CN110564106B - High-strength synthetic resin for glass fiber rod and preparation method thereof - Google Patents

Abstract

The invention discloses a high-strength synthetic resin for a glass fiber rod and a preparation method thereof, belonging to the technical field of synthetic resin products. According to the invention, the cation exchange performance of the sodium bentonite is utilized, cations in the superfine silicon dioxide and the alumina are exchanged and enter the bentonite layer, and then the plasma sputtering is used for carrying out pore forming on the bentonite layer to obtain the plasma modified sodium bentonite, so that the adsorbability of the bentonite is improved, the sodium bentonite also has aging resistance, the high temperature resistance and the mechanical strength of the synthetic resin can be increased, and the high water absorption of the resin can be kept to the maximum extent; the fluidized coating layer material is coated outside the microporous coating reinforcing agent, so that the mechanical strength of the microporous coating reinforcing agent is improved, and the mechanical strength of the obtained synthetic resin is obviously enhanced.

Description

High-strength synthetic resin for glass fiber rod and preparation method thereof

Technical Field

The invention belongs to the technical field of synthetic resin products, and particularly relates to high-strength synthetic resin for a glass fiber rod and a preparation method thereof.

Background

The glass fiber is an inorganic non-metallic material with excellent performance, has various types, has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but the glass fiber product has the same property as glass, is brittle and is easy to break; moreover, the wear resistance is poor, and the wear is easily damaged after long-term use, and once a sharp object scratches the surface of the object, irreparable wear is caused.

The fiberglass rod is a composite material which takes fiberglass and products thereof (glass cloth, belt, felt, yarn and the like) as reinforcing materials and synthetic resin as matrix materials aiming at the defects of the fiberglass. The relative density is between 1.5 and 2.0, only 1/4 to 1/5 of carbon steel is adopted, but the tensile strength is close to or even exceeds that of carbon steel, and the specific strength can be compared with high-grade alloy steel. Therefore, the epoxy FRP has excellent effect in aviation, rocket, spacecraft, high-pressure vessel and other product applications needing to reduce self weight, and the tensile strength, the bending strength and the compressive strength of some epoxy FRP can reach more than 400 MPa.

Since the mechanical strength of the synthetic resin used as the base material of the glass fiber rod determines the mechanical properties of the glass fiber rod, there is a strong demand for a synthetic resin having high strength, good heat resistance and strong flexibility.

Disclosure of Invention

Aiming at the problems, the invention provides a high-strength synthetic resin with high temperature resistance and high flexibility for a glass fiber rod and a preparation method thereof.

The technical scheme of the invention is as follows: a high-strength synthetic resin for glass fiber rods, comprising the following components: 35-40 parts of epoxy resin, 20-25 parts of phenolic resin, 15-20 parts of polyamide resin, 15-18 parts of polyvinyl chloride, 1-2 parts of diethyl phthalate, 1.5-3 parts of polyvinyl acetal, 2-4 parts of plasma modified sodium bentonite, 6-8 parts of microporous coating reinforcing agent and 3-6 parts of flame retardant.

Further, the preparation method of the plasma modified sodium bentonite comprises the following steps: (1) adding 4-5g of superfine silicon dioxide and 2-3g of alumina into a reaction kettle filled with 80mL of sodium hydroxide solution with the concentration of 0.15-0.6mol/L at the temperature of 45-60 ℃, and simultaneously introducing nitrogen with the air flow velocity of 0.6L/min into the reaction kettle and stirring for 2-3h to obtain suspension A; (2) sieving 4-5g of common sodium bentonite by a 60-80 mesh sieve, adding into the suspension A, stirring for 3-5h, and aging for 2-3h to obtain suspension B; (3) washing the suspension B with distilled water for 3-4 times, drying to obtain modified sodium bentonite particles, rotating the particles in a vacuum environment at a rotating speed of 50-65r/min, introducing argon until the vacuum degree is 25-30Pa, ionizing the argon into argon ions, and carrying out plasma sputtering on the surfaces of the modified sodium bentonite particles to form nano-scale micropores on the surfaces of the modified sodium bentonite particles; the sodium bentonite replaces cations in the superfine silicon dioxide and the alumina, exchanges the cations into a bentonite layer, and performs pore forming on the bentonite layer by plasma sputtering to obtain the plasma modified sodium bentonite, so that the adsorbability of the bentonite is improved, the sodium bentonite also has aging resistance, the high temperature resistance and the mechanical strength of the synthetic resin can be improved, and the high water absorbability of the resin can be kept to the maximum extent.

Further, the microporous coating reinforcing agent comprises the following components in percentage by weight: 10-15% of carbon fiber, 3-5% of 1, 3-dioxane, 2-4% of tert-butyl peroxide, 2-3% of diphenylsilanediol, 1-2% of white carbon black, 4-5% of calcium stearate, 3-6% of nano calcium carbonate, 1-2% of borosilicate, 3-5% of polyamide fiber, 2-4% of polyphenylene sulfide, 2-3% of vinyltriethoxysilane, 6-10% of a fluidized coating material and the balance of silicate.

Further, the preparation method of the microporous coating reinforcing agent comprises the following steps: (1) uniformly mixing the silicate, the carbon fiber, the 1, 3-dioxane, the tert-butyl oxide and the diphenylsilanediol in percentage by weight at the temperature of 60-80 ℃, and then carrying out ultrasonic treatment for 2-3h to obtain a mixture A; (2) uniformly mixing the white carbon black and the calcium stearate in percentage by weight at the temperature of 100-150 ℃, then cooling to 55-85 ℃, adding the nano calcium carbonate, the borosilicate, the polyamide fiber, the polyphenylene sulfide and the vinyl triethoxysilane in percentage by weight, uniformly stirring at the speed of 150-200r/min, and then cooling to normal temperature to obtain a mixture B; (3) placing the mixture A, the mixture B and the fluidized coating layer material into a centrifuge, centrifuging at the speed of 2500-, the bearing capacity is improved.

Further, the fluidization coating material comprises, in weight percent: 10-15% of hydroxymethyl cellulose, 3-5% of sodium alginate, 2-3% of sodium chloride and the balance of polyacrylic resin, wherein the fluidized coating layer material formed by the components has good permeability, and is added with insoluble sodium chloride, so that the surface of the film is rough, and the adhesion among particles is reduced.

Furthermore, the flame retardant is a polyborosiloxane flame retardant, and the heat resistance of the synthetic resin is improved through the better flame retardant effect of the polyborosiloxane.

Further, the preparation method of the fluidization coating material comprises the following steps: (1) adding the polyacrylic resin and the sodium alginate in percentage by weight into an ethanol solution, stirring and heating at the rotating speed of 120-150r/min for 2-3h, and then cooling to room temperature; (2) adding hydroxymethyl cellulose into the substance obtained in the step (1), homogenizing at high speed for 20-25min, cooling to normal temperature, adding sodium chloride in the above weight percentage, and continuously stirring for 1-2h to obtain a fluidized coating material; the prepared fluidized coating layer material improves the mechanical strength of the microporous coating reinforcing agent, so that the mechanical strength of the obtained synthetic resin is obviously enhanced.

The invention also provides a preparation method of the high-strength synthetic resin for the glass fiber rod, which mainly comprises the following steps:

s1: adding the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride which are prepared according to the weight components into a reaction kettle, carrying out hydrothermal reaction for 3-5h under the temperature condition of 80-90 ℃ until the components are uniformly mixed, carrying out heat preservation for 30-40min, carrying out micronization treatment for 1-2h by using an airflow pulverizer, then adding 1-2 parts of diethyl phthalate and 1.5-3 parts of polyvinyl acetal which are prepared according to the components into the reaction kettle, carrying out hydrothermal reaction for 2-3h under the temperature of 120-150 ℃ until the components are uniformly mixed, carrying out heat preservation for 25-30min, and then cooling to normal temperature to obtain a material A;

s2: adding the flame retardant with the weight components into the material A, heating to 60-80 ℃, vacuumizing, stirring under the protection of helium to react to obtain a mixture, mixing the plasma modified sodium bentonite with the weight components with the mixture, and adding the mixture into a reciprocating type oscillator to carry out oscillation reaction for 1-2 hours to obtain a material B;

s3: adding the microporous coating reinforcing agent and the material B into an injection molding machine, adjusting the injection molding temperature to 150-160 ℃, completely mixing the microporous coating reinforcing agent and the material B, cooling to room temperature, and quickly drying to obtain the high-strength synthetic resin.

Further, the drying device used in the drying process in the step S3 is a dryer, wherein the drying temperature is 280 ℃ to 320 ℃, and the drying time is 1h to 2 h.

The invention has the beneficial effects that: the invention provides a high-strength synthetic resin for a glass fiber rod and a preparation method thereof, and the high-strength synthetic resin has the following advantages:

1. according to the invention, the cation exchange performance of the sodium bentonite is utilized, cations in the superfine silicon dioxide and the alumina are exchanged and enter the bentonite layer, and then the plasma sputtering is used for carrying out pore forming on the bentonite layer to obtain the plasma modified sodium bentonite, so that the adsorbability of the bentonite is improved, the sodium bentonite also has aging resistance, the high temperature resistance and the mechanical strength of the synthetic resin can be increased, and the high water absorption of the resin can be kept to the maximum extent.

2. The invention improves the mechanical strength of the microporous coating reinforcing agent by wrapping the fluidized coating material outside the microporous coating reinforcing agent, obviously enhances the mechanical strength of the obtained synthetic resin, and simultaneously increases the surface area and the bearing capacity of the microporous coating reinforcing agent by carrying out the swelling and pore-forming treatment on the surface of the fluidized coating material, so that all components of the synthetic resin are fully contacted with the microporous coating reinforcing agent.

3. According to the invention, the added diethyl phthalate is used as a plasticizer, so that the resin has strong dissolving power for various resins, can be well compatible with the resins, increases the plasticity of resin molecules, enhances the flexibility and is easy to process.

4. The invention can increase the adhesive strength between various resin matrixes and auxiliary additives and increase the mechanical strength of the synthetic resin by adding the polyvinyl acetal.

5. The heat resistance of the synthetic resin is improved by adding the flame retardant of the polyborosiloxane.

Detailed Description

The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Example 1

A high-strength synthetic resin for glass fiber rods, comprising the following components: 35 parts of epoxy resin, 20 parts of phenolic resin, 15 parts of polyamide resin, 15 parts of polyvinyl chloride, 1 part of diethyl phthalate, 1.5 parts of polyvinyl acetal, 2 parts of plasma modified sodium bentonite, 6 parts of microporous coating reinforcing agent and 3 parts of polyborosiloxane flame retardant;

the microporous coating reinforcing agent comprises the following components in percentage by weight: 10% carbon fiber, 3% 1, 3-dioxane, 2% t-butyl peroxide, 2% diphenylsilanediol, 1% white carbon black, 4% calcium stearate, 3% nano calcium carbonate, 1% borosilicate, 3% polyamide fiber, 2% polyphenylene sulfide, 2% vinyltriethoxysilane, 6% fluidized coating material, 61% silicate;

the fluidized wrapping layer material comprises the following components in percentage by weight: the fluidized wrapping layer material composed of 10% of hydroxymethyl cellulose, 3% of sodium alginate, 2% of sodium chloride and 85% of polyacrylic resin has good permeability, and insoluble sodium chloride is added to roughen the surface of the film and reduce the adhesion among particles.

Example 2

A high-strength synthetic resin for glass fiber rods, comprising the following components: 40 parts of epoxy resin, 25 parts of phenolic resin, 20 parts of polyamide resin, 18 parts of polyvinyl chloride, 2 parts of diethyl phthalate, 3 parts of polyvinyl acetal, 4 parts of plasma modified sodium bentonite, 8 parts of micropore coating reinforcing agent and 6 parts of polyborosiloxane flame retardant;

the microporous coating reinforcing agent comprises the following components in percentage by weight: 15% carbon fiber, 5% 1, 3-dioxane, 4% tert-butyl peroxide, 3% diphenylsilanediol, 2% white carbon black, 5% calcium stearate, 6% nano calcium carbonate, 2% borosilicate, 5% polyamide fiber, 4% polyphenylene sulfide, 3% vinyltriethoxysilane, 10% fluidized coating material, 36% silicate;

the fluidized wrapping layer material comprises the following components in percentage by weight: the fluidized wrapping layer material composed of 15% of hydroxymethyl cellulose, 5% of sodium alginate, 3% of sodium chloride and 77% of polyacrylic resin has good permeability, and insoluble sodium chloride is added to roughen the surface of the film and reduce the adhesion among particles.

Example 3

A high-strength synthetic resin for glass fiber rods, comprising the following components: 35 parts of epoxy resin, 20 parts of phenolic resin, 15 parts of polyamide resin, 15 parts of polyvinyl chloride, 1 part of diethyl phthalate, 1.5 parts of polyvinyl acetal, 2 parts of plasma modified sodium bentonite, 6 parts of microporous coating reinforcing agent and 3 parts of polyborosiloxane, wherein the heat resistance of the synthetic resin is improved through the better flame retardant effect of the polyborosiloxane;

the preparation method of the plasma modified sodium bentonite comprises the following steps: (1) adding 4g of superfine silicon dioxide and 2g of alumina into a reaction kettle filled with 80mL of 0.15mol/L sodium hydroxide solution at the temperature of 45 ℃, and simultaneously introducing nitrogen with the air flow velocity of 0.6L/min into the reaction kettle and stirring for 2 hours to obtain suspension A; (2) sieving 4g of common sodium bentonite by a 60-mesh sieve, adding the sieved solution into the suspension A, stirring for 3 hours, and aging for 2 hours to obtain a suspension B; (3) washing the suspension B with distilled water for 3 times, drying to obtain modified sodium bentonite particles, putting the particles into a vacuum environment, rotating at a rotating speed of 50r/min, introducing argon until the vacuum degree is 25Pa, ionizing the argon into argon ions, and carrying out plasma sputtering on the surfaces of the modified sodium bentonite particles to form nano-scale micropores on the surfaces of the modified sodium bentonite particles; the sodium bentonite replaces cations in the superfine silicon dioxide and the alumina, exchanges the cations into a bentonite layer, and performs pore-forming on the bentonite layer by plasma sputtering to obtain plasma modified sodium bentonite, so that the adsorbability of the bentonite is improved, the sodium bentonite also has aging resistance, the high temperature resistance and the mechanical strength of the synthetic resin can be improved, and the high water absorbability of the resin can be kept to the maximum extent;

the microporous coating reinforcing agent comprises the following components in percentage by weight: 10% carbon fiber, 3% 1, 3-dioxane, 2% t-butyl peroxide, 2% diphenylsilanediol, 1% white carbon black, 4% calcium stearate, 3% nano calcium carbonate, 1% borosilicate, 3% polyamide fiber, 2% polyphenylene sulfide, 2% vinyltriethoxysilane, 6% fluidized coating material, 61% silicate;

the invention also provides a preparation method of the high-strength synthetic resin for the glass fiber rod, which mainly comprises the following steps:

s1: adding the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride which are prepared according to the weight components into a reaction kettle, carrying out hydrothermal reaction for 3 hours at the temperature of 80 ℃ until the materials are uniformly mixed, carrying out heat preservation for 30min, carrying out micronization treatment for 1 hour by using a jet mill, then adding 1 part of diethyl phthalate and 1.5 parts of polyvinyl acetal which are prepared according to the components into the reaction kettle, carrying out hydrothermal reaction for 2 hours at the temperature of 120 ℃ until the materials are uniformly mixed, carrying out heat preservation for 25min, and then cooling to normal temperature to obtain a material A;

s2: adding the flame retardant with the weight components into the material A, heating to 60 ℃, vacuumizing, stirring under the protection of helium to react to obtain a mixture, mixing the plasma modified sodium bentonite with the weight components with the mixture, and adding the mixture into a reciprocating type oscillator to carry out oscillation reaction for 1h to obtain a material B;

s3: adding the microporous coating reinforcing agent and the material B into an injection molding machine, adjusting the injection molding temperature to 150 ℃, completely mixing the microporous coating reinforcing agent and the material B, cooling to room temperature, and quickly drying by using a dryer, wherein the drying temperature is 280 ℃ and the drying time is 1h, so as to obtain the high-strength synthetic resin.

Example 4

A high-strength synthetic resin for glass fiber rods, comprising the following components: 38 parts of epoxy resin, 23 parts of phenolic resin, 18 parts of polyamide resin, 17 parts of polyvinyl chloride, 1.5 parts of diethyl phthalate, 2 parts of polyvinyl acetal, 3 parts of plasma modified sodium bentonite, 7 parts of microporous coating reinforcing agent and 4 parts of polyborosiloxane, wherein the heat resistance of the synthetic resin is improved through the better flame retardant effect of the polyborosiloxane;

the preparation method of the plasma modified sodium bentonite comprises the following steps: (1) adding 4.5g of superfine silicon dioxide and 2.5g of alumina into a reaction kettle filled with 80mL of 0.3mol/L sodium hydroxide solution at the temperature of 55 ℃, and simultaneously introducing nitrogen with the air flow velocity of 0.6L/min into the reaction kettle and stirring for 2.5 hours to obtain suspension A; (2) sieving 4.5g of common sodium bentonite by a 70-mesh sieve, adding the sieved solution into the suspension A, stirring for 4 hours, and aging for 2.5 hours to obtain a suspension B; (3) washing the suspension B with distilled water for 3 times, drying to obtain modified sodium bentonite particles, putting the particles into a vacuum environment, rotating at a rotating speed of 55r/min, introducing argon until the vacuum degree is 28Pa, ionizing the argon into argon ions, and carrying out plasma sputtering on the surfaces of the modified sodium bentonite particles to form nano-scale micropores on the surfaces of the modified sodium bentonite particles; the sodium bentonite replaces cations in the superfine silicon dioxide and the alumina, exchanges the cations into a bentonite layer, and performs pore-forming on the bentonite layer by plasma sputtering to obtain plasma modified sodium bentonite, so that the adsorbability of the bentonite is improved, the sodium bentonite also has aging resistance, the high temperature resistance and the mechanical strength of the synthetic resin can be improved, and the high water absorbability of the resin can be kept to the maximum extent;

the microporous coating reinforcing agent comprises the following components in percentage by weight: 13% carbon fiber, 4% 1, 3-dioxane, 3% t-butyl peroxide, 2.5% diphenylsilanediol, 1.5% white carbon black, 4.5% calcium stearate, 5% nano calcium carbonate, 1.5% borosilicate, 4% polyamide fiber, 3% polyphenylene sulfide, 2.5% vinyltriethoxysilane, 8% fluidized coating material, 47.5% silicate.

The invention also provides a preparation method of the high-strength synthetic resin for the glass fiber rod, which mainly comprises the following steps:

s1: adding the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride which are prepared according to the weight components into a reaction kettle, carrying out hydrothermal reaction for 4 hours at the temperature of 85 ℃ until the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride are uniformly mixed, keeping the temperature for 35 minutes, carrying out micronization treatment for 1.5 hours by using a jet mill, then adding 1.5 parts of diethyl phthalate and 2 parts of polyvinyl acetal which are prepared according to the components into the reaction kettle, carrying out hydrothermal reaction for 2.5 hours at the temperature of 130 ℃ until the diethyl phthalate and the polyvinyl acetal are uniformly mixed, keeping the temperature for 28 minutes, and then cooling to the normal temperature to obtain a material A;

s2: adding the flame retardant with the weight components into the material A, heating to 70 ℃, vacuumizing, stirring under the protection of helium to react to obtain a mixture, mixing the plasma modified sodium bentonite with the weight components with the mixture, and adding the mixture into a reciprocating type oscillator to carry out oscillation reaction for 1.5 hours to obtain a material B;

s3: adding the microporous coating reinforcing agent and the material B into an injection molding machine, adjusting the injection molding temperature to 155 ℃, completely mixing the microporous coating reinforcing agent and the material B, cooling to room temperature, and quickly drying by using a dryer, wherein the drying temperature is 300 ℃, and the drying time is 1.5 hours, so as to obtain the high-strength synthetic resin.

Example 5

A high-strength synthetic resin for glass fiber rods, comprising the following components: 40 parts of epoxy resin, 25 parts of phenolic resin, 20 parts of polyamide resin, 18 parts of polyvinyl chloride, 2 parts of diethyl phthalate, 3 parts of polyvinyl acetal, 4 parts of plasma modified sodium bentonite, 8 parts of microporous coating reinforcing agent and 6 parts of polyborosiloxane, wherein the heat resistance of the synthetic resin is improved through the better flame retardant effect of the polyborosiloxane;

the preparation method of the plasma modified sodium bentonite comprises the following steps: (1) adding 5g of superfine silicon dioxide and 3g of alumina into a reaction kettle filled with 80mL of 0.6mol/L sodium hydroxide solution at the temperature of 60 ℃, and simultaneously introducing nitrogen with the air flow velocity of 0.6L/min into the reaction kettle and stirring for 3 hours to obtain suspension A; (2) sieving 5g of common sodium bentonite by a 80-mesh sieve, adding the sieved solution into the suspension A, stirring for 5 hours, and aging for 3 hours to obtain a suspension B; (3) washing the suspension B with distilled water for 4 times, drying to obtain modified sodium bentonite particles, putting the particles into a vacuum environment, rotating at a rotating speed of 65r/min, introducing argon until the vacuum degree is 30Pa, ionizing the argon into argon ions, and carrying out plasma sputtering on the surfaces of the modified sodium bentonite particles to form nano-scale micropores on the surfaces of the modified sodium bentonite particles; the sodium bentonite replaces cations in the superfine silicon dioxide and the alumina, exchanges the cations into a bentonite layer, and performs pore-forming on the bentonite layer by plasma sputtering to obtain plasma modified sodium bentonite, so that the adsorbability of the bentonite is improved, the sodium bentonite also has aging resistance, the high temperature resistance and the mechanical strength of the synthetic resin can be improved, and the high water absorbability of the resin can be kept to the maximum extent;

the microporous coating reinforcing agent comprises the following components in percentage by weight: 15% carbon fiber, 5% 1, 3-dioxane, 4% tert-butyl peroxide, 3% diphenylsilanediol, 2% white carbon black, 5% calcium stearate, 6% nano calcium carbonate, 2% borosilicate, 5% polyamide fiber, 4% polyphenylene sulfide, 3% vinyltriethoxysilane, 10% fluidized coating material, 36% silicate.

The invention also provides a preparation method of the high-strength synthetic resin for the glass fiber rod, which mainly comprises the following steps:

s1: adding the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride which are prepared according to the weight components into a reaction kettle, carrying out hydrothermal reaction for 5 hours at the temperature of 90 ℃ until the materials are uniformly mixed, carrying out heat preservation for 40min, carrying out micronization treatment for 2 hours by using a jet mill, then adding 2 parts of diethyl phthalate and 3 parts of polyvinyl acetal which are prepared according to the components into the reaction kettle, carrying out hydrothermal reaction for 3 hours at the temperature of 150 ℃ until the materials are uniformly mixed, carrying out heat preservation for 30min, and then cooling to normal temperature to obtain a material A;

s2: adding the flame retardant with the weight components into the material A, heating to 80 ℃, vacuumizing, stirring under the protection of helium to react to obtain a mixture, mixing the plasma modified sodium bentonite with the weight components with the mixture, and adding the mixture into a reciprocating type oscillator to carry out oscillation reaction for 2 hours to obtain a material B;

s3: adding the microporous coating reinforcing agent and the material B into an injection molding machine, adjusting the injection molding temperature to 160 ℃, completely mixing the microporous coating reinforcing agent and the material B, cooling to room temperature, and quickly drying by using a dryer, wherein the drying temperature is 320 ℃, and the drying time is 2 hours, so as to obtain the high-strength synthetic resin.

Example 6

A high-strength synthetic resin for glass fiber rods, comprising the following components: 38 parts of epoxy resin, 23 parts of phenolic resin, 18 parts of polyamide resin, 17 parts of polyvinyl chloride, 1.5 parts of diethyl phthalate, 2 parts of polyvinyl acetal, 3 parts of plasma modified sodium bentonite, 7 parts of microporous coating reinforcing agent and 4 parts of polyborosiloxane, wherein the heat resistance of the synthetic resin is improved through the better flame retardant effect of the polyborosiloxane;

the preparation method of the plasma modified sodium bentonite comprises the following steps: (1) adding 4.5g of superfine silicon dioxide and 2.5g of alumina into a reaction kettle filled with 80mL of 0.3mol/L sodium hydroxide solution at the temperature of 55 ℃, and simultaneously introducing nitrogen with the air flow velocity of 0.6L/min into the reaction kettle and stirring for 2.5 hours to obtain suspension A; (2) sieving 4.5g of common sodium bentonite by a 70-mesh sieve, adding the sieved solution into the suspension A, stirring for 4 hours, and aging for 2.5 hours to obtain a suspension B; (3) washing the suspension B with distilled water for 3 times, drying to obtain modified sodium bentonite particles, putting the particles into a vacuum environment, rotating at a rotating speed of 55r/min, introducing argon until the vacuum degree is 28Pa, ionizing the argon into argon ions, and carrying out plasma sputtering on the surfaces of the modified sodium bentonite particles to form nano-scale micropores on the surfaces of the modified sodium bentonite particles; the sodium bentonite replaces cations in the superfine silicon dioxide and the alumina, exchanges the cations into a bentonite layer, and performs pore-forming on the bentonite layer by plasma sputtering to obtain plasma modified sodium bentonite, so that the adsorbability of the bentonite is improved, the sodium bentonite also has aging resistance, the high temperature resistance and the mechanical strength of the synthetic resin can be improved, and the high water absorbability of the resin can be kept to the maximum extent;

the microporous coating reinforcing agent comprises the following components in percentage by weight: 13% carbon fiber, 4% 1, 3-dioxane, 3% t-butyl peroxide, 2.5% diphenylsilanediol, 1.5% white carbon black, 4.5% calcium stearate, 5% nano calcium carbonate, 1.5% borosilicate, 4% polyamide fiber, 3% polyphenylene sulfide, 2.5% vinyltriethoxysilane, 8% fluidized coating material, 47.5% silicate;

the preparation method of the microporous coating reinforcing agent comprises the following steps: (1) uniformly mixing the silicate, the carbon fiber, the 1, 3-dioxane, the tert-butyl oxide and the diphenyl silanediol in percentage by weight at the temperature of 70 ℃, and then carrying out ultrasonic treatment for 2.5 hours to obtain a mixture A; (2) uniformly mixing the white carbon black and the calcium stearate in percentage by weight at the temperature of 130 ℃, then cooling to 65 ℃, adding the nano calcium carbonate, the borosilicate, the polyamide fiber, the polyphenylene sulfide and the vinyl triethoxysilane in percentage by weight, uniformly stirring at the speed of 180r/min, and then cooling to normal temperature to obtain a mixture B; (3) placing the mixture A, the mixture B and the fluidized coating layer material into a centrifuge, centrifuging at the speed of 2800r/min to obtain particles, washing and drying the particles by using sterile water, adding the dried substances into a bulking machine, adding 12MPa of bulking pressure into the bulking machine at the temperature of 430 ℃ for processing for 2.5h, cooling to room temperature to obtain a microporous coating reinforcing agent, coating the substances in the microporous coating reinforcing agent by using the fluidized coating layer material to improve the mechanical strength of the microporous coating reinforcing agent, obviously enhancing the mechanical strength of the obtained synthetic resin, enabling the outer wall of the fluidized coating layer material to generate a porous structure by bulking, increasing the surface area of the microporous coating reinforcing agent, enabling all components of the synthetic resin to be in full contact with the microporous coating reinforcing agent, and improving the bearing capacity;

the fluidized wrapping layer material comprises the following components in percentage by weight: 13 percent of hydroxymethyl cellulose, 4 percent of sodium alginate, 2.5 percent of sodium chloride and 70.5 percent of polyacrylic resin, the fluidized wrapping layer material formed by the components has good permeability, and insoluble component sodium chloride is added, so that the surface of the film is rough, and the bonding among particles is reduced;

the preparation method of the fluidized coating material comprises the following steps: (1) adding the polyacrylic resin and the sodium alginate in percentage by weight into an ethanol solution, stirring and heating at the rotating speed of 140r/min for 2.5h, and then cooling to room temperature; (2) adding hydroxymethyl cellulose into the substance obtained in the step (1), homogenizing at high speed for 23min, cooling to normal temperature, adding sodium chloride in the above weight percentage, and continuously stirring for 1.5h to obtain a fluidized coating material; the prepared fluidized coating layer material improves the mechanical strength of the microporous coating reinforcing agent, so that the mechanical strength of the obtained synthetic resin is obviously enhanced.

The invention also provides a preparation method of the high-strength synthetic resin for the glass fiber rod, which mainly comprises the following steps:

s1: adding the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride which are prepared according to the weight components into a reaction kettle, carrying out hydrothermal reaction for 4 hours at the temperature of 85 ℃ until the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride are uniformly mixed, keeping the temperature for 35 minutes, carrying out micronization treatment for 1.5 hours by using a jet mill, then adding 1.5 parts of diethyl phthalate and 2 parts of polyvinyl acetal which are prepared according to the components into the reaction kettle, carrying out hydrothermal reaction for 2.5 hours at the temperature of 130 ℃ until the diethyl phthalate and the polyvinyl acetal are uniformly mixed, keeping the temperature for 28 minutes, and then cooling to the normal temperature to obtain a material A;

s2: adding the flame retardant with the weight components into the material A, heating to 70 ℃, vacuumizing, stirring under the protection of helium to react to obtain a mixture, mixing the plasma modified sodium bentonite with the weight components with the mixture, and adding the mixture into a reciprocating type oscillator to carry out oscillation reaction for 1.5 hours to obtain a material B;

s3: adding the microporous coating reinforcing agent and the material B into an injection molding machine, adjusting the injection molding temperature to 155 ℃, completely mixing the microporous coating reinforcing agent and the material B, cooling to room temperature, and quickly drying by using a dryer, wherein the drying temperature is 300 ℃, and the drying time is 1.5 hours, so as to obtain the high-strength synthetic resin.

Test examples

The relevant performance parameters for high strength synthetic resins for fiberglass rods prepared in accordance with examples 1-6 of the present invention are shown in Table 1:

TABLE 1 relevant Performance parameters of the synthetic resins

As can be seen from Table 1, the synthetic resin prepared in example 6 has the highest flexural strength, tensile strength, and notched impact strength and the highest heat distortion temperature, and thus the synthetic resin prepared in example 6 has the best properties.

Claims (4)

1. A high-strength synthetic resin for glass fiber rods, which is characterized by comprising the following components: 35-40 parts of epoxy resin, 20-25 parts of phenolic resin, 15-20 parts of polyamide resin, 15-18 parts of polyvinyl chloride, 1-2 parts of diethyl phthalate, 1.5-3 parts of polyvinyl acetal, 2-4 parts of plasma modified sodium bentonite, 6-8 parts of microporous coating reinforcing agent and 3-6 parts of flame retardant;

the preparation method of the plasma modified sodium bentonite comprises the following steps: (1) adding 4-5g of superfine silicon dioxide and 2-3g of alumina into a reaction kettle filled with 80mL of sodium hydroxide solution with the concentration of 0.15-0.6mol/L at the temperature of 45-60 ℃, and simultaneously introducing nitrogen with the air flow velocity of 0.6L/min into the reaction kettle and stirring for 2-3h to obtain suspension A; (2) sieving 4-5g of common sodium bentonite by a 60-80 mesh sieve, adding into the suspension A, stirring for 3-5h, and aging for 2-3h to obtain suspension B; (3) washing the suspension B with distilled water for 3-4 times, drying to obtain modified sodium bentonite particles, rotating the particles in a vacuum environment at a rotating speed of 50-65r/min, introducing argon until the vacuum degree is 25-30Pa, ionizing the argon into argon ions, and carrying out plasma sputtering on the surfaces of the modified sodium bentonite particles to form nano-scale micropores on the surfaces of the modified sodium bentonite particles;

the microporous coating reinforcing agent comprises the following components in percentage by weight: 10-15% of carbon fiber, 3-5% of 1, 3-dioxane, 2-4% of tert-butyl peroxide, 2-3% of diphenylsilanediol, 1-2% of white carbon black, 4-5% of calcium stearate, 3-6% of nano calcium carbonate, 1-2% of borosilicate, 3-5% of polyamide fiber, 2-4% of polyphenylene sulfide, 2-3% of vinyltriethoxysilane, 6-10% of a fluidized coating material and the balance of silicate;

the preparation method of the microporous coating reinforcing agent comprises the following steps: (1) uniformly mixing the silicate, the carbon fiber, the 1, 3-dioxane, the tert-butyl peroxide and the diphenylsilanediol in percentage by weight at the temperature of 60-80 ℃, and then carrying out ultrasonic treatment for 2-3h to obtain a mixture A; (2) uniformly mixing the white carbon black and the calcium stearate in percentage by weight at the temperature of 100-150 ℃, then cooling to 55-85 ℃, adding the nano calcium carbonate, the borosilicate, the polyamide fiber, the polyphenylene sulfide and the vinyl triethoxysilane in percentage by weight, uniformly stirring at the speed of 150-200r/min, and then cooling to normal temperature to obtain a mixture B; (3) placing the mixture A, the mixture B and the fluidized coating layer material into a centrifuge, centrifuging at the speed of 2500-;

the fluidized wrapping layer material comprises the following components in percentage by weight: 10-15% of hydroxymethyl cellulose, 3-5% of sodium alginate, 2-3% of sodium chloride and the balance of polyacrylic resin.

2. A high strength synthetic resin for glass fiber rod according to claim 1, wherein the flame retardant is a polyborosiloxane flame retardant.

3. The method of preparing a high-strength synthetic resin for glass fiber rods according to claim 1, mainly comprising the steps of:

s1: adding the epoxy resin, the phenolic resin, the polyamide resin and the polyvinyl chloride which are prepared according to the weight components into a reaction kettle, carrying out hydrothermal reaction for 3-5h under the temperature condition of 80-90 ℃ until the components are uniformly mixed, carrying out heat preservation for 30-40min, carrying out micronization treatment for 1-2h by using an airflow pulverizer, then adding 1-2 parts of diethyl phthalate and 1.5-3 parts of polyvinyl acetal which are prepared according to the components into the reaction kettle, carrying out hydrothermal reaction for 2-3h under the temperature of 120-150 ℃ until the components are uniformly mixed, carrying out heat preservation for 25-30min, and then cooling to normal temperature to obtain a material A;

s2: adding the flame retardant with the weight components into the material A, heating to 60-80 ℃, vacuumizing, stirring under the protection of helium to react to obtain a mixture, mixing the plasma modified sodium bentonite with the weight components with the mixture, and adding the mixture into a reciprocating type oscillator to carry out oscillation reaction for 1-2 hours to obtain a material B;

s3: adding the microporous coating reinforcing agent and the material B into an injection molding machine, adjusting the injection molding temperature to 150-160 ℃, completely mixing the microporous coating reinforcing agent and the material B, cooling to room temperature, and quickly drying to obtain the high-strength synthetic resin.

4. The method of claim 3, wherein the drying process in the step S3 is carried out by using a dryer, wherein the drying temperature is 280-320 ℃ and the drying time is 1-2 h.