CN112876687A - 一种有机硅烷化合物及制备方法和应用 - Google Patents
一种有机硅烷化合物及制备方法和应用 Download PDFInfo
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- 239000010703 silicon Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
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- HTWSCGLHVCBJLZ-UHFFFAOYSA-L 3-oxohexanoate;platinum(2+) Chemical compound [Pt+2].CCCC(=O)CC([O-])=O.CCCC(=O)CC([O-])=O HTWSCGLHVCBJLZ-UHFFFAOYSA-L 0.000 description 1
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- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000000962 organic group Chemical group 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
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
- C08G77/48—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/14—Compositions 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; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
本发明属于高分子材料技术领域,具体涉及一种含柔性硅氧链节的芳香官能化碳硼烷化合物及其制备方法与应用。本发明的制备方法简单,操作方便,适于工业化的大规模生产。而且,本发明的化合物可以作为交联剂或者聚合物的单体引入聚合物中,制备出有机/无机杂化组元的聚合物。所述聚合物因引入柔性硅氧链节使得聚合物的韧性提高,引入碳硼烷赋予聚合物耐更高温度、抗氧化性能提高、极限氧指数和水平垂直燃烧等本征阻燃性能提高、引入三嗪使其含多个乙烯基的硅氧烷链,能提高组合物的固化效率,其进一步用作复合材料应用于电子产品、电子装置中。
Description
技术领域
本发明属于高分子材料技术领域,具体涉及一种含柔性硅氧链节的芳香官能化碳硼烷化合物及其制备方法与应用。
背景技术
电子、电器等高技术领域的不断发展,对聚氨酯、聚酰亚胺、聚酰胺、聚脲、环氧树脂、聚硅氧烷等一系列的高分子材料的使用温度提出了越来越苛刻的需求,这就需要不断提高现有的有机高分子材料的热降解温度。从分子结构设计上引入特殊的结构成为制备先进高分子材料的途径之一。以含硅、硼、氮等无机元素组成的特殊结构受到青睐,比如呈六面体结构的倍半硅氧烷、二十面体的碳硼烷结构等。尤其是作为二十面体结构的碳硼烷,碳硼烷是具有邻位(o-carborane)、间位(m-carborane)、对位(p-carborane)三种异构体的大体积、高含硼量的立体结构。然而,这种特殊结构的碳硼烷是一类易升华的固体,若想在分子水平上将其引入聚合物的结构中,需要对碳硼烷的结构进行修饰,实现碳硼烷的官能化。
因此,如何制备耐高温的有机官能团修饰的笼型碳硼烷结构,可以使得高分子材料的耐高温、抗氧化、抗中子辐照等综合性能都大幅度的提高,成为碳硼烷改性高分子材料的关键技术挑战。
硅橡胶是以-Si-O-键为主链、有机基团为侧基的一类弹性体,自身具有特殊的半有机半无机结构,耐高低温性、耐候性、耐臭氧性、耐老化性、生理惰性和高透气性圴优异,在航空航天、汽车、电子和医疗器械等领域。
发明内容
本发明目的是提供一种在碳硼烷的笼型结构上修饰含柔性硅氧链节的乙烯基官能团,该结构创新性的将柔性硅氧链节与大体积、高含硼量的碳硼烷立体结构结合在一起,并通过活性的乙烯基赋予该结构高反应活性,可以方便的将两种结构在分子水平上引入有机高分子聚合物中,制备得到的有机高分子聚合物作为组合物时,组合物具有较低的介电常数及较高热分解温度、拉伸强度、断裂伸长率。
本发明的目的通过以下技术方案实现:本发明的有机硅烷化合物,结构式如式I所示:
其中,“-CB10H10C-”代表邻位碳硼烷基、间位碳硼烷基或对位碳硼烷基;
R1为-芳基-、-芳基-芳基-、-芳基-芳基-芳基-、或任选被一个或多个C1-10烷基或芳基取代的-芳基-、-芳基-芳基-、-芳基-芳基-芳基-;
R2为选自H、无取代或任选被一个或多个Ra取代的C1-10烷基、C3-20环烷基
R1选自苯基、甲苯基、乙基苯基、联苯基、萘基、蒽基、三联苯基中的一种;
R2选自甲基、乙基、三氟丙基、腈丙基中的一种;
本发明还提供了所述化合物的制备方法,包括以下步骤:
使含有多个乙烯基的环状化合物与含硅氢键化合物在有催化剂1存在的条件下进行硅氢加成反应,生成式I-1;
将式I-1与乙炔在有催化剂2存在的条件下进行硅氢加成反应,生成式I,
所述含有多个乙烯基的环状化合物:
所述含硅氢键化合物:
所述式I-1化合物为:
所述催化剂1优选铂黑、化合物诸如氯铂酸、氯铂酸六水合物、和一元醇的反应产物、双(乙基乙酰乙酸)铂、双(乙酰丙酮酸)铂、二氯化铂和所述化合物与烯烃或低分子量的有机聚硅氧烷或在基质或核壳类型结构中微囊化的铂化合物的复合物。
铂与低分子量的有机聚硅氧烷的复合物,包括具有铂的1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷复合物。这些复合物可于树脂基质中微囊化。
所述催化剂1于所述原料的用量为0.1ppm至1,0000ppm。
所述催化剂2优选钌化合物为羰基氯化钌[RuCl2(CO)3]2、三苯基膦氯化钌RuCl2(P(C6H5)3)3、水合氯化钌RuCl3·3H2O、十二羰基三钌Ru3(CO)12中的一种或者两种以上的混合物。
优选催化剂钌化合物的加入量以钌计为每千克反应体系中含有5~80mg钌。
所述钌化合物直接或者溶解在溶剂中后加入反应体系。优选溶剂为甲醇、乙醇、异丙醇、乙二醇二甲醚、乙二醇二乙醚、1,4-二氧六环中的一种或者两种以上的混合物。
所述反应温度为0~90℃,优选30~80℃。如果低于30℃,反应速率慢,如果高于80℃,会发生二次加成反应,生成大分子化合物。
优选胺类化合物为乙二胺、三乙胺、N,N-二甲基甲酰胺、N,N-二甲基苯胺、N,N’-双(2-氰乙基)二乙胺、1,2-双(2-氰基-2-丙基)肼、苯胺、吩噻嗪中的一种或者两种以上的混合物。
本发明还提供了所述化合物的制备方法,包括以下具体步骤:
(1)将含有多个乙烯基的环状化合物、硅氢键化合物、催化剂1及有机溶剂混合后,加热回流进行硅氢加成反应,生成所述式I-1。其中,所述的有机溶剂可以选自能够将含有多个乙烯基的环状化合物、硅氢键化合物溶解,但不会与含有多个乙烯基的环状化合物、硅氢键化合物、催化剂中任一种反应的有机溶剂,例如苯、甲苯等常见有机溶剂。进一步的,前述硅氢加成反应的条件可以参考“硅氢加成反应与研究”(邵阳师专学报,1998年第2期,p82-84)等文献。
(2)将式I-1、乙炔、助催化剂胺类化合物与催化剂钌化合物构成的反应体系进行反应,制得式I。
本发明还提供如权利要求1或者2所述的化合物的应用,具体是:将式I化合物作为单体:将式I化合物作为聚合单体与其他聚合单体进行反应,得到聚合物;其中,式I化合物具有前述定义。
所述其他聚合单体为具有可与乙烯基进行反应的基团的化合物。所述其他聚合单体优选含氢聚硅氧烷,所述的含氢聚硅氧烷是空间结构的聚硅氧烷,其结构通式如下:(HMe2SiO1/2)c(R3 2SiO2/2)d(R4SiO3/2)e(Ⅱ)缩写成:MHcDdTe式(Ⅱ)中,下标c、d、e表示三个链节之间的摩尔比,三者之间的比例决定这个空间结构的聚硅氧烷的分子量、形态和活性,c和e的比值为0.5~1.2;R3、R4是1~20个碳原子的烷基、烯基或芳基,包括甲基、乙基、丙基、戊基、己基、辛基、癸基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、乙烯基、苯基、苯乙烯;
所述含氢聚硅氧烷的含氢量为0.5~3.0mmol/g;
所述的含氢聚硅氧烷的用量为有机硅组合物总质量的0.1~10%;
进一步地,所述的含氢聚硅氧烷还包含甲基苯基聚硅氧烷;
进一步地,所述的含氢聚硅氧烷还包含结构控制剂,所述的结构控制剂是炔醇类物质(包括乙炔基环己醇、3,5-二甲基-1-己炔-3-醇),用量为有机硅组合物总质量0.1~5%;
进一步地,还包含催化剂3,硅氢加成反应催化剂,其中Pt原子在组合物中的浓度10-100ppm,如卡斯特催化剂、氯铂酸、氯铂酸与四甲基四乙烯基环四硅氧烷络合物;
进一步地,还包括固化剂为有机磷固化促进剂与咪唑基固化促进剂按质量比3:1混合而成。
本发明还记载了如上所述的聚合物在电子产品、电子装置领域的应用。
进一步地,所述的电子产品、电子装置,其特征在于选自以下中的一种:平板显示器、曲面显示器、计算机监视器、医疗监视器、摄像机、取景器、指环扫描器、虚拟现实或增强现实显示器。
本发明的有益效果是:
1.本发明的化合物引入柔性硅氧链节使得聚合物的韧性提高,引入碳硼烷赋予聚合物耐更高温度、抗氧化性能提高、极限氧指数和水平垂直燃烧等本征阻燃性能提高、引入三嗪使其含多个乙烯基的硅氧烷链,能提高组合物的固化效率,其进一步应用于电子装置中。
2.本发明的聚硅氧烷组合物具有较低的介电常数及较高热分解温度、拉伸强度、断裂伸长率。
具体实施方式
实施例1
(1)取0.5g硅氢加成催化剂铂金,加入5mL甲苯稀释,然后加入250mL三颈烧瓶中;
(2)取2.49g1,3,5-三烯丙基-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione,分子量MW=249.27g/mol),加入20mL甲苯稀释后加入三颈烧瓶;
(4)设置油浴温度130℃,开启搅拌,开启冷凝水,至三颈烧瓶内温度为119℃时,反应混合物开始回流;
(5)回流一段时间后,吸取少量反应混合物进行IR测试,以判断反应是否进行完全。
(6)48小时后,IR结果显示无碳碳双键吸收峰则表示反应结束,1H NMR结果显示无乙烯基H,此时将反应混合物转移至旋转蒸发仪蒸出溶剂,析出产物I-1,收率90%。FT-IR:3075~2920,2126,1691,1516,1253,1119,1053,901,836~626cm-1。1H-NMR(CDCl3):δ=0.24ppm(m,12H,CH3),δ=0.6ppm(m,1H,Si-H),δ=1.5ppm(m,4H,-CH2-),δ=6.8ppm(m,20H,C6H5),δ=1.69~2.95ppm(m,10H,B10H10)。
实施例2
在体积为2L的反应釜中,加入式I-1化合物221.49g(0.1mol),再加入催化剂羰基氯化钌[RuCl2(CO)3]2的1,4-二氧六环溶液10mL,使体系中钌的浓度为50μg/kg,加入N,N-二甲基苯胺0.2g,50℃下通入乙炔并搅拌,维持反应容器压力为0.5MPa,24小时后,反应液的GC检测结果显示反应体系组成不再变化,目标产物GC-FID面积归一化法含量为91.2%。FT-IR:3075~2930,2124,1696,1650,1513,1256,1120,1053,905,836~626cm-1;1H-NMR(CDCl3):δ=0.23ppm(m,12H,CH3),δ=1.3ppm(m,1H,CH),δ=1.5ppm(m,4H,-CH2-),δ=4.5ppm(d,2H,CH),δ=6.8ppm(m,20H,C6H5),δ=1.69~2.95ppm(m,10H,B10H10)。
实施例3
在容器中加入50份式I、5份疏水沉淀二氧化硅D10(赢创提供)、2份疏水气相二氧化硅R202(赢创提供),通过高速研磨,使得二氧化硅在其中的分散粒径小于1μm,在200rpm的转速下加入0.2份结构控制剂1-炔基环己醇C,然后再加入4ppm(以铂计)氯铂酸催化剂D,并混合5min,使得催化剂D在其中分散均匀,得到分散体X;保持分散体X的温度在20℃的情况下,保持550rpm的转速,向X中滴加9份含氢聚硅氧烷B-1/甲基苯基聚硅氧烷(折射率1.4630,粘度400.0cPs)混合物,滴加完毕后加入固化剂(有机磷固化促进剂与咪唑基固化促进剂按质量比3:1混合而成),然后在室温条件下缓慢搅拌8h后,保持负压-0.06MPa抽真空60min除去小分子,最后加入0.3份水G,混合均匀,即得到本发明的聚硅氧烷组合物GZ1。
试验例1
将实施例3得到的聚硅氧烷组合物GZ1进行介电常数、热分解温度、耐燃烧性、拉伸强度、断裂伸长率的测试,具体测试标准如下:
1.介电常数:
将材料制成直径为20mm、厚度为2mm的圆片,利用安捷伦4294A型精密阻抗分析仪或同类设备对其介电常数进行测试,测试频率为50Hz-30MHz。
2.热分解温度:
按照IPC-TM-6502.4.26方法进行测定。
3.耐燃烧性(难燃性):
依据UL94法测定。
4.力学性能测试
拉伸强度和断裂伸长率按照GB/T 528-2009进行测试。
具体测试结果见表1。
表1
由表1可知,本发明的聚硅氧烷组合物具有较低的介电常数及较高热分解温度、拉伸强度、断裂伸长率。该聚硅氧烷组合物可用在电子产品、电子装备领域的应用,具体包括平板显示器、曲面显示器、计算机监视器、医疗监视器、摄像机、取景器、指环扫描器、虚拟现实或增强现实显示器上的应用。例如:该聚硅氧烷组合物可很好的应用在指环扫描器的外壳及指环套上,当其应用在指环套上时,可有效避免指环套的断裂、提高指环套的大小适应性,非常适用于穿戴式的电子产品。
以上所述仅是本发明的优选实施方式,本发明的保护范围并不仅局限于上述实施例,凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理前提下的若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (7)
2.根据权利要求1所述的化合物,其特征在于,R1选自苯基、甲苯基、乙基苯基、联苯基、萘基、蒽基、三联苯基中的一种;R2选自甲基、乙基、三氟丙基、腈丙基中的一种。
4.如权利要求1或者2所述的化合物的应用,其特征在于:将式I化合物作为聚合单体与其他聚合单体进行反应,得到聚合物;其中,所述式I化合物具有权利要求1或2所述定义。
5.根据权利要求4所述的应用,其特征在于,所述其他聚合单体为具有可与乙烯基进行反应的基团的化合物。
6.如权利要求4中任一所述的聚合物在电子产品、电子装置领域的应用。
7.如权利要求6所述的电子产品、电子装置,其特征在于选自以下中的一种:平板显示器、曲面显示器、计算机监视器、医疗监视器、摄像机、取景器、指环扫描器、虚拟现实或增强现实显示器。
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