阅读说明：本技术 一种碳硼烷杂化硅氧烷-聚氨酯的制备方法 (Preparation method of carborane hybrid siloxane-polyurethane ) 是由 刘善友 林宏 暴利军 朱晔 郝平 于 2021-09-06 设计创作，主要内容包括：本发明涉及高分子材料领域,特别涉及一种碳硼烷杂化硅氧烷-聚氨酯的制备方法。步骤：1)在氮气条件下,将二烷氧基硅烷与去离子水在一定温度下进行缩聚反应数小时后,得到末端为烷氧基的硅氧烷齐聚物,继续加入双羟基碳硼烷保持75℃下进行醇解反应数小时,升温至85℃蒸出缩聚副产物醇类,获得端基为羟基的碳硼烷杂化硅氧烷齐聚物为A组分；2)将异氰酸酯溶于四氢呋喃溶剂中,加入小分子多元醇,在80℃下反应2 h,旋蒸除去四氢呋喃得到B组分；3)将A组分和B组分按一定质量比混合,加入有机锡类催化剂,搅拌均匀后得到碳硼烷杂化硅氧烷-聚氨酯。本发明制备材料固化过程中安全环保、固化温度低、不产生环境污染的气体。(The invention relates to the field of high polymer materials, in particular to a preparation method of carborane hybrid siloxane-polyurethane. The method comprises the following steps: 1) under the condition of nitrogen, carrying out polycondensation reaction on dialkoxysilane and deionized water at a certain temperature for several hours to obtain siloxane oligomer with an alkoxy end, continuously adding dihydroxy carborane, keeping the temperature at 75 ℃ for alcoholysis reaction for several hours, heating to 85 ℃ to evaporate condensation polymerization by-product alcohol, and obtaining carborane hybrid siloxane oligomer with a hydroxyl end group as component A; 2) dissolving isocyanate in a tetrahydrofuran solvent, adding micromolecular polyol, reacting for 2 hours at 80 ℃, and removing tetrahydrofuran by rotary evaporation to obtain a component B; 3) and mixing the component A and the component B according to a certain mass ratio, adding an organic tin catalyst, and uniformly stirring to obtain the carborane hybrid siloxane-polyurethane. The curing process of the preparation material is safe and environment-friendly, the curing temperature is low, and no gas polluting the environment is generated.)

1. A preparation method of carborane hybrid siloxane-polyurethane is characterized by comprising the following steps:

1) under the condition of nitrogen, carrying out polycondensation reaction on dialkoxysilane and deionized water at 70-80 ℃ for 5-8 hours to obtain siloxane oligomer with an alkoxy end, continuously adding dihydroxy carborane, keeping the temperature at 70-80 ℃ for carrying out alcoholysis reaction for 5-8 hours, heating to 80-90 ℃ to evaporate out a polycondensation byproduct alcohol, and obtaining carborane hybrid siloxane oligomer with a hydroxyl end group as a component A, wherein the molar ratio of the dialkoxysilane, the deionized water and the dihydroxy carborane is (n +1) m: nm: m +1, n is more than or equal to 5 and less than or equal to 20, and m is more than or equal to 1 and less than or equal to 5;

2) dissolving isocyanate in a tetrahydrofuran solvent, adding micromolecular polyol, reacting for 2 hours at 70-90 ℃, and removing tetrahydrofuran by rotary evaporation to obtain a component B, wherein the molar ratio of the isocyanate to the micromolecular polyol is (2-4) to (0-1), and the mass of the tetrahydrofuran is 5 times of the total mass of the isocyanate and the micromolecular polyol;

3) mixing the component A and the component B according to the mass ratio of 1.86-28.17: 1, adding an organic tin catalyst, and uniformly stirring to obtain carborane hybrid siloxane-polyurethane, wherein the organic tin catalyst accounts for 0.1-1% of the total mass of the resin.

2. The method of preparing carborane hybrid siloxane-polyurethane according to claim 1, wherein: the dialkoxysilane in the 1) is:

any one of them.

3. The method of claim 1, wherein the carborane hybrid siloxane-polyurethane is prepared by the following steps: the dihydroxy carborane in the step 1) is as follows:

any one of them.

4. The method of preparing carborane hybrid siloxane-polyurethane according to claim 1, wherein: the carborane hybrid siloxane oligomer with the middle terminal group of 1) as the hydroxyl has the following molecular structure:wherein R is₁And R₂is-CH₃(methyl) orAny one of (phenyl), R₃is-CH₂- (methylene) or-CH₂CH₂CH₂Any one of (propylene) and (meth) acrylic acid.

5. The method of preparing carborane hybrid siloxane-polyurethane according to claim 1, wherein: the isocyanate in the step 2) is any one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and polymethylene polyphenyl polyisocyanate.

6. The method of preparing carborane hybrid siloxane-polyurethane according to claim 1, wherein: the medium and small molecular weight polyol in the step 2) is any one of glycol, butanediol, 1, 2, 6-hexanetriol, glycerol, 1, 2, 4-butanetriol and pentaerythritol.

7. The method of preparing carborane hybrid siloxane-polyurethane according to claim 1, wherein: the organic tin catalyst in the step 3) is any one of dibutyltin dilaurate and stannous octoate.

Technical Field

The invention relates to the field of high and low temperature resistant high polymer materials, in particular to a preparation method of carborane hybrid siloxane-polyurethane.

Background

Polyurethane is synthesized for the first time in 1937 by the German chemist professor Otto Bayer and colleagues, is also called polyurethane, and refers to macromolecules with repeated arrangement of carbamate groups (-NHCOO-) or urea groups (-NHCOONH-) in a molecular chain. The polyurethane has wide application and excellent performance, and different monomers can be utilized to synthesize polyurethane products with different performances. The chemical bonds in the silicone rubber have higher bond energy and the molecular chain is in a higher oxidation state, for example, the bond energy of Si-O bonds is 451kJ/mol, which is greatly higher than the bond energy of C-O bonds 358kJ/mol, the bond energy of Si-C bonds is 324kJ/mol, which is obviously higher than the bond energy of C-C bonds 306kJ/mol, so that the silicone rubber has extremely outstanding heat resistance and oxidation resistance.

Carborane is an icosahedral cage structure composed of carbon atoms, boron atoms and hydrogen atoms, and the special spatial structure and electronic characteristics of carborane enable carborane to have good water resistance, chemical resistance and heat resistance stability, wherein the excellent heat resistance is particularly concerned. The carborane is introduced into a siloxane-polyurethane structure, so that the heat resistance stability of the material can be remarkably improved.

Polysiloxane-polyurethane block copolymers are a class of high molecular materials with great development prospects. From the view of molecular chain segment structure, the organic silicon chain segment can provide excellent thermal stability, dielectricity, flexibility, water resistance, air permeability and biocompatibility; the polyurethane chain segment can provide good mechanical property, wear resistance, oil resistance and the like. Therefore, the material has the excellent performances of both polysiloxane and polyurethane, and shows good water resistance, low-temperature flexibility, surface enrichment, dielectricity and excellent biocompatibility. Not only overcomes the defect of poor mechanical property of polysiloxane, but also makes up the defect of poor weather resistance of polyurethane.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a preparation method of carborane hybrid siloxane-polyurethane, which is a novel high polymer material with high temperature resistance and chemical medium resistance and can be used for developing materials used in extreme fields such as high temperature resistant adhesives, high and low temperature resistant composite materials, space environment, deep sea exploration and the like.

In order to achieve the above object, the present invention provides the following technical solutions:

a preparation method of carborane hybrid siloxane-polyurethane comprises the following steps:

1) carrying out polycondensation reaction on dialkoxysilane and deionized water at 70-80 ℃ for 5-8 hours in a nitrogen atmosphere to obtain siloxane oligomer with an alkoxy end, continuously adding dihydroxy carborane, keeping the temperature at 70-80 ℃ for carrying out alcoholysis reaction for 5-8 hours, heating to 80-90 ℃ to evaporate out condensation byproduct alcohol to obtain carborane hybrid siloxane oligomer with a hydroxyl end group, wherein the molar ratio of dialkoxysilane to deionized water to dihydroxy carborane is (n +1) m: nm: m +1, n is not less than 5 and not more than 20, and m is not less than 1 and not more than 5;

2) dissolving isocyanate in a tetrahydrofuran solvent, adding micromolecular polyol, reacting for 2 hours at 70-90 ℃, and removing tetrahydrofuran by rotary evaporation to obtain a component B, wherein the molar ratio of the isocyanate to the micromolecular polyol is (2-4) to (0-1), and the mass of the tetrahydrofuran is 5 times of the total mass of the isocyanate and the micromolecular polyol;

3) mixing the component A and the component B according to the mass ratio of 1.86-28.17: 1, adding an organic tin catalyst, and uniformly stirring to obtain carborane hybrid siloxane-polyurethane, wherein the organic tin catalyst accounts for 0.1-1% of the total mass of the resin.

Further, the dialkoxysilane in 1) is:

any one of them.

Further, the dihydroxy carborane in the step 1) is:

any one of them.

Further, the carborane hybrid siloxane oligomer with the terminal group of 1) as a hydroxyl group has the following molecular structure:

wherein R is₁And R₂is-CH₃(methyl) orAny one of (phenyl), R₃is-CH₂- (methylene) or-CH₂CH₂CH₂Any one of (propylene) and (meth) acrylic acid.

Further, the isocyanate in 2) is any one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, and polymethylene polyphenyl polyisocyanate.

Further, the small molecular weight polyol in 2) is any one of ethylene glycol, butanediol, 1, 2, 6-hexanetriol, glycerol, 1, 2, 4-butanetriol and pentaerythritol.

The organic tin catalyst in 3) is any one of dibutyltin dilaurate and stannous octoate.

Advantageous effects obtained by the present invention

The material is safe and environment-friendly in the curing process, low in curing temperature and free of environmental pollution gas, the proportion of soft and hard sections of a final product can be regulated and controlled by the mass ratio of the dihydric alcohol to the polyisocyanate, the mechanical parameters and the like of the final product can be controlled, and the material has excellent thermal stability, oil resistance, water resistance and electric insulation performance, and can be used for preparing sealing, high-temperature-resistant adhesives, high-performance composite materials and the like of electronic equipment in airplane fuel tanks and high-temperature-difference environments.

Drawings

FIG. 1 is an IR spectrum of carborane hybrid siloxane polyurethane prepared in example 1 of the present invention.

Detailed Description

The invention relates to a preparation method of carborane hybrid siloxane-polyurethane. The catalyst is prepared by a double-prepolymer method by using dihydric alcohol oligomer and polyisocyanate which are prepared by hydrolyzing dihydroxycarborane and dialkoxysilane to a limited extent as raw materials and organic tin as a catalyst.

In order to make the objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. It is obvious that the described embodiments are only some, not all embodiments of the proposed solution. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

1) Under nitrogen atmosphere, the mixture is subjected to(1.5mol, 180g) and deionized water a (1.25mol, 22.5g) are subjected to polycondensation reaction at 70 ℃ for 5 hours to obtain siloxane oligomer with an alkoxy end, and the siloxane oligomer is continuously added(0.5mol, 102g) keeping at 70 ℃ for alcoholysis reaction for 5 hours, heating to 80 ℃ to evaporate out the polycondensation by-product alcohol, and obtaining carborane hybrid siloxane oligomer A component with hydroxyl as the end group

2) Dissolving toluene diisocyanate (0.6mol, 104.4g) in tetrahydrofuran (614g) under the nitrogen atmosphere, adding glycerol (0.2mol, 18.4g), reacting at 70 ℃ for 2 hours, and removing tetrahydrofuran by rotary evaporation to obtain a component B;

3) the component A (186g) and the component B (100g) were mixed at a mass ratio of 1.86: 1, and 2.86g of an organotin catalyst was added, the organotin catalyst amounting to 1% of the total mass of the resin. Stirring uniformly to obtain the siloxane modified carborane polyurethane.

Example 2

1) Under nitrogen atmosphere, the mixture is subjected to(4.2mol, 764.4g) and deionized water (4mol, 72g) are subjected to polycondensation reaction at 80 ℃ for 8 hours to obtain siloxane oligomer with an alkoxy end, and the siloxane oligomer is continuously added(0.4mol, 81.6g) keeping the mixture at 80 ℃ for alcoholysis reaction for 8 hours, heating to 90 ℃ to evaporate the alcohol as a polycondensation byproduct, and obtaining the carborane hybrid siloxane oligomer A component with the end group of hydroxyl

2) Dissolving diphenylmethane diisocyanate (0.375mol, 93.75g) in tetrahydrofuran (535g) under a nitrogen atmosphere, adding 1, 2, 4-butanetriol (0.125mol, 13.25g), reacting at 90 ℃ for 2h, and removing tetrahydrofuran by rotary evaporation to obtain a component B;

3) the a component (545g) and the B component (100g) were mixed at a mass ratio of 5.45: 1 (total mass: 645g), and 6.45g of an organotin catalyst was added, the organotin catalyst being 1% of the total mass of the resin. Stirring uniformly to obtain the siloxane modified carborane polyurethane.

Example 3

1) Under nitrogen atmosphere, the mixture is subjected to(7.5mol, 1110g) and deionized water (6.25mol, 112.5g) are subjected to polycondensation reaction at the temperature of 80 ℃ for 8 hours to obtain siloxane oligomer with an alkoxy end, and the siloxane oligomer is continuously added(1.5mol, 306g) keeping the temperature at 80 ℃ for alcoholysis reaction for 8 hours, heating to 90 ℃ to evaporate the alcohol of the polycondensation by-product, and obtaining carborane hybrid siloxane oligomer A component with the end group of hydroxyl

2) Under nitrogen atmosphere, dissolving hexamethylene diisocyanate (0.6mol, 100.8g) in tetrahydrofuran (638g), adding 1, 2, 6-hexanetriol (0.2mol, 26.8g), reacting at 70 ℃ for 2h, and removing tetrahydrofuran by rotary evaporation to obtain a component B;

3) the a component (436g) and the B component (100g) were mixed at a mass ratio of 4.36: 1 (total mass: 536g), and 5.36g of an organotin catalyst was added, the organotin catalyst being 1% of the total mass of the resin. Stirring uniformly to obtain the siloxane modified carborane polyurethane.

Example 4

1) Under nitrogen atmosphere, the mixture is subjected to(21mol, 4410g) and deionized water (20mol, 360g) are subjected to polycondensation reaction at 70-80 ℃ for 8 hours to obtain siloxane oligomer with an alkoxy end, and the siloxane oligomer is continuously added(1.2mol, 312g) keeping the temperature at 80 ℃ for alcoholysis reaction for 8 hours, heating to 90 ℃ to evaporate the alcohol of the polycondensation by-product, and obtaining carborane hybrid siloxane oligomer A component with the end group of hydroxyl

2) Dissolving hexamethylene diisocyanate trimer (0.2mol, 100.8g) in tetrahydrofuran (535g) under a nitrogen atmosphere, adding ethylene glycol (0.1mol, 6.2g), reacting at 70 ℃ for 2h, and removing tetrahydrofuran by rotary evaporation to obtain a component B;

3) the A component (2817g) and the B component (100g) were mixed at a mass ratio of 28.17: 1, and 29.17g of an organotin catalyst was added, the organotin catalyst amounting to 1% of the total mass of the resin. Stirring uniformly to obtain the siloxane modified carborane polyurethane.

Example 5

1) Under nitrogen atmosphere, the mixture is subjected to(3.15mol, 768.6g) and deionized water (3mol, 54g) are subjected to polycondensation reaction at 80 ℃ for 8 hours to obtain siloxane oligomer with an alkoxy end, and the siloxane oligomer is continuously added(0.3mol, 61.2g) keeping the mixture at 80 ℃ for alcoholysis reaction for 8 hours, heating to 90 ℃ to evaporate the alcohol as a polycondensation byproduct, and obtaining the carborane hybrid siloxane oligomer A component with the end group of hydroxyl

2) Dissolving isophorone diisocyanate trimer (0.16mol, 106.56g) in tetrahydrofuran (568.8g) under a nitrogen atmosphere, adding butanediol (0.08mol, 7.2g), reacting at 70 ℃ for 2h, and removing tetrahydrofuran by rotary evaporation to obtain a component B;

3) the component A (628g) and the component B (100g) were mixed at a mass ratio of 6.28: 1, and 7.28g of an organotin catalyst was added, the organotin catalyst amounting to 1% of the total mass of the resin. Stirring uniformly to obtain the siloxane modified carborane polyurethane.

Example 6

1) In nitrogenIn the atmosphere, will(1.08mol, 293.76g) and deionized water (0.9mol, 16.2g) are subjected to polycondensation reaction at 70-80 ℃ for 5-8 hours to obtain siloxane oligomer with an alkoxy end, and the siloxane oligomer is continuously added(0.36mol, 93.6g) keeping the mixture at 80 ℃ for alcoholysis reaction for 8 hours, heating to 90 ℃ to evaporate a polycondensation by-product alcohol, and obtaining a carborane hybrid siloxane oligomer A component with a hydroxyl end group;

2) dissolving diphenylmethane diisocyanate (0.4mol, 100g) in tetrahydrofuran (568g) in a nitrogen atmosphere, adding pentaerythritol (0.1mol, 13.6g), reacting at 70-90 ℃ for 2h, and removing tetrahydrofuran by rotary evaporation to obtain a component B;

3) the a component (263g) and the B component (100g) were mixed at a mass ratio of 2.63: 1 (total mass: 363g), and 3.63g of an organotin catalyst was added, the organotin catalyst being 1% of the total mass of the resin. Stirring uniformly to obtain the siloxane modified carborane polyurethane.

Example 7

1) Under nitrogen atmosphere, the mixture is subjected to(2.4mol, 652.8g) and deionized water (2mol, 36g) are subjected to polycondensation reaction at 80 ℃ for 8 hours to obtain siloxane oligomer with an alkoxy end, and the siloxane oligomer is continuously added(0.8mol, 208g) keeping the temperature of 70-80 ℃ for alcoholysis reaction for 5 hours, heating to 90 ℃ to evaporate the condensation polymerization by-product alcohol, and obtaining carborane hybrid siloxane oligomer A component with the end group of hydroxyl

2) Polymethylene polyphenyl polyisocyanate is used as a component B; (M614 g/mol);

3) the A component (533g) and the B component (100g) were mixed at a mass ratio of 5.33: 1, and 6.33g of an organotin catalyst was added, the organotin catalyst amounting to 1% of the total mass of the resin. Stirring uniformly to obtain the siloxane modified carborane polyurethane.