A rubber-modified molded vinyl ester resin and a method for preparing the same

Abstract

The application discloses a rubber-modified mould pressing vinyl ester resin and a preparation method thereof, and relates to the technical field of resin materials. In the preparation of the rubber-modified mould pressing vinyl ester resin, isocyanate carbon black is prepared by reacting carbon black with toluene diisocyanate after oxidation; diallyl polyphosphate is prepared by reacting 2,2'-diallyl bisphenol A with phenyl dichlorophosphate; modified carbon black is prepared by reacting the isocyanate carbon black with the diallyl polyphosphate; and the rubber-modified mould pressing vinyl ester resin is prepared by mixing and vulcanizing natural rubber, vinyl ester resin and the modified carbon black. The rubber-modified mould pressing vinyl ester resin prepared by the application has good tear resistance and flame retardance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of resin materials, and particularly relates to a rubber-modified mold pressing vinyl ester resin and a preparation method thereof. BACKGROUND

[0002] As a thermosetting resin, the vinyl ester resin has excellent properties of epoxy resin and unsaturated polyester resin, and has good corrosion resistance, mechanical properties and electrical insulation properties. For a long time, the vinyl ester resin has been widely used in various fields such as chemical industry, electronic communication, composite pipeline and building materials.

[0003] However, the vinyl ester resin is also flammable, and the fire risk is the main reason why it is difficult to be applied in fields with high flame retardant requirements. Therefore, it is of great significance to modify the vinyl ester resin to obtain green and efficient flame-retardant vinyl ester resin composite materials. SUMMARY

[0004] The application aims to provide a rubber-modified mold pressing vinyl ester resin and a preparation method thereof to solve the problems in the prior art.

[0005] In order to solve the above technical problems, the application provides the following technical scheme:

[0006] A rubber-modified mold pressing vinyl ester resin is prepared by mixing and vulcanizing natural rubber, vinyl ester resin and modified carbon black.

[0007] As an optimization, the modified carbon black is prepared by reacting isocyanate carbon black and diallyl polyphosphate.

[0008] As an optimization, the isocyanate carbon black is prepared by reacting carbon black after oxidation and toluene diisocyanate.

[0009] As an optimization, the diallyl polyphosphate is prepared by reacting 2,2'-diallyl bisphenol A and phenyl dichlorophosphate.

[0010] As an optimization, the preparation method of the rubber-modified mold pressing vinyl ester resin comprises the following preparation steps:

[0011] (1) mixing carbon black with concentrated sulfuric acid with mass fraction of 95-98% according to mass ratio of 1:10-1:12, adding 1-1.2 times of mass of carbon black of potassium permanganate, ultrasonic reaction at 50-60℃, 30-40 kHz for 4-6 h, cooling to 1-5℃, adding 0.1-0.3 times of mass of carbon black of hydrogen peroxide with mass fraction of 30-34%, stirring at 800-1000 r / min for 10-15 min, centrifugal separation and washing with pure water for 3-5 times, drying at 70-80℃, 1-2 kPa for 8-10 h to obtain oxidized carbon black; mixing the oxidized carbon black, toluene diisocyanate, triethylamine and ethylbenzene according to mass ratio of 2:1:0.03:20-3:1:0.05:30, stirring at 0-2℃, 300-500 r / min for 25-35 min, heating to 100-110℃ and continuing stirring for 20-30 min, centrifugal separation and washing with toluene for 3-5 times, drying at 70-80℃, 1-2 kPa for 8-10 h to obtain isocyanate carbon black;

[0012] (2) mixing the isocyanate carbon black, diallyl polyphosphate, dibutyltin dilaurate and ethylbenzene according to mass ratio of 2:1:0.003:40-2:1:0.005:50, ultrasonic at 0-2℃, 30-40 kHz for 20-30 min, heating to 120-130℃ and continuing ultrasonic reaction for 50-70 min, cooling to 50-60℃ and filtering, washing with anhydrous ethanol for 3-5 times, drying at 70-80℃, 1-2 kPa for 8-10 h to obtain modified carbon black;

[0013] (3) mixing natural rubber SCR5 and vinyl ester resin S918 according to mass ratio of 1:2-1:3, plasticizing on a double roller open mill at 60-70℃ for 2-3 min until completely wrapped on the roller to obtain mixed rubber; setting the water temperature of the internal mixer to 90-98℃, placing the mixed rubber into the internal mixer when the internal mixer is preheated to 80℃, stirring for 2-3 min, adding 0.08-0.10 times of mass of the modified carbon black of the mixed rubber, discharging the rubber when the temperature reaches 150℃; placing the obtained rubber into a double roller open mill, mixing uniformly after adding 0.01-0.02 times of mass of sulfur of the natural rubber, thin passing and sheeting to obtain mixed rubber, placing the mixed rubber into a mold, vulcanizing in a flat plate vulcanizing machine at 15-17 MPa, 145-155℃ for 50-60 min to obtain rubber modified mold vinyl ester resin.

[0014] As an optimization, the type of carbon black in step (1) is N134.

[0015] As optimization, the toluene diisocyanate in step (1) is one or more of toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,4-diisocyanate, and toluene-3,5-diisocyanate.

[0016] As optimization, the preparation method of the diallyl polyphosphate in step (2) is as follows: 2,2'-diallyl bisphenol A and anhydrous aluminum chloride are mixed uniformly at a mass ratio of 1:0.01-1:0.02, 2,2'-diallyl bisphenol A is added at a speed of 0.3-0.4 times of the mass of 2,2'-diallyl bisphenol A in phenyl dichlorophosphate at a stirring speed of 300-500 r / min and 60-70 ℃ under a nitrogen atmosphere, after the dropwise addition is completed, the temperature is raised to 90-100 ℃ for continuous stirring for 40-50 min, and then the temperature is raised to 130-140 ℃ for continuous stirring for 40-50 min, and drying is performed at 70-80 ℃ and 50-100 Pa for 8-10 h.

[0017] As optimization, the natural rubber in step (3) is SCR5, and the vinyl ester resin is S918.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] In the preparation of the rubber-modified molded vinyl ester resin, the natural rubber, the vinyl ester resin, and the modified carbon black are mixed and vulcanized to obtain the rubber-modified molded vinyl ester resin.

[0020] First, the diallyl polyphosphate is prepared by reacting 2,2'-diallyl bisphenol A and phenyl dichlorophosphate, and the branched chain of the diallyl polyphosphate contains a large number of allyl groups, which can participate in the vulcanization of the natural rubber and the carbon-carbon double bond of the vinyl ester resin to form chemical cross-linking, thereby improving the tear resistance.

[0021] Second, the isocyanate carbon black is prepared by reacting the oxidized carbon black and toluene diisocyanate; the modified carbon black is prepared by reacting the isocyanate carbon black and the diallyl polyphosphate, the diallyl polyphosphate is grafted on the surface of the modified carbon black, the compatibility of the modified carbon black and other components is improved, the carbon-carbon double bond on the diallyl polyphosphate participates in the vulcanization, the modified carbon black becomes a stress node, thereby improving the tear resistance, and the carbon black in the center of the modified carbon black can be used as a carbon formation core, and the diallyl polyphosphate on the surface accelerates the formation of the carbon layer, thereby improving the flame retardant performance. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of the present application.

[0023] In order to more clearly illustrate the method provided by the present application, the following embodiments are described in detail. In the following embodiments, the test methods of various indexes of the rubber-modified molded vinyl ester resin are as follows:

[0024] Tear resistance: the rubber-modified molded vinyl ester resin obtained in each example and the material of the comparative example are taken in the same size and shape, and the tear resistance is determined according to the standard method of ASTM D624.

[0025] Flame retardance: the rubber-modified molded vinyl ester resin obtained in each example and the material of the comparative example are taken in the same size and shape, and the limiting oxygen index is determined according to the standard method of GB / T2406.

[0026] Example 1

[0027] A preparation method of a rubber-modified molded vinyl ester resin, the preparation method of the rubber-modified molded vinyl ester resin comprising the following preparation steps:

[0028] (1) carbon black N134 is uniformly mixed with concentrated sulfuric acid with a mass fraction of 95% at a mass ratio of 1:10, and an amount of potassium permanganate equal to 1 times the mass of the carbon black is added, and ultrasonic reaction is carried out at 50°C for 6h at 30kHz, the temperature is lowered to 1°C, an amount of hydrogen peroxide with a mass fraction of 34% equal to 0.1 times the mass of the carbon black is added, stirring is carried out at a speed of 800r / min for 10min, centrifugal separation is carried out and washing is carried out with pure water for 3 times, and drying is carried out at 70°C under 1kPa for 10h to obtain oxidized carbon black; the oxidized carbon black, toluene-2,6-diisocyanate, triethylamine and ethylbenzene are uniformly mixed at a mass ratio of 2:1:0.03:20, stirring is carried out at 300r / min at 0°C for 35min in a nitrogen atmosphere, heating is carried out to 100°C and stirring is continued for 20min, centrifugal separation is carried out and washing is carried out with toluene for 3 times, and drying is carried out at 70°C under 1kPa for 10h to obtain isocyanate-converted carbon black;

[0029] (2) mixing 2,2'-diallyl bisphenol A and anhydrous aluminum chloride uniformly at a mass ratio of 1:0.01, adding phenyldichlorophosphate at a mass of 0.3 times that of 2,2'-diallyl bisphenol A at a uniform speed under the condition of nitrogen atmosphere, 60°C, and 300 r / min stirring speed within 30 min, increasing the temperature to 90°C after the end of dropwise addition to continue stirring for 50 min, increasing the temperature to 130°C to continue stirring for 40 min, and drying at 70°C and 50 Pa for 10 h to prepare diallyl polyphosphate; mixing isocyanate carbon black, diallyl polyphosphate, dibutyltin dilaurate, and ethylbenzene uniformly at a mass ratio of 2:1:0.003:40, ultrasonicating at 0-2°C for 30 min, heating to 120°C to continue ultrasonicating for 70 min, cooling to 50°C to filter, washing with anhydrous ethanol for 3 times, and drying at 70°C and 1 kPa for 10 h to prepare modified carbon black;

[0030] (3) mixing natural rubber SCR5 and vinyl ester resin S918 at a mass ratio of 1:2, plasticating on a double roller open mill at 60°C for 3 min until completely wrapped on the roller to obtain a mixed rubber; setting the water temperature of the internal mixer to 90°C, placing the mixed rubber into the internal mixer when the internal mixer is preheated to 80°C, stirring for 2 min, adding modified carbon black at a mass of 0.08 times that of the mixed rubber, discharging the rubber when the temperature reaches 150°C; placing the obtained rubber into a double roller open mill, mixing uniformly after adding sulfur at a mass of 0.01 times that of the natural rubber, thin passing and sheeting to obtain a mixed rubber, placing the mixed rubber into a mold, and vulcanizing in a flat plate vulcanizer at 15 MPa and 145°C for 50 min to prepare a rubber modified mold vinyl ester resin.

[0031] Example 2

[0032] A preparation method of a rubber modified mold vinyl ester resin, the preparation method of the rubber modified mold vinyl ester resin comprising the following preparation steps:

[0033] (1) mixing carbon black N134 and concentrated sulfuric acid with a mass fraction of 96% uniformly at a mass ratio of 1:11, adding potassium permanganate at a mass of 1.1 times that of the carbon black, ultrasonicating at 55°C and 35 kHz for 5 h, cooling to 3°C, adding hydrogen peroxide with a mass fraction of 32% at a mass of 0.2 times that of the carbon black, stirring at a speed of 900 r / min for 12 min, centrifugal separation, and washing with pure water for 4 times, and drying at 75°C and 1.5 kPa for 9 h to prepare oxidized carbon black; mixing the oxidized carbon black, toluene-2,6-diisocyanate, triethylamine, and ethylbenzene uniformly at a mass ratio of 2.5:1:0.04:25, stirring at 1°C and 400 r / min for 30 min in a nitrogen atmosphere, heating to 105°C to continue stirring for 25 min, centrifugal separation, and washing with toluene for 4 times, and drying at 75°C and 1.5 kPa for 9 h to prepare isocyanate carbon black;

[0034] (2) 2,2'-diallyl bisphenol A, anhydrous aluminum chloride were mixed uniformly at a mass ratio of 1:0.015, 2,2'-diallyl bisphenol A was added at a speed of 0.35 times of the mass of 2,2'-diallyl bisphenol A in phenyl dichlorophosphate at a speed of 400 r / min under the condition of nitrogen atmosphere and 65°C, and after the dropwise addition was completed, the temperature was increased to 95°C and the stirring reaction was continued for 45 min, and then the temperature was increased to 135°C and the stirring reaction was continued for 45 min, and then the temperature was increased to 75°C and the drying was continued for 9 h at 70 Pa to obtain diallyl polyphosphate; isocyanate carbon black, diallyl polyphosphate, dibutyltin dilaurate, and ethylbenzene were mixed uniformly at a mass ratio of 2:1:0.004:45, and then ultrasonic treatment was performed at 1°C for 25 min, and then heating was continued to 125°C and the ultrasonic treatment was continued for 60 min, and then the temperature was cooled to 55°C and filtration was performed, and then the obtained product was washed with anhydrous ethanol 4 times, and then the temperature was increased to 75°C and the drying was continued for 9 h at 1.5 kPa to obtain modified carbon black;

[0035] (3) Natural rubber SCR5 and vinyl ester resin S918 were mixed at a mass ratio of 1:2.5, and plasticized on a two-roll open mill at 65°C for 2.5 min until complete wrapping of the roll to obtain a mixed rubber; the water temperature of the internal mixer was set to 94°C, and when the internal mixer was preheated to 80°C, the mixed rubber was put into the internal mixer, and stirred for 2.5 min, and then the modified carbon black was added at 0.09 times of the mass of the mixed rubber, and the temperature was increased to 150°C to discharge the rubber; the obtained rubber was put into a two-roll open mill, and mixed uniformly with sulfur at 0.015 times of the mass of the natural rubber, and then thin-passed and sheeted to obtain a mixed rubber, and then the mixed rubber was put into a mold, and vulcanized in a flat plate vulcanizer at 156 MPa and 150°C for 55 min to obtain a rubber-modified molded vinyl ester resin.

[0036] Example 3

[0037] A method for preparing a rubber-modified molded vinyl ester resin, the method comprising the following preparation steps:

[0038] (1) Carbon black N134 and concentrated sulfuric acid with a mass fraction of 98% were mixed uniformly at a mass ratio of 1:12, and then potassium permanganate was added at 1.2 times of the mass of the carbon black, and then ultrasonic treatment was performed at 60°C for 4 h, and then the temperature was decreased to 5°C, and then hydrogen peroxide with a mass fraction of 34% was added at 0.3 times of the mass of the carbon black, and then stirring was performed at a speed of 1000 r / min for 15 min, and then centrifugal separation was performed and the obtained product was washed with pure water 5 times, and then the temperature was increased to 80°C and the drying was continued for 10 h at 2 kPa to obtain oxidized carbon black; the oxidized carbon black, toluene-2,6-diisocyanate, triethylamine, and ethylbenzene were mixed uniformly at a mass ratio of 3:1:0.05:30, and then stirring was performed at 2°C and 500 r / min for 25 min under the condition of nitrogen atmosphere, and then heating was continued to 110°C and the stirring was continued for 30 min, and then centrifugal separation was performed and the obtained product was washed with toluene 5 times, and then the temperature was increased to 80°C and the drying was continued for 8 h at 2 kPa to obtain isocyanate carbon black;

[0039] (2) 2,2'-diallyl bisphenol A, anhydrous aluminum chloride were mixed uniformly according to the mass ratio of 1:0.02, under the condition of nitrogen atmosphere, 60℃, 300r / min stirring speed, 2,2'-diallyl bisphenol A mass 0.4 times of phenyl dichlorophosphate was added at a uniform speed within 20min, after the end of dropwise addition, the temperature was increased to 100℃ and the stirring reaction was continued for 40min, then the temperature was increased to 140℃ and the stirring reaction was continued for 40min, dried at 80℃, 100Pa for 8h, to obtain diallyl polyphosphate; isocyanate modified carbon black, diallyl polyphosphate, dibutyltin dilaurate, ethylbenzene were mixed uniformly according to the mass ratio of 2:1:0.003:40, then ultrasonic was carried out at 0℃ for 30min, then heated to 120℃ and the ultrasonic reaction was continued for 70min, cooled to 50℃ and filtered, washed with anhydrous ethanol for 3 times, dried at 70℃, 1kPa for 10h, to obtain modified carbon black;

[0040] (3) natural rubber SCR5 and vinyl ester resin S918 were mixed according to the mass ratio of 1:3, plasticized on a double roller open mill at 70℃ for 3min until completely wrapped the roller, to obtain mixed rubber; the water temperature of the internal mixer was set to 98℃, when the internal mixer was preheated to 80℃, the mixed rubber was put in, stirred for 3min, then the modified carbon black was added, the mass of which was 0.10 times of the mixed rubber, when the temperature reached 150℃, the rubber was discharged; the obtained rubber was put on a double roller open mill, mixed uniformly after adding sulfur, the mass of which was 0.02 times of the natural rubber, then thin pass, sheeting to obtain mixed rubber, the mixed rubber was put into a mold, vulcanized in a flat plate vulcanizing machine at 17MPa, 155℃ for 50min, to obtain rubber modified mold vinyl ester resin.

[0041] Comparative Example 1

[0042] A preparation method of a rubber modified mold vinyl ester resin, the preparation method of the rubber modified mold vinyl ester resin comprises the following preparation steps:

[0043] (1) The carbon black N134 is mixed with concentrated sulfuric acid with a mass fraction of 96% at a mass ratio of 1:11, and 1.1 times the mass of carbon black is added with potassium permanganate. The mixture is reacted at 55°C under 35 kHz ultrasonic for 5 hours, and then cooled to 3°C. 0.2 times the mass of carbon black is added with hydrogen peroxide with a mass fraction of 32%, and stirred at a speed of 900 r / min for 12 minutes. After centrifugal separation and washing with pure water for 4 times, the mixture is dried at 75°C under 1.5 kPa for 9 hours to obtain oxidized carbon black. The oxidized carbon black, toluene-2,6-diisocyanate, triethylamine and ethylbenzene are mixed at a mass ratio of 2.5:1:0.04:25. The mixture is reacted at 1°C under nitrogen atmosphere and stirred at a speed of 400 r / min for 30 minutes. The mixture is heated to 105°C and continuously stirred for 25 minutes. After centrifugal separation and washing with toluene for 4 times, the mixture is dried at 75°C under 1.5 kPa for 9 hours to obtain isocyanate carbon black.

[0044] (2) Bisphenol A and anhydrous aluminum chloride are mixed at a mass ratio of 1:0.015. Under the condition of nitrogen atmosphere and stirring at a speed of 400 r / min, phenyldichlorophosphate with 0.35 times the mass of bisphenol A is added at a uniform speed within 25 minutes. After the dropwise addition is completed, the temperature is increased to 95°C, and the mixture is continuously stirred for 45 minutes. The temperature is further increased to 135°C, and the mixture is continuously stirred for another 45 minutes. The mixture is dried at 75°C under 70 Pa for 9 hours to obtain polyphosphate. The isocyanate carbon black, polyphosphate, dibutyltin dilaurate and ethylbenzene are mixed at a mass ratio of 2:1:0.004:45. The mixture is ultrasonically treated at 1°C for 25 minutes, and then heated to 125°C for continuous ultrasonic treatment for 60 minutes. After cooling to 55°C, the mixture is filtered and washed with anhydrous ethanol for 4 times. The mixture is dried at 75°C under 1.5 kPa for 9 hours to obtain modified carbon black.

[0045] (3) Natural rubber SCR5 and vinyl ester resin S918 are mixed at a mass ratio of 1:2.5. The mixture is plasticized on a double roller open mill at 65°C for 2.5 minutes until the mixture is completely wrapped on the roller to obtain a mixed rubber. The water temperature of the internal mixer is set to 94°C. When the internal mixer is preheated to 80°C, the mixed rubber is put into the internal mixer. After stirring for 2.5 minutes, 0.09 times the mass of the mixed rubber is added with modified carbon black. When the temperature reaches 150°C, the rubber is discharged. The obtained rubber is put into a double roller open mill. After mixing uniformly with 0.015 times the mass of sulfur, the rubber is thin passed and sheeted to obtain a mixed rubber. The mixed rubber is put into a mold. The rubber is vulcanized in a flat plate vulcanizing machine at 156 MPa and 150°C for 55 minutes to obtain a rubber modified mold vinyl ester resin.

[0046] Comparative Example 2

[0047] A preparation method of a rubber modified mold vinyl ester resin, the preparation method of the rubber modified mold vinyl ester resin comprises the following preparation steps:

[0048] (1) 2,2'-diallyl bisphenol A, anhydrous aluminum chloride were mixed uniformly according to a mass ratio of 1:0.015, 2,2'-diallyl bisphenol A was added into phenyl dichlorophosphate at a rate of 0.35 times the mass of 2,2'-diallyl bisphenol A under the condition of nitrogen atmosphere, 65°C, 400r / min stirring speed, and the temperature was raised to 95°C after the dropwise addition was completed, and the reaction was continued for 45min, and then the temperature was raised to 135°C, and the reaction was continued for 45min, and then the temperature was raised to 75°C, and the drying was continued for 9h at 70Pa, to obtain diallyl polyphosphate;

[0049] (2) natural rubber SCR5 and vinyl ester resin S918 were mixed according to a mass ratio of 1:2.5, and plasticized on a two-roll open mill at 65°C for 2.5min until the rubber was completely wrapped on the roll to obtain a mixed rubber; the water temperature of the internal mixer was set to 94°C, and when the internal mixer was preheated to 80°C, the mixed rubber was put in, and stirred for 2.5min, then 0.06 times the mass of carbon black N134 and 0.03 times the mass of diallyl polyphosphate of the mixed rubber were added, and the rubber was discharged when the temperature reached 150°C; the obtained rubber was put on a two-roll open mill, and mixed uniformly after adding 0.015 times the mass of sulfur of the natural rubber, and then thin-passed and sheeted to obtain a mixed rubber, and the mixed rubber was put into a mold, and vulcanized in a flat plate vulcanizing machine at 156MPa and 150°C for 55min to obtain a rubber modified molded vinyl ester resin.

[0050] Comparative Example 3

[0051] A method for preparing a rubber modified molded vinyl ester resin, the method comprising the following preparation steps:

[0052] natural rubber SCR5 and vinyl ester resin S918 were mixed according to a mass ratio of 1:2.5, and plasticized on a two-roll open mill at 65°C for 2.5min until the rubber was completely wrapped on the roll to obtain a mixed rubber; the water temperature of the internal mixer was set to 94°C, and when the internal mixer was preheated to 80°C, the mixed rubber was put in, and stirred for 2.5min, then 0.09 times the mass of carbon black N134 of the mixed rubber was added, and the rubber was discharged when the temperature reached 150°C; the obtained rubber was put on a two-roll open mill, and mixed uniformly after adding 0.015 times the mass of sulfur of the natural rubber, and then thin-passed and sheeted to obtain a mixed rubber, and the mixed rubber was put into a mold, and vulcanized in a flat plate vulcanizing machine at 156MPa and 150°C for 55min to obtain a rubber modified molded vinyl ester resin.

[0053] Effect Example

[0054] Table 1 below shows the performance analysis results of the tear resistance and flame retardant properties of the rubber modified molded vinyl ester resins prepared by using the rubber modified molded vinyl ester resins of Examples 1-3 and Comparative Examples 1-3 of the present application.

[0055] Table 1

[0056]

[0057]

[0058] From the experimental data comparison of examples 1-3 and comparative examples 1-3 in table 1, it can be found that the rubber modified molded vinyl ester resin prepared by the present application has good tear resistance and flame retardant properties.

[0059] From the experimental data comparison of examples 1, 2, 3 and comparative examples 1, it can be found that the tear resistance of examples 1, 2, 3 is higher than that of comparative example 1, which shows that compared with directly using bisphenol A for reaction, using 2,2'-diallyl bisphenol A makes the prepared diallyl polyphosphate contain a large number of allyl groups on the branched chain, and the allyl groups can participate in the vulcanization of natural rubber and vinyl ester resin carbon-carbon double bond, and form chemical crosslinking with each other, thereby improving the tear resistance; from the experimental data comparison of examples 1, 2, 3 and comparative example 2, it can be found that the tear resistance and limiting oxygen index of examples 1, 2, 3 are higher than those of comparative example 2, which shows that grafting the diallyl polyphosphate on the surface of carbon black improves the compatibility of modified carbon black and other components, and the carbon-carbon double bond on the diallyl polyphosphate participates in vulcanization, so that the modified carbon black becomes a stress node, thereby improving the tear resistance, and the carbon black at the center of the modified carbon black can act as a carbon formation core, and the diallyl polyphosphate accelerates the formation of carbon layer on the surface, thereby improving the flame retardant properties.

[0060] It is apparent to those skilled in the art that the present application is not limited to the details of the foregoing exemplary embodiments, and that the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the embodiments should be considered in all respects as illustrative and not restrictive, the scope of the present application being defined by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference signs in the claims should not be construed as limiting the claims.

Claims

1. A rubber-modified molding vinyl ester resin, characterized in that, The rubber-modified molding vinyl ester resin is made by vulcanizing a mixture of natural rubber, vinyl ester resin, and modified carbon black. The modified carbon black is prepared by reacting isocyanate-modified carbon black with diallyl polyphosphate. The isocyanate-treated carbon black is prepared by reacting carbon black with toluene diisocyanate after oxidation. The diallyl polyphosphate is prepared by reacting 2,2'-diallyl bisphenol A and phenyl dichlorophosphate. A method for preparing a rubber-modified molding vinyl ester resin, the method comprising the following preparation steps: (1) Mix carbon black with concentrated sulfuric acid (95-98% by mass) at a mass ratio of 1:10 to 1:

12. Add potassium permanganate at 1-1.2 times the mass of carbon black. Sonicate at 50-60℃ and 30-40kHz for 4-6 hours. Cool down to 1-5℃ and add hydrogen peroxide (30-34% by mass) at 0.1-0.3 times the mass of carbon black. Stir at 800-1000r / min for 10-15 minutes. Centrifuge and wash with pure water 3-5 times. Sonicate at 70-80℃ and 1-2kHz for 1-2 hours. Carbon black oxide is obtained by drying at 1 kPa for 8-10 hours. Carbon black oxide, toluene diisocyanate, triethylamine and ethylbenzene are mixed evenly in a mass ratio of 2:1:0.03:20-3:1:0.05:

30. The mixture is stirred at 300-500 r / min for 25-35 minutes at 0-2℃ in a nitrogen atmosphere. The mixture is then heated to 100-110℃ and stirred for another 20-30 minutes. The mixture is centrifuged and washed with toluene 3-5 times. The mixture is then dried at 1-2 kPa for 8-10 hours at 70-80℃ to obtain isocyanated carbon black. (2) Isocyanate-modified carbon black, diallyl polyphosphate, dibutyltin dilaurate, and ethylbenzene are mixed evenly in a mass ratio of 2:1:0.003:40~2:1:0.005:50, and ultrasonicated at 0~2℃ and 30~40kHz for 20~30min. Then, the mixture is heated to 120~130℃ and ultrasonicated for another 50~70min. After cooling to 50~60℃, the mixture is filtered, washed 3~5 times with anhydrous ethanol, and dried at 70~80℃ and 1~2kPa for 8~10h to obtain modified carbon black. (3) Mix natural rubber SCR5 and vinyl ester resin S918 at a mass ratio of 1:2 to 1:3, and plasticize on a two-roll mill at 60 to 70°C for 2 to 3 minutes until the rolls are completely covered to obtain a mixed rubber compound; set the water temperature of the internal mixer to 90 to 98°C, and when the internal mixer is preheated to 80°C, put in the mixed rubber compound and stir for 2 to 3 minutes. Then add 0.08 to 0.10 times the mass of the mixed rubber compound and discharge the rubber when the temperature reaches 150°C; put the obtained rubber compound on a two-roll mill, add 0.01 to 0.02 times the mass of natural rubber sulfur and mix evenly. Then pass through a thin sheet to obtain a mixed rubber compound. Put the mixed rubber compound into a mold and vulcanize in a flat vulcanizing machine at 15 to 17 MPa and 145 to 155°C for 50 to 60 minutes to obtain rubber-modified molding vinyl ester resin; A method for preparing a rubber-modified molding vinyl ester resin, wherein the carbon black in step (1) is of type N134; The toluene diisocyanate mentioned in step (1) is one or a mixture of toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,5-diisocyanate, toluene-2,6-diisocyanate, toluene-3,4-diisocyanate, and toluene-3,5-diisocyanate. The preparation method of diallyl polyphosphate in step (2) is as follows: 2,2'-diallyl bisphenol A and anhydrous aluminum chloride are mixed evenly at a mass ratio of 1:0.01~1:0.

02. Under a nitrogen atmosphere, at 60~70℃ and a stirring speed of 300~500r / min, 0.3~0.4 times the mass of 2,2'-diallyl bisphenol A phenyl dichlorophosphate is added uniformly over 20~30min. After the addition is completed, the temperature is raised to 90~100℃ and the reaction is stirred for 40~50min. Then the temperature is raised to 130~140℃ and the reaction is stirred for 40~50min. The product is then dried at 70~80℃ and 50~100Pa for 8~10h to prepare the product. The natural rubber in step (3) is of type SCR5; the vinyl ester resin is of type S918.

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