High-flame-retardant vinyl ester resin and preparation method thereof

Abstract

The invention discloses high-flame-retardant vinyl ester resin and a preparation method thereof, and relates to the technical field of resin flame retardants, the high-flame-retardant vinyl ester resin comprises matrix resin, a release type flame retardant and an additive type flame retardant; the release type flame retardant comprises a phosphorus-containing polymer and a nitrogen-containing polymer; the additive flame retardant comprises a silicon-containing polymer; on the basis of a traditional polyester resin carrier formula, nitrogen, phosphorus and other bromine-free release type flame retardants are adopted and matched with a high-temperature cured additive type flame retardant to form crosslinking work during flame retardance, so that the flame retardant has the material strength after curing and does not generate uneliminated harmful substances.

Description

Technical Field

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

[0002] Resin flame retardants, through their polyester chain structure combined with bromine bonds, decompose when heated to produce flame-flammable gases, thereby isolating oxidative combustion. They can be applied to industrial production and architectural design, and can effectively protect the safety of production materials in the event of a fire or buy valuable time for fire rescue. However, the flame retardants of the above components have the disadvantages of generating harmful gases when participating in flame retardancy, and the flame retardant effect drops sharply after the flame retardant components therein are completely decomposed. In addition, the physical strength performance of flame retardants with a simple resin base as a carrier is extremely poor. Therefore, it is now necessary to develop new polyester resin flame retardants. Summary of the Invention

[0003] The purpose of the present invention is to address the defects and shortcomings of the existing technology and provide a highly flame-retardant vinyl ester resin and a preparation method thereof. The resin is based on a traditional polyester resin carrier formula, adopts a release-type flame retardant such as nitrogen and phosphorus that does not contain bromine salts, and is combined with a high-temperature curing additive flame retardant to form a cross-linking process during flame retardancy, so that the flame retardant has the material strength obtained after curing and does not produce irreversible harmful substances.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions: It contains base resin, release type flame retardant, and additive type flame retardant; Release-type flame retardants include phosphorus-containing polymers and nitrogen-containing polymers; Additive flame retardants include silicone-containing polymers.

[0005] Preferably, the matrix resin is one or more of bisphenol A epoxy resin and phenol biphenyl epoxy resin.

[0006] Preferably, the phosphorus-containing polymer is one or more of a phosphorus-containing epoxy resin, a catalyst, and modified talc.

[0007] Preferably, the catalyst is one or more of triphenylphosphine and benzyltrimethylammonium chloride.

[0008] Preferably, the nitrogen-containing polymer is a nitrogen-containing polymerization inhibitor.

[0009] Preferably, the nitrogen-containing polymerization inhibitor is one or more of p-hydroxyanisole and 4-tert-butylcatechol.

[0010] Preferably, the silicon-containing polymer is modified talc.

[0011] Preferably, the preparation process of the modified talc powder is: A. Talc is reacted with dilute sulfuric acid. After the reaction is completed, the acid-activated talc is obtained by washing with water or adding a weak base additive to neutral pH. B. reacting the acid-activated talc in step A with a dopamine hydrochloride solution to prepare coated talc; C. reacting the coated talc in step B with hydroxyethylidene diphosphonic acid and epoxy POSS to obtain modified talc.

[0012] Preferably, the preparation method of this scheme is: A. After heating the base resin, adding phosphorus-containing epoxy resin, methacrylic acid and polymerization inhibitor, and heating the reaction to prepare the intermediate; B. Cool the intermediate, add modified talc and cross-linking monomer, and then vacuum stir and solidify.

[0013] Preferably, the cross-linking monomer is one or more of styrene and trimethylolpropane triacrylate.

[0014] Compared with the prior art, the present invention has the following beneficial effects: This solution is based on epoxy resin as the base material, adopts nitrogen-phosphorus and silicon-phosphorus cross-linked flame retardant solutions, and combines the additives and catalysts required in the preparation reaction to jointly prepare nitrogen- and phosphorus-containing polymers. By adding modified talc powder, the mechanical properties of the flame retardant after curing are improved, so that the flame retardant has a certain physical strength and will not release non-decomposable harmful substances. DETAILED DESCRIPTION

[0015] The technical solutions of the present invention are described clearly and completely below. The preferred embodiments described are only used as examples. All other embodiments obtained by those skilled in the art without making any creative work are within the scope of protection of the present invention.

[0016] This specific implementation adopts the following technical solutions: This specific embodiment adopts a combined flame retardant solution, specifically, through the cross-linking effect of the release-type flame retardant and the additive-type flame retardant, when the flame retardant is applied, the phosphorus-containing polymer and the nitrogen-containing polymer are heated to generate flame-flammable gas, and the silicon-containing polymer forms a dense carbonized layer, forming a comprehensive flame retardant solution; Talc modification 1. Acid activation: react talc with 15wt% dilute sulfuric acid (1:30g / mL) at 80℃ for 2h, then wash until neutral; 2. Polydopamine coating: Acid-activated talc was reacted with 20 wt% dopamine hydrochloride solution (1:15 g / mL) in Tris buffer at 50°C for 3 h. 3. Graft modification: The coated talc powder was dispersed in chloroform, and hydroxyethylidene diphosphonic acid (3:10 by mass ratio) and epoxy POSS (5:10 by mass ratio) were added and reacted at 80°C for 4 hours to obtain modified talc powder.

[0017] Resin synthesis: 1. Heat the halogen-free epoxy resin to 80°C, then add the phosphorus-containing epoxy resin, methacrylic acid, polymerization inhibitor (p-hydroxyanisole: 4-tert-butylcatechol = 5:0.7 by mass ratio), and catalyst (a mixture of triphenylphosphine and benzyltrimethylammonium chloride) in sequence. 2. Raise the temperature to 115°C and react until the acid value is less than 14 mgKOH / g and the epoxy value is less than 0.02 eq / 100g; 3. Cool to 80°C, add modified talc (10-20wt%) and cross-linking monomer (styrene: trimethylolpropane triacrylate = 7:3), stir for 1 hour, and then vacuum degassing and solidify.

[0018] Compared with the prior art, the present invention has the following beneficial effects: This solution utilizes grafted hydroxyethylene diphosphonic acid and epoxy POSS in modified talc to introduce phosphorus and silicon complexes. Phosphorus-containing catalysts and nitrogen-containing polymerization inhibitors are used in the resin preparation process to promote the reaction while introducing nitrogen and phosphorus complexes into the polymer. Thus, through the mixed molding of the resin polymer and the modified talc, flame retardancy is achieved by the combined effect of releasing flame-retardant gas and forming a flame-retardant heat-insulating layer during flame retardancy. In addition, the dense layer formed by the modified talc after being heated and decomposed and released effectively enhances the physical strength of the flame retardant.

[0019] For those skilled in the art, they can modify the technical solutions described in the aforementioned embodiments and make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A highly flame-retardant vinyl ester resin, characterized in that: It contains base resin, release type flame retardant, and additive type flame retardant; Release-type flame retardants include phosphorus-containing polymers and nitrogen-containing polymers; Additive flame retardants include silicone-containing polymers.

2. A highly flame retardant vinyl ester resin according to claim 1, characterized in that: The matrix resin is one or more of bisphenol A epoxy resin and phenol biphenyl epoxy resin.

3. The highly flame-retardant vinyl ester resin according to claim 1, wherein: The phosphorus-containing polymer is one or more of a phosphorus-containing epoxy resin, a catalyst, and modified talc.

4. A highly flame-retardant vinyl ester resin according to claim 3, characterized in that: The catalyst is one or more of triphenylphosphine and benzyltrimethylammonium chloride.

5. The highly flame-retardant vinyl ester resin according to claim 1, wherein: The nitrogen-containing polymer is a nitrogen-containing polymerization inhibitor.

6. A highly flame-retardant vinyl ester resin according to claim 5, characterized in that: The nitrogen-containing polymerization inhibitor is one or more of p-hydroxyanisole and 4-tert-butylcatechol.

7. The highly flame-retardant vinyl ester resin according to claim 1, characterized in that: The silicon-containing polymer is modified talc.

8. The highly flame-retardant vinyl ester resin according to claim 7, characterized in that: The preparation process of the modified talcum powder is: A. Talc is reacted with dilute sulfuric acid. After the reaction is completed, the acid-activated talc is obtained by washing with water or adding a weak base additive to neutral pH. B. reacting the acid-activated talc in step A with a dopamine hydrochloride solution to prepare coated talc; C. The coated talc in step B is reacted with hydroxyethylidene diphosphonic acid and epoxy POSS to obtain modified talc.

9. A method for preparing a highly flame-retardant vinyl ester resin: A. After heating the base resin, adding phosphorus-containing epoxy resin, methacrylic acid and polymerization inhibitor, and then heating the reaction to prepare the intermediate; B. Cool the intermediate, add modified talc and cross-linking monomer, and then vacuum stir and solidify.

10. A method for preparing a highly flame-retardant vinyl ester resin according to claim 9, characterized in that: The cross-linking monomer is one or more of styrene and trimethylolpropane triacrylate.