阅读说明：本技术 一种聚氨酯拉挤复合材料用玻璃纤维浸润剂及其制备方法 (Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof ) 是由 刘钢 刘术明 李尚勇 孟凡荣 何文 黄令奇 于 2019-12-20 设计创作，主要内容包括：本发明公开了一种聚氨酯拉挤复合材料用玻璃纤维浸润剂,属于聚氨酯拉挤工艺技术领域。其包括：按百分比计,硅烷偶联剂A 0.2-0.6wt％、硅烷偶联剂B 0.4-0.8wt％、成膜剂6.2-8.2wt％、润滑剂A 0.3-0.7wt％、润滑剂B 0.2-0.8wt％、辅助剂0.2-0.6wt％、pH调节剂0.2-0.4wt％,其余量为水。本发明的玻璃纤维浸润剂与聚氨酯拉挤复合材料相容性高,并且能使使玻璃纤维纱集束性好,毛羽量少,能提高玻璃纤维增强聚氨酯复合材料的力学性能。(The invention discloses a glass fiber impregnating compound for a polyurethane pultrusion composite material, and belongs to the technical field of polyurethane pultrusion processes. It includes: according to percentage, 0.2 to 0.6 weight percent of silane coupling agent A, 0.4 to 0.8 weight percent of silane coupling agent B, 6.2 to 8.2 weight percent of film forming agent, 0.3 to 0.7 weight percent of lubricant A, 0.2 to 0.8 weight percent of lubricant B, 0.2 to 0.6 weight percent of auxiliary agent, 0.2 to 0.4 weight percent of pH regulator and the balance of water. The glass fiber sizing agent has high compatibility with a polyurethane pultrusion composite material, can ensure that glass fiber yarns have good bundling property and small hairiness amount, and can improve the mechanical property of the glass fiber reinforced polyurethane composite material.)

1. A glass fiber impregnating compound for a polyurethane pultrusion composite material is characterized by comprising the following components in percentage by weight: according to percentage, 0.2 to 0.6 weight percent of silane coupling agent A, 0.4 to 0.8 weight percent of silane coupling agent B, 6.2 to 8.2 weight percent of film forming agent, 0.3 to 0.7 weight percent of lubricant A, 0.2 to 0.8 weight percent of lubricant B, 0.2 to 0.6 weight percent of auxiliary agent, 0.2 to 0.4 weight percent of pH regulator and the balance of water;

wherein the silane coupling agent A is 3-aminopropyl triethoxysilane; the silane coupling agent B is methoxy triethylene glycol ether propyl) trimethoxy silane; the film forming agent is modified epoxy emulsion; the lubricant A is polyethylene glycol; and the lubricant B is octadecyl trimethyl ammonium chloride.

2. The glass fiber sizing agent for the polyurethane pultrusion composite material as claimed in claim 1, wherein the preparation method of the modified epoxy emulsion comprises the following steps:

(1) adding chitosan into water, adding citric acid, heating to 30-50 deg.C, stirring to dissolve completely to obtain chitosan water solution; wherein, the adding amount ratio of the water, the chitosan and the citric acid is as follows: 30: (10-15): (10-20);

(2) adding pure bisphenol A epoxy resin into the chitosan aqueous solution, then adding a bisphenol A epoxy resin emulsifier, and stirring and reacting for 2-3h at 60-80 ℃ to prepare the modified epoxy emulsion.

3. A glass fiber sizing for polyurethane pultruded composites according to claim 3, wherein said auxiliary agent comprises a starch nanocrystal modified epoxy resin comprising: 10-20 parts of starch nanocrystal, 50-10 parts of methylene bisacrylamide, 70-80 parts of E51 epoxy resin and 0.1-0.5 part of nano nickel protoxide.

4. The glass fiber impregnating compound for the polyurethane pultrusion composite material as claimed in claim 3, wherein the preparation method of the starch nanocrystal modified epoxy resin comprises the following steps:

adding starch nanocrystals and nano nickel protoxide into butanone solution, performing ultrasonic reaction for 20-40min, adding methylene bisacrylamide at 60-80 ℃ for reaction for 1-3h, adding E51 epoxy resin, heating to 80-100 ℃ for reaction for 2-3h, and performing reduced pressure distillation to remove the solvent to obtain the starch nanocrystal modified epoxy resin.

5. A glass fiber sizing for polyurethane pultruded composites according to any of the claims 1-4, characterized in that said pH adjusting agent is glacial acetic acid.

6. A method for preparing a glass fiber sizing for a polyurethane pultruded composite according to any of claims 1 to 5, comprising the steps of:

(1) adding a pH regulator into water accounting for 40-50% of the total amount to dissolve, regulating the pH value to 3.5-4.5, adding a coupling agent A and a coupling agent B under stirring, and continuously stirring for 0.5-1h until the solution is clear and has no oil droplets on the surface;

(2) diluting the film forming agent with water with the mass of 2-3 times of that of the film forming agent, and adding the diluted film forming agent into the solution in the step (1) under stirring;

(3) diluting the auxiliary agent with water of which the mass is 5-7 times that of the auxiliary agent, and adding the auxiliary agent into the solution in the step (2) under stirring;

(4) diluting the lubricant with water of which the mass is 8-10 times that of the lubricant, and adding the diluted lubricant into the solution in the step (3) under stirring;

(5) diluting the lubricant A and the lubricant B with water of which the mass is 3-5 times that of the lubricant A, adding the diluted lubricant A and the lubricant B into the solution obtained in the step (4) under stirring, supplementing and adding the rest water, and uniformly stirring to obtain the glass fiber impregnating compound for the polyurethane pultrusion composite material.

Technical Field

The invention relates to the technical field of polyurethane pultrusion processes, in particular to a glass fiber impregnating compound for a polyurethane pultrusion composite material and a preparation method thereof.

Background

In recent years, the polyurethane resin reinforced composite material prepared by the polyurethane pultrusion process is unique due to the advantages of good toughness, fast curing, no styrene smoke and the like. In the pultrusion process of polyurethane, reinforced glass fiber is used to prepare the high-strength, high-modulus and light-weight polymer composite material. Meanwhile, due to the excellent impact strength, tensile strength and interlaminar shear strength of the polyurethane, the product can be made thinner and lighter. Pultruded articles of polyurethane include profiles, rods and panels, such as doors and windows, ladder poles, tool handles, utility pole crossarms, utility poles, hockey sticks, dock stakes, cargo container panels, and the like. For example: the glass fiber reinforced polyurethane pultruded door and window profile is produced by taking glass fiber as a reinforcing material and polyurethane as a matrix through an advanced injection gum dipping pultrusion process.

The glass fiber is treated by the water-based sizing agent after flowing out of the bushing, so that the glass fiber has good processing performance and excellent mechanical property of a composite material. Because the wire drawing process is in a high-speed operation state, the prior glass fiber impregnating compound has the problems of poor stability and large hairiness amount in the use process.

Disclosure of Invention

The invention aims to provide a glass fiber impregnating compound for a polyurethane pultrusion composite material and a preparation method thereof, and aims to solve the problems of poor stability and large hairiness amount in the using process of the existing glass fiber impregnating compound.

The technical scheme for solving the technical problems is as follows:

a glass fiber sizing for a polyurethane pultruded composite, comprising: according to percentage, 0.2 to 0.6 weight percent of silane coupling agent A, 0.4 to 0.8 weight percent of silane coupling agent B, 6.2 to 8.2 weight percent of film forming agent, 0.3 to 0.7 weight percent of lubricant A, 0.2 to 0.8 weight percent of lubricant B, 0.2 to 0.6 weight percent of auxiliary agent, 0.2 to 0.4 weight percent of pH regulator and the balance of water;

wherein the silane coupling agent A is 3-aminopropyl triethoxysilane; the silane coupling agent B is 3- (2-aminoethylamino) propyl trimethoxy silane; the film forming agent is modified epoxy emulsion; the lubricant A is polyethylene glycol; and the lubricant B is octadecyl trimethyl ammonium chloride.

Further, in a preferred embodiment of the present invention, the preparation method of the modified epoxy emulsion comprises the following steps:

(1) adding chitosan into water, adding citric acid, heating to 30-50 deg.C, stirring to dissolve completely to obtain chitosan water solution; wherein, the adding amount ratio of the water, the chitosan and the citric acid is as follows: 30: (10-15): (10-20);

(2) adding pure bisphenol A epoxy resin into the chitosan aqueous solution, then adding a bisphenol A epoxy resin emulsifier, and stirring and reacting for 2-3h at 60-80 ℃ to prepare the modified epoxy emulsion.

Further, in a preferred embodiment of the present invention, the adjuvant comprises a starch nanocrystal modified epoxy resin, and the starch nanocrystal modified epoxy resin comprises: 10-20 parts of starch nanocrystal, 50-10 parts of methylene bisacrylamide, 70-80 parts of E51 epoxy resin and 0.1-0.5 part of nano nickel protoxide.

Further, in a preferred embodiment of the present invention, the preparation method of the starch nanocrystal modified epoxy resin comprises the following steps:

adding starch nanocrystals and nano nickel protoxide into butanone solution, performing ultrasonic reaction for 20-40min, adding methylene bisacrylamide at 60-80 ℃ for reaction for 1-3h, adding E51 epoxy resin, heating to 80-100 ℃ for reaction for 2-3h, and performing reduced pressure distillation to remove the solvent to obtain the starch nanocrystal modified epoxy resin.

Further, in a preferred embodiment of the present invention, the pH adjuster is glacial acetic acid.

The preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material is characterized by comprising the following steps of:

(1) adding a pH regulator into water accounting for 40-50% of the total amount to dissolve, regulating the pH value to 3.5-4.5, adding a coupling agent A and a coupling agent B under stirring, and continuously stirring for 0.5-1h until the solution is clear and has no oil droplets on the surface;

(2) diluting the film forming agent with water with the mass of 2-3 times of that of the film forming agent, and adding the diluted film forming agent into the solution in the step (1) under stirring;

(3) diluting the auxiliary agent with water of which the mass is 5-7 times that of the auxiliary agent, and adding the auxiliary agent into the solution in the step (2) under stirring;

(4) diluting the lubricant with water of which the mass is 8-10 times that of the lubricant, and adding the diluted lubricant into the solution in the step (3) under stirring;

(5) diluting the lubricant A and the lubricant B with water of which the mass is 3-5 times that of the lubricant A, adding the diluted lubricant A and the lubricant B into the solution obtained in the step (4) under stirring, supplementing and adding the rest water, and uniformly stirring to obtain the glass fiber impregnating compound for the polyurethane pultrusion composite material.

The invention has the following beneficial effects:

1. the glass fiber sizing agent has high compatibility with a polyurethane pultrusion composite material, can ensure that glass fiber yarns have good bundling property and small hairiness amount, and can improve the mechanical property of the glass fiber reinforced polyurethane composite material.

2. According to the invention, the amino silane coupling agent and the alcohol ether silane coupling agent are compounded to obtain the high-efficiency silane coupling agent, the alcohol ether silane coupling agent has stronger wettability and adhesive force, and the alcohol ether silane coupling agent is compounded with the amino silane coupling agent, so that the wettability of the wetting agent on the surface of the polyurethane material can be improved, and the adhesive force of the wetting agent on the surface of the substrate can be promoted. Compared with the single use of the aminosilane coupling agent, the silane coupling agent obtained by compounding reduces the using amount of the coupling agent, thereby reducing the possibility of yellowing of the impregnating compound.

3. According to the chitosan modified epoxy emulsion, chitosan is used as a natural high-molecular nitrogen-containing polysaccharide substance, the biocompatibility is good, the viscosity of the epoxy emulsion is improved and the binding force and the compatibility are improved through the chitosan modified epoxy emulsion, and the chitosan plays a role in bundling protection on glass fibers, so that broken filaments generated in weaving can be reduced

4. The starch nanocrystal adopted by the invention has the advantages of wide source, low cost, good biodegradability and biocompatibility, large specific surface area, compact structure and high rigidity, and the surface contains active hydroxyl groups, and the hydrophilic nano nickel protoxide is added, so that the starch nanocrystal can be uniformly dispersed on the surface of the starch nanocrystal and can be subjected to chemical reaction with epoxy resin or form strong intermolecular action, the wettability of polyurethane is increased, the bundling protection effect and the lubricity of glass fiber are increased, broken filaments generated during weaving are reduced, and the wear resistance is also improved.

Detailed Description

The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.