阅读说明：本技术 耐高温1,7-二巯基-1,7-碳硼烷/苯乙炔基硅烷杂化树脂及其制备方法 (High-temperature-resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin and preparation method thereof ) 是由 倪礼忠 周权 舒佩玲 于 2019-01-09 设计创作，主要内容包括：本发明公开了一种耐高温1,7-二巯基-1,7-碳硼烷/苯乙炔基硅烷杂化树脂及其制备方法,属于高分子材料及其制备技术领域。它的原料配方按照质量份数比计算：二苯乙炔基硅烷树脂100份,1,7-二巯基-1,7-碳硼烷1～100份。它在生产反应过程中,不使用重金属催化剂,反应条件温和,反应不受氧气和水的影响；通过巯基-炔点击化学反应完成固化,反应快速、简单、高效且无挥发性副产物生成；制备的树脂溶解性能良好,易于加工成型并且具备优异的耐热及热氧化性能。(The invention discloses a high-temperature-resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin and a preparation method thereof, belonging to the technical field of high polymer materials and preparation thereof. The raw material formula of the medicine is calculated according to the mass part ratio: 100 parts of tolane silane resin and 1-100 parts of 1, 7-dimercapto-1, 7-carborane. In the production reaction process, a heavy metal catalyst is not used, the reaction condition is mild, and the reaction is not influenced by oxygen and water; the curing is completed through a thiol-alkyne click chemical reaction, the reaction is rapid, simple and efficient, and no volatile by-product is generated; the prepared resin has good solubility, is easy to process and form, and has excellent heat resistance and thermal oxidation performance.)

1. The high-temperature-resistant 1, 7-dimercapto-1, 7-carborane/phenylacetylene silane hybrid resin is characterized in that the formula of the raw materials comprises the following components in parts by mass: 100 parts of tolane silane resin and 1-100 parts of 1, 7-dimercapto-1, 7-carborane; the structural formula of the diphenyl acetenyl silane resin is shown in (1), and the structural formula of the 1, 7-dimercapto-1, 7-carborane is shown in (2):

wherein: r1 and R2 are alkyl, aryl or hydrogen atoms

2. The preparation method of the high temperature resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin is characterized by comprising the following steps:

(1) weighing 100 parts of tolane silane resin and 1-100 parts of 1, 7-dimercapto-1, 7-carborane according to the mass part ratio;

(2) fully mixing the tolane silane resin and the 1, 7-dimercapto-1, 7-carborane in the acetone organic solvent according to the mass ratio;

(3) performing click chemical reaction under ultraviolet UV irradiation by using benzoin dimethyl ether (DMPA) as a photoinitiator, wherein the concentration of the photoinitiator is 1-3 wt%, and the reaction time is 10-30 minutes;

(4) and distilling the product to remove the solvent to obtain the 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin.

Technical Field

The invention relates to a high-temperature-resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin and a preparation method thereof, belonging to the technical field of high polymer materials and preparation thereof.

Background

The silicon alkyne resin is an organic-inorganic hybrid polymer, has extremely high heat resistance and good processing performance, and simultaneously has excellent dielectric property and high-temperature mechanical property, thereby being widely applied to the high-tech fields of aerospace and the like. The prior methyldiphenylethynyl silane resin (MDPES) has good heat resistance and easy processing and molding, and can be used for preparing various advanced composite materials; however, with the development of aerospace and defense industries, higher requirements are also made on the performance of materials, and the developed silicone resin cannot meet the requirements on the thermal oxidation resistance, so that how to improve the thermal oxidation resistance is very important.

Carborane (Carborane) is a compound containing carbon, boron and hydrogen elements at the same time, wherein 2 carbon atoms and 10 boron atoms form an icosahedral cage structure, the structure can play a role of an energy tank, so that the whole molecule is very stable, and meanwhile, the super-aromatic cage structure has a large volume, has a shielding effect on adjacent groups and endows the molecule and derivatives thereof with high thermal stability, so that the introduction of Carborane groups can obviously improve the heat resistance of substances. The Olin group is introduced into a polysiloxane system by the company of Olin in the United states to prepare a high temperature resistant elastomer (carborane-siloxane copolymer) with excellent performance and carry out commercial production.

At present, a small amount of carborane modified phenylethynyl silane resin is reported at home and abroad, and carborane is generally reacted with a strongly basic organic lithium reagent to obtain a nucleophile, and then the nucleophile is further reacted with an electrophile (chlorosilane and the like) to be copolymerized into a system, so that the thermal oxidation performance of the phenylethynyl silane resin is improved. The modification method disclosed by the invention has the advantages of mild reaction conditions, no influence of oxygen and water, quick, simple and efficient reaction and capability of fully making up the defects of the former method. In addition, the 1, 7-dimercapto-1, 7-carborane/phenylacetylene silane hybrid resin prepared by the invention has excellent heat resistance and thermal oxidation resistance, is crosslinked and cured under the action of light, heat or a chemical catalyst to form a three-dimensional network structure, can form a ceramic structure after being further treated at high temperature, can be used for preparing a high-temperature resistant ceramic matrix composite material with excellent performance, and has very wide application prospect.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the high temperature resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin and the preparation method thereof are provided, and the problems that the polymerization condition is harsh, the conversion rate is low, the product is not easy to purify and the industrial production is not facilitated in the reaction process are solved.

The technical problem to be solved by the invention is realized by adopting the following technical scheme:

the high-temperature resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin comprises the following raw materials in parts by weight: 100 parts of tolane silane resin and 1-100 parts of 1, 7-dimercapto-1, 7-carborane; the structural formula of the diphenyl acetenyl silane resin is shown in (1), and the structural formula of the 1, 7-dimercapto-1, 7-carborane is shown in (2):

wherein: r1 and R2 are alkyl, aryl or hydrogen atoms

The preparation method of the high-temperature resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin comprises the following steps:

(1) weighing 100 parts of tolane silane resin and 1-100 parts of 1, 7-dimercapto-1, 7-carborane according to the mass part ratio;

(2) fully mixing the tolane silane resin and the 1, 7-dimercapto-1, 7-carborane in the acetone organic solvent according to the mass ratio;

(3) performing click chemical reaction under ultraviolet UV irradiation by using benzoin dimethyl ether (DMPA) as a photoinitiator, wherein the concentration of the photoinitiator is 1-3 wt%, and the reaction time is 10-30 minutes;

(4) and distilling the product to remove the solvent to obtain the 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin.

The invention has the beneficial effects that: (1) heavy metal catalysts are not used, the reaction conditions are mild, and the reaction is not influenced by oxygen and water; (2) the curing is completed through a thiol-alkyne click chemical reaction, the reaction is rapid, simple and efficient, and no volatile by-product is generated; (3) the prepared resin has good solubility, is easy to process and form, and has excellent heat resistance and thermal oxidation performance.

Detailed Description

In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below.

The high-temperature resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin comprises the following raw materials in parts by weight: 100 parts of tolane silane resin and 1-100 parts of 1, 7-dimercapto-1, 7-carborane.

The preparation method of the high-temperature resistant 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin comprises the following steps:

(1) weighing 100 parts of tolane silane resin and 1-100 parts of 1, 7-dimercapto-1, 7-carborane according to the mass part ratio;

(2) fully mixing the tolane silane resin and the 1, 7-dimercapto-1, 7-carborane in the acetone organic solvent according to the mass ratio;

(3) performing click chemical reaction under ultraviolet UV irradiation by using benzoin dimethyl ether (DMPA) as a photoinitiator, wherein the concentration of the photoinitiator is 1-3 wt%, and the reaction time is 10-30 minutes;

(4) and distilling the product to remove the solvent to obtain the 1, 7-dimercapto-1, 7-carborane/phenylethynyl silane hybrid resin.

Td in air₅The value of (DEG C) and the mass retention rate at 800 ℃ are two important indexes for judging the properties of the 1, 7-dimercapto-1, 7-carborane/methyldiphenylacetylene silane hybrid resin. The high values of the two indicate more excellent heat resistance and thermal oxidation performance.