阅读说明：本技术 一种耐老化的高分子阻燃防水材料及其制备方法 (Anti-aging high-molecular flame-retardant waterproof material and preparation method thereof ) 是由 石旭艳 于 2019-12-20 设计创作，主要内容包括：本发明提供了一种耐老化的高分子阻燃防水材料的制备方法,其特征在于,包括如下步骤：步骤S1、基于三氟对苯二腈三嗪类聚合型单体的制备；步骤S2、共聚物的制备；步骤S3、高分子防水材料的成型。本发明还公开了根据所述一种耐老化的高分子阻燃防水材料的制备方法制备得到的高分子防水材料。本发明公开的高分子防水材料机械力学性能、耐候性、耐老化性和阻燃性优异,防水效果显著,经济价值和社会价值高。(The invention provides a preparation method of an anti-aging high-molecular flame-retardant waterproof material, which is characterized by comprising the following steps: step S1, preparing a triazine polymerized monomer based on trifluoroterephthalonitrile; step S2, preparation of a copolymer; and step S3, molding the high polymer waterproof material. The invention also discloses a macromolecular waterproof material prepared by the preparation method of the anti-aging macromolecular flame-retardant waterproof material. The high polymer waterproof material disclosed by the invention has excellent mechanical property, weather resistance, aging resistance and flame retardance, and is remarkable in waterproof effect and high in economic value and social value.)

1. The preparation method of the anti-aging high-molecular flame-retardant waterproof material is characterized by comprising the following steps of:

step S1, preparation of triazine based trifluoroterephthalonitrile-based polymerizable monomer: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2-amino-3, 5, 6-trifluoro terephthalonitrile, a basic catalyst and a polymerization inhibitor into an organic solvent, stirring and reacting for 4-6 hours at 70-80 ℃, removing the organic solvent by rotary evaporation, adding dichloromethane and water in a mass ratio of 1 (2-3), layering, taking an organic phase, removing water by anhydrous magnesium sulfate, filtering, and finally removing dichloromethane by rotary evaporation to obtain the triazine polymerized monomer based on trifluoro terephthalonitrile;

step S2, preparation of copolymer: adding the trifluoro-terephthalonitrile triazine-based polymerized monomer prepared in the step S1, methyl vinyl di (butanone oxime) silane, 4-vinylaniline, allyl boronic acid pinacol ester and an initiator into a high-boiling-point solvent, performing ultrasonic treatment for 10-20 minutes, performing ultrasonic microwave treatment for 20-30 minutes at 70-80 ℃ in the atmosphere of nitrogen or inert gas, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain a copolymer;

step S3, forming the high polymer waterproof material: uniformly mixing the copolymer prepared in the step S2, ethylene propylene diene monomer, PVC resin, plasticizer, 2-bis- (4-glycinyloxybenzene) propane and azobisisobutyronitrile, then putting into a hot mixer, stirring for 20-30 minutes at 80-90 ℃, then raising the temperature to 110-120 ℃, and stirring again for 15-20 minutes to obtain a mixture; and then putting the obtained mixture into an extruder, and rolling, drawing, rolling and molding the extrudate to obtain the high-molecular waterproof material.

2. The preparation method of the aging-resistant, flame-retardant and waterproof polymer material according to claim 1, wherein the molar ratio of the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the 2-amino-3, 5, 6-trifluoroterephthalonitrile to the basic catalyst to the polymerization inhibitor to the organic solvent is 1:2 (0.8-1.2) to 0.3 (10-15).

3. The method for preparing the aging-resistant, flame-retardant and waterproof polymer material according to claim 1, wherein the basic catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; the polymerization inhibitor is at least one of chloranil and 1, 4-naphthoquinone; the organic solvent is one of tetrahydrofuran, acetone, chloroform and acetonitrile.

4. The method for preparing an anti-aging, flame-retardant and waterproof polymer material according to claim 1, wherein the mass ratio of the trifluoroterephthalonitrile-based triazine type polymerizable monomer, the methyl vinyl bis (butanone oxime) silane, the 4-vinylaniline, the allyl boronic acid pinacol ester, the initiator and the high boiling point solvent in step S2 is 1:0.5:0.8:0.3 (0.02-0.04): 10-15.

5. The method for preparing the aging-resistant, flame-retardant and waterproof polymer material according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the inert gas is one of helium, neon and argon.

6. The preparation method of the aging-resistant, flame-retardant and waterproof polymer material according to claim 1, wherein the ultrasonic microwave treatment conditions are as follows: the ultrasonic power is 500-1000W, and the microwave power is 300-500W.

7. The method for preparing an anti-aging, flame-retardant and waterproof polymer material according to claim 1, wherein the mass ratio of the copolymer, the ethylene propylene diene monomer, the PVC resin, the plasticizer, the 2, 2-bis- (4-glycidyloxybenzene) propane and the azobisisobutyronitrile in step S3 is (25-35): (10-20): (8-15): (3-5): (1-2).

8. The method for preparing the anti-aging, flame-retardant and waterproof polymer material according to claim 1, wherein the plasticizer is at least one of epoxidized soybean oil, epoxidized acetyl methyl linoleate, epoxidized butyl furoate and epoxidized butyl pupate oleate.

9. The high molecular flame-retardant waterproof material prepared by the preparation method of the aging-resistant high molecular flame-retardant waterproof material according to any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to an anti-aging high polymer flame-retardant waterproof material and a preparation method thereof.

Background

In recent years, with the improvement of science and technology and the improvement of living standard, the number of urban municipal infrastructure and houses is greatly increased, the demand of people for improving the living environment is increasingly urgent, and the quality requirement of waterproof materials is higher and higher. The waterproof material is used for the building envelope to prevent the penetration of rainwater, snow water and underground water; to prevent the erosion of moisture, steam and other harmful gases and liquids in the air; the partition structure is to prevent the infiltration of the water supply and drainage. These materials that resist permeation, leakage and erosion are collectively referred to. The waterproof material with excellent quality is necessary requirement for ensuring the quality of building engineering and hydraulic engineering.

The waterproof material generally has the characteristics of low-temperature flexibility, good self-healing property and good bonding property, can be constructed at normal temperature, has high construction speed and meets the requirement of environmental protection. Particularly, the construction is carried out without hot melting, so that the fire hazard is avoided. The waterproof material has good low temperature resistance, and is suitable for the water proofing, moisture proofing and sealing of roofs, basements, rooms, municipal works, water reservoirs, swimming pools, subways and tunnels of industrial and civil buildings. It is especially suitable for military facilities needing cold construction and petroleum depot, chemical plant, textile plant, grain depot and other waterproof and anticorrosive engineering where open flame is not suitable. In the prior art, common waterproof materials are traditional asphalt-based waterproof materials, which have low peel strength and insufficient waterproof performance on one hand, and the waterproof performance is weakened along with the prolonging of the service time; on the other hand, the use of asphalt-based materials brings about the problem of environmental pollution and influences the health of constructors.

The high-molecular waterproof material is used for replacing a high-molecular material of petroleum asphalt felt which is easy to leak and short in service life in waterproof engineering, and has the characteristics of elastoplasticity or high elasticity, aging resistance, light weight, low pollution, excellent waterproof performance, simplicity in construction, cold operation and strong adaptability to base expansion or cracking. At present, common polymer waterproof materials include SBS waterproof roll, EPDM waterproof material (ethylene propylene diene monomer), TPO waterproof material (thermoplastic polyolefin waterproof material). About 80% of raw materials in SBS waterproof coiled materials in the prior art are asphalt, so that the production process can cause great pollution, and the environmental protection pressure of asphalt waterproof materials is increased along with the deepening of environmental protection consciousness. The bonding properties, mechanical strength and aging problems of EPDM waterproofing materials limit their widespread use. The TPO waterproof material is the most ideal waterproof coiled material in various waterproof materials, but the price is high, and no raw material producer exists in China, so the development of the waterproof material in China is slow. Besides, the high polymer coiled materials on the market also have the defects of high manufacturing cost, easy damage, poor waterproof effect, aging resistance, flame retardance, puncture resistance, corrosion resistance and the like, and insufficient adhesive property.

Patent CN2014101614049 discloses a method for manufacturing a non-asphalt waterproof material with a changed nano-scale filler, which comprises the following components by weight: 25-45 parts of rubber oil, 1-5 parts of hot melt adhesive grade elastomer, 1-11 parts of styrene-butadiene-styrene block copolymer, 1-8 parts of tackifying rubber, 4-16 parts of desulfurized rubber, 5-8 parts of high-temperature resin, 10-25 parts of tackifying resin, 4-35 parts of nanoscale talcum powder and 1-2 parts of white carbon black powder, and has good self-healing capability and stripping capability. However, the components and the preparation method are complex, the requirements on raw materials are strict, the nano-scale talcum powder and the superfine white carbon black powder are needed, and the self-healing capability and the stripping capability of the product depend on the fineness of the white carbon black, so that the production cost of the product is greatly increased, and the product is not suitable for wide application.

Therefore, the development of a high-molecular waterproof material with remarkable waterproof effect, excellent weather resistance, mechanical property and flame retardance and high bonding strength has very important significance for promoting the development of waterproof material industry.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide an anti-aging high-molecular flame-retardant waterproof material and a preparation method thereof, wherein the preparation method has the advantages of simple process, convenience in operation, low requirements on equipment and reaction conditions, and suitability for continuous large-scale production; the prepared macromolecular waterproof material has excellent mechanical property, weather resistance, aging resistance and flame retardance, obvious waterproof effect and high economic value and social value.

The invention is realized by the following technical scheme: the preparation method of the anti-aging high-molecular flame-retardant waterproof material is characterized by comprising the following steps of:

step S1, preparation of triazine based trifluoroterephthalonitrile-based polymerizable monomer: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2-amino-3, 5, 6-trifluoro terephthalonitrile, a basic catalyst and a polymerization inhibitor into an organic solvent, stirring and reacting for 4-6 hours at 70-80 ℃, removing the organic solvent by rotary evaporation, adding dichloromethane and water in a mass ratio of 1 (2-3), layering, taking an organic phase, removing water by anhydrous magnesium sulfate, filtering, and finally removing dichloromethane by rotary evaporation to obtain the triazine polymerized monomer based on trifluoro terephthalonitrile;

step S2, preparation of copolymer: adding the trifluoro-terephthalonitrile triazine-based polymerized monomer prepared in the step S1, methyl vinyl di (butanone oxime) silane, 4-vinylaniline, allyl boronic acid pinacol ester and an initiator into a high-boiling-point solvent, performing ultrasonic treatment for 10-20 minutes, performing ultrasonic microwave treatment for 20-30 minutes at 70-80 ℃ in the atmosphere of nitrogen or inert gas, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and drying in a vacuum drying oven at 80-90 ℃ to constant weight to obtain a copolymer;

step S3, forming the high polymer waterproof material: uniformly mixing the copolymer prepared in the step S2, ethylene propylene diene monomer, PVC resin, plasticizer, 2-bis- (4-glycinyloxybenzene) propane and azobisisobutyronitrile, then putting into a hot mixer, stirring for 20-30 minutes at 80-90 ℃, then raising the temperature to 110-120 ℃, and stirring again for 15-20 minutes to obtain a mixture; and then putting the obtained mixture into an extruder, and rolling, drawing, rolling and molding the extrudate to obtain the high-molecular waterproof material.

Preferably, the molar ratio of the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the 2-amino-3, 5, 6-trifluoroterephthalonitrile to the basic catalyst to the polymerization inhibitor to the organic solvent is 1:2 (0.8-1.2) to 0.3 (10-15).

Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.

Preferably, the polymerization inhibitor is at least one of chloranil and 1, 4-naphthoquinone.

Preferably, the organic solvent is one of tetrahydrofuran, acetone, chloroform and acetonitrile.

Preferably, the mass ratio of the trifluoroterephthalonitrile-based triazine type polymerizable monomer, the methylvinyldi (butanone oxime) silane, the 4-vinylaniline, the allyl boronic acid pinacol ester, the initiator and the high-boiling-point solvent in the step S2 is 1:0.5:0.8:0.3 (0.02-0.04): 10-15).

Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the inert gas is one of helium, neon and argon.

Preferably, the ultrasonic microwave treatment conditions are as follows: the ultrasonic power is 500-1000W, and the microwave power is 300-500W.

Further, in the step S3, the mass ratio of the copolymer, the ethylene propylene diene monomer, the PVC resin, the plasticizer, the 2, 2-bis- (4-glycidyloxybenzene) propane and the azobisisobutyronitrile is 100 (25-35): 10-20): 8-15: (3-5): 1-2).

Preferably, the plasticizer is at least one of epoxidized soybean oil, epoxy acetyl methyl linoleate, epoxy butyl furoate and epoxy butyl pupate oleate.

The invention also aims to provide the high-molecular flame-retardant waterproof material prepared by the preparation method of the aging-resistant high-molecular flame-retardant waterproof material.

Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:

(1) the anti-aging high-molecular flame-retardant waterproof material provided by the invention is simple and easy to operate in a preparation method, convenient to construct, low in requirements on equipment and reaction conditions, and suitable for continuous large-scale production.

(2) The aging-resistant high-molecular flame-retardant waterproof material provided by the invention overcomes the defects that the traditional high-molecular coiled material on the market is generally high in manufacturing cost, easy to damage, poor in performances such as waterproof effect, aging resistance, flame retardance, puncture resistance and corrosion resistance and insufficient in adhesive performance, and has the advantages of excellent mechanical property, weather resistance, aging resistance and flame retardance, remarkable waterproof effect and high economic value and social value.

(3) The invention provides an aging-resistant high-molecular flame-retardant waterproof material which is prepared by extrusion molding of a copolymer, ethylene propylene diene monomer, PVC resin, a plasticizer, 2-bis- (4-glycinyloxybenzene) propane, azobisisobutyronitrile and the like, combines the performance advantages of the ethylene propylene diene monomer, the PVC resin, a copolymer based on trifluoro-p-phenylenedinitrile triazine polymerization type monomer/methyl vinyl bis (butanone oxime) silane/4-vinylaniline/allyl boronic acid pinacol ester, has good weather resistance, obvious waterproof effect and excellent mechanical property, wherein the molecular chain of the copolymer contains the trifluoro-p-phenylenedinitrile and triazine structures, under the combined action of the conjugate effect, the electronic effect and the steric effect, the weather resistance and the waterproof performance of the paint are obviously improved, and the performance stability is effectively improved. Methyl vinyl di (butanone oxime) silane structural units introduced into a copolymer molecular chain and active hydroxyl and amino groups on the trifluoro-terephthalonitrile triazine-based polymer monomer can effectively improve the bonding strength of the material through a bridging effect, and the introduction of allyl boronic acid pinacol ester structural units can simultaneously improve the flame retardance, the waterproofness and the weather resistance of the material. The introduction of the 4-vinylaniline structural unit provides a reaction site for subsequent crosslinking, curing and forming.

(4) According to the aging-resistant high-molecular flame-retardant waterproof material provided by the invention, amino groups on the copolymer are easy to chemically react with chlorine on PVC resin and 2, 2-bis- (4-glycinyloxybenzene) propane on a cross-linking agent in a forming stage to form a three-dimensional network structure, and under the action of azodiisobutyronitrile, the copolymer, ethylene propylene diene monomer and PVC resin are easy to undergo a free radical graft polymerization reaction, so that the crosslinking degree is further improved, and the comprehensive performance of the material is effectively improved; the addition of the ethylene propylene diene monomer can also endow the material with excellent toughness.

(5) According to the aging-resistant high-molecular flame-retardant waterproof material provided by the invention, in the preparation process of the copolymer, ultrasonic microwave synergistic effect treatment is adopted, so that the reaction can be accelerated, and the obtained copolymer has higher yield and better comprehensive performance.

Detailed Description

In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.

The raw materials used in the following examples of the present invention were all purchased commercially, wherein the PVC resin was purchased from Ningxia jin Yi Yuan chemical group Co., Ltd., model SG-4. The ethylene propylene diene monomer is unvulcanized ethylene propylene diene monomer and is purchased from ethylene propylene diene monomer company Limited.