CN112321985B

CN112321985B - MMA (methyl methacrylate) polymer material and preparation method thereof

Info

Publication number: CN112321985B
Application number: CN202011313844.3A
Authority: CN
Inventors: 韩嘉成; 王鹏; 安泰; 陈伟清; 许欣; 于翔; 吕凤浩; 赵洁
Original assignee: Tianjin Highway Engineering General Co
Current assignee: Tianjin Highway Engineering General Co
Priority date: 2020-11-20
Filing date: 2020-11-20
Publication date: 2022-09-30
Anticipated expiration: 2040-11-20
Also published as: CN112321985A

Abstract

The application relates to an MMA polymer material and a preparation method thereof, which belong to the technical field of anti-skid pavement materials and comprise a mixture, anti-skid aggregates and an additive; the mixture comprises, by weight, 80-90 parts of methyl methacrylate, 20-30 parts of lauryl acrylate and 20-40 parts of epoxy resin modified acrylate; the anti-skid aggregate comprises 5-8 parts of bauxite, 10-20 parts of quartz sand, 5-10 parts of diamond and 3-5 parts of basalt particles; the additive comprises 0.2-0.3 part of accelerant, 0.25-0.4 part of curing agent, 0.5-0.7 part of p-dimethylaminomethylbenzene, 1-2 parts of anti-cracking fiber and 2-3 parts of inorganic filler. The application has the effect of improving the weather resistance and the folding resistance of the anti-skid pavement material.

Description

MMA polymer material and preparation method thereof

Technical Field

The application relates to the field of anti-skid pavement materials, in particular to an MMA (methyl methacrylate) polymer material and a preparation method thereof.

Background

China's economy develops rapidly, cars keep a certain amount to increase in a blowout mode, and the traditional cement and asphalt roads cannot meet the requirements of novel urbanization. In order to prevent and reduce the occurrence of safety accidents, all countries in the world are dedicated to the functional safety research of road traffic, colored anti-skid road surfaces are paved on sidewalks, drivers can judge and decelerate in advance by spraying striking road markings and warning slogans, and diversion guide lanes and the like are arranged at crossroads.

At present, the epoxy resin material is widely applied to the field of color antiskid pavement due to the excellent adhesive property of the epoxy resin material. However, epoxy resin cementing materials belong to brittle materials, and cracks and interlayer cracks are easily generated under the action of impact load of vehicles; in addition, the epoxy resin is easy to age under long-term ultraviolet irradiation, the toughness of the epoxy resin is further reduced, and the cracking condition of the anti-skid thin layer of the epoxy resin is increased.

In view of the above-mentioned related art, the inventors consider that the existing anti-skid pavement material has the defect of poor weather resistance and folding resistance.

Disclosure of Invention

In order to improve the weather resistance and the folding resistance of the antiskid pavement material, the application provides an MMA polymer material and a preparation method thereof.

In a first aspect, the present application provides an MMA polymer material, which adopts the following technical scheme:

an MMA polymer material comprises a mixture, an anti-skid aggregate and an additive; the mixture comprises, by weight, 80-90 parts of methyl methacrylate, 20-30 parts of lauryl acrylate and 20-40 parts of epoxy resin modified acrylate;

the anti-skid aggregate comprises 5-8 parts of bauxite, 10-20 parts of quartz sand, 5-10 parts of diamond and 3-5 parts of basalt particles;

the additive comprises 0.2-0.3 part of accelerant, 0.25-0.4 part of curing agent, 0.5-0.7 part of p-dimethylaminomethylbenzene, 1-2 parts of anti-cracking fiber and 2-3 parts of inorganic filler.

By adopting the technical scheme, the methyl methacrylate has better strength, the lauryl acrylate has better toughness, and the methyl methacrylate and the lauryl acrylate are matched to achieve the interpenetrating of molecular size and show obvious interpenetrating synergistic effect, so that a polymer formed by copolymerization has better mechanical property. Meanwhile, in the copolymerization process of methyl methacrylate and lauryl acrylate, the methyl methacrylate and the acrylic ester modified by epoxy resin are subjected to reaction and organic synthesis, the cross permeation and the mutual interweaving action among molecular chains are further increased, and different molecular chains are intertwined to enable microstructures of different tissues to be refined, so that the dispersibility of a system is improved, the compatibility of each component is improved, the purpose of polymer performance complementation is achieved, and the weather resistance, the breaking strength and the compressive strength of the polymer are improved.

In addition, the epoxy resin contains polar groups and active groups such as epoxy groups, ether groups and hydroxyl groups, so that the epoxy resin has excellent adhesive property, wear resistance and temperature resistance, and therefore, the epoxy resin is introduced into the acrylate to obtain the epoxy resin modified acrylate, so that the prepared polymer has good adhesive property, the increase of the connection strength among materials is facilitated, and the cracking condition is reduced. Meanwhile, the bonding firmness of the anti-skid aggregate can be increased, and the condition that the anti-skid aggregate is separated due to rolling of a vehicle is reduced, so that the MMA anti-skid material has a better anti-skid effect.

The antiskid aggregate is prepared by the cooperation of bauxite, quartz sand, diamond and basalt particles, so that the prepared MMA polymer antiskid material can form an antiskid pavement surface layer with larger structural depth and high friction force, the friction coefficient of an MMA polymer thin layer is effectively increased, and the antiskid effect is improved.

In addition, the crack resistant fibers increase the toughness of the MMA polymer, thereby increasing the flexural strength of the MMA polymer and reducing the cracking condition of the MMA polymer material. The p-dimethylaminotoluene has excellent sun-proof, ultraviolet-proof and ageing-resistant performances, and is beneficial to improving the weather resistance of the MMA polymer, so that the service life of the MMA polymer is prolonged.

Preferably, the particle size of the anti-slip aggregate is 1-4 mm.

Preferably, the preparation method of the epoxy resin modified acrylate comprises the following steps:

(1) preparing a modified solution, namely mixing 5.5-6.5 parts of epoxy resin E-44, 0.1-0.2 part of chain transfer agent and 30-40 parts of solvent, and heating and dissolving at 60-80 ℃ to obtain the modified solution;

(2) preparing a monomer solution, namely mixing 75-85 parts of acrylic monomers and 2-3 parts of an initiator to obtain the monomer solution;

(3) and (3) preparing modified acrylic ester, namely heating the modified solution to 120-130 ℃, dropwise adding the monomer solution into the modified solution under the condition of continuous stirring, and continuously stirring for 1-3h after dropwise adding is finished to obtain the epoxy resin modified acrylic ester.

By adopting the technical scheme, the acrylate modified by the epoxy resin has the characteristics of high modulus, high strength, chemical resistance and excellent corrosion resistance of the epoxy resin, and good glossiness, fullness and weather resistance of the acrylic resin, and meanwhile, the acrylate modified by the epoxy resin has good flexibility, adhesive force and impact resistance.

Preferably, the acrylic monomer comprises a soft monomer, a hard monomer and a functional monomer, wherein the weight ratio of the soft monomer to the hard monomer to the functional monomer is (25-35) to 10 (2-3); the soft monomer comprises one or more of ethyl acrylate, butyl acrylate and isooctyl acrylate; the hard monomer comprises one or two of acrylonitrile and styrene; the functional monomer comprises one or more of acrylic acid and hydroxyethyl acrylate.

By adopting the technical scheme, the acrylic monomer is composed of the soft monomer, the hard monomer and the functional monomer, so that the prepared epoxy resin modified acrylate has multiple performances, and the comprehensive performance of the epoxy resin modified acrylate is improved.

The glass transition temperature of the soft monomer is low, so that the adhesive property of the epoxy resin modified acrylate can be improved, but the problem of reduced cohesive force of the epoxy resin modified acrylate is easily caused by the high content of the soft monomer; the glass transition temperature of the hard monomer is higher, so that the cohesive force of the epoxy resin modified acrylate can be increased; meanwhile, the functional monomer can endow the epoxy resin modified acrylate with reaction characteristics, and acrylic polymer chains are mutually connected, so that the cohesive strength of the epoxy resin modified acrylate is greatly improved. The soft monomer, the hard monomer and the functional monomer are cooperatively matched and jointly play a role, and the hard monomer and the functional monomer can make up for the defect of insufficient cohesive force of the soft monomer, so that the adhesive property, the cracking resistance and other properties of the epoxy resin modified acrylate are improved.

Preferably, the inorganic filler is an iron oxide toner.

Preferably, the accelerant is one or more of cobalt naphthenate, N-dimethylaniline and vanadium phosphate. More preferably, the accelerator is N, N-dimethylaniline.

By adopting the technical scheme, the N, N-dimethylaniline is mainly used as a curing accelerator for unsaturated resin, so that the curing speed is accelerated, and in addition, the N, N-dimethylaniline can absorb ultraviolet rays, so that the ageing resistance of the MMA polymer is improved.

Preferably, the curing agent is one or more of dibenzoyl peroxide, cyclohexanone peroxide and methyl ethyl ketone peroxide.

By adopting the technical scheme, dibenzoyl peroxide, cyclohexanone peroxide and methyl ethyl ketone peroxide are adopted as curing agents, so that on one hand, the reaction is complete, the quality of the prepared polymer is stable, and on the other hand, the reaction speed is convenient to control artificially; in addition, dibenzoyl peroxide, cyclohexanone peroxide and methyl ethyl ketone peroxide are all normal-temperature curing agents, so that the use conditions are mild, and the operation is convenient.

Preferably, the additive also comprises 1-2 parts of nitrogen-doped nano titanium dioxide, and the preparation method of the nitrogen-doped nano titanium dioxide comprises the following steps: soaking 2-3 parts of nano titanium dioxide in 50-60mL ammonia water with the molar concentration of 0.15-0.25mol/L, filtering, drying, and calcining at the temperature of 500-600 ℃ for 30-40min to obtain the nitrogen-doped nano titanium dioxide.

By adopting the technical scheme, the nano titanium dioxide has the functions of super-hydrophilicity, photocatalysis, organic matter decomposition, negative oxygen ion release and the like under the irradiation of light, namely the self-cleaning function. The nanometer titanium dioxide is doped with nitrogen element, so that a doping energy level can be introduced into a forbidden band, the forbidden band is narrowed, light with longer wavelength can be absorbed, the edge of a light absorption band is red-shifted, the light response range is widened, the quantum efficiency is improved, the photocatalysis efficiency is improved, the efficiency of degrading organic pollutants by the nanometer titanium dioxide under the irradiation of sunlight is improved, and the self-cleaning function of an MMA polymer material is further improved.

Preferably, the nitrogen-doped nano titanium dioxide adopts modified nitrogen-doped nano titanium dioxide, and the modification method comprises the following steps:

1) adding 1.0-2.0 parts of the obtained nitrogen-doped nano titanium dioxide into an ethanol solution, and continuously stirring to obtain a dispersion liquid;

2) adding 1.0-2.0 parts of organosilane coupling agent into the dispersion liquid, continuously stirring for 2.5-3.5h, filtering, and drying to obtain the modified nitrogen-doped nano titanium dioxide, wherein the organosilane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (2-methoxyethoxy) silane.

By adopting the technical scheme, the silane coupling agent containing vinyl is adopted to carry out silanization treatment on the silicon dioxide coated on the surface of the nitrogen-doped nano titanium dioxide, so that the surface of the nitrogen-doped nano titanium dioxide contains vinyl, the compatibility of the nitrogen-doped nano titanium dioxide and a monomer can be improved, the agglomeration is avoided, and the vinyl can be copolymerized with an acrylic monomer, so that the reaction stability in the polymerization process is ensured. In addition, the organosilane coupling agent is beneficial to increasing the connection strength among the raw materials, so that the falling-off condition of the anti-skid aggregate is reduced, and the anti-skid effect of the MMA polymer anti-skid material is ensured.

In a second aspect, the present application provides a method for preparing an MMA polymer material, which adopts the following technical scheme:

a method for preparing an MMA polymer material comprises the following steps:

s1, mixing methyl methacrylate, lauryl acrylate and epoxy resin modified acrylate, and uniformly stirring to obtain a mixture;

s2, adding an accelerant into the mixture obtained in the step S1, uniformly stirring, sealing and standing for 0.8-1.0h for polymerization reaction to obtain an MMA polymer;

and S3, adding the anti-skid aggregate into the MMA polymer in the step S2, uniformly stirring, adding the rest additive, and stirring to obtain the MMA polymer anti-skid material.

In summary, the present application includes at least one of the following beneficial technical effects:

1. according to the application, methyl methacrylate, lauryl acrylate and epoxy resin modified acrylate are matched with each other, so that different molecular chains are subjected to cross permeation and are interwoven with each other, the compatibility of each component is improved, the purpose of polymer performance complementation is achieved, and the weather resistance, the breaking strength and the compressive strength of the polymer are improved;

2. the acrylate modified by the epoxy resin has the characteristics of high modulus, high strength and corrosion resistance of the epoxy resin and good weather resistance of the acrylate, so that the acrylate modified by the epoxy resin has good flexibility, adhesive force and impact resistance;

3. the epoxy resin has excellent adhesive property, and the modified acrylate has good adhesive property by adopting the epoxy resin, so that the connection strength among the raw materials is increased, the anti-cracking property is improved, and the cracking condition of the antiskid pavement is reduced;

4. by doping nitrogen elements in the nano-silica, the photocatalytic blanking of the nano-silica can be improved, so that the efficiency of degrading organic pollutants is improved, and the self-cleaning function of an MMA polymer material is improved;

5. the application's MMA polymer anti-skidding material is the anti-skidding thin layer that is formed by closely knit anti-skidding aggregate cementation, has better conduction and the effect of decomposing the audio frequency, can reduce the noise that vehicle tire and anti-skidding thin layer contact produced in going, can also produce the diffuse reflection phenomenon and pass on the partial noise consumption on the road surface with the sound of engine totally, reaches the effect of making an uproar.

Detailed Description

The present application will be described in further detail with reference to examples and comparative examples.

In the following examples:

the anti-cracking fiber is purchased from Wuhan Henhuanda New Material Co.

Preparation example 1

The preparation method of the epoxy resin modified acrylate comprises the following steps:

(1) preparing a modified solution, namely mixing 5.5g of epoxy resin E-44, 0.2g of dodecyl mercaptan and 30g of propylene glycol monomethyl ether acetate, and heating and dissolving at 80 ℃ to obtain the modified solution;

(2) preparing a monomer solution, namely mixing 75g of acrylic monomers and 3g of azodiisobutyronitrile to obtain the monomer solution; the acrylic monomer comprises ethyl acrylate, acrylonitrile and acrylic acid, and the weight ratio of the ethyl acrylate, the acrylonitrile and the acrylic acid is 25:10: 3;

(3) and (3) preparing modified acrylic ester, namely heating the modified solution to 120 ℃, dropwise adding the monomer solution into the modified solution under the condition of continuous stirring, and continuously stirring for 3 hours after dropwise adding is finished to obtain the epoxy resin modified acrylic ester.

Preparation example 2

(1) preparing a modified solution, namely mixing 5g of epoxy resin E-44, 0.15g of dodecyl mercaptan and 35g of propylene glycol methyl ether acetate, and heating and dissolving at 70 ℃ to obtain the modified solution;

(2) preparing a monomer solution, namely mixing 80g of acrylic monomers and 2.5g of azobisisobutyronitrile to obtain the monomer solution; the acrylic monomer comprises isooctyl acrylate, styrene and hydroxyethyl acrylate, and the weight ratio of the isooctyl acrylate, the styrene and the hydroxyethyl acrylate is 30:10: 2.5;

(3) and (3) preparing modified acrylic ester, namely heating the modified solution to 125 ℃, dropwise adding the monomer solution into the modified solution under the condition of continuous stirring, and continuously stirring for 2 hours after dropwise adding is finished to obtain the epoxy resin modified acrylic ester.

Preparation example 3

(1) preparing a modified solution, namely mixing 6.5g of epoxy resin E-44, 0.1g of dodecyl mercaptan and 40g of propylene glycol monomethyl ether acetate, and heating and dissolving at 60 ℃ to obtain the modified solution;

(2) preparing a monomer solution, namely mixing 85g of acrylic monomers and 2g of azodiisobutyronitrile to obtain the monomer solution; the acrylic monomer comprises isooctyl acrylate, styrene and hydroxyethyl acrylate, and the weight ratio of isooctyl acrylate, styrene and hydroxyethyl acrylate is 35:10: 2;

(3) and (3) preparing modified acrylic ester, namely heating the modified solution to 130 ℃, dropwise adding the monomer solution into the modified solution under the condition of continuous stirring, and continuously stirring for 1h after dropwise adding is finished to obtain the epoxy resin modified acrylic ester.

Preparation example 4

The preparation method of the nitrogen-doped titanium dioxide comprises the following steps: soaking 2g of nano titanium dioxide in 60mL of ammonia water with the molar concentration of 0.25mol/L for 20min, filtering, drying, calcining at 500 ℃ for 40min, and cooling to obtain the nitrogen-doped nano titanium dioxide.

Preparation example 5

The preparation method of the nitrogen-doped titanium dioxide comprises the following steps: soaking 2.5g of nano titanium dioxide in 55mL of ammonia water with the molar concentration of 0.2mol/L for 20min, filtering, drying, calcining at 550 ℃ for 35min, and cooling to obtain the nitrogen-doped nano titanium dioxide.

Preparation example 6

The preparation method of the nitrogen-doped titanium dioxide comprises the following steps: 3g of nano titanium dioxide is soaked in 50mL of ammonia water with the molar concentration of 0.15mol/L for 20min, then the nano titanium dioxide is filtered, dried, calcined at 600 ℃ for 35min and cooled to obtain the nitrogen-doped nano titanium dioxide.

Preparation example 7

The preparation method of the modified nitrogen-doped titanium dioxide comprises the following steps:

1) adding 1.0g of the obtained nitrogen-doped nano titanium dioxide into 20mL of 75% ethanol solution, and continuously stirring to obtain a dispersion liquid;

2) and adding 2.0g of vinyltriethoxysilane into the dispersion, continuously stirring for 2.5h, carrying out suction filtration, and drying to obtain the modified nitrogen-doped nano titanium dioxide.

Preparation example 8

1) adding 1.5g of the obtained nitrogen-doped nano titanium dioxide into 20mL of 75% ethanol solution, and continuously stirring to obtain a dispersion liquid;

2) and adding 1.5g of vinyl trimethoxy silane into the dispersion liquid, continuously stirring for 3 hours, carrying out suction filtration, and drying to obtain the modified nitrogen-doped nano titanium dioxide.

Preparation example 9

1) adding 2g of the obtained nitrogen-doped nano titanium dioxide into 20mL of 75% ethanol solution, and continuously stirring to obtain a dispersion liquid;

2) and adding 1g of vinyl tri (2-methoxyethoxy) silane into the dispersion, continuously stirring for 3.5 hours, carrying out suction filtration, and drying to obtain the modified nitrogen-doped nano titanium dioxide.

Example 1

An MMA polymer material produced by the process comprising the steps of:

s1, mixing 80g of methyl methacrylate, 30g of lauryl acrylate and 20g of the epoxy resin modified acrylate prepared in the preparation example 1, and uniformly stirring to obtain a mixture;

s2, adding 0.3g of cobalt naphthenate into the mixture obtained in the step S1, uniformly stirring, and sealing and standing for 0.8h to perform polymerization reaction to obtain an MMA polymer;

s3, adding 8g of bauxite, 10g of quartz sand, 10g of diamond and 3g of basalt particles into the MMA polymer in the step S2, uniformly stirring, then sequentially adding 0.7g of p-dimethylaminomethyl toluene, 1g of anti-cracking fiber, 3g of iron oxide toner and 0.25g of dibenzoyl peroxide, and stirring for 5min to obtain an MMA polymer anti-skid material; wherein the particle sizes of the bauxite, the quartz sand, the diamond and the basalt particle are all 1-4 mm.

Example 2

An MMA polymer material produced by the process comprising the steps of:

s1, mixing 85g of methyl methacrylate, 30g of lauryl acrylate and 30g of the epoxy resin modified acrylate prepared in the preparation example 2, and uniformly stirring to obtain a mixture;

s2, adding 0.25g of N, N-dimethylaniline into the mixture obtained in the step S1, uniformly stirring, and standing in a sealed state for 0.9h to perform polymerization reaction to obtain an MMA polymer;

and S3, adding 6.5g of bauxite, 15g of quartz sand, 8g of diamond and 4g of basalt particles into the MMA polymer in the step S2, uniformly stirring, then sequentially adding 0.6g of p-dimethylaminomethylbenzene, 1.5g of anti-cracking fibers, 2.5g of iron oxide toner and 0.3g of cyclohexanone peroxide, and stirring for 5min to obtain the MMA polymer anti-skid material, wherein the particle sizes of the bauxite, the quartz sand, the diamond and the basalt particles are all 1-4 mm.

Example 3

An MMA polymer material produced by the process comprising the steps of:

s1, mixing 90g of methyl methacrylate, 20g of lauryl acrylate and 40g of the epoxy resin modified acrylate prepared in the preparation example 3, and uniformly stirring to obtain a mixture;

s2, adding 0.2g of vanadium phosphate into the mixture obtained in the step S1, uniformly stirring, and standing in a sealed state for 1 hour to perform polymerization reaction to obtain an MMA polymer;

s3, adding 5g of bauxite, 20g of quartz sand, 5g of diamond and 5g of basalt particles into the MMA polymer in the step S2, uniformly stirring, then sequentially adding 0.5g of p-dimethylaminotoluene, 2g of anti-cracking fiber, 1g of iron oxide toner and 0.4g of methyl ethyl ketone peroxide, and stirring for 5min to obtain the MMA polymer anti-skid material.

Example 4

An MMA polymer material was produced by a method different from example 2 in that 1g of the nitrogen-doped nano titanium dioxide obtained in production example 4 was further added before adding p-dimethylaminotoluene in step S2.

Example 5

An MMA polymer material obtained by the following method differs from example 2 in that 1.5g of the nitrogen-doped nano titanium dioxide obtained in production example 5 was further added before p-dimethylaminotoluene was added in step S2.

Example 6

An MMA polymer material was produced by a method different from example 2 in that, in step S2, 2g of the nitrogen-doped nano titanium dioxide obtained in production example 6 was further added before the addition of p-dimethylaminotoluene.

Example 7

An MMA polymer material was produced by a method different from example 5 in that, in step S2, the modified nitrogen-doped nano titanium dioxide produced in production example 7 was used as the nitrogen-doped nano titanium dioxide.

Example 8

An MMA polymer material was produced by a method different from example 5 in that, in step S2, the modified nitrogen-doped nano titanium dioxide produced in production example 8 was used as the nitrogen-doped nano titanium dioxide.

Example 9

An MMA polymer material was produced by a method different from example 5 in that, in step S2, the nitrogen-doped nano titania was produced using the modified nitrogen-doped nano titania produced in production example 9.

Comparative example 1

An MMA polymer material was prepared by the following method, differing from example 2 in that 70g of methyl methacrylate, 35g of lauryl acrylate, 15g of epoxy resin-modified acrylate, 10g of bauxite, 8g of quartz sand, 13g of diamond, 2g of basalt particles, 0.4g of N, N-dimethylaniline, 0.9g of p-dimethylaminotoluene, 0.5g of anti-cracking fiber, 4g of iron oxide toner and 0.1g of cyclohexanone peroxide were used.

Comparative example 2

An MMA polymer material was produced by the following method, differing from example 2 in that 100g of methyl methacrylate, 15g of lauryl acrylate, 45g of epoxy-modified acrylate, 3g of bauxite, 25g of quartz sand, 3g of diamond, 8g of basalt particles, 0.1g of N, N-dimethylaniline, 0.15g of p-dimethylaminotoluene, 0.9g of anti-cracking fiber, 1g of iron oxide toner, and 0.5g of cyclohexanone peroxide.

Comparative example 3

An MMA polymer material was prepared by the following method, differing from example 2 in that the epoxy-modified acrylic resin was replaced with an equal amount of unmodified acrylic resin.

Comparative example 4

An MMA polymer material was prepared by the following method, differing from example 2 in that no anti-splitting fibres were added.

Performance detection

The MMA polymer non-slip materials obtained in examples 1 to 9 and comparative examples 1 to 4 were subjected to performance tests, the results of which are shown in Table 1, and the specific tests were as follows:

1. the compressive strength, the flexural strength, the tensile bonding strength and the dry friction coefficient were determined according to GB/T22374-2008.

2. Durability was measured according to JG/T25-1999.

TABLE 1 test results

Combining examples 1-9 and comparative examples 1-4, and combining table 1, it can be seen that the folding strength, compressive strength, tensile bonding strength, dry friction coefficient and durability of the MMA polymer anti-skid materials in examples 1-9 are all superior to those of comparative examples 1-4, which indicates that the formulation and proportion of the application are scientific and reasonable, and the prepared MMA polymer anti-skid materials have better folding strength, compressive strength, weather resistance and anti-skid performance through the synergistic interaction among the raw materials.

By combining examples 7-9 and example 5, and by combining table 1, it can be seen that the dry friction coefficient in examples 7-9 is better than that in example 5, which indicates that the nano-silica modified by the organosilicon coupling agent can increase the connection strength among the raw materials, thereby reducing the falling off of the anti-skid aggregate, improving the dry friction coefficient of the MMA polymer anti-skid material, and ensuring the anti-skid effect of the MMA polymer anti-skid material.

By combining the example 2 and the comparative example 3 and the table 1, the flexural strength, the compressive strength and the tensile bonding strength in the example 2 are higher than those in the comparative example 1, which shows that the acrylate is modified by the epoxy resin, so that the epoxy resin modified acrylate has the characteristics of high modulus, high strength, chemical resistance and excellent corrosion resistance of the epoxy resin, and good weather resistance of the acrylic resin, and meanwhile, the epoxy resin modified acrylate has good flexibility, adhesive force and impact resistance.

Combining example 2 and comparative example 4, and table 1, it can be seen that the flexural strength in example 2 is that comparative example 4, which illustrates that the addition of crack resistant fibers increases the toughness of the MMA polymer, thereby increasing the flexural strength of the MMA polymer and reducing the instances of cracking of the MMA polymer material.

The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.

Claims

1. An MMA polymeric material, characterized by: comprises a mixture, an anti-skid aggregate and an additive; the mixture comprises, by weight, 80-90 parts of methyl methacrylate, 20-30 parts of lauryl acrylate and 20-40 parts of epoxy resin modified acrylate;

the additive comprises 0.2 to 0.3 portion of accelerant, 0.25 to 0.4 portion of curing agent, 0.5 to 0.7 portion of p-dimethylaminomethylbenzene, 1 to 2 portions of anti-cracking fiber and 2 to 3 portions of inorganic filler;

the additive also comprises 1-2 parts of nitrogen-doped nano titanium dioxide, and the preparation method of the nitrogen-doped nano titanium dioxide comprises the following steps: soaking 2-3 parts of nano titanium dioxide in 50-60mL ammonia water with the molar concentration of 0.15-0.25mol/L, filtering, drying, and calcining at the temperature of 500-600 ℃ for 30-40min to obtain nitrogen-doped nano titanium dioxide;

the nitrogen-doped nano titanium dioxide adopts modified nitrogen-doped nano titanium dioxide, and the modification method comprises the following steps:

2) adding 1.0-2.0 parts of organosilane coupling agent into the dispersion liquid, continuously stirring for 2.5-3.5h, carrying out suction filtration, and drying to obtain the modified nitrogen-doped nano titanium dioxide, wherein the organosilane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (2-methoxyethoxy) silane.

2. An MMA polymer material according to claim 1, wherein: the particle size of the antiskid aggregate is 1-4 mm.

3. An MMA polymer material according to claim 1, wherein: the preparation method of the epoxy resin modified acrylate comprises the following steps:

4. An MMA polymer material according to claim 3, wherein: the acrylic monomer comprises a soft monomer, a hard monomer and a functional monomer, wherein the weight ratio of the soft monomer to the hard monomer to the functional monomer is (25-35) to (2-3) 10; the soft monomer comprises one or two of ethyl acrylate and isooctyl acrylate; the hard monomer comprises one or two of acrylonitrile and styrene; the functional monomer comprises one or more of acrylic acid and hydroxyethyl acrylate.

5. An MMA polymer material according to claim 1, wherein: the inorganic filler is ferric oxide toner.

6. An MMA polymer material according to claim 1, wherein: the accelerant adopts one or more of cobalt naphthenate, N-dimethylaniline and vanadium phosphate.

7. An MMA polymer material according to claim 1, wherein: the curing agent is one or more of dibenzoyl peroxide, cyclohexanone peroxide and methyl ethyl ketone peroxide.

8. A method for preparing an MMA polymer material according to any one of claims 1 to 7, comprising the steps of: