阅读说明：本技术 改性端羟基聚丁二烯液体橡胶光热双重固化材料及制法 (Modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material and preparation method thereof ) 是由 李阳雪 彭楚堂 朱宏亮 王琳 陈龙 张洋 于 2019-11-19 设计创作，主要内容包括：本发明涉及一种改性端羟基聚丁二烯液体橡胶光热双重固化材料的制备方法,通过先将丙烯酰氯改性端羟基聚丁二烯液体橡胶置于真空条件下,以排除体系中的气泡和小分子杂质；之后加入填料、光引发剂、热引发剂混匀后制得胶液,将所述胶液涂布于模具上先进行紫外光固化,再进行热固化,最终制得光热双重固化橡胶材料,通过先利用光固化使胶液快速转化为固体膜,利用紫外吸收光引发链式反应合成聚合物,之后对紫外光固化后的橡胶进行热固化处理,使橡胶固化更完全,各物质分子链间粘结更加紧密,增强橡胶材料的综合性能,本发明所述光热双重固化橡胶材料具有优异的力学性能、耐热性、耐水性能和耐酸性腐蚀性能。(The invention relates to a preparation method of a modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material, which comprises the steps of placing acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber under a vacuum condition to remove bubbles and small molecular impurities in a system; and then adding a filler, a photoinitiator and a thermal initiator, uniformly mixing to obtain a glue solution, coating the glue solution on a mold, performing ultraviolet curing, and then performing thermal curing to finally obtain the photo-thermal dual-curing rubber material, wherein the glue solution is quickly converted into a solid film by photo-curing, ultraviolet absorption light is used for initiating a chain reaction to synthesize a polymer, and then the rubber subjected to ultraviolet curing is subjected to thermal curing treatment, so that the rubber is cured more completely, the molecular chains of all substances are bonded more tightly, and the comprehensive performance of the rubber material is enhanced.)

1. The modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material is characterized by comprising the following raw material components:

50-60 parts by weight of acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber;

31-50 parts by weight of a filler;

1-10 parts of photoinitiator;

0.5-1 weight portion of thermal initiator.

2. The modified hydroxyl-terminated polybutadiene liquid rubber photothermal dual-curing material as claimed in claim 1, wherein the filler is one or more of aluminum powder, potassium chloride, iron powder, aluminum chloride, magnesium chloride, carbon black and silica.

3. The modified hydroxyl-terminated polybutadiene liquid rubber photothermal dual-curing material as claimed in claim 2, wherein the filler is a mixture of aluminum powder and potassium chloride in a mass ratio of 1-10: 30-40.

4. The modified hydroxyl-terminated polybutadiene liquid rubber photothermal dual-curing material as claimed in claim 1, wherein the photoinitiator is one or a mixture of photoinitiators 819, 907, 651 and 127.

5. The modified hydroxyl-terminated polybutadiene liquid rubber photothermal dual-curing material as claimed in claim 1, wherein the thermal initiator is benzoyl peroxide.

6. The method for preparing the modified hydroxyl-terminated polybutadiene liquid rubber photothermal dual-curing material as described in any one of claims 1-5, wherein the steps include:

(1) placing acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber under a vacuum condition to remove bubbles and micromolecular impurities in a system;

(2) respectively taking a filler, a photoinitiator and a thermal initiator according to the weight parts, adding the filler, the photoinitiator and the thermal initiator into the acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber treated in the step (1), and fully and uniformly mixing to obtain a glue solution;

(3) coating the glue solution on a mold, and curing under the ultraviolet light condition to obtain a glue layer;

(4) and thermally curing the adhesive layer to obtain the modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material.

7. The method according to claim 6, wherein in the step (1), the acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber is treated at 37-43 ℃ under vacuum for 45-50 h.

8. The method according to claim 6, wherein in the step (3), the coating-UV curing is repeated 3 times, specifically: coating 1/3 of the glue solution obtained in the step (2) on a mould, and then carrying out primary curing under the ultraviolet condition to obtain a first glue layer; coating 1/3 of the glue solution obtained in the step (2) on the first glue layer, and then carrying out secondary curing under the ultraviolet light condition to obtain a second glue layer; and coating the rest 1/3 glue solution on a second glue layer, and then curing for the third time under the ultraviolet light condition to obtain the glue layer.

9. The preparation method of claim 8, wherein the wavelength of the ultraviolet light is 365nm-405nm, and the time for the first curing, the second curing and the third curing is 4-7 min.

10. The method as set forth in claim 6, wherein in the step (4), the temperature for carrying out the thermal curing is 37-43 ℃ and the time for carrying out the curing is 110-130 h.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material and a preparation method thereof.

Background

The liquid rubber is a low molecular weight prepolymer and exhibits good fluidity at room temperature. Therefore, when the liquid rubber is used for manufacturing products, no solvent is required to be added, and the method has the advantages of safety, greenness and environmental protection. The liquid rubber is suitable for a pouring forming process, the process flow is simple, the operation is easy, the continuous mechanical automatic production is convenient, and the advantage provides conditions for the wide application of the liquid rubber. Products made of the liquid rubber are widely applied to the fields of military, aerospace, scientific research, automobiles, construction, medical treatment and the like.

At present, liquid rubber containing photosensitive groups obtained through chemical modification has the capability of rapid photocuring under ultraviolet irradiation, but when thick products are manufactured through 3D printing, ultraviolet light cannot be irradiated to the deep parts of the products, so that defects are generated among layers, and the products with excellent mechanical properties and mechanical properties cannot be obtained. Researchers use acrylic-based photosensitive resin for UV curing, bisphenol A diglycidyl ether and fatty acid anhydride are thermally cured at 150 ℃, and the photo-cured resin and the thermally cured resin are compounded to obtain the dual-cured polymer composite material suitable for 3D printing, which has higher tensile strength.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material and a preparation method thereof.

The technical scheme adopted by the invention is as follows:

a modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material comprises the following raw material components:

50-60 parts by weight of acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber;

31-50 parts by weight of a filler;

1-10 parts of photoinitiator;

0.5-1 weight portion of thermal initiator.

The filler is one or a mixture of more of aluminum powder, potassium chloride, iron powder, aluminum chloride, magnesium chloride, carbon black and silicon dioxide.

The filler is a mixture of aluminum powder and potassium chloride according to the mass ratio of 1-10: 30-40.

The photoinitiator is one or a mixture of a plurality of photoinitiators 819, 907, 651 and 127.

The thermal initiator is benzoyl peroxide.

The preparation method of the modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material comprises the following steps:

(1) placing acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber under a vacuum condition to remove bubbles and micromolecular impurities in a system;

(2) respectively taking a filler, a photoinitiator and a thermal initiator according to the weight parts, adding the filler, the photoinitiator and the thermal initiator into the acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber treated in the step (1), and fully and uniformly mixing to obtain a glue solution;

(3) coating the glue solution on a mold, and curing under the ultraviolet light condition to obtain a glue layer;

(4) and thermally curing the adhesive layer to obtain the modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material.

In the step (1), the acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber is treated for 45-50h at 37-43 ℃ under a vacuum condition.

In the step (3), the coating-ultraviolet light curing is repeated for 3 times, specifically: coating 1/3 of the glue solution obtained in the step (2) on a mould, and then carrying out primary curing under the ultraviolet condition to obtain a first glue layer; coating 1/3 of the glue solution obtained in the step (2) on the first glue layer, and then carrying out secondary curing under the ultraviolet light condition to obtain a second glue layer; and coating the rest 1/3 glue solution on a second glue layer, and then curing for the third time under the ultraviolet light condition to obtain the glue layer.

The wavelength of the ultraviolet light is 365nm-405nm, and the time of the first curing, the second curing and the third curing is 4-7 min.

In the step (4), the temperature for performing the thermal curing is 37-43 ℃, and the time for performing the curing is 110-130 h.

The invention has the beneficial effects that:

the preparation method of the modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material comprises the steps of placing acryloyl chloride modified hydroxyl-terminated polybutadiene liquid rubber under a vacuum condition to remove bubbles and small molecular impurities in a system; and then adding a filler, a photoinitiator and a thermal initiator, uniformly mixing to obtain a glue solution, coating the glue solution on a mold, performing ultraviolet curing, and performing thermal curing to finally obtain the modified hydroxyl-terminated polybutadiene liquid rubber photo-thermal dual-curing material which has excellent mechanical property, heat resistance, water resistance and acid corrosion resistance. The reason is that the inventor of the present application found in long-term research that the liquid glue solution is quickly converted into a solid film by photo-curing, in the photo-curing process, the chain reaction is initiated by ultraviolet absorption light to synthesize the polymer, and in the polymerization process, the light is only used as an initiating tool and does not affect the chain propagation and chain termination. The UV curing speed is high, heating is not needed, curing can be carried out at room temperature, and energy waste is avoided. No solvent is needed for curing, and volatilization and emission of toxic and organic solvents are avoided. And in the second stage of thermal curing, the rubber subjected to ultraviolet curing is subjected to thermal curing treatment, so that the rubber is cured more completely, the bonding among molecular chains of various substances is tighter, and the comprehensive performance of the rubber material is enhanced.

Detection data show that the photo-thermal dual-curing rubber material disclosed by the invention has excellent mechanical property, heat resistance, water resistance and acid corrosion resistance. Mechanical properties: the tensile strength reaches 24MPa, and is improved by 40-50% compared with the traditional polybutadiene rubber; hot water resistance: the material is soaked in distilled water at the temperature of 100 ℃ for 8 hours, the mass loss rate is only 0.79 percent, and the mass loss is reduced by 20 to 30 percent compared with the traditional rubber, so that the material obtained by the invention has better hot water resistance; water resistance: the water absorption rate is 1.2% after the rubber material is soaked in distilled water for 24 hours at room temperature, and the water absorption rate is only 2.3% after the rubber material is soaked for 120 hours, so that the water absorption rate is greatly reduced compared with that of the traditional rubber material, and the material has good water resistance; acid and alkali corrosion resistance: after the material is soaked in buffer solutions with pH values of 2, 4, 6, 8 and 10 for 36 hours, the decomposition rate of a sample in the buffer solution is between 0.7 and 1.1 percent, and compared with common rubber, the decomposition rate is greatly reduced, so that the material has good acid and alkali resistance.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.

In the following examples 1g is represented by 1 part by weight.