CN114933781A - Method for improving wear resistance of halogen-free epoxy glass fiber board - Google Patents

Abstract

The invention discloses a method for improving the wear resistance of halogen-free epoxy glass fiber board, which specifically comprises the following steps: (1) pretreatment and compounding of fillers; (2) modification treatment of curing agent; (3) halogen-free Preparation of epoxy resin glue; (4) surface treatment of glass fiber cloth; (5) curing of halogen-free epoxy resin glue and molding of glass fiber board. The method of the invention can well improve the wear resistance of the halogen-free epoxy glass fiber board through the heat treatment and alcohol washing of the glass fiber cloth, the surface modification of the curing agent, and the pretreatment and compounding of different fillers at the same time. The preparation method of the invention is simple and feasible, the raw materials are abundant and easy to obtain, the process is green and economical, the mixed materials are uniformly dispersed, and the obtained halogen-free epoxy glass fiber board has excellent wear resistance.

Description

A method for improving wear resistance of halogen-free epoxy glass fiber board

technical field

The invention belongs to the technical field of epoxy resins, and particularly relates to a method for improving the wear resistance of a halogen-free epoxy glass fiber board.

Background technique

Epoxy glass fiber board is a board formed by pressing epoxy resin glue and glass fiber cloth together through suitable curing and molding processes. It has the characteristics of various forms, convenient curing, strong adhesion, low shrinkage, heat and moisture resistance, etc. , usually can be used as high-insulation structural parts for machinery, electrical appliances and electronics, and is suitable for electronic packaging, aerospace, construction, rail transit and other fields. However, during the use of epoxy glass fiber board, serious wear may occur due to long-term frictional contact, which will greatly reduce the working performance of the board and shorten its service life.

In recent years, there have been attempts to use nano-inorganic particles to improve the wear resistance of polymer products. At present, the common inorganic wear-resistant materials are SiC, TiO ₂ , SiO ₂ , BaSO ₄ , etc. A small amount of addition can effectively reduce the friction coefficient of the polymer. However, due to the small particle size, large specific surface area and surface High energy, it is easy to cause agglomeration, the dispersion effect in epoxy resin is not ideal, it is easy to cause the roughness of the board to increase, the surface is uneven, and even white wires or cracks appear, so that the mechanical properties of the material cannot be reduced. Requirements. Therefore, improving the dispersibility of wear-resistant particles in epoxy resin, solving the compatibility between reinforcing agent and matrix, and strengthening the synergistic effect of each component will be beneficial to the improvement of mechanical properties such as wear resistance of epoxy glass fiber board.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide a method for improving the wear resistance of a halogen-free epoxy glass fiber board. The prepared epoxy glass fiber board is halogen-free, has high hardness and has excellent wear resistance.

The purpose of the present invention is achieved through the following technical solutions.

A method for improving the wear resistance of halogen-free epoxy glass fiber board, comprising the following steps:

(1) Pretreatment and compounding of fillers

First, tetrabutyl titanate, acid-terminated block copolymer, silane coupling agent, and nano-alumina were pretreated with alcohol washing respectively; The mass ratio of 5~10:5~10:10~15:500~575 to obtain composite filler component A;

(2) Modification of curing agent

Modification of curing agent by adding acid-terminated block copolymers to dicyandiamide (DCD), 2-methylimidazole (MI), N, N-dimethylformamide (DMF), dicyandiamine The mass ratio of (DCD), 2-methylimidazole (MI), N, N-dimethylformamide (DMF), and acid-terminated block copolymer is 116~130:4~5:600~625:5 ~6, stirring to obtain a clear solidified component solution B;

(3) Preparation of halogen-free epoxy resin glue

Stir and mix the composite filler component A and the curing component solution B evenly; then add the halogen-free epoxy resin C, and continue to stir until uniform to obtain halogen-free epoxy resin glue, halogen-free epoxy resin C, and curing component solution B , The mass ratio of composite filler component A is 1000~1050:145~155:256~265;

(4) Surface treatment of glass fiber cloth

The glass fiber cloth is heat-treated at 200-250℃ for 5-10min, and after cooling, further alcohol washing pretreatment and air-drying are carried out;

(5) Curing of halogen-free epoxy resin glue and forming of glass fiber board

The halogen-free epoxy resin glue obtained in step (3) is coated on the glass fiber cloth treated in step (4) to form a halogen-free epoxy glass fiber material, and then placed in an oven for heating to complete curing to obtain a halogen-free epoxy glass fiber. Fiberboard.

Further, in step (1), the alcohol is absolute ethanol, and the mass ratio of absolute ethanol to tetrabutyl titanate is 750-800:5-10; the temperature of alcohol washing pretreatment is 30-45 °C, The time is 1~2 h.

Further, the silane coupling agent is KH-550.

Further, the acid end group block copolymer is AFCONA-7520, pH=3.

Further, in step (2), the modification is carried out under stirring conditions, the stirring temperature is 30-45°C, and the stirring time is 30-45 min.

Further, the epoxy resin is halogen-free G10.

Further, in step (3), the stirring temperature for mixing A and B is 30-45 °C, and the stirring time is 10-30 min; after adding C, the stirring temperature is 30-45 °C, and the stirring time is 45-60 min.

Further, the glass fiber cloth is 7628 glass fiber cloth.

Further, in step (4), the heat treatment is carried out in an oven, and absolute ethanol is used for the alcohol washing of glass fiber cloth, and the temperature of the alcohol washing is 30-45° C. and the time is 10-30 min.

Further, in step (5), after coating the halogen-free epoxy resin adhesive, the resin is heated at 80-90° C. for 10-15 minutes, and then heated at 95-120° C. for 10-15 minutes to complete curing.

Further, in step (2) and step (3), the stirring speed is 1600-2000 r/min.

The beneficial effects of the present invention are:

(1) The present invention significantly improves the dispersion performance of wear-resistant particles nano-alumina in epoxy resin, and at the same time, tetrabutyl titanate can also be alcoholyzed to form uniformly dispersed nano-titanium dioxide wear-resistant particles in the process, and the dispersion performance is excellent. The composite nano wear-resistant particle filler can significantly improve the wear resistance of halogen-free epoxy glass fiber board.

(2) The present invention can effectively improve the excellent interface bonding between the matrix and the glass fiber cloth through the surface treatment of the glass fiber cloth heat treatment and alcohol washing, and avoid the local concentration of the plate stress as much as possible, resulting in the generation and expansion of cracks. , The glass fiber cloth with excellent performance bears most of the stress, so that its wear resistance has been greatly improved. However, it is necessary to control the dosage ratio of glass fiber cloth to the matrix. Excessive addition of glass fiber cloth will cause uneven dispersion of the matrix, and the glass fiber cloth cannot be well infiltrated, resulting in uneven stress distribution and reduced friction performance.

(3) In the present invention, by modifying the curing agent and adding an accelerator, the compatibility of the curing agent and the matrix resin can be well increased, the curing acceleration effect and bonding performance can be improved, the process stability can be improved, and it is also beneficial to Long-term storage use and application performance improvement of epoxy resin curing system.

(4) The present invention improves the surface properties of fillers through alcohol washing pretreatment of different fillers; composites different fillers and adds dispersant to synergistically promote the dispersion performance of fillers, enhance their surface adsorption, and improve the adhesion with the matrix. Compatibility and bonding properties make the filler well dispersed in the resin and improve the compactness of the epoxy glass fiber board structure. The halogen-free epoxy glass fiber board prepared by the method of the invention has high hardness and excellent wear resistance.

Detailed ways

In order to better understand the present invention, the present invention will be further described in detail below in conjunction with the embodiments, but the scope of protection claimed in the present invention is not limited to the scope represented by the embodiments.

Example 1

(1) Pretreatment and compounding of fillers

First, tetrabutyl titanate, acid-terminated block copolymer, KH-550, and nano-alumina were pretreated by immersion in absolute ethanol, and stirred at 30 °C for 1 h; The components are mixed in a certain proportion to obtain the composite filler component A.

(2) Modification of curing agent

Add AFCONA-7520 to DCD, MI and DMF, and keep stirring at 1800 r/min for 30 min at 45 °C to obtain a clear solidified component solution B.

(3) Preparation of halogen-free epoxy resin adhesive

Mix the composite filler component A and the curing component solution B, and stir at 45 °C for 10 min until uniform; then add halogen-free epoxy resin G10, keep the rotation speed of 1800 r/min, and continue to stir for 1 h until uniform, and obtain no Halogen epoxy glue.

(4) Surface treatment of glass fiber cloth

The 7628 glass fiber cloth was heat-treated in an oven at 250 °C for 10 min. After cooling, it was further soaked with absolute ethanol for 10 min, and then air-dried.

(5) Curing of halogen-free epoxy resin glue and forming of glass fiber board

The halogen-free epoxy resin glue was coated on the treated glass fiber cloth to form a halogen-free epoxy glass fiber material, which was heated in an oven at 80 °C for 10 min, and then heated at 112 °C for 10 min to complete the curing to obtain a halogen-free epoxy resin. Fiberglass panels.

In the composite filler component A, the mixed mass ratio of tetrabutyl titanate, acid end-group block copolymer, KH-550, nano-alumina, and anhydrous ethanol is 10:5:15:500:750.

The mixing mass ratio of DCD, MI, DMF and AFCONA-7520 in the curing component solution B is 116:4:600:5.

The halogen-free epoxy resin adhesive is composed of halogen-free epoxy resin C, curing component solution B and composite filler component A in a mass ratio of 1000:145:256.

Example 2

(1) Pretreatment and compounding of fillers

First, tetrabutyl titanate, acid-terminated block copolymer, KH-550, and nano-alumina were pretreated with absolute ethanol, respectively, and stirred at 30 °C for 2 h; The components are mixed in a certain proportion to obtain the composite filler component A.

(2) Modification of curing agent

Add AFCONA-7520 to DCD, MI and DMF, and keep stirring at 1800 r/min for 45 min at 30 °C to obtain a clear solidified component solution B.

(3) Preparation of halogen-free epoxy resin glue

Mix the composite filler component A and the curing component solution B, and stir at 30 °C for 30 min until uniform; then add halogen-free epoxy resin G10, keep the rotation speed of 1800 r/min, and continue to stir for 45 min to uniform, and obtain no Halogen epoxy glue.

(4) Surface treatment of glass fiber cloth

The 7628 glass fiber cloth was heat-treated in an oven at 250 °C for 15 min. After cooling, it was further soaked with absolute ethanol for 30 min, and then air-dried.

(5) Curing of halogen-free epoxy resin glue and forming of glass fiber board

The halogen-free epoxy resin glue was coated on the treated glass fiber cloth to form a halogen-free epoxy glass fiber material, which was heated in an oven at 80 °C for 15 min, and then heated at 120 °C for 10 min to complete the curing to obtain a halogen-free epoxy resin. Fiberglass panels.

In the composite filler component A, the mixed mass ratio of tetrabutyl titanate, acid end group block copolymer, KH-550, nano-alumina, and absolute ethanol is 8:8:10:525:725.

The mixing mass ratio of DCD, MI, DMF and AFCONA-7520 in the curing component solution B is 120:5:610:5.

The halogen-free epoxy resin adhesive is composed of halogen-free epoxy resin C, curing component solution B and composite filler component A in a mass ratio of 1025:150:262.

Example 3

(1) Pretreatment and compounding of fillers

First, tetrabutyl titanate, acid-terminated block copolymer, KH-550, and nano-alumina were pretreated with anhydrous ethanol, and stirred at 40 °C for 1.5 h; The components are mixed in a certain proportion to obtain the composite filler component A.

(2) Modification of curing agent

Add AFCONA-7520 to DCD, MI and DMF, and keep stirring at 1800 r/min for 40 min at 40 °C to obtain a clear solidified component solution B.

(3) Preparation of halogen-free epoxy resin glue

Mix the composite filler component A and the curing component solution B, and stir at 35 ° C for 25 min until uniform; then add halogen-free epoxy resin G10, keep the rotation speed of 1800 r/min, and continue to stir for 50 min to uniform, and obtain no Halogen epoxy glue.

(4) Surface treatment of glass fiber cloth

The 7628 glass fiber cloth was heat-treated in an oven at 250 °C for 8 min, and after cooling, it was further soaked with anhydrous ethanol for 15 min, and then air-dried.

(5) Curing of halogen-free epoxy resin glue and forming of glass fiber board

The halogen-free epoxy resin glue was coated on the treated glass fiber cloth to form a halogen-free epoxy glass fiber material, which was heated in an oven at 85 °C for 12 min, and then heated at 105 °C for 12 min to complete the curing to obtain a halogen-free epoxy resin. Fiberglass panels.

In the composite filler component A, the mixed mass ratio of tetrabutyl titanate, acid end group block copolymer, KH-550, nano-alumina, and anhydrous ethanol is 6:8:12:575:775.

The mixing mass ratio of DCD, MI, DMF and AFCONA-7520 in the curing component solution B is 124:4.5:610:5.5.

The halogen-free epoxy resin adhesive is composed of halogen-free epoxy resin C, curing component solution B and composite filler component A in a mass ratio of 1000:153:264.

Example 4

(1) Pretreatment and compounding of fillers

First, tetrabutyl titanate, acid-terminated block copolymer, KH-550, and nano-alumina were pretreated with anhydrous ethanol, and stirred at 35 °C for 1.5 h; The components are mixed in a certain proportion to obtain the composite filler component A.

(2) Modification of curing agent

Add AFCONA-7520 to DCD, MI and DMF, and keep stirring at 1800 r/min for 35 min at 40 °C to obtain a clear solidified component solution B.

(3) Preparation of halogen-free epoxy resin adhesive

Mix the composite filler component A and the curing component solution B, and stir at 40 °C for 25 min until uniform; then add halogen-free epoxy resin G10, keep the rotation speed of 1800 r/min, and continue to stir for 55 min to uniform, and obtain no Halogen epoxy glue.

(4) Surface treatment of glass fiber cloth

The 7628 glass fiber cloth was heat-treated in an oven at 250 °C for 6 min. After cooling, it was further soaked with absolute ethanol for 25 min, and then air-dried.

(5) Curing of halogen-free epoxy resin glue and forming of glass fiber board

The halogen-free epoxy resin glue was coated on the treated glass fiber cloth to form a halogen-free epoxy glass fiber material, which was heated in an oven at 85 °C for 12 min, and then heated at 100 °C for 15 min to complete curing to obtain a halogen-free epoxy resin. Fiberglass panels.

In the composite filler component A, the mixed mass ratio of tetrabutyl titanate, acid end-group block copolymer, KH-550, nano-alumina, and anhydrous ethanol is 9:4:12:550:760.

The mixing mass ratio of DCD, MI, DMF and AFCONA-7520 in the curing component solution B is 124:5:615:6.

The halogen-free epoxy resin adhesive is composed of halogen-free epoxy resin C, curing component solution B and composite filler component A in a mass ratio of 1030:148:261.

Comparative Example 1

The other conditions are the same as those in Example 1, except that tetrabutyl titanate, acid end-group block copolymer and KH-550 of the composite filler component A are not added.

Comparative Example 2

The other conditions are the same as those in Example 2, the difference is that tetrabutyl titanate, acid-terminated block copolymer, silane coupling agent, nano-alumina and glass fiber cloth are not pretreated by anhydrous ethanol impregnation and alcohol washing.

Comparative Example 3

The other conditions are the same as those in Example 3, except that AFCONA-7520 and accelerator MI are not added in the modification treatment step of the curing agent.

Comparative Example 4

The other conditions are the same as those in Example 4, the difference is that tetrabutyl titanate is not added to the composite filler component A.

The hardness and friction properties of the epoxy glass fiber boards of Examples 1 to 4 and Comparative Examples 1 to 4 were tested, and the results are shown in Table 1.

It can be seen from Table 1 that the epoxy glass fiber board prepared by the method of the present invention has high hardness and low wear mass percentage, the addition of composite filler components, the alcohol washing surface pretreatment of composite filler components and fiber cloth. It can greatly improve the wear resistance of epoxy glass fiber board. Alcohol washing improves the surface properties of glass fiber cloth and wear-resistant particle filler, and can enhance its compatibility with epoxy resin under the action of coupling agent. At the same time, tetrabutyl titanate can form uniformity during alcohol washing Dispersed nano titanium dioxide wear-resistant particles; the modification treatment of curing agent can effectively improve the bonding performance with epoxy resin, thereby enhancing the bond between the matrix and the reinforcement, and improving the mechanical properties of the material. In the present invention, the dispersibility of the nano wear-resistant particles is improved, the surface adhesion performance of the curing agent is improved, and the composite synergistic effect of the filler makes the wear resistance of the halogen-free epoxy glass fiber board well improved.

Table 1 Performance characterization of epoxy glass fiber boards of Examples 1-4 and Comparative Examples 1-4

Shore hardness Wear mass percentage Example 1 99 0.02986 Example 2 98 0.04092 Example 3 98 0.04001 Example 4 98 0.04795 Comparative Example 1 91 0.14722 Comparative Example 2 93 0.12776 Comparative Example 3 92 0.10309 Comparative Example 4 93 0.11398

Claims (10)

1. A method for improving the wear resistance of a halogen-free epoxy glass fiber board is characterized by comprising the following steps:

(1) pretreatment and compounding of fillers

Firstly, respectively carrying out alcohol washing pretreatment on tetrabutyl titanate, an acid end group block copolymer, a silane coupling agent and nano aluminum oxide; then, mixing tetrabutyl titanate, an acid-terminated block copolymer, a silane coupling agent and nano-alumina in a mass ratio of 5-10: 10-15: 500-575 to obtain a composite filler component A;

(2) modification treatment of curing agent

Adding an acid-terminated block copolymer into dicyandiamide, 2-methylimidazole and N, N-dimethylformamide to modify a curing agent, wherein the mass ratio of dicyandiamide to 2-methylimidazole to N, N-dimethylformamide to the acid-terminated block copolymer is 116-130: 4-5: 600-625: 5-6, and stirring to obtain a clear curing component solution B;

(3) preparation of halogen-free epoxy resin adhesive

Uniformly stirring and mixing the composite filler component A and the curing component solution B; then adding halogen-free epoxy resin C, and continuously stirring until the mixture is uniform to obtain a halogen-free epoxy resin adhesive, wherein the mass ratio of the halogen-free epoxy resin C, the curing component solution B and the composite filler component A is 1000-1050: 145-155: 256-265;

(4) surface treatment of glass fiber cloth

Carrying out heat treatment on the glass fiber cloth at the temperature of 200-250 ℃ for 5-10min, cooling, then further carrying out alcohol washing pretreatment and airing;

(5) curing of halogen-free epoxy resin glue and molding of glass fiber board

And (4) coating the halogen-free epoxy resin glue obtained in the step (3) on the glass fiber cloth treated in the step (4) to form a halogen-free epoxy glass fiber material, and then placing the halogen-free epoxy glass fiber material in an oven to heat and finish curing to obtain the halogen-free epoxy glass fiber plate.

2. The method for improving the wear resistance of the halogen-free epoxy glass fiber board as claimed in claim 1, wherein in the step (1), the alcohol is absolute ethyl alcohol, and the mass ratio of the absolute ethyl alcohol to the tetrabutyl titanate is 750-800: 5-10; the temperature of the alcohol washing pretreatment is 30-45 ℃, and the time is 1-2 h.

3. The method for improving the abrasion resistance of the halogen-free epoxy glass fiber board according to claim 1, wherein the silane coupling agent is KH-550.

4. The method for improving the abrasion resistance of the halogen-free epoxy glass fiber board according to claim 1, wherein the acid-terminated block copolymer is AFCONA-7520, pH = 3.

5. The method for improving the wear resistance of the halogen-free epoxy glass fiber board as claimed in claim 1, wherein in the step (2), the modification is performed under stirring conditions, the stirring temperature is 30-45 ℃, the stirring time is 30-45 min, and the stirring speed is 1600-2000 r/min.

6. The method for improving the abrasion resistance of the halogen-free epoxy glass fiber board according to claim 1, wherein the epoxy resin is halogen-free G10.

7. The method for improving the wear resistance of the halogen-free epoxy glass fiber board according to claim 1, wherein in the step (3), the mixing temperature of the mixture A and the mixture B is 30-45 ℃, and the mixing time is 10-30 min; after the C is added, the temperature for continuously stirring is 30-45 ℃, the stirring time is 45-60 min, and the stirring speed is 1600-2000 r/min.

8. The method for improving the abrasion resistance of the halogen-free epoxy glass fiber board according to claim 1, wherein the glass fiber cloth is 7628 glass fiber cloth.

9. The method for improving the wear resistance of the halogen-free epoxy glass fiber board according to claim 1, wherein in the step (4), the heat treatment is performed in an oven, absolute ethyl alcohol is adopted for alcohol washing of the glass fiber cloth, the temperature of the alcohol washing is 30-45 ℃, and the time is 10-30 min.

10. The method for improving the wear resistance of the halogen-free epoxy glass fiber board according to claim 1, wherein in the step (5), the halogen-free epoxy resin adhesive is coated, heated at 80-90 ℃ for 10-15 min, and then heated at 95-120 ℃ for 10-15 min to complete the curing.