，其中a是1。
在一个实施方案中，A选自(A-i)–(A-xiii)中的任意一种，且Z1和Z2中的R16选自CH2＝CH2-(CH2)a-、CH2＝CH2-(CH2)a-O-，其中a是0-10；且R17选自C2-C10二价烷基、-O-(CH2)b-或–O-C(O)-(CH2)b-，其中b是2-10；且Z3中的R19选自R17。在一个实施方案中，A选自(A-i)–(A-xiii)中的任意一种；R16选自CH2＝CH2-(CH2)a-O-，其中a是0，且R17选自-O-(CH2)b-，其中b是2。在一个实施方案中，A选自(A-i)–(A-xiii)中的任意一种；R16选自CH2＝CH2-(CH2)a-O-，其中a是0，且R17选自-O-(CH2)b-，其中b是3。在一个实施方案中，A选自(A-i)–(A-xiii)中的任意一种；R16选自CH2＝CH2-(CH2)a-O-，其中a是1，且R17选自-O-(CH2)b-，其中b是2。在一个实施方案中，A选自(A-i)–(A-xiii)中的任意一种；R16选自CH2＝CH2-(CH2)a-O-，其中a是1，且R17选自-O-(CH2)b-，其中b是3。
在一个实施方案中，聚合物可具有关于前述实施方案中任一项所述的式，其中以下任一项可单独或彼此组合地应用：
·m是1-100；m是5-90；m是10-80；m是20-75；m是30-60；或m是40-50；
·x是1-200；x是10-175；x是25-150；x是50-150；x是75-125；x是80-100；
·y是1-200；y是10-175；y是25-150；y是50-150；y是75-125；y是80-100。
将理解的是，可以将数值组合以形成新的未指定的范围。
本发明的聚合物可以经由适当的不饱和化合物和硅烷基氢化物在催化剂的存在下的氢化硅烷化而形成。提供Z1-Z3基团的不饱和化合物可以具有式R16-A-R16'，其中A如上所述，并且R16和R16'独立地选自烯丙基、乙烯基、烯丙氧基、乙烯氧基、丙烯酸酯或甲基丙烯酸酯。在实施方案中，R16和R16’独立地选自CH2＝CH2-(CH2)a-、CH2＝CH2-(CH2)a-O-、CH2＝CH2-(CH2)a-C(O)-O-，其中a是0-10。硅烷基氢化物可以是例如具有末端硅烷基氢化物官能团或在硅氧烷的主链内具有含Si-H基团的硅氧烷。
有用的催化剂包括可以催化反应性的含SiH部分或取代基与碳-碳键如碳-碳双键之间的氢化硅烷化反应的那些化合物或分子。此外，在一种或多种实施方案中，这些催化剂可以溶于反应介质中。催化剂的类型包括过渡金属化合物，所述过渡金属化合物包括包括VIII族金属的那些化合物。示例性的VIII族金属包括钯、铑、锗和铂。示例性的催化剂化合物包括氯铂酸、单质铂、六水合氯铂酸、氯铂酸与对称二乙烯基四甲基二硅氧烷的络合物、二氯-双(三苯基膦)铂(II)、顺式-二氯-双(乙腈)铂(II)、二羰基二氯铂(II)、氯化铂和氧化铂、零价铂金属络合物如Karstedt催化剂、[Cp*Ru(MeCN)3]PF6、[PtCl2(环辛二烯)]、负载在载体(如氧化铝、二氧化硅或炭黑)上的固体铂、铂-乙烯基硅氧烷络合物(例如Ptn(ViMe2SiOSiMe2Vi)c和Pt[(MeViSiO)4]d)、铂-膦络合物(例如Pt(PPh3)4和Pt(PBU3)4)和铂-亚磷酸酯络合物(例如Pt[P(Oph)3]4和Pt[P(Obu)3]4)，其中Me代表甲基，Bu代表丁基，“Vi”代表乙烯基并且Ph代表苯基，并且c和d代表整数。其他包括RhCl(PPh3)3、RhCl3、Rh/Al2O3、RuCl3、IrCl3、FeCl3、AlCl3、PdCl2.2H2O、NiCl2、TiCl4等。
在一个实施方案中，硅酮聚合物的数均分子量为约1000g/mol至约50000g/mol；约2000g/mol至约40000g/mol；甚至约3000g/mol至约10000g/mol。分子量可以通过GPC、光散射确定。
所述聚合物表现出使其可用于多种应用的性质。可以通过控制聚合物的各个方面来控制或调节聚合物的性质或状态。特别地，可以通过控制聚合度、硅酮链长和分子量，将聚合物作为液体、胶或固体来提供。
已经发现本发明的聚合物表现出可以使其适合于多种应用的期望性质。所述聚合物具有高的热稳定性、折射率和热导率。
在一个方面，可以将聚合物提供为与导热填料的复合物。当与无机填料结合时，聚合物表现出优异的润湿行为，使填料易于分散在聚合物中。这些性质允许提供具有优异导热性的材料。这样的材料可以用于多种应用的产品中，包括例如汽车、电子、建筑、航空航天、航空、医疗、个人护理等。包括作为与导热填料的复合物的聚合物可以用作热界面材料。
合适的导热填料的实例包括但不限于氮化硼，二氧化硅，玻璃纤维，金属氧化物例如氧化锌、氧化镁、氧化铍、氧化钛、氧化锆、氧化钇等，碳酸钙，滑石，云母，硅灰石，粘土，剥离型粘土，氧化铝，氮化铝，石墨，金属粉末例如铝、铜、青铜、黄铜等，或其两种或更多种的组合。
所述填料材料的粒度可以根据特定目的或预期应用的需要来选择。在实施方案中，填料材料平均粒度为约0.01μm至约500μm；约0.1至约250μm；约1至约100μm；约5至约75μm；甚至约10至约50μm。应当理解，组合物可以包含不同平均粒度的无机填料的组合。这样的组合可以根据特定目的或预期应用的需要来选择。在一个实施方案中，组合物包含平均粒度为约0.01至约0.1μm的第一有机填料；平均粒度为约1μm至约25μm的第二填料；和任选的平均粒度为约50μm至约100μm的第三填料。第一、第二和第三填料在填料的化学组成方面可以彼此相同或不同。
硅酮聚合物可以与硅酮流体共混以形成物理凝胶。如本文所用，“物理凝胶”是指包含化合物的材料，所述化合物能够以在主液相中的细分散的固相的形式排列并且能够形成容易由于弱键的存在而拆解的低密度的网络，所述网络是可逆的。
硅酮流体可选自任何合适的硅酮流体，例如，硅酮流体可为有机聚硅氧烷、硅酮共聚醇、二硅氧烷、三硅氧烷、四硅氧烷、聚三甲基硅氧烷(trimethicone)、烷基硅氧烷或环聚硅氧烷，或其组合。
合适的硅酮流体的实例包括支化的、非支化的、线性的或环状的硅酮流体，例如粘度≤8厘沲，并且具有例如2至7个硅原子的那些硅酮流体，这些硅酮任选地包含具有以下1至12个碳原子的烷基、聚醚-或烷氧基基团。合适的硅酮流体的一些非限制性实例包括八甲基环四硅氧烷、十甲基环戊硅氧烷、十二甲基环己硅氧烷、七甲基己基三硅氧烷、七甲基辛基三硅氧烷、六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、十二甲基五硅氧烷、辛基聚甲基硅氧烷(capryl methicone)、PEG/PPG 5/3聚甲基硅氧烷，或其两种或更多种的混合物。
其他合适的硅酮流体包括例如聚二甲基硅氧烷(PDMS)，在硅酮链末端和/或侧位包含烷基、聚醚-或烷氧基基团的聚二甲基硅氧烷，所述烷基和烷氧基各自具有1至12个碳原子，苯基化的硅酮诸如乙基聚甲基硅氧烷、庚基聚甲基硅氧烷、己基聚甲基硅氧烷、丙基聚甲基硅氧烷、异丙基聚甲基硅氧烷、庚基聚甲基硅氧烷、仲丁基聚甲基硅氧烷、叔丁基聚甲基硅氧烷、戊基聚甲基硅氧烷、苯基聚三甲基硅氧烷、苯基聚二甲基硅氧烷、苯基三甲基硅烷氧基二苯基硅氧烷、二苯基聚二甲基硅氧烷、二苯基甲基二苯基三硅氧烷和(2-苯基乙基)三甲基硅烷氧基硅酸盐。
适合作为硅酮流体的三硅氧烷的一些非限制性实例包括线性烷基三硅氧烷。烷基三硅氧烷的实例是乙基三硅氧烷、辛基三硅氧烷、己基三硅氧烷等。一些具体的三硅氧烷包括1,1,1,3,5,5,5-七甲基-3-乙基三硅氧烷、1,1,1,3,5,5,5-七甲基-3-辛基三硅氧烷、1,1,1,3,5,5,5-七甲基-3-己基三硅氧烷及其两种或更多种的组合。在本文的一个具体实施方案中，三硅氧烷可以是例如在美国专利申请公开号2004/0197284A1或美国专利申请公开号2005/0069564A1中描述的那些的三硅氧烷，其各自的内容通过引用整体并入本文。三硅氧烷的更多具体实例包括：3-戊基-1,1,1,3,5,5,5-七甲基三硅氧烷；1,1,1,3,5,5,5-七甲基-3-辛基三硅氧烷，例如由Momentive Performance Materials Inc.以名称“Silsoft034”出售；1,1,1,3,5,5,5-七甲基-3-己基三硅氧烷；3-(1-乙基丁基)-1,1,1,3,5,5,5-七甲基三硅氧烷；1,1,1,3,5,5,5-七甲基-3-(1-甲基戊基)三硅氧烷；1,1,1,3,5,5,5-七甲基-3-(1-甲基丙基)三硅氧烷；3-(1,1-二甲基乙基)-1,1,1,3,5,5,5-七甲基三硅氧烷；1,1,1,5,5,5-六甲基-3,3-二(1-甲基乙基)三硅氧烷；3-(3,3-二甲基丁基)-1,1,1,3,5,5,5-七甲基三硅氧烷；1,1,1,3,5,5,5-七甲基-3-(3-甲基丁基)三硅氧烷；1,1,1,3,5,5,5-七甲基-3-(3-甲基戊基)三硅氧烷；1,1,1,3,5,5,5-七甲基-3-(2-甲基丙基)三硅氧烷；1,1,1,3,5,5,5-七甲基-3-丙基三硅氧烷；3-异己基-1,1,1,3,5,5,5-七甲基三硅氧烷；3-叔戊基-1,1,1,3,5,5,5-七甲基三硅氧烷；3-新戊基-1,1,1,3,5,5,5-七甲基三硅氧烷；1,1,1,5,5,5-六甲基-3,3-二丙基三硅氧烷；3,3-二乙基-1,1,1,5,5,5-六甲基三硅氧烷；3,3-二丁基-1,1,1,5,5,5-六甲基三硅氧烷；3-乙基-1,1,1,3,5,5,5-七甲基三硅氧烷；3-庚基-1,1,1,3,5,5,5-七甲基三硅氧烷；1,1,1,5,5,5-六甲基-3,3-二乙基三硅氧烷；1,1,1,3,5,5,5-七甲基-3-丁基三硅氧烷，及其两种或更多种的组合。
另外，其他市售的聚硅氧烷包括但不限于来自Dow Coming Inc.的Toray FZ-3196、来自Clariant Inc.的SilCare Silicone 41M15、来自Gelest的Sibrid AM 108，或其组合。还有，诸如但不限于Hydrobrite 2000Gel(来自Chemtura，以前是Witco)或辛基聚二甲基硅氧烷中的SilCare 51M15三甲基硅烷氧基硅酸酯(来自Clariant)的混合物是适用于硅酮流体的聚硅氧烷。
在实施方案中，本发明的共聚物还可以用作触变剂或流变改性剂。如本文所用，“触变剂”是增加包含其的组合物的触变性，促进剪切稀化并能够使用减小的注射力的触变剂。
本发明的聚合物可以是可固化的或不可固化的。可固化聚合物将通常包含连接至聚合物的可固化官能团。可通过缩合固化机理或热固化机理来固化可固化聚合物。在一个实施方案中，聚合物是可缩合固化的。可以使用任何合适的组分来促进缩合固化，例如促进完全或部分水解的面漆材料的缩合的缩合催化剂。所述催化剂可以是适合于促进硅氧烷固化的催化剂。有利地，可以使用缩合催化剂。合适的缩合催化剂包括但不限于二羧酸二烷基锡(例如二月桂酸二丁基锡和二月桂酸二辛基锡)、叔胺、羧酸的亚锡盐(例如辛酸亚锡和乙酸亚锡)等。其他有用的催化剂包括含锆、含铝和含铋的配合物，例如由King Industries,Inc.供应的
XC6212、
5218和
348；钛螯合物，例如可获得自DuPont公司的
型，和可获得自Kenrich Petrochemical,Inc.的KR型；和其他有机金属催化剂，例如包含诸如Al、Zn、Co、Ni、Fe等金属的那些。
在一个实施方案中，聚合物是可热固化的并且包含热固化催化剂。在一个实施方案中，热固化催化剂选自羧酸烷基铵。羧酸烷基铵可以是羧酸二铵、羧酸三铵或羧酸四铵。在一个实施方案中，所述催化剂选自下式的羧酸四丁铵：[(C4H9)4N]+[OC(O)—R]-，其中R选自由以下组成的组：氢、含有约1至约8个碳原子的烷基和含有约6至20个碳原子的芳族基团。在实施方案中，R为含有约1至4个碳原子的基团，例如甲基、乙基、丙基、丁基和异丁基。示例性的催化剂是乙酸四正丁铵(TBAA)、甲酸四正丁铵、苯甲酸四正丁铵、2-乙基己酸四正丁铵、对乙基苯甲酸四正丁铵和丙酸四正丁铵，或其两种或更多种的组合。特别合适的催化剂是乙酸四正丁铵和甲酸四正丁铵、乙酸四甲铵、苯甲酸四甲铵、乙酸四己铵、甲酸二甲基苯铵(dimethylanilium formate)、乙酸二甲铵、羧酸四甲铵、2-乙基己酸四甲铵、乙酸苄基三甲铵、乙酸四乙铵、乙酸四异丙铵、乙酸三乙醇甲基铵、乙酸二乙醇二甲基铵、乙酸单乙醇三甲基铵、乙酸乙基三苯基鏻。
通常，催化剂的加入量应将不影响或损害涂层的物理性质，但应足以催化固化反应。在一个实施方案中，所述催化剂以1ppm至约75ppm，约10ppm至约70ppm，甚至约20ppm至约60ppm的范围的量提供。在此，如说明书和权利要求书中的其它地方，数值可以组合以形成新的和未公开的范围。催化剂的“ppm”值可以定义为催化剂总摩尔数/涂层总固体重量。
本发明的硅酮聚合物或采用这样的聚合物的组合物可用于多种组合物和应用中，包括但不限于个人护理、保健、家用、油漆、汽车、涂料、衣物洗涤剂、纺织品处理、石油和天然气、燃料电池、建筑产品、航空航天产品、医疗产品、电子应用、农业、膜、粘合剂、密封剂、可注塑和可压塑的橡胶和塑料，和各种硅酮基橡胶。
所述聚合物与硅酮流体的共混物可以提供适用于个人护理应用和组合物中的物理凝胶，所述个人护理应用和组合物例如但不限于化妆品、防晒剂、发用产品(如洗发剂或护发素)、乳液、霜等。个人护理产品的实例包括但不限于止汗剂/除臭剂，包括喷雾剂，棒和滚珠产品，剃须产品，护肤液，保湿剂，调色剂，沐浴产品，清洁产品，洗发剂，护发素，组合的洗发水/护发素，摩丝，定型凝胶，喷发剂，染发剂，头发着色剂，漂发剂，卷发产品，直发剂，指甲油，指甲油去除剂，护甲霜和乳液，角质层软化剂，防晒剂，驱虫剂，抗衰老产品，口红，粉底，扑面粉，眼线产品，眼影，腮红，彩妆，睫毛膏，保湿制剂，粉底，身体和手部制剂，皮肤护理制剂，脸部和颈部制剂，滋补品，敷料，头发梳理助剂，气溶胶固定剂，香味制剂，须后水，彩妆制剂，柔焦应用，夜间和日间皮肤护理制剂，无着色头发制剂，晒黑制剂，合成和非合成皂条，洗手液，鼻贴，个人护理用无纺布应用，婴儿乳液，婴儿沐浴露和洗发剂，婴儿护发素，剃须制剂，黄瓜片，皮肤垫，卸妆剂，洁面产品，冷霜，防晒产品，摩丝，喷雾，糊剂面膜和泥，面膜，古龙水和淡香水，毛外皮凃剂，沐浴露，面部和身体洗涤剂，个人护理冲洗产品，凝胶，泡沫浴，擦洗清洁剂，收敛剂，指甲调理剂，眼影棒，用于脸部或眼部的粉剂，润唇膏，唇彩，护发泵喷雾剂和其他非气溶胶喷雾剂，毛发卷曲控制凝胶，免洗护发素，润发油，头发去缠结产品，头发固定剂，头发漂白产品，皮肤乳液，剃须前产品和电动剃须前产品，无水霜和乳液，油/水，水/油，多乳液和粗乳液和微乳液，防水霜和乳液，抗粉刺制剂，漱口水，按摩油，牙膏，透明凝胶和棒，软膏基质，局部伤口愈合产品，气溶胶滑石，屏障喷雾剂，维生素和抗衰老制剂，草药提取制剂，沐浴盐，沐浴乳和身体乳，头发造型助剂，头发、眼睛、指甲和皮肤柔软固体应用，控释个人护理产品，护发雾，护肤保湿雾，皮肤擦拭剂，毛孔皮肤擦拭剂，毛孔清洁剂，淡斑剂，皮肤去角质剂，皮肤脱屑强化剂，皮肤湿巾纸和布，脱毛制剂，个人护理润滑剂，指甲着色制剂，防晒剂，化妆品，护发产品，护肤产品，牙膏，用于皮肤的药物组合物的局部施用的药物递送***，和包含至少一种前述应用的组合。个人护理组合物可包含各种成分，例如载体、颜料、成膜剂、乳化剂、维生素、增塑剂、表面活性剂、抗氧化剂、蜡、油、溶剂等。
在一个实施方案中，个人护理产品可任选地包含0-90重量份的颜料。适用于本发明的颜料是所有无机和有机色素/颜料。这些通常是铝、钡或钙盐或色淀。色淀是用固体稀释剂扩展或调淡(reduced)的颜料，或通过水溶性染料在吸附性表面(通常是铝水合物)上沉淀而制备的有机颜料。色淀也由来自酸性或碱性染料的不溶性盐的沉淀形成。钙色淀和钡色淀也用于本文。合适的色淀包括但不限于，红3铝色淀、红21铝色淀、红27铝色淀、红28铝色淀、红33铝色淀、黄5铝色淀、黄6铝色淀、黄10铝色淀、橙5铝色淀和蓝1铝色淀、红6钡色淀、红7钙色淀。组合物中也可以包括其它色素和颜料，如珍珠、氧化钛、红6、红21、蓝1、橙5和绿5染料、白垩、滑石、氧化铁和云母钛(titanated micas)。
个人护理组合物可任选地包含0-99重量份的现有技术中已知的有机成膜剂。成膜剂可以是化妆品可接受的任何成膜剂。有用的成膜剂的实例包括天然蜡，聚合物如聚乙烯聚合物，和PVP的共聚物、乙烯乙酸乙烯酯、聚二甲基硅氧烷胶，和树脂如虫胶、聚萜烯。
个人护理组合物可任选地包括0-50重量份的阻隔性或吸收性防晒剂。阻隔性防晒剂通常是无机的，如各种铯氧化物、铬氧化物、钴氧化物、铁氧化物、红凡士林、硅酮和其它处理过的二氧化钛、二氧化钛、氧化锌和/或氧化锆、BaTiO3、CaTiO3、SrTiO3和SiC。通常是有机物质的吸收性防晒剂是特别有用的。这样的吸收性防晒剂包括但不限于：通常吸收紫外光谱的320至400nm区域的辐射的UV-A吸收剂，例如邻氨基苯甲酸酯、二苯甲酮和二苯甲酰甲烷；和通常吸收在紫外光谱的280至320nm区域的辐射的UV-B吸收剂，例如对氨基苯甲酸衍生物、樟脑衍生物、肉桂酸酯和水杨酸酯。有机防晒剂的具体实例包括对氨基苯甲酸、阿伏苯宗西诺沙酯、二羟苯宗、胡莫柳酯、薄荷醇邻氨基苯甲酸酯、奥克立林、甲氧基肉桂酸辛酯、水杨酸辛酯、氧苯酮、帕地马酯、苯基苯并咪唑磺酸、磺异苯酮、三乙醇胺水杨酸酯、氨基苯甲酸、戊基二甲基对氨基苯甲酸、二乙醇胺对甲氧基肉桂酸酯、棓酰棓酸三油酸酯、2-乙基己基-2-氰基-3,3-二苯基丙烯酸酯、乙基己基对甲氧基肉桂酸酯、水杨酸-2-乙基己基酯、氨基苯甲酸甘油酯、水杨酸高孟酯、胡莫柳酯、3-咪唑-4-基丙烯酸及其乙酯、邻氨基苯甲酸甲酯、辛基二甲基对氨基苯甲酸、2-苯基苯并咪唑-5-磺酸和盐、磺异苯酮、三乙醇胺水杨酸酯、N,N,N-三甲基-4-(2-氧基冰片-3-烯甲基)苯胺甲基硫酸酯、氨基苯甲酸酯、4-异丙基苄醇水杨酸酯、4-甲氧基肉桂酸2-乙基己酯、二异丙基肉桂酸甲酯、4-甲氧基肉桂酸异戊酯、二乙醇胺4-甲氧基肉桂酸酯、3-(4'-三甲基铵)-苯亚甲基-樟脑甲基硫酸酯(3-(4'-trimethylammonium)-benzyliden-boman-2-one methylsulfate)、2-羟基-4-甲氧基苯甲酮、2-羟基-4-甲氧基苯甲酮-5-磺酸酯、2,4-二羟基苯甲酮、2,2',4,4'-四羟基苯甲酮、2,2'-二羟基-4,4'二甲氧基苯甲酮、2-羟基-4-正辛氧基苯甲酮、2-羟基-4-甲氧基-4'-甲氧基苯甲酮、ca-(2-氧代冰片-3-亚基)-甲苯基-4-磺酸及其可溶盐、3-(4'-磺基)亚苄基樟脑及其可溶盐、3-(4'-甲基亚苄基)-d,l-樟脑、3-亚苄基-d,l-樟脑、苯1,4-二(3-亚甲基-10-樟脑磺)酸及其盐、咪唑丙烯酸、2,4,6-三-(2'-乙基己基-1'-氧基羰基)-苯胺醇(anilinol)1,3,5-三嗪、2-(对(叔丁基酰胺基)苯胺醇-4,6-二(对-(2'-乙基己基1'-氧基羰基)苯胺醇1,3,5-三嗪、2,4-二{1,4-(2-乙基己氧基)-2-羟基-苯基}-6-(4-甲氧基苯基)-1,3,5-三嗪、N-(2et4)-(2-氧代冰片-3-亚基)甲基苄基丙烯酰胺的聚合物、1,4-二苯并咪唑基-亚苯基-3,3',5,5'-四磺酸及其盐、亚苄基丙二酸酯取代的聚有机硅氧烷、苯并***取代的聚有机硅氧烷(甲酚曲唑三硅氧烷)、溶解的2,2'-亚甲基-二-1,6-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚、2-甲基二苯甲酰基甲烷、4-甲基二苯甲酰基甲烷、4-异丙基二苯甲酰基甲烷、4-叔丁基二苯甲酰基甲烷、2,4-二甲基二苯甲酰基甲烷、2,5-二甲基二苯甲酰基甲烷、4,4'-二异丙基二苯甲酰基甲烷、4,4'-二甲氧基二苯甲酰基甲烷、4-叔丁基-4'-甲氧基二苯甲酰基甲烷、2-甲基-5-异丙基-4'-甲氧基二苯甲酰基甲烷、2-甲基-5-叔丁基-4'-甲氧基二苯甲酰基甲烷、2,4-二甲基-4'-甲氧基二苯甲酰基甲烷、2,6-二甲基-4-叔丁基-4'-甲氧基二苯甲酰基甲烷，以及包含至少一种前述防晒剂的组合。
个人护理组合物可以被具体地配制用作但不限于色彩化妆品、防晒剂、护发素、保湿剂等。用于这样的应用的合适形式和制剂是本领域普通技术人员已知的。例如，当配制用作防晒剂时，所述组合物可以是层状乳液、微乳液或纳米乳液的形式。此外，所述乳液可以是流体简单乳液、流体多重乳液、硬质简单乳液或硬质多重乳液。简单乳液或多重乳液可以包含含有分散的脂质囊泡或油滴的连续水相，或含分散的脂质囊泡或水滴的连续脂肪相。在一种实施方案中，防晒剂应用是具有连续水相的乳液，并且可以是棒、乳液、凝胶、喷雾等形式。用于形成防晒乳液的合适乳化剂包括例如本领域已知的乙氧基化表面活性剂，如聚山梨醇酯-20、月桂醇聚醚-7、月桂醇聚醚-4、可从SEPPIC获得的
305；油如植物油和矿物油；动物和/或合成蜡，例如蜂蜡、石蜡、米糠蜡、小烛树蜡、巴西棕榈蜡及其衍生物；和烃凝胶或膨润土型凝胶，如凝胶SS71、凝胶EA2786、季铵盐-18膨润土、38CE、凝胶ISD V或凝胶ISD；和有机硅乳化剂，如可从Goldschmidt Chemical公司获得的十六烷基聚二甲基硅氧烷共聚醇-聚甘油基4-异硬脂酸酯-己基月桂酸酯(
WE 09)，山嵛酸酯聚二甲基硅氧烷、十六烷基聚二甲基硅氧烷共聚醇(
EM 90)、(
EM 97)、月桂基聚甲基硅氧共聚醇(5200)、环聚甲基硅氧烷和聚二甲基硅氧烷共聚醇(DC5225C和DC3225C)、环五硅氧烷和聚二甲基硅氧烷共聚醇(SF1528)。
个人护理组合物可任选地包含维生素或皮肤营养剂。一些合适的试剂是神经酰胺、透明质酸、泛醇、肽(铜六肽-3)、AHA’s(乳酸)、视黄醇(棕榈酸视黄酯)-维他命A衍生物，维生素C(L-抗坏血酸)、BHA’s(水杨酸)、茶(绿茶、白茶、红茶)、大豆和其它植物衍生物、异黄酮(葡萄籽提取物)、六胜肽、巴西莓。
还可以向制剂中加入增塑剂以改善所得制剂的柔性和化妆性质。增塑剂经常用于避免成膜剂的脆性和破裂，并且包括例如卵磷脂、聚山梨醇酯、聚二甲基硅氧烷共聚醇、二醇、柠檬酸酯、甘油和聚二甲基硅氧烷。本领域技术人员可以基于所需的性质和设想的应用常规地改变所需增塑剂的量。
本发明的聚合物可以被掺入载体中，例如在施用后快速挥发的挥发性载体。挥发性载体可选自挥发性烃、挥发性硅酮及其混合物。
可用于个人护理产品的烃油包括沸点在60-260℃范围内的那些，包括具有约C8至约C20链长的烃油，甚至C8至C20异链烷烃。实例包括异十二烷、异十六烷、异二十烷(isoeocosane)、2,2,4-三甲基戊烷、2,3-二甲基己烷及其两种或更多种的混合物。
合适的挥发性硅酮流体包括具有对应于式(R2SiO)x的3、4和5元环结构的环聚甲基硅氧烷，其中x为约3至约6。
以上描述的内容包括本说明书的实例。当然，不可能为了描述本说明书而描述组分或方法的每个可想到的组合，但是本领域的普通技术人员可以认识到，本说明书的许多进一步的组合和排列是可能的。因此，本说明书旨在涵盖落入所附权利要求书的精神和范围内的所有这样的变更、修改和变化。此外，就在详细描述或权利要求书中使用术语“包括”而言，这一术语旨在以与术语“包含”相似的方式为包含性的，如在权利要求书中作为过渡词使用时所解释的“包含”。
实施例
实施例1：带有末端烯丙氧基醚基团的二苯砜官能化的聚有机硅氧烷
在氮气环境下，在配有回流冷凝器、滴液漏斗和机械搅拌器的三颈圆底烧瓶中，向烯丙氧基二苯砜(16.9g，0.051mol)和Karstedt催化剂(5ppm 2wt％Pt)溶于甲苯(100mL)中的溶液中，在30min时间内逐滴添加带有末端氢化物基团(氢化物(Hyd)当量0.952)的聚二甲基硅氧烷(334.52g，0.151mol)。将反应温度升高至85℃并继续，直到所有的氢化物峰从1H-NMR消失。将所得烯丙氧基醚封端的聚合物在150摄氏度下真空汽提3h以去除挥发性化合物和溶剂。获得产品为高粘度液体。(GPC：Mn＝12392，PDI-1.8；粘度：6Pa.S)。
实施例2：带有末端氢化物基团的二苯砜官能化的聚有机硅氧烷
在75℃下，向烯丙氧基二苯砜(25g，0.076mol)和Karstedt催化剂(0.09g，5ppm2wt％Pt)的甲苯(150mL)溶液中，在30min时间内逐滴添加带有末端氢化物基团(氢化物当量0.952)的聚二甲基硅氧烷(334.52g，0.151mol)。随后将反应温度升高至85℃并继续，直到所有的烯丙基峰从1H-NMR消失。将所得氢化物封端的聚合物在150摄氏度下真空汽提3h以去除挥发性化合物和溶剂。获得产品为低粘度液体。(GPC：Mn＝3069g/mol，PDI-1.7；粘度：0.33Pa.S)。
实施例3：带有末端乙烯基基团的二苯砜官能化的聚有机硅氧烷
向氢化物封端的二苯砜官能化的聚有机硅氧烷(71.9g)(在实施例2中获得)、甲苯(30mL)和铂催化剂(5ppm 2％Pt)的反应混合物中添加1,3-二乙烯基四甲基二硅氧烷(8.88g，0.048mol)并在110摄氏度下回流。继续反应，直到所有氢化物信号从1H-NMR消失。最后将所得聚合物在150摄氏度下真空汽提3h以去除挥发性化合物和溶剂。获得最终产品为低粘度液体。(GPC：Mn＝5014g/mol，PDI-1.9；粘度：0.56Pa.S)。
实施例4：带有末端环氧醚基团的二苯砜官能化的聚有机硅氧烷
向氢化物封端的二苯砜官能化的聚有机硅氧烷(43.1g)(在实施例2中获得)、甲苯(20mL)和铂催化剂(5ppm 2％Pt)的反应混合物中添加烯丙基缩水甘油醚(2.72g，0.024mol)并在75摄氏度下继续回流，直到所有氢化物都被环氧醚封端。通过在90摄氏度下真空汽提反应混合物4h来回收聚合物。获得产品为低粘度液体。(GPC：Mn＝4073g/mol，PDI-1.6；粘度：0.41Pa.S)。
实施例5：带有末端环氧基团的二苯砜官能化的聚有机硅氧烷
向氢化物封端的二苯砜官能化的聚有机硅氧烷(185.5g)(在实施例2中获得)、甲苯(80mL)和铂催化剂(5ppm 2％Pt)的反应混合物中添加1,2-环氧-4-乙烯基环己烯(12.71g，0.102mol)并在75摄氏度下继续回流，直到所有氢化物都被乙烯基环己基环氧化物封端。通过在90摄氏度下真空汽提反应混合物4h来回收聚合物。获得产品为低粘度液体。(GPC：Mn＝3992g/mol，PDI-1.7；粘度：0.47Pa.S)
实施例6：带有末端甲基丙烯酸酯基团的二苯砜官能化的聚有机硅氧烷
向氢化物封端的二苯砜官能化的聚有机硅氧烷(86.3g)(在实施例2中获得)、甲苯(40mL)、氢醌单甲醚(300ppm)和铂催化剂(5ppm 2％Pt)的反应混合物中添加甲基丙烯酸烯丙酯(6.01g，0.048mol)并在75摄氏度下继续反应，直到所有氢化物都被甲基丙烯酸酯官能团封端。通过在110摄氏度下真空汽提反应混合物5h来回收聚合物。获得产品为低粘度液体。(GPC：Mn＝5754g/mol，PDI-1.9；粘度：0.53Pa.S)
实施例7：带有末端三甲氧基硅烷基基团的二苯砜官能化的聚有机硅氧烷向氢化物封端的二苯砜官能化的聚有机硅氧烷(50.3g)(在实施例3中获得)、甲苯(20mL)和铂催化剂(5ppm 2％Pt)的反应混合物中添加乙烯基三甲氧基硅烷(4.9g，0.033mol)并在110摄氏度下继续反应，直到所有氢化物都被三甲氧基硅烷封端。通过在150摄氏度下真空汽提反应混合物3h来回收聚合物。获得产品为低粘度液体。(GPC：Mn＝3431g/mol，PDI-1.9；粘度：0.41Pa.S)
虽然上述的描述包含许多细节，但这些细节不应被解释为对本发明范围的限制，而仅作为其优选实施方案的示例。本领域技术人员可以设想在所附权利要求限定的本发明的范围和精神内的许多其它可能的变化方案。
Claims (12)
1.一种下式的聚合物：
其中R1-R12独立地选自氢、任选地含有杂原子的C1-C10一价烃基、任选地含有杂原子的C6-C20一价芳族基团、和任选地含有杂原子的C4-C30一价饱和或不饱和环烷基团、含1-20个硅原子的硅烷氧基团、Z1或Z2；
Z1和Z2独立地选自氢、任选地含有杂原子的C1-C10烃基、-OH、-NH2、-COOH或R16-A-R17-，其中A选自包含不饱和环状基团的基团，其选自芳族基团、官能化芳族基团、任选地包含杂原子的稠合芳族基团、不饱和脂环族基团、不饱和杂环基团或其两种或更多种的组合；R16和R17独立地选自无、任选地含有杂原子的C1-C10烃基、任选地含有杂原子的C6-C20芳族基团和任选地含有杂原子的C4-C30饱和或不饱和环烷基团；
Z3选自–R19-A-R19-，其中A选自包含不饱和环状部分的基团，其选自芳族基团、稠合芳族基团、不饱和脂环族基团、不饱和杂环基团，或其两种或更多种的组合；且R19选自无、任选地含有杂原子的C1-C10烃基、任选地含有杂原子的C6-C20芳族基团和任选地含有杂原子的C4-C30饱和或不饱和环烷基团；
m是1-100；x是0-200；且y是0-200，其中x+y≥1。
2.如权利要求1所述的聚合物，其中A独立地选自：C6至C12芳族基团；C10至C36稠合芳族环基团；C4-C36不饱和脂环族基团；和C4-C36不饱和杂环基团。
3.如权利要求1所述的聚合物，其中Z1、Z2和Z3中的一个或多个中的A选自式–A1-R18-A2-的基团，其中A1和A2独立地选自C6至C12芳基、C12-C36稠合芳族环基团、C5-C36不饱和脂环族基团和C5-C36不饱和杂环基团；且R18选自直接键、–(CH2)n-、-C(CH3)2-、-O-、-S-、-S(O)2-、-C(O)-、C(O)-NH-、-NH-C(O)-NH-、C(O)-O-、-CH＝N-或-CH＝N-N＝CH-，其中n是1-10。
4.如权利要求3所述的聚合物，其中A独立地选自：(A-i)；(A-ii)；
5.如权利要求1所述的聚合物，其中Z1、Z2和Z3中的A是
6.如权利要求1所述的聚合物，其中Z1、Z2和Z3中的A是
7.如权利要求1所述的聚合物，其中Z1和Z2中的R16选自CH2＝CH2-(CH2)a-、CH2＝CH2-(CH2)a-O-，其中a是0-10；且R17选自C2-C10二价烷基、-O-(CH2)b-或–O-C(O)-(CH2)b-，其中b是2-10；且Z3中的R19选自R17。
8.如权利要求1-7中任一项所述的聚合物，其数均分子量为约1000g/mol至约50000g/mol。
9.一种包含如权利要求1-8中任一项所述聚合物的汽车产品、家用产品、油漆、涂料、衣物洗涤剂、纺织品处理剂、石油或天然气产品、燃料电池、电子产品、农产品、航空航天产品、医疗或保健产品、膜、建筑产品、粘合剂、密封剂、可注塑和可压塑的橡胶或塑料、或硅酮基橡胶。
10.如权利要求9所述的产品，其选自：发光设备，计算机设备，叠层裸片，移动电话，平板电脑，倒装芯片封装，混合内存立方体，触摸屏，Wi-Fi设备，汽车技术hifi***，硅通孔设备，和音频***，在太阳能加热的供暖中的热管和水箱之间的连接中，在燃料电池和风力涡轮机中，在制造计算机芯片、游戏机、数据传输设备中，在照明设备中，电池，在外壳中，冷却器，热交换设备，电线，电缆，加热电线，冰箱，洗碗机，空调，蓄能器，变压器，激光器，功能性服装，汽车座椅，医疗设备，消防，电动机，飞机，和火车，作为3D打印材料的细丝，药物输送***，透皮贴剂，伤口愈合贴剂，伤口敷料贴剂，减疤贴剂，透皮离子电渗疗法，组织工程支架，抗微生物装置，伤口处理装置，眼科设备，生物***物，假体，身体植入物，油漆，结构涂料，砖石涂料，或船舶涂料，种子涂料，超级散播剂或控释肥料。
11.一种个人护理产品，其包含如权利要求1-8中任一项所述的聚合物。
12.如权利要求11所述的个人护理产品，其形式为：止汗剂/除臭剂，剃刮产品，皮肤乳液，保湿剂，调色剂，沐浴产品，清洁产品，洗发剂，护发素，组合洗发剂/护发素，摩丝，定型凝胶，喷发剂，染发剂，头发着色剂，漂发剂，卷发剂，直发剂，指甲油，指甲油去除剂，护甲霜或乳液，角质层软化剂，防晒剂，驱虫剂，抗衰老产品，口红，粉底，扑面粉，眼线产品，眼影，腮红，彩妆，睫毛膏，保湿制剂，粉底，身体和手部制剂，皮肤护理制剂，面部和颈部制剂，滋补品，敷料，头发梳理助剂，气溶胶固定剂，香味制剂，须后水，彩妆制剂，柔焦应用，夜间和日间护肤制剂，无着色头发制剂，晒黑制剂，合成的和非合成的皂条，洗手液，鼻贴，个人护理用无纺布应用，婴儿乳液，婴儿洗发剂，婴儿护发素，剃须制剂，黄瓜片，皮肤护垫，卸妆剂，面部清洁产品，冷霜，防晒产品，喷雾，糊剂面膜和泥，面膜，古龙水和淡香水，毛外皮凃剂，沐浴露，面部和身体洗涤剂，个人护理冲洗产品，凝胶，泡沫浴，擦洗清洁剂，收敛剂，指甲调理剂，眼影棒，用于脸部或眼睛的粉剂，润唇膏，唇彩，护发泵喷雾剂，毛发卷曲控制凝胶，免洗护发素，润发油，头发去缠结产品，头发固定剂，头发漂白剂，皮肤乳液，剃须前和电动剃须前产品，无水霜和乳液，油/水乳液，水/油乳液，抗水霜或乳液，抗粉刺制剂，漱口水，按摩油，牙膏，透明凝胶或棒，软膏基质，局部伤口愈合产品，气溶胶滑石，屏障喷雾剂，维生素和抗衰老制剂，草药提取制剂，沐浴盐，沐浴乳和身体乳，头发造型助剂，头发、眼部、指甲和皮肤柔软固体应用，控释个人护理产品，护发雾，护肤保湿雾，皮肤擦拭剂，毛孔皮肤擦拭剂，毛孔清洁剂，淡斑剂，皮肤去角质剂，皮肤脱屑强化剂，皮肤湿巾纸或布，脱毛制剂，或个人护理润滑剂。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/928,511 | 2018-03-22 | ||
| US15/928,511 US11472925B2 (en) | 2018-03-22 | 2018-03-22 | Silicone polymer |
| PCT/US2019/022243 WO2019182857A1 (en) | 2018-03-22 | 2019-03-14 | Silicone polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112189029A true CN112189029A (zh) | 2021-01-05 |
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Family Applications (1)
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|---|---|---|---|
| CN201980034728.7A Pending CN112189029A (zh) | 2018-03-22 | 2019-03-14 | 硅酮聚合物 |
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| Country | Link |
|---|---|
| US (1) | US11472925B2 (zh) |
| EP (1) | EP3768762A1 (zh) |
| JP (1) | JP7471228B2 (zh) |
| KR (1) | KR20200138261A (zh) |
| CN (1) | CN112189029A (zh) |
| TW (1) | TWI823914B (zh) |
| WO (1) | WO2019182857A1 (zh) |
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Also Published As
| Publication number | Publication date |
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| KR20200138261A (ko) | 2020-12-09 |
| WO2019182857A1 (en) | 2019-09-26 |
| TWI823914B (zh) | 2023-12-01 |
| US20190292323A1 (en) | 2019-09-26 |
| JP2021518468A (ja) | 2021-08-02 |
| EP3768762A1 (en) | 2021-01-27 |
| JP7471228B2 (ja) | 2024-04-19 |
| US11472925B2 (en) | 2022-10-18 |
| TW201940556A (zh) | 2019-10-16 |
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