Flame-retardant epoxy vinyl ester resin and preparation method thereof

Abstract

The invention discloses flame-retardant epoxy vinyl ester resin and a preparation method thereof, and belongs to the technical field of flame-retardant materials. The flame-retardant epoxy vinyl ester resin comprises the following components in parts by weight: 50-100 parts of epoxy vinyl ester resin, 1-10 parts of a curing agent, 0.5-1.5 parts of an accelerant and 10-20 parts of modified talcum powder, the modified talcum powder is added into the formula, so that the mechanical and flame-retardant properties of the epoxy vinyl ester resin are remarkably improved, and the epoxy vinyl ester resin can be applied to the field of flue gas desulfurization with relatively high requirements on flame-retardant properties.

Description

Technical Field

[0001] The invention relates to the technical field of flame retardant materials, and in particular to a flame retardant epoxy vinyl ester resin and a preparation method thereof. Background Art

[0002] Epoxy vinyl ester resin is made by the ring-opening addition chemical reaction of epoxy resin and unsaturated monobasic acid. It retains the basic chain segment of epoxy resin and has the good process performance of unsaturated polyester resin. It inherits the excellent characteristics of epoxy resin, and is more outstanding in curing and forming properties. It can be dissolved in styrene and acrylic monomers. Due to its advantages of both epoxy and unsaturation, its application field is constantly expanding. It is mainly used in chemical fields with harsh requirements such as chemical corrosion resistance, acid and alkali resistance, such as new energy wind power generation, the manufacture of desulfurization and denitrification equipment in the environmental protection industry, the preparation of sewage pipes in the papermaking industry, and applications in high-end fields such as cruise ships and high-speed railways. With the expansion of the application field of vinyl ester resin, its application in some special fields needs to have flame retardant functions, such as in the field of flue gas desulfurization.

[0003] Chinese patent document CN 110499004A discloses a trapezoidal POSS modified vinyl ester resin containing phenyl and vinyl at the same time and a preparation method thereof. The invention provides a trapezoidal POSS modified vinyl ester resin containing phenyl and vinyl at the same time, which has good mechanical properties, low smoke and low heat release during combustion. The invention provides a preparation method of the trapezoidal POSS modified vinyl ester resin containing phenyl and vinyl at the same time, which has a simple process, a short cycle, and is suitable for mass production. Only one flame retardant is added to the invention formula, and the mechanical and flame retardant properties of the vinyl ester resin obtained therefrom still have room for further improvement. Summary of the invention

[0004] The main purpose of the invention is to provide an epoxy vinyl ester resin with good mechanical and flame retardant properties. The mechanical and flame retardant properties of the resin are significantly improved by adding modified talcum powder into the resin.

[0005] To achieve the above object, the present invention provides a flame retardant epoxy vinyl ester resin, comprising the following components in parts by weight: 50-100 parts of epoxy vinyl ester resin, 1-10 parts of curing agent, 0.5-1.5 parts of accelerator, and 10-20 parts of modified talc.

[0006] Preferably, the curing agent is at least one of methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, tert-butyl perbenzoate, and cumene hydroperoxide.

[0007] Preferably, the accelerator is at least one of cobalt isooctanoate, cobalt cyclohexaneate, dimethylaniline, diethylaniline, dimethyl-p-methylaniline, and triethylenediamine.

[0008] Preferably, the preparation method of the modified talc is as follows:

[0009] (1) adding talc to a 10-20 wt % aqueous solution of dilute sulfuric acid and heating to 80-90° C. for reaction for 2-4 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and then drying to obtain pretreated talc;

[0010] (2) preparing a dopamine hydrochloride aqueous solution, mixing the pretreated talc powder with the dopamine hydrochloride aqueous solution, adding a Tris buffer, reacting at 40-60° C. for 2-4 hours, filtering and collecting the solid, and drying to obtain a polydopamine-coated talc powder;

[0011] (3) Dispersing the polydopamine-coated talc in chloroform, adding aminophenyl POSS, hydroxyethylidene diphosphonic acid, and epichlorohydrin, stirring and mixing evenly, reacting at 50-80° C. for 4-6 hours, and after the reaction is completed, filtering, collecting the solid, and drying to obtain modified talc.

[0012] Preferably, the ratio of talcum powder to dilute sulfuric acid solution in step (1) is 1-2 g:30-40 mL.

[0013] Preferably, the concentration of the dopamine hydrochloride aqueous solution in step (2) is 20-30wt%; the dosage ratio of the pretreated talcum powder, dopamine hydrochloride aqueous solution and Tris buffer is 1g:10-20mL:1-3mL.

[0014] Preferably, in the step (3), the mass ratio of polydopamine-coated talc, aminophenyl POSS, hydroxyethylidene diphosphonic acid, and epichlorohydrin is 10-18:5-8:3-5:6-10.

[0015] Talc is an inorganic nano flame retardant. Adding talc to epoxy vinyl ester resin can improve the flame retardancy of the resin. Treating talc with dilute sulfuric acid is beneficial to enhancing its reaction activity. Then coating with polydopamine can introduce active amino groups on the surface of talc. Finally, under the action of epichlorohydrin, aminophenyl POSS and hydroxyethylidene diphosphonic acid are grafted on the surface of talc. By modifying talc, the high free energy of the talc surface is reduced, its polarity is reduced, and its uniform dispersion in epoxy vinyl ester resin is improved, thereby improving the mechanical properties of epoxy vinyl ester resin. At the same time, polydopamine, hydroxyethylidene diphosphonic acid and aminophenyl POSS can form nitrogen-silicon-phosphorus synergistic flame retardant. Hydroxyethylidene diphosphonic acid plays a role in the condensed phase to promote the carbonization of the matrix, while polydopamine generates non-flammable gas in the gas phase to achieve the effect of synergistic flame retardancy. In addition, the cage structure in aminophenyl POSS makes the flame retardancy and thermal stability of the resin more excellent.

[0016] The present invention also discloses a method for preparing the flame retardant epoxy vinyl ester resin, comprising the following steps:

[0017] Weigh each component according to the formula, mix the epoxy vinyl ester resin and modified talc, and stir evenly at 50-70° C. to obtain a mixture 1; control the temperature of the mixture 1 to be 20-40° C., add an accelerator and a curing agent to the mixture 1, mix and stir evenly, perform vacuum degassing treatment, and cure to obtain the flame-retardant epoxy vinyl ester resin.

[0018] Preferably, the vacuum degassing treatment conditions are a vacuum degree of -0.01 to -0.09 MPa and a degassing time of 3 to 5 min.

[0019] Preferably, the flame retardant epoxy vinyl ester resin can be applied to the resin matrix of composite materials, anti-corrosion coatings, petroleum, chemical industry, environmental protection, housing construction, transportation, aerospace, and flue gas desulfurization technology fields.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) The epoxy vinyl ester resin of the present invention uses modified talc as a flame retardant, which has strong flame retardancy, good thermal stability, good compatibility with vinyl ester resin, and does not contain halogen. It can achieve flame retardancy, low toxicity and smoke suppression effects at the same time. The preparation method is simple and suitable for industrial production. It can be applied to resin matrix of composite materials, anti-corrosion coatings, petroleum, chemical industry, environmental protection, house construction, transportation, aerospace, flue gas desulfurization and technical fields;

[0022] (2) The present invention reduces the high free energy of the talc surface and its polarity by modifying the talc, thereby improving its uniform dispersion in the epoxy vinyl ester resin, thereby improving the mechanical properties of the epoxy vinyl ester resin. At the same time, polydopamine, hydroxyethylene diphosphonic acid, and aminophenyl POSS can form a nitrogen-silicon-phosphorus synergistic flame retardant. Hydroxyethylene diphosphonic acid plays a role in the condensed phase to promote carbonization of the matrix, while polydopamine generates a non-flammable gas in the gas phase to achieve a synergistic flame retardant effect. In addition, the cage structure in the aminophenyl POSS makes the flame retardancy and thermal stability of the resin more excellent. DETAILED DESCRIPTION

[0023] To avoid redundancy, the items used in the following examples are all commercially available products unless otherwise specified, and the methods used are all conventional methods unless otherwise specified.

[0024] The sources of some raw materials used in the present invention are as follows:

[0025] Epoxy vinyl ester resin, bisphenol A type, was purchased from Shandong Ruiding Chemical Co., Ltd.

[0026] Talc, hardness 5.5HB, density 2.45g / cm 3 , purchased from Lingshou County Malin Mineral Products Processing Plant.

[0027] Amine phenyl POSS, purchased from Angxing New Carbon Materials Changzhou Co., Ltd.

[0028] Hydroxyethylidene diphosphonic acid, model 220-552-8, was purchased from Shandong New Kinetic Energy Chemical Co., Ltd.

[0029] Example 1

[0030] A method for preparing a flame retardant epoxy vinyl ester resin comprises the following steps:

[0031] 70 g of bisphenol A epoxy vinyl ester resin and 16.5 g of modified talc are mixed and stirred at 60° C. to obtain a mixture 1; the temperature of the mixture 1 is controlled to 30° C., 1.2 g of cobalt isooctanoate and 6.8 g of methyl ethyl ketone peroxide are added to the mixture 1, the mixture is mixed and stirred evenly, and a vacuum degassing treatment is performed at a vacuum degree of -0.06 MPa for 5 minutes, and then the mixture is cured to obtain the flame-retardant epoxy vinyl ester resin.

[0032] The preparation method of the modified talcum powder is as follows:

[0033] (1) adding 16 g of talc to 350 mL of a 20 wt % dilute sulfuric acid aqueous solution and heating to 80° C. for reaction for 3 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and then drying to obtain pretreated talc;

[0034] (2) preparing a 30 wt% dopamine hydrochloride aqueous solution, mixing 15 g of pretreated talc with 200 mL of dopamine hydrochloride aqueous solution, adding 30 mL of Tris buffer, reacting at 50° C. for 3 h, filtering and collecting the solid, and drying to obtain polydopamine-coated talc;

[0035] (3) Disperse 16.8 g of polydopamine-coated talc in 200 mL of chloroform, add 6.5 g of aminophenyl POSS, 4.3 g of hydroxyethylidene diphosphonic acid, and 8.2 g of epichlorohydrin, stir and mix evenly, react at 80 ° C for 6 h, and after the reaction is completed, filter, collect the solid and dry to obtain modified talc.

[0036] Example 2

[0037] A method for preparing a flame retardant epoxy vinyl ester resin comprises the following steps:

[0038] 50 g of bisphenol A epoxy vinyl ester resin and 10.3 g of modified talc are mixed and stirred at 50° C. to obtain a mixture 1; the temperature of the mixture 1 is controlled to 20° C., 0.5 g of cobalt isooctanoate and 1.5 g of methyl ethyl ketone peroxide are added to the mixture 1, the mixture is mixed and stirred evenly, and a vacuum degassing treatment is performed at a vacuum degree of -0.01 MPa for 3 minutes, and then the mixture is cured to obtain the flame-retardant epoxy vinyl ester resin.

[0039] The preparation method of the modified talcum powder is as follows:

[0040] (1) adding 12 g of talc to 300 mL of a 10 wt % aqueous solution of dilute sulfuric acid and heating to 80° C. for 2 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and then drying to obtain pretreated talc;

[0041] (2) preparing a 20 wt% dopamine hydrochloride aqueous solution, mixing 15 g of pretreated talc with 200 mL of dopamine hydrochloride aqueous solution, adding 30 mL of Tris buffer, reacting at 50° C. for 3 h, filtering and collecting the solid, and drying to obtain polydopamine-coated talc;

[0042] (3) Disperse 10 g of polydopamine-coated talc in 200 mL of chloroform, add 5.3 g of aminophenyl POSS, 3 g of hydroxyethylidene diphosphonic acid, and 6 g of epichlorohydrin, stir and mix evenly, react at 50 ° C for 6 h, and after the reaction is completed, filter, collect the solid and dry to obtain modified talc.

[0043] Example 3

[0044] A method for preparing a flame retardant epoxy vinyl ester resin comprises the following steps:

[0045] 100 g of bisphenol A epoxy vinyl ester resin and 20 g of modified talc are mixed and stirred at 70° C. to obtain a mixture 1; the temperature of the mixture 1 is controlled to 40° C., 1.5 g of cobalt isooctanoate and 10 g of methyl ethyl ketone peroxide are added to the mixture 1, the mixture is mixed and stirred evenly, and a vacuum degassing treatment is performed at a vacuum degree of -0.09 MPa for 5 minutes, and then the mixture is cured to obtain the flame-retardant epoxy vinyl ester resin.

[0046] The preparation method of the modified talcum powder is as follows:

[0047] (1) adding 20 g of talc to 400 mL of a 20 wt % aqueous solution of dilute sulfuric acid and heating to 90° C. for 2 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and then drying to obtain pretreated talc;

[0048] (2) preparing a 20 wt% dopamine hydrochloride aqueous solution, mixing 15 g of pretreated talc with 200 mL of dopamine hydrochloride aqueous solution, adding 30 mL of Tris buffer, reacting at 50° C. for 3 h, filtering and collecting the solid, and drying to obtain polydopamine-coated talc;

[0049] (3) Disperse 18 g of polydopamine-coated talc in 200 mL of chloroform, add 8 g of aminophenyl POSS, 5 g of hydroxyethylidene diphosphonic acid, and 10 g of epichlorohydrin, stir and mix evenly, react at 80 ° C for 4 h, and after the reaction is completed, filter, collect the solid and dry to obtain modified talc.

[0050] Comparative Example 1

[0051] A method for preparing a flame retardant epoxy vinyl ester resin is similar to Example 1, except that the talc is not modified, and specifically comprises the following steps:

[0052] 70 g of bisphenol A epoxy vinyl ester resin and 16.5 g of talc are mixed and stirred at 60° C. to obtain a mixture 1; the temperature of the mixture 1 is controlled to 30° C., 1.2 g of cobalt isooctanoate and 6.8 g of methyl ethyl ketone peroxide are added to the mixture 1, the mixture is mixed and stirred evenly, and a vacuum degassing treatment is performed at a vacuum degree of -0.06 MPa for 5 minutes, and then the mixture is cured to obtain the flame-retardant epoxy vinyl ester resin.

[0053] Comparative Example 2

[0054] A method for preparing a flame retardant epoxy vinyl ester resin is similar to Example 1, except that the pretreated talc in the modified talc is not coated with polydopamine, and specifically comprises the following steps:

[0055] 70 g of bisphenol A epoxy vinyl ester resin and 16.5 g of modified talc are mixed and stirred at 60° C. to obtain a mixture 1; the temperature of the mixture 1 is controlled to 30° C., 1.2 g of cobalt isooctanoate and 6.8 g of methyl ethyl ketone peroxide are added to the mixture 1, the mixture is mixed and stirred evenly, and a vacuum degassing treatment is performed at a vacuum degree of -0.06 MPa for 5 minutes, and then the mixture is cured to obtain the flame-retardant epoxy vinyl ester resin.

[0056] The preparation method of the modified talcum powder is as follows:

[0057] (1) adding 16 g of talc to 350 mL of a 20 wt % dilute sulfuric acid aqueous solution and heating to 80° C. for reaction for 3 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and then drying to obtain pretreated talc;

[0058] (2) Disperse 16.8 g of pretreated talc in 200 mL of chloroform, add 6.5 g of aminophenyl POSS, 4.3 g of hydroxyethylidene diphosphonic acid, and 8.2 g of epichlorohydrin, stir and mix evenly, heat and stir at 80° C. for 6 h. After the reaction is completed, filter, collect the solid and dry to obtain modified talc.

[0059] Comparative Example 3

[0060] A method for preparing a flame retardant epoxy vinyl ester resin is similar to Example 1, except that phenylamine POSS is not added to the modified talc, and specifically comprises the following steps:

[0061] 70 g of bisphenol A epoxy vinyl ester resin and 16.5 g of modified talc are mixed and stirred at 60° C. to obtain a mixture 1; the temperature of the mixture 1 is controlled to 30° C., 1.2 g of cobalt isooctanoate and 6.8 g of methyl ethyl ketone peroxide are added to the mixture 1, the mixture is mixed and stirred evenly, and a vacuum degassing treatment is performed at a vacuum degree of -0.06 MPa for 5 minutes, and then the mixture is cured to obtain the flame-retardant epoxy vinyl ester resin.

[0062] The preparation method of the modified talcum powder is as follows:

[0063] (1) adding 16 g of talc to 350 mL of a 20 wt % aqueous solution of dilute sulfuric acid and heating to 80° C. for 3 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and drying to obtain pretreated talc;

[0064] (2) preparing a 30 wt% dopamine hydrochloride aqueous solution, mixing 15 g of pretreated talc with 200 mL of dopamine hydrochloride aqueous solution, adding 30 mL of Tris buffer, reacting at 50° C. for 3 h, filtering and collecting the solid, and drying to obtain polydopamine-coated talc;

[0065] (3) Disperse 16.8 g of polydopamine-coated talc in 200 mL of chloroform, add 4.3 g of hydroxyethylidene diphosphonic acid and 8.2 g of epichlorohydrin, stir and mix evenly, stir at 80° C. for 6 h, and after the reaction is completed, filter, collect the solid and dry to obtain modified talc.

[0066] Comparative Example 4

[0067] A method for preparing a flame retardant epoxy vinyl ester resin is similar to Example 1, except that hydroxyethylidene diphosphonic acid is not added to the modified talc, and specifically comprises the following steps:

[0068] 70 g of bisphenol A epoxy vinyl ester resin and 16.5 g of modified talc are mixed and stirred at 60° C. to obtain a mixture 1; the temperature of the mixture 1 is controlled to 30° C., 1.2 g of cobalt isooctanoate and 6.8 g of methyl ethyl ketone peroxide are added to the mixture 1, the mixture is mixed and stirred evenly, and a vacuum degassing treatment is performed at a vacuum degree of -0.06 MPa for 5 minutes, and then the mixture is cured to obtain the flame-retardant epoxy vinyl ester resin.

[0069] The preparation method of the modified talcum powder is as follows:

[0070] (1) adding 16 g of talc to 350 mL of a 20 wt % dilute sulfuric acid aqueous solution and heating to 80° C. for reaction for 3 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and then drying to obtain pretreated talc;

[0071] (2) preparing a 30 wt% dopamine hydrochloride aqueous solution, mixing 15 g of pretreated talc with 200 mL of dopamine hydrochloride aqueous solution, adding 30 mL of Tris buffer, reacting at 50° C. for 3 h, filtering and collecting the solid, and drying to obtain polydopamine-coated talc;

[0072] (3) Disperse 16.8 g of polydopamine-coated talc in 200 mL of chloroform, add 6.5 g of aminophenyl POSS and 8.2 g of epichlorohydrin, stir and mix evenly, stir at 80 ° C for 6 h, and after the reaction is completed, filter, collect the solid and dry to obtain modified talc.

[0073] Performance Testing

[0074] The flame retardant epoxy vinyl ester resin prepared in Examples 1-3 and Comparative Examples 1-4 was poured into a mold according to standard size to prepare the test specimens. The smoke density was tested according to ISO5659-2 standard, and the radiation cone was selected to be 50kW / m 2 , flameless; heat release test uses cone calorimeter, according to ISO5660-1 standard, radiation power is 50kW / m 2 The mechanical properties test of the resin casting body was conducted in accordance with GB / T2567-2021 standard, and the sample size was 100mm×15mm×4mm. The performance test results of the flame retardant epoxy vinyl ester resin are shown in Table 1:

[0075] Table 1 Performance test results of flame retardant epoxy vinyl ester resin

[0076]

[0077]

[0078] It can be seen from the experimental data in Table 1 that the flame retardant epoxy vinyl ester resin prepared in the embodiment of the present invention has good mechanical and flame retardant properties.

[0079] The above are only preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention may have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the patent protection scope of the present invention.

Claims

1. A flame retardant epoxy vinyl ester resin, characterized in that: The invention comprises the following components in parts by weight: 50-100 parts of epoxy vinyl ester resin, 1-10 parts of curing agent, 0.5-1.5 parts of accelerator and 10-20 parts of modified talc.

2. The flame retardant epoxy vinyl ester resin according to claim 1, characterized in that: The curing agent is at least one of methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, tert-butyl perbenzoate, and cumene hydroperoxide.

3. The flame retardant epoxy vinyl ester resin according to claim 1, characterized in that: The accelerator is at least one of cobalt isooctanoate, cobalt naphthenate, dimethylaniline, diethylaniline, dimethyl-p-methylaniline and triethylenediamine.

4. The flame retardant epoxy vinyl ester resin according to claim 1, characterized in that: The preparation method of the modified talcum powder is as follows: (1) adding talc to a 10-20 wt % aqueous solution of dilute sulfuric acid and heating to 80-90° C. for reaction for 2-4 h, filtering and collecting the filter cake, washing the filter cake with water until the pH value is neutral, and then drying to obtain pretreated talc; (2) preparing a dopamine hydrochloride aqueous solution, mixing the pretreated talc powder with the dopamine hydrochloride aqueous solution, adding a Tris buffer, reacting at 40-60° C. for 2-4 hours, filtering and collecting the solid, and drying to obtain a polydopamine-coated talc powder; (3) Dispersing the polydopamine-coated talc in chloroform, adding aminophenyl POSS, hydroxyethylidene diphosphonic acid, and epichlorohydrin, stirring and mixing evenly, reacting at 50-80° C. for 4-6 hours, and after the reaction is completed, filtering, collecting the solid, and drying to obtain modified talc.

5. The flame retardant epoxy vinyl ester resin according to claim 4, characterized in that: In the step (1), the ratio of talcum powder to dilute sulfuric acid solution is 1-2 g: 30-40 mL.

6. The flame retardant epoxy vinyl ester resin according to claim 4, characterized in that: The concentration of the dopamine hydrochloride aqueous solution in step (2) is 20-30wt%; the dosage ratio of the pretreated talcum powder, dopamine hydrochloride aqueous solution and Tris buffer is 1g:10-20mL:1-3mL.

7. The flame retardant epoxy vinyl ester resin according to claim 4, characterized in that: In the step (3), the mass ratio of polydopamine-coated talcum powder, aminophenyl POSS, hydroxyethylidene diphosphonic acid, and epichlorohydrin is 10-18:5-8:3-5:6-10.

8. A method for preparing the flame retardant epoxy vinyl ester resin according to any one of claims 1 to 7, characterized in that: The steps include: Weigh each component according to the formula, mix the epoxy vinyl ester resin and modified talc, and stir evenly at 50-70° C. to obtain a mixture 1; control the temperature of the mixture 1 to be 20-40° C., add an accelerator and a curing agent to the mixture 1, mix and stir evenly, perform vacuum degassing treatment, and cure to obtain the flame-retardant epoxy vinyl ester resin.

9. The preparation method according to claim 8, characterized in that: The vacuum degassing treatment conditions are as follows: vacuum degree is -0.01 to -0.09 MPa, and degassing time is 3 to 5 minutes.

10. Use of the flame retardant epoxy vinyl ester resin according to any one of claims 1 to 7, characterized in that: Used in resin matrix of composite materials, anti-corrosion coatings, petroleum, chemical industry, environmental protection, housing construction, transportation, aerospace and flue gas desulfurization technology fields.

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