阅读说明：本技术 一种高机械性能的SiO2-石墨烯改性酚醛树脂材料及其制法 (SiO with high mechanical property2-graphene modified phenolic resin material and preparation method thereof ) 是由 刘裕玲 于 2020-07-08 设计创作，主要内容包括：本发明涉及酚醛树脂技术领域,且公开了一种高机械性能的SiO<Sub>2</Sub>-石墨烯改性酚醛树脂材料,首先以羟基化石墨烯为原料,十六烷三甲基溴化铵为模板剂,正硅酸乙酯为硅源,通过软模板法,制备得到SiO<Sub>2</Sub>修饰石墨烯复合材料,该一种高机械性能的SiO<Sub>2</Sub>-石墨烯改性酚醛树脂材料,硅烷偶联剂γ-(2,3-环氧丙氧)丙基三甲氧基硅烷通过环氧键和Si-O与酚醛树脂中的羟甲基和酚羟基聚合,增加了改性后酚醛树脂的固化交联度,使复合后的酚醛树脂材料力学性能得到了极大提高,同时SiO<Sub>2</Sub>-石墨烯复合材料具有非常好的机械性能,可以进一步提升酚醛树脂的弯曲强度和压缩强度等机械性能,而腰果酚的引入使改性酚醛树脂的分子量提高,树脂黏结SiO<Sub>2</Sub>的能力提高。(The invention relates to the technical field of phenolic resin, and discloses SiO with high mechanical property 2 Firstly, hydroxylated graphene is used as a raw material, cetyl trimethyl ammonium bromide is used as a template agent, tetraethoxysilane is used as a silicon source, and a soft template method is used to prepare the SiO modified phenolic resin material 2 Modified graphene composite material, high mechanical properties SiO 2 Graphene modified phenolic resin material, silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and hydroxymethyl in phenolic resin through epoxy bond and Si-OThe polymerization of the base and phenolic hydroxyl increases the curing crosslinking degree of the modified phenolic resin, greatly improves the mechanical property of the compounded phenolic resin material, and simultaneously improves the SiO property 2 The-graphene composite material has very good mechanical properties, can further improve the mechanical properties such as bending strength, compression strength and the like of the phenolic resin, and the introduction of cardanol improves the molecular weight of the modified phenolic resin and the SiO bonding of the resin 2 The ability of (a) to be improved.)

1. SiO with high mechanical property₂-a graphene-modified phenolic resin material, characterized in that: the high mechanical properties of SiO₂The preparation method of the graphene modified phenolic resin material comprises the following steps:

(1) adding hydroxylated graphene into a distilled water solvent, performing ultrasonic treatment for 60-120min by an ultrasonic device to obtain a hydroxylated graphene suspension, adding hexadecyl trimethyl ammonium bromide into the graphene suspension, adjusting the pH to 8-10, adding tetraethoxysilane, and performing magnetic stirring for 18-24h at the temperature of 30-50 ℃, wherein the mass ratio of the hydroxylated graphene to the hexadecyl trimethyl ammonium bromide to the tetraethoxysilane is 100:1800 plus 2200:800 plus 1000, washing and drying the product, and preparing to obtain SiO₂Modifying the graphene composite material;

(2) adding silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and SiO into absolute ethyl alcohol₂Carrying out ultrasonic reaction on graphene for 5-10h, drying the product, and preparing the epoxy functionalized SiO₂-graphene;

(3) adding cardanol and phenolic resin into a flask, stirring in water bath at 60-70 ℃, adding sodium hydroxide, stirring uniformly, and adding paraformaldehyde and functionalized SiO₂Reacting for 2-4h, heating to 80-100 ℃, and continuing to react for 40-60 min;

(4) filling the reaction material into a mold, carrying out hot press molding by a flat vulcanizing machine, cooling and demolding to prepare the SiO with high mechanical property₂-a graphene modified phenolic resin material.

2. A high mechanical property SiO as claimed in claim 1₂-a graphene-modified phenolic resin material, characterized in that: the ultrasonic device in the step (1) comprises a dispersing barrel, the inner wall of the dispersing barrel is fixedly connected with fillers, the inner wall of the fillers is fixedly connected with a dispersing chamber, the bottom of the inner wall of the dispersing barrel is fixedly connected with a spring, the top of the spring is fixedly connected with a buffering base, and the upper surface of the buffering base is fixedly connected with an ultrasonic dispersing deviceThe ultrasonic dispersion device comprises an ultrasonic dispersion device and is characterized in that an inclined plate is fixedly connected to the top of the ultrasonic dispersion device, a vibrating motor is fixedly connected to the lower surface of the inclined plate, a first feeding bin is fixedly connected to the upper surface of a dispersion barrel, a second feeding bin is fixedly connected to the right side of the first feeding bin, a stirring motor is fixedly connected to the left side of the second feeding bin, a stirring shaft is fixedly connected to the bottom of the stirring motor, and stirring blades are fixedly connected to the outer wall of the stirring shaft.

3. A high mechanical property SiO as claimed in claim 1₂-a graphene-modified phenolic resin material, characterized in that: the silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and SiO in the step (2)₂The mass ratio of graphene is 100: 40-60.

4. A high mechanical property SiO as claimed in claim 1₂-a graphene-modified phenolic resin material, characterized in that: the cardanol, the phenol, the sodium hydroxide, the paraformaldehyde and the functionalized SiO in the step (3)₂The mass ratio of graphene is 10-20:100:1-1.3:40-45: 0.5-3.

5. The high-mechanical-property SiO 2-graphene modified phenolic resin material as claimed in claim 1, wherein: the hot-press molding process in the step (4) is carried out for 6-8h under the condition of 70-90 ℃, and then is carried out for 8-10h under the condition of 110-130 ℃.

Technical Field

The invention relates to the technical field of phenolic resin, in particular to SiO with high mechanical property₂-graphene modified phenolic resin material and a preparation method thereof.

Background

The graphene being carbon atoms sp²After hybridization, the two-dimensional honeycomb network structure is formed by arranging the two-dimensional honeycomb network structure,the graphene is a novel two-dimensional nano material which is discovered to date and has the highest strength, the best toughness and the largest specific surface area, the special structure of the graphene endows the graphene with excellent mechanical properties, if the graphene is introduced into a high polymer material, the mechanical properties of the material can be effectively enhanced, and the graphene is widely applied to the fields of nano composite materials, energy storage, sensors and the like, while nano SiO₂Is a nano material with great industrial application prospect, has wide application field, and modified SiO₂Can be used as an additive to be added into materials such as rubber, plastics and the like, and can improve mechanical properties such as toughness, strength, wear resistance and the like of the plastics.

The phenolic resin is a general name of resins formed by phenols and aldehydes under the action of an acidic or basic catalyst, is the earliest synthetic polymer material in industrialization, has good heat resistance and forming performance, can be used as a material adhesive of a reinforcement, but the phenolic resin still has certain defects in certain aspects, such as large brittleness and poor toughness, because the structure of the phenolic resin is only a structure that methylene is connected with benzene rings, and the defects of the phenolic resin limit the application of the phenolic resin in certain fields, so that the mechanical performance of the phenolic resin needs to be improved.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides SiO with high mechanical property₂The graphene modified phenolic resin material and the preparation method thereof solve the problem of poor mechanical properties of phenolic resin such as bending strength, compression strength and the like.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: SiO with high mechanical property₂-graphene modified phenolic resin material, said high mechanical properties of SiO₂The preparation method of the graphene modified phenolic resin material comprises the following steps:

(1) adding hydroxylated graphene into distilled water solvent, performing ultrasonic treatment for 60-120min by an ultrasonic device to obtain hydroxylated graphene suspension, adding hexadecyl trimethyl ammonium bromide into the graphene suspension, adjusting pH to 8-10, adding tetraethoxysilane, and magnetically stirring at 30-50 DEG CStirring for 18-24h, wherein the mass ratio of the hydroxylated graphene to the hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:1800-2200:800-1000, washing and drying the product, and preparing to obtain SiO₂Modifying the graphene composite material;

(2) adding silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and SiO into absolute ethyl alcohol₂Carrying out ultrasonic reaction on graphene for 5-10h, drying the product, and preparing the epoxy functionalized SiO₂-graphene;

(3) adding cardanol and phenolic resin into a flask, stirring in water bath at 60-70 ℃, adding sodium hydroxide, stirring uniformly, and adding paraformaldehyde and functionalized SiO₂Reacting for 2-4h, heating to 80-100 ℃, and continuing to react for 40-60 min;

(4) filling the reaction material into a mold, carrying out hot press molding by a flat vulcanizing machine, cooling and demolding to prepare the SiO with high mechanical property₂-a graphene modified phenolic resin material.

Preferably, the ultrasonic device in step (1) includes the dispersion bucket, the inner wall fixedly connected with filler of dispersion bucket, the inner wall fixedly connected with dispersion room of filler, the bottom fixedly connected with spring of dispersion bucket inner wall, the top fixedly connected with buffer base of spring, buffer base's last fixed surface is connected with ultrasonic dispersion device, ultrasonic dispersion device's top fixedly connected with swash plate, the lower fixed surface of swash plate is connected with vibrating motor, the last fixed surface of dispersion bucket is connected with feeding storehouse one, the right side fixedly connected with feeding storehouse two of feeding storehouse, the left side fixedly connected with agitator motor of feeding storehouse two, agitator motor's bottom fixedly connected with (mixing) shaft, the outer wall fixedly connected with stirring leaf of (mixing) shaft.

Preferably, the silane coupling agents in the step (2) are gamma- (2, 3-glycidoxy) propyltrimethoxysilane and SiO₂The mass ratio of graphene is 100: 40-60.

Preferably, the cardanol, phenol, sodium hydroxide, paraformaldehyde and functionalized SiO in the step (3)₂-grapheneThe mass ratio of the components is 10-20:100:1-1.3:40-45: 0.5-3.

Preferably, the hot-press molding process in the step (4) is carried out for 6-8h at 70-90 ℃ and then for 8-10h at 110-130 ℃.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the SiO with high mechanical property₂Firstly, hydroxylated graphene is used as a raw material, cetyl trimethyl ammonium bromide is used as a template agent, tetraethoxysilane is used as a silicon source, and a soft template method is used to prepare the SiO modified phenolic resin material₂Modified graphene composite material, hydroxylated graphene and SiO₂The surface is rich in hydroxyl and-Si (OC) on the silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane₂H₅)₃The groups are subjected to chemical reaction to obtain epoxy functionalized SiO₂Graphene, then cardanol, phenol and paraformaldehyde are taken as polymerization monomers, and epoxy functionalized SiO is added₂Graphene, which is dehydrated and condensed in a water bath, then the reaction material is filled into a mould, and the SiO with high mechanical property is prepared by hot-press molding₂-a graphene modified phenolic resin material.

The SiO with high mechanical property₂The graphene modified phenolic resin material is prepared by polymerizing silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane with hydroxymethyl and phenolic hydroxyl in phenolic resin through epoxy bonds and Si-O, the dispersibility and compatibility of the resin are improved in a chemical bond mode, the curing crosslinking degree of the modified phenolic resin is increased, and a good blocking effect is achieved on chain section movement, so that the mechanical property of the compounded phenolic resin material is greatly improved, and meanwhile, SiO is utilized₂The-graphene composite material has very good mechanical properties, the mechanical properties such as bending strength, compression strength and the like of the phenolic resin can be further improved, the introduction of cardanol improves the molecular weight of the modified phenolic resin, the viscosity of a system is increased, and the resin is bonded with SiO₂The ability of (a) to be improved.

Drawings

FIG. 1 is a front sectional view of an ultrasound device;

fig. 2 is a partially enlarged view of the buffer structure.

1-a dispersion barrel; 2-a filler; 3-a dispersion chamber; 4-a spring; 5-a buffer base; 6-ultrasonic dispersing device; 7-a vibration motor; 8-sloping plate; 9-feeding bin I; 10-feeding bin II; 11-a stirring motor; 12-a stirring shaft; 13-stirring blade.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: SiO with high mechanical property₂-graphene modified phenolic resin material, high mechanical properties SiO₂The preparation method of the graphene modified phenolic resin material comprises the following steps:

(1) adding hydroxylated graphene into a distilled water solvent, passing through an ultrasonic device, wherein the ultrasonic device comprises a dispersion barrel, the inner wall of the dispersion barrel is fixedly connected with a filler, the inner wall of the filler is fixedly connected with a dispersion chamber, the bottom of the inner wall of the dispersion barrel is fixedly connected with a spring, the top of the spring is fixedly connected with a buffer base, the upper surface of the buffer base is fixedly connected with an ultrasonic dispersion device, the top of the ultrasonic dispersion device is fixedly connected with an inclined plate, the lower surface of the inclined plate is fixedly connected with a vibration motor, the upper surface of the dispersion barrel is fixedly connected with a feeding bin I, the right side of the feeding bin I is fixedly connected with a feeding bin II, the left side of the feeding bin II is fixedly connected with a stirring motor, the bottom of the stirring motor is fixedly connected with a stirring shaft, the outer wall of the stirring shaft is fixedly connected with stirring blades, performing ultrasonic, adjusting the pH value to 8-10, adding ethyl orthosilicate, magnetically stirring for 18-24h at the temperature of 30-50 ℃, wherein the mass ratio of hydroxylated graphene to hexadecyl trimethyl ammonium bromide to the ethyl orthosilicate is 100:1800-2200:800-1000, washing and drying the product, and preparing the SiO₂Modifying the graphene composite material;

(2) adding silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and SiO into absolute ethyl alcohol₂Graphene, wherein the silane coupling agent gamma- (2, 3-glycidoxy) propyltrimethoxysilane siliconAlkane and SiO₂The mass ratio of graphene to graphene is 100:40-60, the epoxy functionalized SiO is prepared after drying the product after ultrasonic reaction for 5-10h₂-graphene;

(3) adding cardanol and phenolic resin into a flask, stirring in water bath at 60-70 ℃, adding sodium hydroxide, stirring uniformly, and adding paraformaldehyde and functionalized SiO₂Graphene, wherein cardanol, phenol, sodium hydroxide, paraformaldehyde and functionalized SiO₂The mass ratio of graphene is 10-20:100:1-1.3:40-45:0.5-3, after reacting for 2-4h, heating to 80-100 ℃, and continuing to react for 40-60 min;

(4) filling the reaction materials into a mold, carrying out hot press molding by a flat vulcanizing machine, treating for 6-8h under the condition of 70-90 ℃, then treating for 8-10h under the condition of 110-130 ℃, cooling and demolding to prepare the SiO with high mechanical property₂-a graphene modified phenolic resin material.