CN110790519B - Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof - Google Patents
Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110790519B CN110790519B CN201911325210.7A CN201911325210A CN110790519B CN 110790519 B CN110790519 B CN 110790519B CN 201911325210 A CN201911325210 A CN 201911325210A CN 110790519 B CN110790519 B CN 110790519B
- Authority
- CN
- China
- Prior art keywords
- lubricant
- glass fiber
- water
- weight percent
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/465—Coatings containing composite materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Composite Materials (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
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.
Description
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.
Example 1:
the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following components: according to percentage, 0.2 weight percent of silane coupling agent A, 0.4 weight percent of silane coupling agent B, 6.2 weight percent of film forming agent, 0.3 weight percent of lubricant A, 0.2 weight percent of lubricant B, 0.2 weight percent of auxiliary agent, 0.2 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; lubricant B is octadecyl trimethyl ammonium chloride; the pH regulator is glacial acetic acid; the auxiliary agent comprises starch nanocrystal modified epoxy resin.
The preparation method of the modified epoxy emulsion comprises the following steps:
(1) adding chitosan into water, adding citric acid, heating to 30 ℃, and stirring until the chitosan is completely dissolved to obtain a chitosan aqueous solution; wherein the adding amount ratio of the water, the chitosan and the citric acid is 30: 10: 10;
(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 2h at 60 ℃ to prepare the modified epoxy emulsion.
Wherein, the starch nanocrystal modified epoxy resin comprises: 10 parts of starch nanocrystal, 5 parts of methylene bisacrylamide, 70 parts of E51 epoxy resin and 0.1 part of nano nickel protoxide. The preparation method of the powder nanocrystalline modified epoxy resin comprises the following steps:
adding starch nanocrystals and nano nickel protoxide into butanone solution, performing ultrasonic reaction for 20min, adding methylene bisacrylamide at 60 ℃ for reaction for 1h, adding E51 epoxy resin, heating to 80 ℃ for reaction for 2h, and performing reduced pressure distillation to remove the solvent to obtain the starch nanocrystal modified epoxy resin.
The preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following steps:
(1) adding a pH regulator into water accounting for 40 percent of the total amount for dissolving, regulating the pH value to 3.5, adding a coupling agent A and a coupling agent B under stirring, and continuously stirring for 0.5h until the solution is clear and has no oil drops on the surface;
(2) diluting the film forming agent with water with the mass of 2 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 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 with the mass of 8 times of 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 times that of the lubricant A and the lubricant B, 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.
Example 2:
the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following components: 0.3 wt% of silane coupling agent A, 0.5 wt% of silane coupling agent B, 6.5 wt% of film forming agent, 0.4wt% of lubricant A, 0.4wt% of lubricant B, 0.3 wt% of auxiliary agent, 0.25 wt% 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; lubricant B is octadecyl trimethyl ammonium chloride; the pH regulator is glacial acetic acid; the auxiliary agent comprises starch nanocrystal modified epoxy resin.
The preparation method of the modified epoxy emulsion comprises the following steps:
(1) adding chitosan into water, adding citric acid, heating to 40 ℃, and stirring until the chitosan is completely dissolved to obtain a chitosan aqueous solution; wherein the adding amount ratio of the water, the chitosan and the citric acid is 30: 12: 15;
(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 2h at 70 ℃ to prepare the modified epoxy emulsion.
Wherein, the starch nanocrystal modified epoxy resin comprises: 15 parts of starch nanocrystal, 7 parts of methylene bisacrylamide, 75 parts of E51 epoxy resin and 0.3 part of nano nickel protoxide. The preparation method of the powder nanocrystalline modified epoxy resin comprises the following steps:
adding starch nanocrystals and nano nickel protoxide into butanone solution, performing ultrasonic reaction for 30min, adding methylene bisacrylamide at 70 ℃ for reaction for 2h, adding E51 epoxy resin, heating to 90 ℃ for reaction for 2h, and performing reduced pressure distillation to remove the solvent to obtain the starch nanocrystal modified epoxy resin.
The preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following steps:
(1) adding a pH regulator into water accounting for 45 percent of the total amount of the pH regulator for dissolving, regulating the pH value to 4, adding a coupling agent A and a coupling agent B under stirring, and continuously stirring for 0.5h 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 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 with the mass of 6 times of 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 with the mass of 9 times of 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 4 times that of the lubricant A and the lubricant B, 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.
Example 3:
the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following components: according to the percentage, 0.4wt% of silane coupling agent A, 0.6wt% of silane coupling agent B, 7.0 wt% of film forming agent, 0.5 wt% of lubricant A, 0.5 wt% of lubricant B, 0.4wt% of auxiliary agent, 0.3 wt% 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; lubricant B is octadecyl trimethyl ammonium chloride; the pH regulator is glacial acetic acid; the auxiliary agent comprises starch nanocrystal modified epoxy resin.
The preparation method of the modified epoxy emulsion comprises the following steps:
(1) adding chitosan into water, adding citric acid, heating to 40 ℃, and stirring until the chitosan is completely dissolved to obtain a chitosan aqueous solution; wherein, the adding amount ratio of the water, the chitosan and the citric acid is as follows: 30: 15: 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 3 hours at 80 ℃ to prepare the modified epoxy emulsion.
Wherein, the starch nanocrystal modified epoxy resin comprises: 20 parts of starch nanocrystal, 10 parts of methylene bisacrylamide, 80 parts of E51 epoxy resin and 0.5 part of nano nickel protoxide. The preparation method of the powder nanocrystalline modified epoxy resin comprises the following steps:
adding starch nanocrystals and nano nickel protoxide into butanone solution, performing ultrasonic reaction for 40min, adding methylene bisacrylamide at 80 ℃ for reaction for 3h, adding E51 epoxy resin, heating to 100 ℃ for reaction for 3h, and performing reduced pressure distillation to remove the solvent to obtain the starch nanocrystal modified epoxy resin.
The preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following steps:
(1) adding a pH regulator into water accounting for 50% of the total amount of the pH regulator for dissolving, regulating the pH to 4.5, adding a coupling agent A and a coupling agent B under stirring, and continuously stirring for 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 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 with the mass of 7 times of 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 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 5 times that of the lubricant A and the lubricant B, 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.
Example 4:
the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following components: 0.5 wt% of silane coupling agent A, 0.7wt% of silane coupling agent B, 7.5 wt% of film forming agent, 0.6wt% of lubricant A, 0.6wt% of lubricant B, 0.5 wt% of adjuvant, 0.35 wt% 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; lubricant B is octadecyl trimethyl ammonium chloride; the pH regulator is glacial acetic acid; the auxiliary agent comprises starch nanocrystal modified epoxy resin.
The modified epoxy emulsion of this example was prepared in accordance with example 3.
The composition and preparation method of the starch nanocrystal modified epoxy resin of this example are consistent with example 3.
The preparation method of the glass fiber sizing agent for the polyurethane pultrusion composite material is consistent with that of the example 3.
Example 5:
the glass fiber impregnating compound for the polyurethane pultrusion composite material comprises the following components: 0.6wt% of silane coupling agent A, 0.8wt% of silane coupling agent B, 8.2wt% of film forming agent, 0.7wt% of lubricant A, 0.8wt% of lubricant B, 0.6wt% of adjuvant, 0.4wt% 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; lubricant B is octadecyl trimethyl ammonium chloride; the pH regulator is glacial acetic acid; the auxiliary agent comprises starch nanocrystal modified epoxy resin.
The modified epoxy emulsion of this example was prepared in accordance with example 3.
The composition and preparation method of the starch nanocrystal modified epoxy resin of this example are consistent with example 3.
The preparation method of the glass fiber sizing agent for the polyurethane pultrusion composite material is consistent with that of the example 3.
Comparative example 1
The composition and preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material of the comparative example are the same as those of the example 3, and the difference is that the silane coupling agent B is reduced.
Comparative example 2
The composition and preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material of the comparative example are the same as those of the example 3, and the difference is that unmodified epoxy emulsion is adopted.
Comparative example 3
The composition and preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material of the comparative example are the same as those of the example 3, and the difference is that the auxiliary agent is reduced.
Comparative example 4
The composition and preparation method of the glass fiber impregnating compound for the polyurethane pultrusion composite material of the comparative example are the same as those of the example 3, and the difference is that the auxiliary agent is starch.
The glass fiber sizing agents for the polyurethane pultrusion composite materials prepared in the examples 1-5 and the comparative examples 1-4 are applied to the production of transparent plate yarns, the drawing process generally adopted is 2400-hole platinum bushing drawing, the fiber diameter is 22 +/-1 mu m, the drying process can adopt steam and hot air for drying, the drying time is 13.5 hours, the final product is 2400Te, and the LOI% is 0.55 +/-0.15%. And the interface bonding strength is tested by using a pull-out experiment, the tensile strength and the elongation at break of the interface are measured according to the standard GB/T1447-2005, the bending strength of the interface is measured according to the standard GB/T1449-2005, and the impact strength of the interface is measured according to the standard GB/T1451-2005, and the results are as follows:
as can be seen from the above table, the glass fiber sizing agent for the polyurethane pultrusion composite material of the invention has the advantages of obviously reduced hairiness content and obviously improved tensile strength, bending strength and impact strength compared with the comparative example.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
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; lubricant B is octadecyl trimethyl ammonium chloride;
the adjuvant comprises a starch nanocrystal modified epoxy resin, and the starch nanocrystal modified epoxy resin comprises: 10-20 parts of starch nanocrystal, 5-10 parts of methylene bisacrylamide, 70-80 parts of E51 epoxy resin and 0.1-0.5 part of nano nickel protoxide.
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 mass ratio of the water to the chitosan to 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. The glass fiber impregnating compound for the polyurethane pultrusion composite material as claimed in claim 1, 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.
4. A glass fiber sizing for polyurethane pultruded composites according to any of the claims 1-3, wherein said pH modifier is glacial acetic acid.
5. A method for preparing a glass fiber sizing for a polyurethane pultruded composite according to any of claims 1 to 4, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325210.7A CN110790519B (en) | 2019-12-20 | 2019-12-20 | Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325210.7A CN110790519B (en) | 2019-12-20 | 2019-12-20 | Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110790519A CN110790519A (en) | 2020-02-14 |
| CN110790519B true CN110790519B (en) | 2022-01-11 |
Family
ID=69448529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911325210.7A Active CN110790519B (en) | 2019-12-20 | 2019-12-20 | Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110790519B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112279525A (en) * | 2020-10-30 | 2021-01-29 | 重庆三磊玻纤股份有限公司 | Glass fiber impregnating compound for reinforcing polyurethane, preparation method and application thereof |
| CN112321991B (en) * | 2020-11-25 | 2023-03-21 | 四川四众玄武岩纤维技术研发有限公司 | Method for treating basalt fibers |
| CN112521030B (en) * | 2020-12-07 | 2022-08-23 | 巨石集团有限公司 | High-mechanical-property glass fiber impregnating compound and preparation method and application thereof |
| CN113858660A (en) * | 2021-09-15 | 2021-12-31 | 山东明珠材料科技有限公司 | Preparation process of wear-resistant fiber polyurethane composite film and composite film profile |
| CN114438639A (en) * | 2022-02-10 | 2022-05-06 | 苏州市星京泽纤维科技有限公司 | Wear-resistant vortex spinning core-spun yarn and manufacturing process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516714A (en) * | 2011-11-29 | 2012-06-27 | 武汉理工大学 | Preparation method of nano epoxy resin composite material |
| CN106007408A (en) * | 2016-05-16 | 2016-10-12 | 常州天马集团有限公司（原建材二五三厂） | Compound type glass fiber direct roving sizing agent and preparation method thereof |
| JP2017179265A (en) * | 2016-03-31 | 2017-10-05 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| CN107417136A (en) * | 2017-09-05 | 2017-12-01 | 山东玻纤集团股份有限公司 | One kind enhancing polyurethane pultrusion alkali-free glass fibre direct roving sizing agent |
| CN107987670A (en) * | 2017-12-08 | 2018-05-04 | 枞阳县新天地高新材料有限公司 | A kind of preparation method of ageing-resistant aqueous epoxide resin paint |
| CN108913074A (en) * | 2018-05-31 | 2018-11-30 | 计蛟昇 | Modified epoxide resin adhesive and preparation method thereof |
-
2019
- 2019-12-20 CN CN201911325210.7A patent/CN110790519B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516714A (en) * | 2011-11-29 | 2012-06-27 | 武汉理工大学 | Preparation method of nano epoxy resin composite material |
| JP2017179265A (en) * | 2016-03-31 | 2017-10-05 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| CN106007408A (en) * | 2016-05-16 | 2016-10-12 | 常州天马集团有限公司（原建材二五三厂） | Compound type glass fiber direct roving sizing agent and preparation method thereof |
| CN107417136A (en) * | 2017-09-05 | 2017-12-01 | 山东玻纤集团股份有限公司 | One kind enhancing polyurethane pultrusion alkali-free glass fibre direct roving sizing agent |
| CN107987670A (en) * | 2017-12-08 | 2018-05-04 | 枞阳县新天地高新材料有限公司 | A kind of preparation method of ageing-resistant aqueous epoxide resin paint |
| CN108913074A (en) * | 2018-05-31 | 2018-11-30 | 计蛟昇 | Modified epoxide resin adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110790519A (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110790519B (en) | Glass fiber impregnating compound for polyurethane pultrusion composite material and preparation method thereof | |
| George et al. | Mechanical properties of flax fibre reinforced epoxy composites | |
| CN104389176B (en) | Emulsion type carbon fiber sizing agent containing graphene oxide and preparation method thereof | |
| US8791195B2 (en) | Compositions useful for non-cellulose fiber sizing, coating or binding compositions, and composites incorporating same | |
| DE102005048190A1 (en) | Reinforced composites with concrete matrix have fibers with a sizing composition and a further coating forming an acid barrier layer interacting with the concrete | |
| CN107118528A (en) | A kind of tossa strengthens the preparation method of lactic acid composite material | |
| CN110818284A (en) | Glass fiber strand twistless roving impregnating compound, preparation method, product and application | |
| JP3255414B2 (en) | Glass sizing composition and glass fiber coated therewith | |
| CN106587658A (en) | Glass fiber sizing agent and application thereof | |
| CN107236267A (en) | A kind of surface is modified the preparation method of jute lactic acid composite material | |
| CN113234296A (en) | Glass fiber reinforced PMMA (polymethyl methacrylate) composite material and preparation method thereof | |
| CN112429978A (en) | Glass fiber material modification reinforced molding treatment method | |
| CN111663332B (en) | Direct yarn impregnating compound for glass fiber multi-axial fabric and preparation method and application thereof | |
| CN106751799B (en) | A kind of basalt fibre reinforced polyamide composite material and preparation method | |
| CN111517671B (en) | Alkali-free glass fiber impregnating compound, and preparation method, product and application thereof | |
| DE1469166B2 (en) | Use of the aqueous solution of a mixture of aminoalkylalkoxysilane, water-soluble epoxy compound and water-soluble amine for improving the adhesive properties of glass fibers | |
| Saravanan et al. | Effect of cassava tuber nanocellulose and satin weaved bamboo fiber addition on mechanical, wear, hydrophobic, and thermal behavior of unsaturated polyester resin composites | |
| CN108440902B (en) | Epoxy resin reinforced and toughened blending material | |
| CN106188426B (en) | A kind of film-forming agent for glass fiber injection yarn and preparation method thereof | |
| CN112376279B (en) | Preparation method of impregnating compound for producing glass fiber continuous felt | |
| CN113173715A (en) | Glass fiber impregnating compound for reinforcing polyvinyl chloride and preparation method and application thereof | |
| CN113233790A (en) | Glass fiber impregnating compound for enhancing PMMA (polymethyl methacrylate), and preparation method and application thereof | |
| CN113088017A (en) | Glass fiber reinforced polyvinyl chloride composite material and preparation method thereof | |
| CN113213780A (en) | Glass fiber impregnating compound and preparation method and application thereof | |
| US20210070924A1 (en) | An epoxy resin system for structural composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |