阅读说明：本技术 一种人造板用氧化石墨烯改性磷酸铝胶粘剂及其制备方法 (Graphene oxide modified aluminum phosphate adhesive for artificial board and preparation method thereof ) 是由 谢拥群 吴振增 陈汀杰 李德宏 魏微 侯鑫均 魏起华 牛敏 林铭 刘景宏 于 2019-10-11 设计创作，主要内容包括：本发明公开了一种人造板用氧化石墨烯改性磷酸铝胶粘剂及其制备方法,其是采用氧化石墨烯对PVA-磷酸铝胶粘剂进行改性,得到一种粘度为150-600 mPa·S、固含量为40-80%的无醛环保人造板用胶粘剂,其具有强度好、耐高温、阻燃防霉等特点。本发明原料来源广泛、价格低廉、操作简便易行、生产过程不产生有毒有害物质,且产品具有良好的力学、阻燃防霉能性能等,有望成为新型的环保型人造板胶粘剂。(The invention discloses an alumina graphene modified aluminum phosphate adhesive for an artificial board and a preparation method thereof, wherein the PVA-aluminum phosphate adhesive is modified by adopting the alumina graphene to obtain an aldehyde-free environment-friendly adhesive for the artificial board with the viscosity of 150-600 mPa & S and the solid content of 40-80%, and the adhesive has the characteristics of good strength, high temperature resistance, flame retardance, mildew resistance and the like. The invention has the advantages of wide raw material source, low price, simple and easy operation, no toxic and harmful substances generated in the production process, good mechanical property, flame-retardant and mildew-proof performance and the like, and is expected to become a novel environment-friendly artificial board adhesive.)

1. The preparation method of the graphene oxide modified aluminum phosphate adhesive for the artificial board is characterized by comprising the following steps of: the method comprises the following steps:

(1) phosphoric acid or hydrogen phosphate and an aluminum compound are used as raw materials, and the solid content of the adhesive is designed according to a certain phosphorus-aluminum ratio;

(2) heating a certain amount of phosphoric acid or hydrogen phosphate salt bath, and adding a certain amount of PVA and a catalyst for reaction for a period of time;

(3) slowly adding a certain amount of aluminum compound into the mixture obtained in the step (2) according to the phosphorus-aluminum ratio for reaction for a period of time;

(4) and (3) adding graphene oxide into the mixture obtained in the step (3) according to a certain proportion, and carrying out ultrasonic treatment for a certain time to obtain the graphene oxide modified aluminum phosphate adhesive for the artificial board.

2. The preparation method of the graphene oxide modified aluminum phosphate adhesive for the artificial board according to claim 1, wherein the graphene oxide modified aluminum phosphate adhesive comprises the following steps: the hydrogen phosphate salt in the step (1) comprises dihydrogen phosphate and monohydrogen phosphate; the aluminum compound comprises aluminum hydroxide, aluminum oxide and aluminum nitride; the phosphorus-aluminum ratio is 2.0:1-4.0: 1;

the solid content of the adhesive is 40-85%.

3. The preparation method of the graphene oxide modified aluminum phosphate adhesive for the artificial board according to claim 1, wherein the graphene oxide modified aluminum phosphate adhesive comprises the following steps: the temperature for heating the water bath in the step (2) is 70-100 ℃; the addition amount of PVA is 0.1-5.0% of the total mass of the phosphorus-aluminum raw material; the used catalyst is urea, and the adding amount of the urea is 0.1-10% of the total mass of the phosphorus-aluminum raw material; the reaction time is 20-300 min.

4. The preparation method of the graphene oxide modified aluminum phosphate adhesive for the artificial board according to claim 1, wherein the graphene oxide modified aluminum phosphate adhesive comprises the following steps: the reaction time in the step (3) is 20-300 min.

5. The preparation method of the graphene oxide modified aluminum phosphate adhesive for the artificial board according to claim 1, wherein the graphene oxide modified aluminum phosphate adhesive comprises the following steps: in the step (4), the addition amount of the graphene oxide is 0.1-5.0% of the designed solid content; the ultrasonic power is 10-4000W, and the ultrasonic treatment time is 1-300 min.

6. The graphene oxide modified aluminum phosphate adhesive prepared by the method of claim 1, wherein: the viscosity of the graphene oxide modified aluminum phosphate adhesive is 150-600 mPa & S.

7. A method for preparing an artificial board by using the graphene oxide modified aluminum phosphate adhesive as claimed in claim 6, wherein the method comprises the following steps: uniformly mixing the graphene oxide modified aluminum phosphate adhesive and a curing agent, spraying the mixture on the surfaces of wood shavings and fibers or directly coating the mixture on the surface of a veneer according to a certain proportion, and then hot-pressing the glued wood shavings, fibers or veneer under certain conditions to form the artificial board.

8. The method for preparing the artificial board by using the graphene oxide modified aluminum phosphate adhesive as claimed in claim 7, wherein the graphene oxide modified aluminum phosphate adhesive comprises the following steps: the amount of the curing agent is 1-10% of the mass of the graphene oxide modified aluminum phosphate adhesive;

the curing agent is magnesium oxide, aluminum oxide, copper oxide, zinc oxide, iron oxide or aluminum nitride.

9.The method for preparing the artificial board by using the graphene oxide modified aluminum phosphate adhesive as claimed in claim 7, wherein the graphene oxide modified aluminum phosphate adhesive comprises the following steps: the glue application amount of the wood shavings and the fibers is 8 to 30 percent of the absolute dry mass of the prepared artificial board; the single board is at 100-300g/m²And (4) performing double-sided sizing.

10. The method for preparing the artificial board by using the graphene oxide modified aluminum phosphate adhesive as claimed in claim 7, wherein the graphene oxide modified aluminum phosphate adhesive comprises the following steps: the hot pressing temperature of the wood shavings and the fibers is 150-200 ℃, the hot pressing time is 0.5-2min/mm, and the hot pressing pressure is 0.5-2.0 MPa;

the hot pressing temperature of the single board is 150-200 ℃, the hot pressing time is 0.5-2min/mm, and the hot pressing pressure is 0.5-2.0 MPa.

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a method for preparing a phosphorus-aluminum inorganic adhesive for a graphene oxide modified artificial board.

Background

Graphene Oxide (GO) is a Graphene monolith formed by exfoliation of Graphite Oxide (Graphite Oxide). Graphite oxide is a graphite derivative prepared by oxidizing crystalline flake graphite with a strong oxidizing agent. After oxidation treatment, hydroxyl groups and epoxy groups are randomly distributed on the graphene oxide single sheet, and carboxyl groups and carbonyl groups are introduced at the edge of the single sheet. During the oxidation treatment process although SP²The hybridized carbon atom network structure is destroyed, but GO still maintains excellent mechanical properties. Due to the fact that a large number of oxygen-based active functional groups are introduced into graphene, the surface of the graphene which is originally inert becomes extremely active, and chemical reactions based on the active functional groups are abundant and diverse.

Polyvinyl alcohol (PVA) is a hydrophilic organic high molecular polymer having a large number of hydroxyl groups on its C — C chain. A large number of hydroxyl groups on the PVA main chain can be connected with GO through hydrogen bonds and covalent bonds. Therefore, the GO/PVA composite material has excellent mechanical property, optical property, magnetism and shape memory property. The invention aims to modify a PVA-aluminum phosphate adhesive by using graphene oxide so as to improve the mechanical strength of the adhesive in a plywood.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides the graphene oxide modified aluminum phosphate adhesive for the artificial board and the preparation method thereof, and the graphene oxide modified aluminum phosphate adhesive has good mechanical property, flame-retardant and mildew-proof properties and the like, and is expected to become a novel environment-friendly artificial board adhesive.

In order to realize the purpose of the invention, the invention adopts the following technical scheme:

a preparation method of graphene oxide modified aluminum phosphate adhesive for artificial boards comprises the following steps:

(1) phosphoric acid or hydrogen phosphate and an aluminum compound are used as raw materials, and the solid content of the adhesive is designed according to a certain phosphorus-aluminum ratio;

(2) heating a certain amount of phosphoric acid or hydrogen phosphate salt bath, and adding a certain amount of PVA and a catalyst for reaction for a period of time;

(3) slowly adding a certain amount of aluminum compound into the mixture obtained in the step (2) according to the phosphorus-aluminum ratio for reaction for a period of time;

(4) and (3) adding graphene oxide into the mixture obtained in the step (3) according to a certain proportion, and performing ultrasonic treatment for a certain time to uniformly disperse the graphene oxide in the aluminum phosphate adhesive, so as to obtain the graphene oxide modified aluminum phosphate adhesive for the artificial board.

The hydrogen phosphate salt in the step (1) comprises dihydrogen phosphate and monohydrogen phosphate; the aluminum compound comprises aluminum hydroxide, aluminum oxide and aluminum nitride; the ratio of phosphorus to aluminum (molar ratio of phosphorus to aluminum) is 2.0:1-4.0: 1; the solid content of the adhesive is 40-85%.

The temperature for heating the water bath in the step (2) is 70-100 ℃; the addition amount of PVA is 0.1-5.0% of the total mass of the phosphorus-aluminum raw material; the used catalyst is urea, and the adding amount of the urea is 0.1-10% of the total mass of the phosphorus-aluminum raw material; the reaction time is 20-300 min.

The reaction time in the step (3) is 20-300 min.

In the step (4), the addition amount of the graphene oxide is 0.1-5.0% of the designed solid content; the ultrasonic power is 10-4000W, and the ultrasonic treatment time is 1-300 min.

The viscosity of the obtained graphene oxide modified aluminum phosphate adhesive is 150-600 mPa & S.

The method for preparing the artificial board by using the graphene oxide modified aluminum phosphate adhesive comprises the steps of uniformly mixing the graphene oxide modified aluminum phosphate adhesive with a curing agent, spraying the mixture on the surfaces of wood shavings and fibers according to a certain proportion or directly coating the mixture on the surface of a veneer, and then carrying out hot pressing on the glued wood shavings, fibers or veneer under certain conditions to form the artificial board.

Wherein the amount of the curing agent is 1-10% of the mass of the graphene oxide modified aluminum phosphate adhesive; the curing agent is magnesium oxide, aluminum oxide, copper oxide, zinc oxide, iron oxide or aluminum nitride.

The glue application amount of the wood shavings and the fibers is 8 to 30 percent of the absolute dry mass of the prepared artificial board; the single board is at 100-300g/m²And (4) performing double-sided sizing.

The hot pressing temperature of the wood shavings and the fibers is 150-200 ℃, the hot pressing time is 0.5-2min/mm, and the hot pressing pressure is 0.5-2.0 MPa;

the hot pressing temperature of the single board is 150-200 ℃, the hot pressing time is 0.5-2min/mm, and the hot pressing pressure is 0.5-2.0 MPa.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention provides a formaldehyde-free aluminum phosphate adhesive for artificial boards, which has the advantages of rich raw material sources, low price, simple and pollution-free production process, no pollution of wastes to the environment and natural degradation.

(2) The artificial board prepared by the aluminum phosphate adhesive has good mechanical strength, and the related physical and chemical properties such as mildew resistance, corrosion resistance and the like are improved; particularly, the flame retardant property is obviously enhanced, the flame retardant grade reaches B2 grade specified in the building interior decoration design fire protection code, and the smoke quantity is small in the combustion process.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.