阅读说明：本技术 一种主链掺锆的绿色环保耐高温杂化有机硅树脂及其制备方法 (Green environment-friendly high-temperature-resistant hybrid organic silicon resin with zirconium-doped main chain and preparation method thereof ) 是由 刘丽 姜警 黄玉东 于 2019-11-04 设计创作，主要内容包括：本发明公开了一种主链掺锆的绿色环保耐高温杂化有机硅树脂,其特征在于所述有机硅树脂的结构式如下：(R<Sub>2</Sub>SiO<Sub>2/2</Sub>)<Sub>x</Sub>(RSiO<Sub>3/2</Sub>)<Sub>y</Sub>(ZrO<Sub>4/2</Sub>)<Sub>z</Sub>(S)<Sub>k</Sub>；式中,R<Sub>2</Sub>SiO<Sub>2/2</Sub>、RSiO<Sub>3/2</Sub>、ZrO<Sub>4/2</Sub>分别表示D单元硅氧烷、T单元硅氧烷和有机锆源；x、y、z、k分别表示R<Sub>2</Sub>SiO<Sub>2/2</Sub>、RSiO<Sub>3/2</Sub>、ZrO<Sub>4/2</Sub>及S的结构单元数目；R独立地表示甲基或苯基；S来自硅氧烷基团-Si(OH)<Sub>3</Sub>、-RSi(OH)<Sub>2</Sub>、-R<Sub>2</Sub>Si(OH)、-R<Sub>2</Sub>SiOR、-RSiOR<Sub>2</Sub>、-SiOR<Sub>3</Sub>中的一种；ZrO<Sub>4/2</Sub>选自有机锆源。本发明通过采用新颖的改性共聚方式,使得该树脂材料比现有的硅树脂材料更加耐高温,可用作基体树脂制备复合材料及耐高温粘接剂。(The invention discloses a green environment-friendly high-temperature-resistant hybrid organic silicon resin with a main chain doped with zirconium, which is characterized in that the structural formula of the organic silicon resin is as follows: (R) 2 SiO 2/2 ) x (RSiO 3/2 ) y (ZrO 4/2 ) z (S) k (ii) a In the formula, R 2 SiO 2/2 、RSiO 3/2 、ZrO 4/2 Respectively represent D unit siloxane, T unit siloxane and an organic zirconium source; x, y, z and k respectively represent R 2 SiO 2/2 、RSiO 3/2 、ZrO 4/2 And the number of structural units of S; r independently represents methyl or phenyl; s is from siloxane groups-Si (OH) 3 、‑RSi(OH) 2 、‑R 2 Si(OH)、‑R 2 SiOR、‑RSiOR 2 、‑SiOR 3 One of (1); ZrO (ZrO) 4/2 Selected from the group consisting of organozirconium sources. The invention adopts a novel modified copolymerization modeCompared with the existing silicon resin material, the resin material is more resistant to high temperature, and can be used as matrix resin for preparing composite materials and high-temperature-resistant adhesives.)

1. The environment-friendly high-temperature-resistant hybrid organic silicon resin with the main chain doped with zirconium is characterized by having the following structural formula:

(R₂SiO_2/2)_x(RSiO_3/2)_y(ZrO_4/2)_z(S)_k；

in the formula, R₂SiO_2/2、RSiO_3/2、ZrO_4/2Respectively represent D unit siloxane, T unit siloxane and an organic zirconium source; x, y, z and k respectively represent R₂SiO_2/2、RSiO_3/2、ZrO_4/2And number of structural units of SMesh, wherein: x is 0 or a positive integer, y, z, k are positive integers; r independently represents methyl or phenyl; s is from siloxane groups-Si (OH)₃、-RSi(OH)₂、-R₂Si(OH)、-R₂SiOR、-RSiOR₂、-SiOR₃One of (1); ZrO (ZrO)_4/2Selected from the group consisting of organozirconium sources; in the structural formula, the molar ratio of silicon atoms to zirconium atoms is 1-10: 1, and the molar ratio of R to silicon atoms is 1-1.6: 1.

2. The main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as claimed in claim 1, wherein the organic zirconium source is one or more of zirconium n-propoxide, zirconium n-butoxide, zirconium isopropoxide, zirconium octoate oxychloride and zirconium acetylacetonate.

3. A method for preparing the main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as described in any one of claims 1-2, which is characterized by comprising the following steps:

step one, weighing siloxane R₂SiO_2/2、RSiO_3/2Dissolving into absolute ethyl alcohol, then slowly dripping deionized water for hydrolysis, and recording as a solution A;

step two, weighing an organic zirconium source, dissolving the organic zirconium source into a chelating agent, and recording the solution as a solution B;

step three, slowly adding the solution B into the solution A, then slowly adding a catalyst, and carrying out hydrolytic polycondensation reaction to obtain a zirconium-containing organic silicon resin prepolymer, wherein: the reaction temperature is 30-80 ℃; the rotating speed is 200-1000 rpm/min; the reaction time is 2-10 h;

and step four, washing the zirconium-containing organic silicon resin prepolymer with deionized water to be neutral, and carrying out reduced pressure distillation for 1-3 h at 100-150 ℃ and under the vacuum condition of-0.2-0.1 MPa after liquid separation to obtain the zirconium-containing organic silicon resin.

4. The preparation method of the green environment-friendly high-temperature-resistant hybrid organic silicon resin with the zirconium-doped main chain as claimed in claim 3, wherein the siloxane is one or more of methyltriethoxysilane, methyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane and dimethyldiethoxysilane, and preferably one or more of methyltriethoxysilane, phenyltrimethoxysilane and methylphenyldiethoxysilane.

5. The preparation method of the main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as claimed in claim 3, characterized in that the chelating agent is an organic unsaturated oxygen-containing acidic substance.

6. The preparation method of the main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as claimed in claim 5, characterized in that the organic unsaturated oxygen-containing acidic substance is one or more of acetylacetone, acrylic acid, methacrylic acid and resorcinol, preferably one or more of acetylacetone and methacrylic acid.

7. The preparation method of the main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as claimed in claim 3 or 5, wherein the molar ratio of the chelating agent to the organic zirconium source is 1.5-2.5: 1.

8. The preparation method of the main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as claimed in claim 3, characterized in that the reaction temperature is 60-75 ℃; the rotating speed is 300-700 rpm/min; the reaction time is 3-8 h.

9. The preparation method of the main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as claimed in claim 3, characterized in that the catalyst is one or more of hydrochloric acid, ethylenediamine, diethylamine and triethylamine, preferably hydrochloric acid.

10. The preparation method of the main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin as claimed in claim 3 or 9, wherein the molar ratio of the catalyst to the alkoxy group is 0.0001-0.005: 1.

Technical Field

The invention relates to an organic silicon resin and a preparation method thereof, in particular to an environment-friendly high-temperature-resistant hybrid organic silicon resin with a main chain doped with zirconium and a preparation method thereof.

Background

Since the 20 th century and the 40 th era, the organic silicon resin is widely applied to the fields of electric protective sleeves, traffic equipment, high-temperature-resistant adhesives and the like due to the unique three-dimensional structure and a plurality of excellent properties such as weather resistance, high temperature resistance, insulation, low surface tension and the like.

The organic silicon resin is structurally highly crosslinked polysiloxane, the main chain of the organic silicon resin is a Si-O-Si structure, wherein the bond energy of Si-O bonds is about 456kJ/mol, the bond energy of Si-C bonds is about 347kJ/mol, and in general organic resin, the bond energy of C-C bonds is about 332kJ/mol, so that the Si-O bond structure in the organic silicon resin is not easy to damage, and the organic silicon resin has excellent thermal stability and wide application prospects in the aspects of preparing fireproof and heat-resistant materials and the like.

Among high temperature resistant coating materials, silicone resins are widely used because of their stable structure and large bond energy. In addition, the structure is controllable and modified, and after the heteroatom is doped and modified, the heat resistance, the oil resistance, the shock resistance and the like of the composite material are greatly improved. At present, the organic silicon resin is initially decomposed at 360-400 ℃, but in the field of aerospace, materials need to be used for a long time at the temperature of over 1000 ℃, and the organic silicon resin is difficult to be widely applied to aerospace industry, so that structural modification is carried out on the organic silicon resin, and the problem of improving the heat-resistant temperature of the organic silicon resin is urgently needed to be solved.

Disclosure of Invention

The invention aims to provide a main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin and a preparation method thereof, and the resin material is more high-temperature-resistant than the existing silicon resin material by adopting a novel modification copolymerization mode and can be used as matrix resin to prepare composite materials and high-temperature-resistant adhesives.

The purpose of the invention is realized by the following technical scheme:

a main chain zirconium-doped green environment-friendly high-temperature-resistant hybrid organic silicon resin has the following structural formula:

(R₂SiO_2/2)_x(RSiO_3/2)_y(ZrO_4/2)_z(S)_k；

in the formula, R₂SiO_2/2、RSiO_3/2、ZrO_4/2Respectively represent D unit siloxane, T unit siloxane and an organic zirconium source; x, y, z and k respectively represent R₂SiO_2/2、RSiO_3/2、ZrO_4/2And the number of structural units of S, wherein: x is 0 or a positive integer, y, z, k are positive integers; r independently represents methyl or phenyl; s is from siloxane groups-Si (OH)₃、-RSi(OH)₂、-R₂Si(OH)、-R₂SiOR、-RSiOR₂、-SiOR₃One of (1); ZrO (ZrO)_4/2Is selected from organic zirconium source, which is selected from one or more of zirconium n-propoxide, zirconium n-butoxide, zirconium isopropoxide, zirconium oxychloride octahydrate and zirconium acetylacetonate; in the structural formula, the molar ratio of silicon atoms to zirconium atoms is 1-10: 1, and the molar ratio of R to silicon atoms is 1-1.6: 1.

A preparation method of the green environment-friendly high-temperature-resistant hybrid organic silicon resin with the main chain doped with zirconium comprises the following steps of selecting a chelating agent to perform coordination treatment with an organic zirconium source, then dropwise adding the mixed solution into siloxane for hydrolytic polymerization to form a Si-O-Zr structure, and performing polycondensation reaction at a certain temperature to obtain the zirconium-containing organic silicon resin, wherein the preparation method comprises the following specific steps:

step one, weighing siloxane R₂SiO_2/2、RSiO_3/2Dissolving into absolute ethyl alcohol, then slowly dripping deionized water for hydrolysis, and recording as a solution A, wherein: the siloxane can be selected from one or more of but not limited to methyltriethoxysilane, methyltrimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane and dimethyldiethoxysilane; considering the difference of the hydrolysis rates of the siloxanes, in order to ensure that the copolymerization rates are close, one or more of methyl triethoxysilane, phenyl trimethoxysilane and methyl phenyl diethoxysilane are preferred;

step two, weighing an organic zirconium source, dissolving the organic zirconium source into a chelating agent, and recording the solution as a solution B, wherein: the chelating agent is selected from organic unsaturated oxygen-containing acidic substances, including but not limited to one or more of acetylacetone, acrylic acid, methacrylic acid and resorcinol, preferably one or more of acetylacetone and methacrylic acid; the molar ratio of the chelating agent to the organic zirconium source is 1.5-2.5: 1;

step three, slowly adding the solution B into the solution A, then slowly adding a catalyst, and carrying out hydrolytic polycondensation reaction to obtain a zirconium-containing organic silicon resin prepolymer, wherein: the reaction temperature is 30-80 ℃, and preferably 60-75 ℃; the rotating speed is 200-1000 rpm/min, preferably 300-700 rpm/min; the reaction time is 2-10 h, preferably 3-8 h; the catalyst is selected from one or more of hydrochloric acid, ethylenediamine, diethylamine and triethylamine, preferably hydrochloric acid; the molar ratio of the catalyst to the alkoxy is 0.0001-0.005: 1;

and step four, washing the zirconium-containing organic silicon resin prepolymer with deionized water to be neutral, and carrying out reduced pressure distillation for 1-3 h at 100-150 ℃ and under the vacuum condition of-0.2-0.1 MPa after liquid separation to obtain the zirconium-containing organic silicon resin.

Compared with the prior art, the invention has the following advantages:

1. the invention contains R₂SiO_2/2(D Unit), RSiO_3/2An organic zirconium source is introduced into silane of the (T unit), and a zirconium element is introduced into a three-dimensional structure of the traditional organic silicon resin by controlling the hydrolysis and self-polymerization rates of the organic zirconium source to form a Si-O-Zr structure, so that the heat resistance stability of the organic silicon resin is improved.

2. The element zirconium is a metal with extremely high melting point, corrosion resistance, high hardness and high strength, the melting point is as high as 1850 ℃, and the melting points of oxides and carbides of the element zirconium are higher than those of silicon compounds, so that the heat resistance of the resin can be improved by doping the zirconium element into the main chain of the organic silicon resin.

3. Considering that the hydrolysis rate and self-polymerization rate of the organozirconium source are too fast and faster under acidic or basic conditions of the catalyst, it is difficult to introduce them into the main chain of the silicone resin. To this end, the invention proposes to reduce the rate of hydrolysis and self-polymerisation of the zirconium source during the reaction by complexing with a chelating agent to satisfy the rate of hydrolysis and self-polymerisation of the siloxane.

4. The siloxane, the organic zirconium source and the ethanol solvent system selected by the invention have low toxicity and are relatively friendly to the environment, the adopted operation steps are suitable for industrial large-scale production, and the prepared zirconium-containing organic silicon resin has excellent heat resistance.

Detailed Description

The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.