阅读说明：本技术 一种无机纳米pvb树脂粉的生产方法 (Production method of inorganic nano PVB resin powder ) 是由 叶卫民 梁飞 申坤 朱明臣 于 2019-10-28 设计创作，主要内容包括：本发明涉及PVB树脂粉技术领域,具体涉及一种无机纳米PVB树脂粉的生产方法,包括以下步骤：S1：制备碳基固体酸；S2：预处理；S3：缩合反应。本发明的利用纳米氧化石墨烯作为载体,通过浓硫酸浸渍,使制备的碳基固体酸具有较强的反应活性,经磺化后,吸附更多的酸,从而使更多的酸中心得到暴露,得到具有更多酸性位的碳基固体酸；本发明采用的生产方法简单,生产的无机纳米PVB树脂粉具有高分散性、可塑性好、抗氧化剂优异等特点。(The invention relates to the technical field of PVB resin powder, in particular to a production method of inorganic nano PVB resin powder, which comprises the following steps: s1: preparing carbon-based solid acid; s2: pre-treating; s3: and (3) condensation reaction. According to the invention, nano graphene oxide is used as a carrier, the prepared carbon-based solid acid has stronger reaction activity by concentrated sulfuric acid impregnation, and more acid is adsorbed after sulfonation, so that more acid centers are exposed, and the carbon-based solid acid with more acid sites is obtained; the production method adopted by the invention is simple, and the produced inorganic nano PVB resin powder has the characteristics of high dispersibility, good plasticity, excellent antioxidant and the like.)

1. A production method of inorganic nano PVB resin powder is characterized by comprising the following steps:

s1: preparing carbon-based solid acid; putting 0.1-0.2 wt% of nano graphene oxide solution into a reaction kettle, adding concentrated sulfuric acid into the reaction kettle at the temperature of 250-260 ℃, and stirring, wherein the volume ratio of the nano graphene oxide solution to the concentrated sulfuric acid is 1: (1-1.5), sulfonating for 18-20h, controlling the rotation speed to be 1000-;

s2: pre-treating; adding polyvinyl alcohol into a reaction bottle for dispersion, adding deionized water, preparing a mixed solution A with the concentration of 5%, controlling the rotating speed of 1300-;

s3: condensation reaction; and (2) installing a water separator and a spherical reflux condenser pipe, adding the carbon-based solid acid into the mixed solution B, refluxing along with heating in the reaction process until no obvious water drops appear in the water separator, continuing to react for 30-40min, cooling to room temperature, filtering and separating the carbon-based solid acid, washing the filtrate for 3-5 times by using deionized water, and drying in a dryer to obtain inorganic nano PVB resin powder.

2. The method for producing inorganic nano PVB resin powder as claimed in claim 1, wherein the nano graphene oxide solution in S1 is prepared by Hummers method, comprising the following steps: a reaction bottle is assembled in an ice-water bath, a proper amount of concentrated sulfuric acid is added, a solid mixture of 1-2g of graphite powder and 0.5-1g of sodium nitrate is added under stirring, 4-6g of potassium permanganate is added, the reaction temperature is controlled not to exceed 10 ℃, the mixture is stirred and reacted for a period of time, then heating to about 35 ℃, continuing to stir for 30min, then slowly adding a certain amount of deionized water, continuing to stir for 20min, adding appropriate amount of hydrogen peroxide to reduce residual oxidant to make the solution become bright yellow, filtering when it is hot, washing with 5% hydrochloric acid solution and deionized water until no sulfate radical is detected in the filtrate, drying the filter residue in a vacuum drying oven at 60 deg.C to obtain graphene oxide, dispersing the graphite oxide in water solution, obtaining a brownish yellow suspension, and dispersing for 2 hours under the ultrasonic condition to obtain a stable nano graphene oxide solution.

3. The process of claim 1, wherein the mass ratio of polyvinyl alcohol, butanol, carbon-based solid acid, plasticizer, dispersant and antioxidant in S2 is: (30-40): (20-25): (2-6): (10-15): (5-15): (4-8).

4. The process of claim 3 wherein said plasticizer is biphenyl.

5. The process of claim 3, wherein the dispersing agent is one of calcium stearate, magnesium stearate, copper stearate, and cadmium stearate.

6. The process of claim 3, wherein the antioxidant is one of butylated hydroxyanisole, butylated hydroxytoluene, and tertiary butyl hydroquinone.

Technical Field

The invention relates to the technical field of PVB resin powder, in particular to a production method of inorganic nano PVB resin powder.

Background

PVB (polyvinyl butyral) is a high molecular material-PVB intermediate film which is plasticized and extruded by a plasticizer, has the appearance of a semitransparent film, no impurities, a smooth surface, certain roughness and good flexibility, has good cohesive force on inorganic glass, and has the characteristics of transparency, heat resistance, cold resistance, moisture resistance, high mechanical strength and the like, is an optimal adhesive material for manufacturing interlayers and safety glass in the world at present, and also has wide application in the building fields of building curtain walls, covering sheds, show windows, bank counters, prison detection windows, steel furnace screens, various bulletproof glasses and the like.

At present, PVB resin powder is produced by adopting two-step low-temperature precipitation, the reaction time is long, refrigeration equipment is required, and the energy consumption is high; moreover, the PVB resin powder material has single performance and cannot meet the actual requirement.

Disclosure of Invention

The invention aims to provide a production method of inorganic nano PVB resin powder, which is simple and low in cost, and the produced inorganic nano PVB resin powder has the characteristics of high dispersibility, good plasticity, excellent antioxidant and the like.

In order to achieve the above purpose, the invention provides the following technical scheme:

a production method of inorganic nano PVB resin powder comprises the following steps:

s1: preparing carbon-based solid acid; putting 0.1-0.2 wt% of nano graphene oxide solution into a reaction kettle, adding concentrated sulfuric acid into the reaction kettle at the temperature of 250-260 ℃, and stirring, wherein the volume ratio of the nano graphene oxide solution to the concentrated sulfuric acid is 1: (1-1.5), sulfonating for 18-20h, controlling the rotation speed to be 1000-;

s2: pre-treating; adding polyvinyl alcohol into a reaction bottle for dispersion, adding deionized water, preparing a mixed solution A with the concentration of 5%, controlling the rotating speed of 1300-;

s3: condensation reaction; and (2) installing a water separator and a spherical reflux condenser pipe, adding the carbon-based solid acid into the mixed solution B, refluxing along with heating in the reaction process until no obvious water drops appear in the water separator, continuing to react for 30-40min, cooling to room temperature, filtering and separating the carbon-based solid acid, washing the filtrate for 3-5 times by using deionized water, and drying in a dryer to obtain inorganic nano PVB resin powder.

The carbon-based solid acid used in the invention has the advantages of good thermal stability, strong proton acidity, high catalytic activity, reusability and the like, is a green environment-friendly catalyst material, is low in price and wide in applicability compared with the traditional acid catalyst, such as concentrated sulfuric acid, but is difficult to separate from reactants and products, difficult to recycle and cause huge pollution to the environment.

According to the pretreatment provided by the invention, polyethylene, butanol, the plasticizer, the dispersant and the antioxidant are fully stirred before condensation reaction, so that the full dispersion of all materials can be ensured, the local condensation generated in the condensation reaction process is avoided, and the condensation reaction is more sufficient.

According to the pretreatment, the plasticizer, the dispersing agent and the antioxidant auxiliary agent are added before condensation reaction, and different from the prior art that the auxiliary agent is added after condensation, the problem of poor compatibility of PVB resin powder and various auxiliary agents is solved.

Specifically, the nano graphene oxide solution in S1 is prepared by a Hummers method, and the specific steps are as follows: a reaction bottle is assembled in an ice-water bath, a proper amount of concentrated sulfuric acid is added, a solid mixture of 1-2g of graphite powder and 0.5-1g of sodium nitrate is added under stirring, 4-6g of potassium permanganate is added, the reaction temperature is controlled not to exceed 10 ℃, the mixture is stirred and reacted for a period of time, then heating to about 35 ℃, continuing to stir for 30min, then slowly adding a certain amount of deionized water, continuing to stir for 20min, adding appropriate amount of hydrogen peroxide to reduce residual oxidant to make the solution become bright yellow, filtering when it is hot, washing with 5% hydrochloric acid solution and deionized water until no sulfate radical is detected in the filtrate, drying the filter residue in a vacuum drying oven at 60 deg.C to obtain graphene oxide, dispersing the graphite oxide in water solution, obtaining a brownish yellow suspension, and dispersing for 2 hours under the ultrasonic condition to obtain a stable nano graphene oxide solution.

According to the invention, nano graphene oxide is used as a carrier, and the prepared carbon-based solid acid has stronger reaction activity due to the huge specific surface area and a large amount of oxygen-containing groups, and can adsorb more acid after sulfonation, so that the carbon-based solid acid with more acid sites can be obtained; in addition, the nano graphene oxide has stable performance and is not easy to carbonize.

Specifically, the mass ratio of polyvinyl alcohol, butanol, carbon-based solid acid, plasticizer, dispersant and antioxidant in S2 is: (30-40): (20-25): (2-6): (10-15): (5-15): (4-8).

Specifically, the plasticizer is biphenyl.

The biphenyl used in the invention is a flaky solid, and has the melting point: 68-70 ℃, density (20 ℃): 1.04kg/m³The molecular formula is as follows: C12H10, molecular weight: 154.21, boiling point: 255 ℃, self-ignition point: 540 ℃, research octane number: 140, biphenyl is dissolved in gasoline, toluene, xylene and trimethylbenzene, and is widely used in the fields of medicines, pesticides, dyes, liquid crystal materials and the like. Can be used for synthesizing plasticizer, and can also be used for manufacturing fuel, engineering plastics, high-energy fuel and the like.

Specifically, the dispersing agent is one of calcium stearate, magnesium stearate, copper stearate and cadmium stearate.

The dispersing agent used in the invention is a higher fatty acid metal salt dispersing agent, can reduce the time and energy required for completing the dispersing process, stabilize the dispersed dispersion, modify the surface property of dispersion particles, adjust the mobility of dispersion particles, and has the characteristics of improving the luster, increasing the leveling effect, reducing the viscosity, reducing the flocculation and the like.

Specifically, the antioxidant is one of butyl hydroxy anisol, dibutyl hydroxy toluene and tert-butyl hydroquinone.

The antioxidant used in the invention is a synthetic antioxidant which is used for preventing the polymer material from losing strength and toughness due to oxidative degradation.

The invention has the beneficial effects that:

(1) according to the preparation method, nano graphene oxide is used as a carrier, the prepared carbon-based solid acid has strong reaction activity through concentrated sulfuric acid impregnation, and more acid is adsorbed after sulfonation, so that more acid centers are exposed, and the carbon-based solid acid with more acid sites is obtained; in addition, the nano graphene oxide has stable performance and is not easy to carbonize;

(2) according to the pretreatment, polyethylene, butanol, a plasticizer, a dispersing agent and an antioxidant are fully stirred before condensation reaction, so that all materials can be fully dispersed, local condensation generated in the condensation reaction process is avoided, and the condensation reaction is more sufficient;

(3) according to the pretreatment, the plasticizer, the dispersing agent and the antioxidant auxiliary agent are added before condensation reaction, and different from the prior art that the auxiliary agent is added after condensation, the problem of poor compatibility of PVB resin powder and various auxiliary agents is solved;

(4) the invention has the advantages of easily obtained raw materials, low cost, no pollution, environmental protection, high use value and good application prospect;

(5) the production method adopted by the invention is simple, and the produced inorganic nano PVB resin powder has the characteristics of high dispersibility, good plasticity, excellent antioxidant and the like.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

In the following embodiments, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art.