阅读说明：本技术 一种有机硅烷化合物及制备方法和应用 (Organosilane compound, preparation method and application ) 是由 杨心怀 周洁 高文中 于 2021-01-15 设计创作，主要内容包括：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。(The invention belongs to the technical field of high polymer materials, and particularly relates to an aromatic functionalized carborane compound containing flexible silica chain links, and a preparation method and application thereof. The preparation method is simple, convenient to operate and suitable for industrial large-scale production. Moreover, the compound of the present invention can be introduced into a polymer as a crosslinking agent or a monomer of the polymer to prepare a polymer of an organic/inorganic hybrid component. The toughness of the polymer is improved due to the introduction of the flexible silica chain link, intrinsic flame retardant properties such as higher temperature resistance, improved oxidation resistance, limited oxygen index, horizontal and vertical combustion and the like are improved due to the introduction of carborane, and curing efficiency of the composition can be improved due to the introduction of triazine to enable the triazine to contain a plurality of vinyl siloxane chains, so that the polymer is further used as a composite material to be applied to electronic products and electronic devices.)

1. An organosilane compound having a formula shown in formula I:

wherein "-CB 10H 10C-" represents an ortho-carboranyl group, a meta-carboranyl group or a para-carboranyl group;

r1 is-aryl-, -aryl-, or-aryl-, -aryl-optionally substituted with one or more C1-10 alkyl or aryl;

r2 is selected from H, C1-10 alkyl, unsubstituted or optionally substituted with one or more Ra, C3-20 cycloalkyl;

n＝1-10。

2. the compound of claim 1, wherein R1 is selected from one of phenyl, tolyl, ethylphenyl, biphenyl, naphthyl, anthracenyl, and terphenyl; r2 is selected from one of methyl, ethyl, trifluoropropyl and cyanopropyl.

3. A process for the preparation of a compound according to claim 1 or 2, comprising the steps of:

carrying out hydrosilylation reaction on a cyclic compound containing a plurality of vinyl groups and a silicon-containing hydrogen bond compound in the presence of a catalyst (1) to generate a formula I-1;

carrying out hydrosilylation reaction on formula I-1 and acetylene in the presence of a catalyst (2) to generate formula I,

the cyclic compound containing a plurality of vinyl groups is as follows:

the silicon-hydrogen bond-containing compound is as follows:

the formula I-1:

the acetylene:

4. use of a compound according to claim 1 or 2, wherein: reacting a compound shown in the formula I as a polymerization monomer with other polymerization monomers to obtain a polymer; wherein the compound of formula I has the definition as defined in claim 1 or 2.

5. Use according to claim 4, wherein the other polymeric monomer is a compound having a group reactive with a vinyl group.

6. Use of the polymer according to claim 4 in the field of electronic products, electronic devices.

7. The electronic product, electronic device, of claim 6, wherein one of the following is selected: a flat panel display, a curved display, a computer monitor, a medical monitor, a camera, a viewfinder, a ring scanner, a virtual reality or augmented reality display.

Technical Field

The invention belongs to the technical field of high polymer materials, and particularly relates to an aromatic functionalized carborane compound containing flexible silica chain links, and a preparation method and application thereof.

Background

The continuous development of high-tech fields such as electronics and electrical appliances has raised more and more demanding requirements on the use temperature of a series of high polymer materials such as polyurethane, polyimide, polyamide, polyurea, epoxy resin, polysiloxane and the like, which requires to continuously increase the thermal degradation temperature of the existing organic high polymer materials. Introduction of a special structure from the aspect of molecular structure design becomes one of the approaches for preparing advanced polymer materials. Specific structures composed of inorganic elements such as silicon, boron, and nitrogen are favored, for example, silsesquioxane having a hexahedral structure, an icosahedral carborane structure, and the like. Specifically, carboranes are bulky, high boron-containing steric structures having three isomers, ortho (o-carbon), meta (m-carbon), and para (p-carbon), which are icosahedral carboranes. However, the carborane with the special structure is an easily sublimable solid, and if the carborane is introduced into the structure of a polymer on a molecular level, the structure of the carborane needs to be modified to realize the functionalization of the carborane.

Therefore, how to prepare the high-temperature-resistant organic functional group modified cage-type carborane structure can greatly improve the comprehensive properties of high-temperature resistance, oxidation resistance, neutron irradiation resistance and the like of the high polymer material, and becomes a key technical challenge of the carborane modified high polymer material.

The silicone rubber is an elastomer with a-Si-O-bond as a main chain and an organic group as a side group, has a special semi-organic and semi-inorganic structure, is excellent in high and low temperature resistance, weather resistance, ozone resistance, aging resistance, physiological inertia and high air permeability and is used in the fields of aerospace, automobiles, electronics, medical appliances and the like.

Disclosure of Invention

The invention aims to provide a method for modifying a vinyl functional group containing a flexible silica chain link on a cage-shaped structure of carborane, the structure innovatively combines the flexible silica chain link with a large-volume and high-boron-content carborane three-dimensional structure, the structure is endowed with high reaction activity through active vinyl, two structures can be conveniently introduced into an organic high molecular polymer at a molecular level, and when the prepared organic high molecular polymer is used as a composition, the composition has a lower dielectric constant, a higher thermal decomposition temperature, tensile strength and elongation at break.

The purpose of the invention is realized by the following technical scheme: the structural formula of the organosilane compound is shown as the formula I:

wherein "-CB 10H 10C-" represents an ortho-carboranyl group, a meta-carboranyl group or a para-carboranyl group;

r1 is-aryl-, -aryl-, or-aryl-, -aryl-optionally substituted with one or more C1-10 alkyl or aryl;

r2 is selected from H, C1-10 alkyl which is unsubstituted or optionally substituted by one or more Ra, C3-20 cycloalkyl

R1 is selected from one of phenyl, tolyl, ethylphenyl, biphenyl, naphthyl, anthryl and terphenyl;

r2 is selected from one of methyl, ethyl, trifluoropropyl and cyanopropyl;

the invention also provides a preparation method of the compound, which comprises the following steps:

carrying out hydrosilylation reaction on a cyclic compound containing a plurality of vinyl groups and a silicon-containing hydrogen bond compound in the presence of a catalyst 1 to generate a formula I-1;

carrying out hydrosilylation reaction on formula I-1 and acetylene in the presence of a catalyst 2 to generate formula I,

the cyclic compound containing a plurality of vinyl groups:

the silicon-hydrogen bond-containing compound:

the compound of formula I-1 is:

the acetylene:

the catalyst 1 is preferably platinum black, the reaction product of compounds such as chloroplatinic acid, chloroplatinic acid hexahydrate, and monoalcohols, bis (ethylacetoacetate) platinum, bis (acetylacetonato) platinum, platinum dichloride and complexes of said compounds with olefins or low molecular weight organopolysiloxanes or platinum compounds microencapsulated in a matrix or core-shell type structure.

Complexes of platinum with low molecular weight organopolysiloxanes, including complexes of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane with platinum. These complexes can be microencapsulated in a resin matrix.

The amount of the catalyst 1 used in the raw material is 0.1ppm to 1,0000 ppm.

The catalyst 2 is preferably ruthenium carbonyl chloride [ RuCl ] as a ruthenium compound₂(CO)₃]₂Ruthenium (III) chloride (RuCl)₂(P(C₆H₅)₃)₃Ruthenium chloride hydrate RuCl₃·3H₂O, dodecacarbonyltriruthenium Ru₃(CO)₁₂One or a mixture of two or more of them.

Preferably, the addition amount of the catalyst ruthenium compound is 5-80 mg of ruthenium in each kilogram of reaction system in terms of ruthenium.

The ruthenium compound is added to the reaction system directly or after being dissolved in a solvent. The solvent is preferably one or a mixture of more than two of methanol, ethanol, isopropanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and 1, 4-dioxane.

The reaction temperature is 0-90 ℃, and preferably 30-80 ℃. If the temperature is lower than 30 ℃, the reaction rate is slow, and if the temperature is higher than 80 ℃, a secondary addition reaction occurs to form a macromolecular compound.

The preferable amine compound is one or a mixture of two or more of ethylenediamine, triethylamine, N-dimethylformamide, N-dimethylaniline, N' -bis (2-cyanoethyl) diethylamine, 1, 2-bis (2-cyano-2-propyl) hydrazine, aniline, and phenothiazine.

The invention also provides a preparation method of the compound, which comprises the following specific steps:

(1) mixing a cyclic compound containing a plurality of vinyl groups, a silicon-hydrogen bond compound, a catalyst 1 and an organic solvent, heating and refluxing to perform hydrosilylation reaction, and generating the formula I-1. The organic solvent may be selected from organic solvents which can dissolve the cyclic compound containing a plurality of vinyl groups and the silicon hydrogen bond compound, but do not react with any of the cyclic compound containing a plurality of vinyl groups, the silicon hydrogen bond compound and the catalyst, and may be, for example, common organic solvents such as benzene and toluene. Further, the conditions of the hydrosilylation reaction can be referred to in the literature "hydrosilylation reaction and research" (Schedule, 2 nd 1998, p 82-84).

(2) Reacting a reaction system formed by a formula I-1, acetylene, a cocatalyst amine compound and a catalyst ruthenium compound to obtain a formula I.

The invention also provides the use of a compound according to claim 1 or 2, in particular: using as monomers a compound of formula I: reacting a compound shown in the formula I as a polymerization monomer with other polymerization monomers to obtain a polymer; wherein the compounds of formula I have the aforementioned definitions.

The other polymerizable monomer is a compound having a group reactive with a vinyl group. The other polymerized monomer is preferably hydrogenpolysiloxane, and the hydrogenpolysiloxane is polysiloxane with a spatial structure and has the following structural formula: (^HMe₂SiO_1/2)c(R³ ₂SiO_2/2)_d(R⁴SiO_3/2)_e(II) abbreviated to: in the MHcDdTe formula (II), subscripts c, d and e represent the molar ratio among three chain elements, the ratio of the three chain elements determines the molecular weight, the form and the activity of the polysiloxane with the space structure, and the ratio of c to e is 0.5-1.2; r³、R⁴Alkyl, alkenyl or aryl with 1-20 carbon atoms, including methyl, ethyl, propyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, vinyl, phenyl, styrene;

the hydrogen content of the hydrogenpolysiloxane is 0.5-3.0 mmol/g;

the dosage of the hydrogen-containing polysiloxane is 0.1-10% of the total mass of the organic silicon composition;

further, the hydrogenpolysiloxane further comprises methyl phenyl polysiloxane;

further, the hydrogen-containing polysiloxane also comprises a structure control agent, wherein the structure control agent is an alkynol substance (comprising ethynylcyclohexanol and 3, 5-dimethyl-1-hexyne-3-ol), and the using amount of the structure control agent is 0.1-5% of the total mass of the organosilicon composition;

further, a catalyst 3, a hydrosilylation catalyst in which the concentration of Pt atoms in the composition is 10 to 100ppm, such as a Karster catalyst, chloroplatinic acid, a complex of chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane;

further, the curing agent is prepared by mixing an organic phosphorus curing accelerator and an imidazole curing accelerator according to the mass ratio of 3: 1.

The invention also describes the application of the polymer in the fields of electronic products and electronic devices.

Further, the electronic product and the electronic device are characterized by being selected from one of the following: a flat panel display, a curved display, a computer monitor, a medical monitor, a camera, a viewfinder, a ring scanner, a virtual reality or augmented reality display.

The invention has the beneficial effects that:

1. according to the compound disclosed by the invention, the toughness of the polymer is improved by introducing the flexible silica chain, the intrinsic flame retardant properties such as higher temperature resistance, improved oxidation resistance, limited oxygen index, horizontal and vertical combustion and the like are improved by introducing the carborane to the polymer, and the curing efficiency of the composition can be improved by introducing the triazine to enable the triazine to contain a plurality of vinyl siloxane chains, so that the compound is further applied to an electronic device.

2. The polysiloxane composition has the advantages of low dielectric constant, high thermal decomposition temperature, high tensile strength and high elongation at break.

Detailed Description

Example 1

Formula I-1Can be synthesized by the following steps:

(1) taking 0.5g of hydrosilylation catalyst platinum, adding 5mL of toluene for dilution, and then adding the diluted platinum into a 250mL three-neck flask;

(2) taking 2.49g of 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione (1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H) -trione with the molecular weight MW of 249.27g/mol), adding 20mL of toluene for dilution, and adding the mixture into a three-neck flask;

(3) taking 19.69g of silicon-hydrogen bond-containing compoundAdding 25mL of toluene for dilution, and then adding the diluted solution into a three-neck flask;

(4) setting the oil bath temperature at 130 ℃, starting stirring, starting condensed water, and starting refluxing the reaction mixture when the temperature in the three-neck flask is 119 ℃;

(5) after a period of reflux, a small amount of the reaction mixture was aspirated for IR testing to determine if the reaction was complete.

(6) After 48 hours, the reaction was complete as indicated by the IR result showing no absorption peak at the carbon-carbon double bond and no vinyl H as indicated by the 1H NMR result, whereupon the reaction mixture was transferred to a rotary evaporator to evaporate the solvent and precipitate the product I-1 in 90% yield. FT-IR: 3075 to 2920,2126,1691,1516,1253,1119,1053,901,836 to 626 cm-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)。

Example 2

Formula ISynthesized by the following steps:

221.49g (0.1mol) of the compound of formula I-1 was charged in a 2L reactor, followed by the catalyst ruthenium carbonyl chloride [ RuCl ]₂(CO)₃]₂Adding 0.2g of N, N-dimethylaniline into the 1, 4-dioxane solution to ensure that the concentration of ruthenium in the system is 50 mu g/kg, introducing acetylene at 50 ℃ and stirring the mixture, maintaining the pressure of a reaction container at 0.5MPa, and after 24 hours, wherein the GC detection result of the reaction liquid shows that the composition of the reaction system is not changed and the GC-FID area normalization method content of a target product is 91.2 percent. FT-IR: 3075-2930, 2124,1696,1650, 1513,1256,1120,1053,905, 836-626 cm-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)。

example 3

Adding 50 parts of formula I, 5 parts of hydrophobic precipitated silica D10 (provided by winning) and 2 parts of hydrophobic fumed silica R202 (provided by winning) into a container, grinding at high speed to enable the dispersed particle diameter of the silica in the container to be less than 1 mu m, adding 0.2 part of structure control agent 1-alkynyl cyclohexanol C at the rotating speed of 200rpm, then adding 4ppm (calculated by platinum) of chloroplatinic acid catalyst D, and mixing for 5min to enable the catalyst D to be uniformly dispersed in the container to obtain a dispersion X; keeping the temperature of the dispersion X at 20 ℃, keeping the rotation speed of 550rpm, dropwise adding 9 parts of a mixture of hydrogenpolysiloxane B-1/methylphenylpolysiloxane (with the refractive index of 1.4630 and the viscosity of 400.0cPs) into the X, adding a curing agent (formed by mixing an organophosphorus curing accelerator and an imidazolyl curing accelerator according to the mass ratio of 3: 1) after the dropwise adding is finished, slowly stirring for 8 hours at room temperature, keeping the negative pressure of-0.06 MPa, vacuumizing for 60 minutes to remove small molecules, finally adding 0.3 part of water G, and uniformly mixing to obtain the polysiloxane composition GZ 1.

Test example 1

The silicone composition GZ1 obtained in example 3 was subjected to the tests for dielectric constant, thermal decomposition temperature, flame resistance, tensile strength, and elongation at break, and the specific test criteria were as follows:

1. dielectric constant:

the material is made into a wafer with the diameter of 20mm and the thickness of 2mm, and the dielectric constant of the wafer is tested by utilizing an Agilent 4294A type precision impedance analyzer or the like, wherein the testing frequency is 50Hz-30 MHz.

2. Thermal decomposition temperature:

the measurement was carried out according to the IPC-TM-6502.4.26 method.

3. Flame resistance (flame retardancy):

measured according to the UL94 method.

4. Mechanical Property test

Tensile strength and elongation at break were tested in accordance with GB/T528-2009.

The specific test results are shown in table 1.

TABLE 1

As can be seen from Table 1, the polysiloxane compositions of the present invention have a relatively low dielectric constant and relatively high thermal decomposition temperature, tensile strength, and elongation at break. The polysiloxane composition can be applied to the fields of electronic products and electronic equipment, and specifically comprises the application on flat panel displays, curved surface displays, computer monitors, medical monitors, video cameras, viewfinders, ring scanners and virtual reality or augmented reality displays. For example: the polysiloxane composition can be well applied to a shell of a ring scanner and a ring sleeve, can effectively avoid the breakage of the ring sleeve and improve the size adaptability of the ring sleeve when being applied to the ring sleeve, and is very suitable for wearable electronic products.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.