CN107873033B - 高ri硅氧烷单体、其聚合和应用 - Google Patents
高ri硅氧烷单体、其聚合和应用 Download PDFInfo
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- CN107873033B CN107873033B CN201680028002.9A CN201680028002A CN107873033B CN 107873033 B CN107873033 B CN 107873033B CN 201680028002 A CN201680028002 A CN 201680028002A CN 107873033 B CN107873033 B CN 107873033B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- QTEONXCRDRLVKU-UHFFFAOYSA-N diphenoxy(phenyl)silane Chemical compound O([SiH](Oc1ccccc1)c1ccccc1)c1ccccc1 QTEONXCRDRLVKU-UHFFFAOYSA-N 0.000 description 3
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 3
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- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 description 3
- LCOUXOWOYGPJPD-UHFFFAOYSA-N trimethyl-[3-phenoxysilyl-2,6-bis(trimethylsilyloxy)phenoxy]silane Chemical compound C[Si](OC1=C(C(=C(C=C1)[SiH2]OC1=CC=CC=C1)O[Si](C)(C)C)O[Si](C)(C)C)(C)C LCOUXOWOYGPJPD-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- PSAJMSZFTLLTNB-UHFFFAOYSA-N trimethoxy-(4-phenoxyphenyl)silane Chemical compound C1=CC([Si](OC)(OC)OC)=CC=C1OC1=CC=CC=C1 PSAJMSZFTLLTNB-UHFFFAOYSA-N 0.000 description 1
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- IXJNGXCZSCHDFE-UHFFFAOYSA-N triphenoxy(phenyl)silane Chemical compound C=1C=CC=CC=1O[Si](C=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 IXJNGXCZSCHDFE-UHFFFAOYSA-N 0.000 description 1
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- 238000007514 turning Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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Abstract
苯氧基苯基硅烷单体的合成和聚合。该聚合物具有高折射率和优异的UV和热稳定性。它们的水和氧气渗透性比商业苯基硅氧烷弹性体低。它们与金属氧化物纳米颗粒显示良好的相容性。本发明的聚合物适合作为LED封装剂,在CMOS图像传感器中,在OLED器件、激光器和其他光学领域中的光导材料。(p‑Ph‑O‑Ph)2Si(X)2 I p‑PhOPh‑Si(X)3 IIa p‑PhOPhOPh‑Si(X)3 IIb PhOPhOPh‑Si(X)3 IIc。
Description
技术领域
本发明涉及硅烷单体。特别地,本发明涉及高RI的硅氧烷单体、合成这种单体的方法和单体的聚合以产生高折射率和优异稳定性和良好水氧阻隔性的聚合物。
背景技术
照明行业正在迅速转向LED照明系统。典型LED的效率和功率输出已迅速上升。环氧化合物传统上被用作封装剂,但传统材料不能再处理最先进的LED产生的强光通量和热量。作为用于电子器件的已知封装材料的二甲基硅氧烷(PDMS),由于比环氧化合物更耐用、更耐黄,近来越来越多地用作LED的封装剂。
就涉及二甲基硅氧烷的使用而言,参考美国专利说明书No.4,278,784、No.6,492,204和No.6,806,509。
然而,相比于LED芯片(“epi”,例如InGaN,RI~2.5)以及白光LED中使用的许多发光材料(例如钇铝石榴石,“YAG”,RI~1.85),PDMS具有相对较低的折射率(RI~1.4)。这种折射率不匹配产生内部反射,降低了器件的光输出和效率。用较高RI的苯基硅氧烷(RI~1.50-1.55)代替PDMS稍微改善了这种情况,但仍然需要更高RI的材料,能够承受LED内部的条件而不发黄,并且适用于LED制造。
发明内容
技术问题
本发明的目的是消除与已知解决方法有关的至少一部分问题,并提供具有高折射率和优异稳定性的新型聚合物材料。
本发明的另一个目的是提供新型单体。
本发明的第三个目的是提供由单体生产聚合物的方法。
本发明的第四个目的是提供新型聚合物材料的应用。
技术问题的解决方法
关于本发明,令人惊讶地发现,苯氧基苯基硅烷和双-苯氧基苯基硅烷是适用于例如用作LED封装剂的聚合物的优良单体。
本发明提供了具有下式的硅氧烷单体
(p-Ph-O-Ph)2Si(X)2 I
其中,
每个X为独立地选自氢和任选地含有烷氧基取代基的低级烷氧基、卤素、羟基或-OSiMe3的可水解基团。
本发明还提供了具有下式的硅氧烷单体
p-(PhO)yPh-Si(X)3 II
其中,
每个X为独立地选自氢和任选地含有烷氧基取代基的低级烷氧基、卤素、羟基或-OSiMe3的可水解基团,且y为1或2。
由苯氧基苯基硅烷和/或双-苯氧基苯基硅烷衍生的聚合物。
更具体地说,根据本发明所述的单体的特征在于权利要求1、2、3和4中所述的内容。
从单体获得的聚合物的特征在于权利要求6的特征部分所述的内容。
所述聚合物的应用的特征在于权利要求15-18中所述的内容。
发明的有益效果
本发明的单体是二-或三苯基醚硅烷。
通过本发明可获得相当大的优点。因此,许多由苯氧基苯基硅烷和/或双-苯氧基苯基硅烷衍生的聚合物,例如通过常规的水解和聚合方法得到的聚合物,具有高于苯基硅氧烷或苯基硅酮的折射率。这些聚合物对UV-A和蓝光具有抗性,并具有高的热稳定性。典型地,本发明聚合物的氧气透过率(OTR)和水蒸气透过率(WVTR)小于苯基硅氧烷弹性体的OTR和WVTR的50%。
接下来,将更详细地描述本技术的实施方式。
附图的简要说明
图1显示了双(苯氧基苯基)-双(三甲基甲硅烷氧基)硅烷的质谱图;
图2显示了三(三甲基甲硅烷氧基)-苯氧基苯基硅烷的质谱图;和
图3显示了PhOPhOPhTMOS的质谱图。
实施方式
第一个实施方式包含具有下式的硅氧烷单体A
(p-Ph-O-Ph)2Si(X)2 I
其中,
每个X为独立地选自氢和任选地含有烷氧基取代基的低级烷氧基、卤素、乙酰氧基、羟基或-OSiMe3的可水解基团。
第二个实施方式包含具有下式的硅氧烷单体B
p-PhOPh-Si(X)3 IIa
其中,
每个X为独立地选自氢和任选地含有烷氧基取代基的低级烷氧基、卤素、乙酰氧基、羟基或-OSiMe3的可水解基团。
第三个实施方式包含具有下式的硅氧烷单体C
p-PhOPhOPh-Si(X)3 IIb
其中,
每个X为独立地选自氢和任选地含有烷氧基取代基的低级烷氧基、卤素、乙酰氧基、羟基或-OSiMe3的可水解基团。
在通常的实施方式中,硅氧烷单体C符合通式(IIc):
PhOPhOPh-Si(X)4-k IIc
其中,
每个X为独立地选自氢和任选地含有烷氧基取代基的低级烷氧基、卤素、乙酰氧基、羟基或-OSiMe3的可水解基团,且k为1-3的整数。
式IIc的实施方式具有式p-PhOPhOPh-Si(X)4-k,其中X和k具有与以上相同的含义。
优选地,在X的含义上,低级烷氧基代表具有1-6个碳原子,特别是1-4个碳原子的烷氧基。这样的烷氧基的例子包括甲氧基(-OMe)、乙氧基(-OEt)、正丙氧基和异丙氧基(-OPr)、正丁氧基、异丁氧基和叔丁氧基(-OBu)。其他例子包括烷氧基醚,例如-O-CH2CH2-O-CH3。
在卤素的含义上,X优选代表氯(Cl)或溴(Br)。
根据上式的单体的具体例子是:
双(苯氧基苯基)-二甲氧基硅烷;
双(苯氧基苯基)-二羟基硅烷;
双(苯氧基苯基)-双(三甲基甲硅烷氧基)硅烷;
对苯氧基苯基三羟基硅烷;和
对苯氧基苯氧基苯基三甲氧基硅烷。
本发明的单体是苯基醚硅烷,其不含任何与硅烷键合的不可水解基团,例如苯基。
所述单体通过格氏合成方便地制备,使用四烷氧基硅烷作为起始单体和溴苯基苯基醚或溴苯基苯基二苯醚作为有机卤化物。
如果需要额外的功能,起始硅烷也可以是甲基三烷氧基硅烷或乙烯基三烷氧基硅烷。例如,乙烯基三甲氧基硅烷可以通过乙烯基的自由基或氢化硅烷化固化机理进行交联。氯硅烷如二氯硅烷也可用于苯氧基苯基硅烷或苯氧基苯氧基苯基硅烷单体的格氏合成。
在一个实施方式中,式I或II的单体可以通过常规的水解聚合而聚合。因此,式I的单体或式IIa-IIc中的任何一个单体可以均聚或者可以与另一个式(IIa-IIc或I)的单体共聚。
因此,在一个实施方式中,聚合物通过式IIb或IIc的单体任选地与选自具有式I、IIa或IIc或IIb的硅氧烷单体的一种或两种或三种单体水解和聚合获得。
也可以使用选自硅烷、锗烷和锆醇盐及其组合的另一单体制备具有式I或II单体的共聚物。因此,也可以生产三元共聚物。
从聚合物合成中使用的式I和IIa-IIc的单体获得的部分的组合摩尔%为总单体量的至少10摩尔%。
在实施方式中,使用碱性或酸性催化剂。
在一个实施方式中,在缩合反应之前,一些或全部的烷氧基被水解成硅烷醇基。碱催化有利于烷氧基与硅烷醇基之间的反应,这一特性可用于确保不同硅烷单体之间的成功共聚反应。如果存在对酸敏感的官能团如乙烯基醚,碱催化也是有利的。
例如,双(对苯氧基苯基)二甲氧基硅烷(Bis(PhOPh)DMOS)可用稀盐酸水解,得到双(对苯氧基苯基)二羟基硅烷,由于双芳基硅烷二醇相对较好的一般储存稳定性,因此可以分离和储存。
然后,使用碱金属氢氧化物如LiOH、NaOH、KOH、Ba(OH)2或它们的醇盐如NaOMe、氨、胺、各种磷腈超碱、胍或四烷基氢氧化铵如四丙基氢氧化铵,使其与例如甲基丙烯酰氧基甲基三甲氧基硅烷(MAMTMOS)聚合。
杂缩合的副产物是甲醇,而硅烷醇-硅烷醇均聚反应往往只是一个小的副反应。如果单体在其一般反应性方面具有高差异性,则碱催化剂是有利的。
烷氧基硅烷(或甲硅烷基卤化物或酰氧基硅烷)的酸催化聚合通过使用稀酸溶液同时水解和聚合硅烷单体来完成。然而,水解和聚合反应有时也可以分开进行。如果碱敏感的官能团存在,那么在催化反应过程中不希望发生反应(如Si-H或某些酯键),酸催化是有利的聚合方法。通常使用稀释的无机酸,如d.HCl、d.H2SO4或d.HNO3。也可以使用羧酸如乙酸或草酸。各种膦酰氯也被认为是优异的硅烷醇缩合催化剂。最后,一些弱酸性盐也可以促进硅烷醇缩合,如吡啶盐酸盐。
稀酸的浓度通常是0.001M-1M,特别是0.01-0.5M。
通常在任何上述共聚物中,聚合物合成中单体A(式I的单体)和单体B(式IIa-IIc的单体)的组合摩尔%为总单体量的至少10摩尔%,优选为至少20摩尔%,例如至少30摩尔%、至少40摩尔%、至少50摩尔%、至少60摩尔%、至少70摩尔%、至少80摩尔%或至少90摩尔%。
聚合可以在升高的温度下任选地在添加的催化剂(0.0001-5摩尔%,例如0.001-2.5摩尔%,从单体和催化剂的总摩尔量计算)的存在下进行。
在添加的催化剂存在下,聚合通常在约10-200℃,例如20-180℃、或30-170℃、或40-150℃的低或中等温度下进行。
典型地,在不添加催化剂的情况下,温度在200-500℃的范围内,例如200-400℃、例如200-350℃。特别是在没有缩合催化剂的情况下,通常需要200-400℃的温度。
除了上面讨论的碱性或酸性催化剂之外,所用的催化剂可以选自锆醇盐或钛醇盐催化剂。
在一个实施方式中,水解和聚合在水存在下进行。
在一个实施方式中,水解和聚合在没有水的情况下进行。
溶剂如丙酮、异丙醇、甲苯或甲醇可用于使组分进入单一相或促进适当的搅拌。
无水聚合也可以用来形成硅氧烷聚合物。例如,烷氧基硅烷和酰氧基硅烷之间的反应产生硅氧烷聚合物,并被钛或锆的醇盐催化。在甲氧基硅烷和乙酰氧基硅烷的情况下,缩合副产物是酯,例如乙酸甲酯。
可用于聚合本发明的硅烷单体的第四反应是酸或碱催化的环状硅氧烷的开环聚合。例如双(苯氧基苯基)-二甲氧基硅烷(Bis(PhOPh)DMOS)可以水解并缩合成环状三聚体、四聚体或五聚体,其可以在适当条件下开环以产生线性聚合物。其他环状硅烷可与环状双(苯氧基苯基)硅氧烷一起共聚。
聚合物基本上可以是线性的或者它可以含有一个或多个提供主链侧基的单体。分子量可以在500-1,000,000g/mol之间变化,更优选在500-10,000g/mol之间变化。
在一个实施方式中,聚合物链通过选自Si-OH、Si-OMe、Si-OEt、Si-H、乙烯基、丙烯酰基、甲基丙烯酰基、环氧基、乙酰氧基和巯基中的至少一种的可交联基团交联。
交联的一个目的是凝固材料,使其不再流动。一些交联体系是一个组分,另一些是两个组分。例如,过氧化物固化是一种组分体系,而铂可固化组合物由两种组分组成,第一种具有含Si-乙烯基的聚合物和铂,如铂-二乙烯基四甲基二硅氧烷络合物(Karstedt催化剂)加上任选的抑制剂如ETCH(1-乙炔基环己醇)和膦,第二种成分具有带Si-H官能团的硅氧烷聚合物。此外,即使在不存在任何特定交联基团的情况下,硅氧烷树脂有时也可以通过加热使残余硅烷醇基团交联而被热固化。
在一个实施方式中,通过任何上述实施方式获得的聚合物表现出小于苯基硅氧烷弹性体相应的OTR和WVTR值的50%的氧气透过率(OTR)和水蒸气透过率(WVTR)。
在一个实施方式中,提供了聚合物复合材料。特别地,所述复合材料尤其由根据上文公开的任何实施方式的聚合物与金属、氧化硅或金刚石的结合制成的颗粒、薄片、纳米颗粒或纳米棒形式提供。
在一个实施方式中,所述聚合物还可与气相二氧化硅,炭黑,金属氧化物如ZrO2、TiO2、Ta2O5、Al2O3,银颗粒,纳米金刚石,金纳米棒,玻璃纤维,彩色油墨或其它聚合物共混以便定制聚合物体系的特定性质。例如,可以使用氧化钛和氧化锆纳米颗粒来进一步增加聚合物的折射率。
在一个实施方式中,取决于固化体系和预期应用,可以加入热酸产生剂、热碱产生剂、自由基引发剂、贵金属催化剂如铂、光诱导自由基、碱或酸产生剂、锡催化剂和钛醇盐以促进聚合物交联。
而且,可以包含商业用热和光稳定剂如受阻胺、膦类化合物、酚类稳定剂以进一步增强这些性能。
通常,任何上述实施方式的聚合物复合材料中添加的组分的量通常为聚合物复合材料总重量的0.1-75重量%,典型地为1-50重量%,例如2.5-40重量%,或5至30重量%。
所述聚合物和聚合物复合材料可用于生产薄膜。典型地,这样的膜具有在0.01μm-3mm范围内的厚度,例如0.05-500μm。
由上述实施方式的聚合物或聚合物复合物制成的膜可以通过选自旋涂、喷涂、浸涂、狭缝涂布或丝网印刷聚合物的技术来制备,然后任选地通过水分、热、或UV进行干燥和固化。
所述聚合物或聚合物复合材料,任选地以薄膜的形式,可以用于以下应用中,提及几种:
-LED器件,
-CMOS图像传感器,
-液晶显示器和OLED器件,和
-光学领域。
实施例
实施例1
在干燥的氮气下,将THF(150g)、镁(26g)、四甲氧基硅烷(150g)置于1L三颈烧瓶中并加热回流。缓慢滴入对溴苯基醚。逐渐加入更多的THF(~200mL)以促进磁力搅拌。当通过GC/MS判断反应结束时,加入庚烷以沉淀镁盐。过滤后,在旋转蒸发器中除去溶剂。蒸馏粗产物,得到沸点为120℃/0.1mbar的(PhOPh)Si(OMe)3和沸点为220℃/0.1mbar的双(PhOPh)Si(OMe)2的两个级分。
实施例2a
将双(PhOPh)DMOS(10g)水解于含10g甲醇和1g 0.1M HCl的100mL烧瓶中。当形成单相时,逐渐加入更多的DIW(10g)并搅拌1小时。然后,加入更多的DIW(50g)以沉淀为白色固体的双(PhOPh)Si(OH)2。倾析水层,固体用DIW洗涤两次并干燥过夜。固体的GPC只显示一个尖峰,表明材料是纯的。
实施例2b
将双(PhOPh)Si(OH)2(0.1g)溶解于8mL玻璃小瓶中的无水THF中,并快速加入三乙胺(1mL)和三甲基氯硅烷(1mL)。振荡小瓶2分钟,过滤除去TEA-盐。样品的GPC和GC/MS(图)在m/z=544处显示的峰,对应于预期的双(苯氧基苯基)-双(三甲基甲硅烷氧基)硅烷。它的分子量为544.85。
双(苯氧基苯基)-双(三甲基甲硅烷氧基)硅烷的质谱图如图1所示。
实施例3.PhOPhSi(OH)3
将来自实施例1的PhOPhTMOS(20g)用甲醇(20g)稀释。加入0.1M HCl(1g),然后缓慢加入DIW(100g)。形成白色粉末沉淀。将其过滤,用DIW洗涤并在35℃下真空干燥2小时。将小样品(0.1g)粉末溶解于THF(1mL)中,通过将其快速添加到MTBE(4mL)、三甲基氯硅烷(TMSCL,1mL)和无水三乙胺(1.5mL)的溶液中进行TMS甲硅烷基化。样品的GC/MS在m/z=464处得到的峰(图),对应于三(三甲基甲硅烷氧基)苯氧基苯基硅烷。这表明,白色粉末是对苯氧基苯基三羟基硅烷,PhOPhSi(OH)3。它的分子量为464.85。
三(三甲基甲硅烷氧基)苯氧基苯基硅烷的质谱图如图2所示。
实施例4.PhOPhOPhTMOS
将对溴苯基苯基醚(20g)、对溴苯酚(9g)、K3PO4(17g)、Cu(BiPy)2BF4(1g,“Cu*”,可溶性铜催化剂,N.Jiajia et.al.,J.Org.Chem.2008,73,7814-7817)和二甲基甲酰胺(DMF,60mL)置于250mL具有松散栓的烧瓶中,并将该体系在100℃下加热并搅拌三天。将溶液倒入水中,并将有机物溶于二氯甲烷(DCM)中。在溶剂蒸发和真空蒸馏(<1mbar,180℃)后,获得7克对(苯氧基苯氧基)溴苯(PhOPhOPhBr)。通过从MeOH重结晶进一步纯化,得到纯净的白色结晶。将6克PhOPhOPhBr溶于无水THF(15克)中,加入镁屑(1克)和TMOS(5克)。该体系回流2小时,在此期间发生反应。然后蒸发THF,产物在甲苯/DIW中洗涤。
在<1mbar/~200℃下蒸馏后,通过GC/MS获得纯度为95+%的~5克苯氧基苯氧基苯基三甲氧基硅烷(PhOPhOPhTMOS)。单体在丙酮中用稀盐酸水解和聚合,得到低聚物和聚合物的混合物(通过GPC,Mw/Mn=2325/1924),聚合物通过旋涂和在250℃下固化形成无色膜。该膜具有高折射率(在633nm下RI=1.612)。
PhOPhOPhTMOS的质谱图如图3所示。
聚合物实施例1
将PhOPhOPhTMOS(3g)在丙酮(3g)中用稀盐酸(1g)水解和聚合,得到低聚物和聚合物部分的混合物(通过GPC,Mw/Mn=2325/1924),聚合物通过旋涂和在250℃下固化形成无色膜。该膜具有高折射率(在633nm下RI=1.612)。
聚合物实施例2
将来自实施例2的所有粗制双(PhOPh)Si(OH)2、PhOPhTMOS(5g)、甲基丙烯酰氧基甲基三甲氧基硅烷(2g)和0.2g 5%Ba(OH)2的甲醇溶液置于烧瓶中。将烧瓶加热至80℃,同时搅拌1小时。将反应物冷却至室温后,用过量的HCl中和氢氧化钡,并用DCM溶液中的DIW洗涤至中性。在95℃/1mbar下干燥,得到13.8克聚合物,Mw/Mn=1389/884,折射率为1.60171。用1173(2%)配制,在365nm(6J/cm2,30秒)的汞灯下固化。获得柔软的无色膜。
聚合物实施例3
将PhOPhTMOS(6.5g)和3-甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTM,4.5g)与0.5mL Ba(OH)2/甲醇溶液(5%)一起置于100mL烧瓶中。将烧瓶加热至70℃,在温度升至80℃的同时逐渐加入双(PhOPh)Si(OH)2(10g)和PhOPhSi(OH)3(2.15g)。反应2小时后,将聚合物用0.1M HCl和DIW在甲苯中洗涤至中性,并从甲醇中沉淀两次。干燥后,获得Mw/Mn=2147/1265和RI=1.59408的透明聚合物。用1173(2%)配制,在365nm(6J/cm2,30秒)汞灯下固化。获得柔软的无色膜。
聚合物实施例4
将PhOPhTMOS(15g)和双(PhOPh)DMOS(5g)置于含有0.5mL Ba(OH)2/甲醇溶液(5%)的50mL烧瓶中。将烧瓶加热至85℃,逐渐加入双(PhOPh)Si(OH)2(25g)。温度升至90℃。反应1小时后,将聚合物用0.1M HCl和DIW在甲苯中洗涤至中性,并从甲醇中沉淀两次。干燥后,得到Mw/Mn=2325/1580的透明聚合物(42g)。将聚合物溶于丙酮(80g)中并加入5滴cHCl,然后缓慢加入DIW(~100mL)。这样,末端Si-OMe基团被水解成Si-OH基团。
将聚合物(通过GPC,Mw/Mn=1483/916)分离、干燥,并分成两份~18g部分“A”和“B”。“A”部分用30mL THF稀释,并加入1,3-二乙烯基四甲基二硅氮烷(5g)以及少量的全氟苯胺-三氟甲磺酸盐作为催化剂。使反应在室温下进行24小时。同样地处理部分“B”,但是使用1,1,3,3-四甲基二硅氮烷作为Si-OH基团的甲硅烷基化剂。两种聚合物的分子量为:A-Mw/Mn=1870/1348,B-Mw/Mn=1714/1164。
蒸发“A”和“B”,用甲苯稀释,用稀盐酸和DIW洗涤几次,然后用旋转蒸发器干燥。
固化:“A”部分用Karstedt铂(来自Aldrich的2%二甲苯溶液)配制为20ppm的Pt。将等同量的部分“B”与上述A部分和铂的混合物混合。在150℃/1小时的烘箱中固化成50μm厚的薄膜。该膜具有98.5%的初始透明度,在UV-A照射(8J/cm2,2周)下不变。另外,在190℃下加热300小时后,透明度大于95%。对于厚度为0.56mm的膜,测量的氧气透过率(OTR)为240cc/m2/天(23℃)和水蒸气透过率(WVTR)3.4g/m2/天,90%RT,23℃。因此,这种材料的OTR比市售的苯基硅氧烷弹性体(~1120,T×0.91mm)小约3倍,WVTR小约31/2倍(~19,T×0.91mm)。这是重要的,因为与LED-硅氧烷树脂混合以得到高CRI(显色指数)白光的一些荧光粉对水分和氧气是敏感的。通过从20%二甲苯溶液中旋转浇铸形成混合物部分A+部分B的较薄膜,然后在150℃/1小时下烘烤。通过Woollam椭偏仪测量获得在633nm处具有T×~1μm和RI~1.61的无色膜。
还用ZrO2-纳米颗粒(2g,27%的MIBK溶液(住友商事的MZ-300B),聚合物:ZrO2-np~1:1)配制了部分A+部分B的1:1混合物(总计0.5g)。将溶液通过0.45μPTFE过滤器过滤并旋涂在硅晶片上。在150℃下固化1小时后,形成透明的1.5微米薄膜,RI=1.72。在190℃的烘箱中,薄膜保持无色,表明具有良好的热稳定性。
工业适用性
本发明的聚合物适合作为LED封装剂,CMOS图像传感器,OLED器件、激光器和其他光学应用中的光导材料。
引用列表
专利文献
US 4,278,784,
US 6,492,204
US 6,806,509
US 2009146324
非专利文献
N.Jiajia et.al.,J.Org.Chem.2008,73,7814-7817。
Claims (16)
1.通过具有式I、IIa、IIb和IIc的单体中的两种、三种或四种的水解和聚合获得的聚合物,
(p-Ph-O-Ph)2Si(X)2 I
p-PhOPh-Si(X)3 IIa
p-PhOPhOPh-Si(X)3 IIb
PhOPhOPh-Si(X)3 IIc
其中,每个X为独立地选自氢、具有1-6个碳原子的烷氧基、卤素、乙酰氧基、羟基或-OSiMe3。
2.根据权利要求1所述的聚合物,其特征在于,每个X为独立地选自-OMe、-OEt、-OPr和-OBu,-Cl,-Br,乙酰氧基,氢,-OH和-OSiMe3。
3.根据权利要求1所述的聚合物,其特征在于,其进一步含有选自硅烷、锗烷和锆醇盐及其组合的单体的部分,在聚合物合成中使用的根据式I和IIa-IIc的单体的组合摩尔%为总单体量的至少10摩尔%。
4.根据权利要求1-3中任一项所述的聚合物,其特征在于,其通过在催化剂存在下聚合获得。
5.根据权利要求4所述的聚合物,其特征在于,所述催化剂为碱性催化剂,酸性催化剂,锆醇盐催化剂或钛醇盐催化剂。
6.根据权利要求1-3中任一项所述的聚合物,其特征在于,其通过在升高的温度下进行水解和聚合获得,任选地在不添加催化剂的情况下进行。
7.权利要求1-3中任一项所述的聚合物,其特征在于,其通过在存在或不存在水的情况下水解和聚合获得。
8.根据权利要求1-3中任一项所述的聚合物,其特征在于,所述聚合物通过选自Si-OH、Si-OMe、Si-OEt、Si-H、乙烯基、丙烯酰基、甲基丙烯酰基、环氧基、乙酰氧基和巯基中的至少一种的可交联基团交联。
9.权利要求1-3中任一项所述的聚合物,其特征在于,所述聚合物的氧气透过率(OTR)和水蒸气透过率(WVTR)小于苯基硅氧烷弹性体OTR和WVTR的50%。
10.由根据权利要求1-9中任一项所述的聚合物与金属、氧化硅、金属氧化物或金刚石的结合制成的颗粒、薄片或纳米棒形式的聚合物复合材料。
11.根据权利要求10所述的聚合物复合材料,其特征在于,所述聚合物复合材料的形式为纳米颗粒。
12.由权利要求1-9中任一项所述的聚合物或权利要求10或11所述的聚合物复合材料通过旋涂、喷涂、浸涂、狭缝涂布或丝网印刷聚合物,然后任选地通过热或UV进行干燥和固化制成的膜。
13.权利要求1-9中任一项所述的聚合物或权利要求10或11所述的聚合物复合材料在LED器件中的应用。
14.权利要求1-9中任一项所述的聚合物或权利要求10或11所述的聚合物复合材料在CMOS图像传感器中的应用。
15.权利要求1-9中任一项所述的聚合物或权利要求10或11所述的聚合物复合材料在LCD显示器和OLED器件中的应用。
16.权利要求1-9中任一项所述的聚合物或权利要求10或11所述的聚合物复合材料在光学领域中的应用。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3385878A (en) * | 1965-03-04 | 1968-05-28 | Gen Electric | Cyclopolysiloxanes |
US4756971A (en) * | 1984-12-28 | 1988-07-12 | Ksv-Chemicals Oy | Surface treatment agents and polymers comprising substituted phenyl silanes and siloxanes |
US20100233632A1 (en) * | 2009-03-13 | 2010-09-16 | Jsr Corporation | Silicon-containing film-forming composition, silicon-containing film, and pattern forming method |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU27905A1 (ru) | 1931-05-06 | 1932-09-30 | Всесоюзный научно-исследовательский институт строительных материалов (ВНИСМ) | Калориметр дл в зких и порошкообразных веществ |
US2258221A (en) * | 1940-04-27 | 1941-10-07 | Gen Electric | Aroxy silicones and insulated conductors and other products utilizing the same |
US2813887A (en) * | 1953-11-20 | 1957-11-19 | Metal & Thermit Corp | Preparation of arylhalosilanes |
US3114759A (en) * | 1960-11-25 | 1963-12-17 | Gen Electric | High temperature fluids |
SU427943A1 (ru) | 1972-09-13 | 1974-05-15 | Способ получения ялрл-замещенных феноксифенилхлорсиланов | |
US4278784A (en) | 1980-02-06 | 1981-07-14 | Western Electric Company, Inc. | Encapsulated electronic devices and encapsulating compositions |
US6492204B1 (en) | 1999-01-26 | 2002-12-10 | Jp Ox Engineering | Electronic devices having thermodynamic encapsulant portions predominating over thermostatic encapsulant portions |
TW200427111A (en) | 2003-03-12 | 2004-12-01 | Shinetsu Chemical Co | Material for coating/protecting light-emitting semiconductor and the light-emitting semiconductor device |
US8029904B2 (en) * | 2006-12-01 | 2011-10-04 | Rohm And Haas Company | Aryl (thio)ether aryl polysiloxane composition and methods for making and using same |
JP5302586B2 (ja) * | 2007-07-27 | 2013-10-02 | ローム アンド ハース カンパニー | (チオ)フェノキシフェニルシラン組成物およびその製造方法 |
US8637627B2 (en) | 2007-12-06 | 2014-01-28 | Rohm And Haas Company | Phenoxyphenyl polysiloxane composition and method for making and using same |
KR101876600B1 (ko) * | 2011-03-30 | 2018-07-09 | 제이에스알 가부시끼가이샤 | 다층 레지스트 공정 패턴 형성 방법 및 다층 레지스트 공정용 무기막 형성 조성물 |
US8450445B2 (en) | 2011-08-17 | 2013-05-28 | Rohm And Haas Electronic Materials Llc | Light emitting diode manufacturing method |
US8455607B2 (en) | 2011-08-17 | 2013-06-04 | Rohm And Haas Electronic Materials Llc | Curable liquid composite light emitting diode encapsulant |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3385878A (en) * | 1965-03-04 | 1968-05-28 | Gen Electric | Cyclopolysiloxanes |
US4756971A (en) * | 1984-12-28 | 1988-07-12 | Ksv-Chemicals Oy | Surface treatment agents and polymers comprising substituted phenyl silanes and siloxanes |
US20100233632A1 (en) * | 2009-03-13 | 2010-09-16 | Jsr Corporation | Silicon-containing film-forming composition, silicon-containing film, and pattern forming method |
Non-Patent Citations (2)
Title |
---|
RN号1443342-27-5;STN;《STN》;20130708;19页 * |
synthesis of organosilicon monomers containing radicals with ether bonds;sobolev, ES et al.;《ZHURNAL OBSHCHEI KHIMII》;19691231;表1 * |
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