CN110591567A - Preparation method of phosphorus-aluminum formaldehyde-free adhesive for artificial board - Google Patents
Preparation method of phosphorus-aluminum formaldehyde-free adhesive for artificial board Download PDFInfo
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- CN110591567A CN110591567A CN201910962562.7A CN201910962562A CN110591567A CN 110591567 A CN110591567 A CN 110591567A CN 201910962562 A CN201910962562 A CN 201910962562A CN 110591567 A CN110591567 A CN 110591567A
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- aluminum
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- free adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/02—Mixing the material with binding agent
- B27N1/0209—Methods, e.g. characterised by the composition of the agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J1/00—Adhesives based on inorganic constituents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a preparation method of a phosphorus-aluminum aldehyde-free adhesive for artificial boards, which is an aldehyde-free environment-friendly adhesive for artificial boards, and the adhesive has the viscosity of 30-600 mPa.S and the solid content of 40-85 percent, and is prepared by carrying out hydrothermal reaction on phosphoric acid, an aluminum compound, a multivalent metal salt or oxide and a boride. The product 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, flame-retardant and mildew-proof performances of the product and the like, and is expected to become a novel environment-friendly artificial board adhesive.
Description
Technical Field
The invention relates to the technical field of artificial board adhesives, in particular to a preparation method of a phosphorus-aluminum inorganic adhesive for artificial boards.
Background
With the increasing concern of people on environment and ecology, many researchers find inspiration from nature and apply the green concept to life. Wood and wood composites are renewable, degradable, environmentally friendly materials that have been widely used in homes and public places. The wood products such as shaving board, plywood and medium density fiberboard are most widely used. The wood material needs a large amount of adhesive in the production and use processes, and the formaldehyde-based adhesive has the largest using amount, low cost, high activity and good binding power to the wood material. However, these formaldehyde-based adhesives release formaldehyde under certain conditions. Formaldehyde is a dangerous genotoxic substance that is classified as a human carcinogen by the U.S. environmental protection agency. To solve this problem, non-formaldehyde-based adhesives, such as wheat flour, lignin, starch, soy protein, polyvinyl acetate, and the like, have been extensively studied for the preparation of formaldehyde-free adhesives. However, in practical application, these adhesives also have the defects of poor wet strength, poor corrosion and mildew resistance, insufficient bonding strength and the like.
Phosphoric acid based adhesives are the products of the reaction of phosphoric acid solutions with metal oxides such as magnesium oxide, aluminum oxide, iron oxide. The phosphorus-aluminum adhesive as a phosphate-based adhesive has the advantages of no aldehyde, low raw material cost, wide source and the like. After being cured, the phosphorus-aluminum adhesive can form a continuous chain structure or a three-dimensional net structure, and the structure can ensure that the bonded objects have high strength. Meanwhile, the phosphorus-aluminum adhesive has good thermal stability, is antibacterial and anticorrosive, and has a long service life. The phosphoaluminate adhesives have also been used as heterogeneous catalysts to convert biomass materials into hydrocarbons, as ceramic coatings for metal or concrete outer layers, as structural adhesives for rockets or other high temperature oxidizing and corrosive environments. However, the phosphor-aluminum inorganic composite has not been used as an adhesive for wood-based composite materials.
The invention aims to prepare a phosphorus-aluminum adhesive for an artificial board without formaldehyde release by using phosphoric acid and aluminum hydroxide.
Disclosure of Invention
The invention aims to provide a method for preparing a phosphorus-aluminum adhesive for an artificial board aiming at the defects of the prior art. The artificial board prepared by the invention has better mechanical, flame retardant and mildew proof properties.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a phosphorus-aluminum formaldehyde-free adhesive for artificial boards comprises the following steps:
(1) taking phosphoric acid solution or hydrogen phosphate solution with certain concentration and an aluminum compound as raw materials, wherein phosphorus and aluminum elements form a certain phosphorus-aluminum ratio, and the solid content of the adhesive is designed;
(2) heating a phosphoric acid solution or a hydrogen phosphate solution in water bath, and then adding an aluminum compound to react for a period of time;
(3) and adding a polyvalent metal salt or a polyvalent metal oxide and a boride into the solution, continuously reacting for a period of time, and cooling to obtain the phosphorus-aluminum formaldehyde-free adhesive for the artificial board.
The hydrogen phosphate in the step (1) comprises one of soluble dihydrogen phosphate and soluble monohydrogen phosphate; the aluminum compound comprises one of aluminum hydroxide, aluminum oxide and aluminum nitride; the phosphorus-aluminum ratio is the molar ratio of phosphorus element to aluminum element, and ranges from 2.0:1 to 4.0: 1; the solid content of the adhesive is 40-85%.
The water bath temperature in the step (2) is 50-150 ℃, and the reaction time is 20-300 min.
The polyvalent metal salt and the polyvalent metal oxide in the step (3) are salts and oxides consisting of Zn, Mg, Fe, Cu and Cr, and have the functions of increasing nodes of an inorganic network and improving the bonding strength of the adhesive; the boride is borax or boric acid; the reaction time is 20-120 min.
The viscosity of the phosphorus-aluminum formaldehyde-free adhesive for the artificial board is 30-600 mPa.S.
The method for preparing the artificial board by using the phosphorus-aluminum formaldehyde-free adhesive for the artificial board comprises the following steps: uniformly mixing a phosphorus-aluminum formaldehyde-free adhesive for the artificial board and a curing agent, and spraying the mixture on the surfaces of wood shavings or fibers or coating the mixture on the surfaces of veneers according to a certain proportion; and then hot-pressing the glued fibers, shavings or veneers according to certain hot-pressing conditions to form the artificial board.
The curing agent is magnesium oxide, aluminum oxide, copper oxide, zinc oxide, iron oxide or aluminum nitride.
The glue application amount of the fiber and the wood shavings is 8-30% of the absolute dry mass of the prepared artificial board, and the veneer is 300g/m of 100-2And (4) performing double-sided sizing.
The hot pressing temperature of the fiber and the wood shavings 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 improves the relevant physical and chemical properties of the prepared product, such as good mechanical strength, mildew resistance, corrosion resistance and the like, for the formaldehyde-free phosphorus-aluminum adhesive for the artificial board; particularly, the flame retardant property is obviously enhanced, and the flame retardant grade reaches B2 grade specified in the building interior decoration design fire standard;
(2) the product has the advantages of abundant raw material sources, low cost, simple production process, no pollution, no environmental pollution caused by waste, natural degradation, and less smoke generation in the combustion process.
(3) Compared with the existing phosphorus-aluminum-based adhesive, the product has the advantages of low viscosity, low curing temperature, flame retardance, mildew resistance and the like. Meanwhile, the product is cured in a thermosetting mode in the production process of the artificial board, and compared with other phosphate adhesives (cold-pressing curing) used in the field of artificial boards, the product has the characteristics of continuous production, short production period and high production efficiency.
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.
Example 1
Pouring 300g of a 65wt% diluted solution of 85% phosphoric acid into a three-neck flask, heating the solution to 90 ℃ in a water bath, adding 72g of aluminum hydroxide, and reacting for 30min, wherein the molar ratio of phosphorus to aluminum is 2.8: 1, the solid content of the adhesive is designed to be 65%. 9.81g of copper oxide (3 percent of phosphoric acid and aluminum hydroxide) and 6.54 g of boric acid (2 percent of phosphoric acid and aluminum hydroxide) are added into the solution to continue to react for 30min, and then the mixture is cooled to obtain the phosphorus-aluminum adhesive with the viscosity of 50 mPa.S. Uniformly mixing the prepared phosphorus-aluminum adhesive with 10g of ferric oxide (3 percent of the mass of the adhesive), and then applying 200g/m of adhesive according to the double-side adhesive application amount2And coating on the surface of the veneer. The veneer is hot-pressed (hot-pressing temperature: 160 ℃, hot-pressing time: 2min/mm, hot-pressing pressure: 1.0 MPa) to prepare the plywood.
Respectively measuring the oxygen index, the mechanical property and the mildew-proof property of the sample according to the Chinese national standards GB/T8924-2005, GB/T17657-2013 and GB/T18261-2013; the oxygen index is 32.2 percent, the bonding strength is 2.2 MPa, the elastic modulus is 2800 MPa, the static bending strength is 40 MPa, and the mould control efficiency is 80 percent.
Example 2
Pouring 300g of phosphoric acid solution with the concentration of 85 percent and the dilution of 67 percent by weight into a three-neck flask, heating the solution to 92 ℃ in a water bath, adding 69.9g of aluminum hydroxide, and reacting for 35min, wherein the molar ratio of phosphorus to aluminum is 2.9: 1, the solids content of the adhesive is designed to be 67%. 10.4g of copper oxide (3.2 percent of phosphoric acid and aluminum hydroxide) and 7.1g of boric acid (2.2 percent of phosphoric acid and aluminum hydroxide) are added into the solution to continue to react for 35min, and then the mixture is cooled to obtain the phosphorus-aluminum adhesive with the viscosity of 42 mPa & S. Uniformly mixing the prepared phosphorus-aluminum adhesive with ferric oxide (3.2% of the mass of the adhesive), and then applying adhesive according to the double-side adhesive application amount of 210g/m2And coating on the surface of the veneer. Hot pressing the single board(hot pressing temperature: 165 ℃, hot pressing time: 1.7min/mm, hot pressing pressure: 1.1 MPa) to prepare the plywood.
Respectively measuring the oxygen index, the mechanical property and the mildew-proof property of the sample according to the Chinese national standards GB/T8924-2005, GB/T17657-2013 and GB/T18261-2013; the oxygen index is 32.5%, the bonding strength is 2.3 MPa, the elastic modulus is 2900 MPa, the static bending strength is 41MPa, and the mould control efficiency is 84%.
Example 3
300g of phosphoric acid solution with the concentration of 85 percent and the dilution of 66 percent by weight is poured into a three-neck flask, after the solution is heated to 95 ℃ in a water bath, 75g of aluminum hydroxide is added for reaction for 38min, the molar ratio of phosphorus to aluminum is 2.7:1, and the solid content of the designed adhesive is 66 percent. 10.9g of copper oxide (3.3 percent of phosphoric acid and aluminum hydroxide) and 6.93g of boric acid (2.1 percent of phosphoric acid and aluminum hydroxide) are added into the solution to continue to react for 38min, and then the mixture is cooled to obtain the phosphorus-aluminum adhesive with the viscosity of 78 mPa.S. Uniformly mixing the prepared phosphorus-aluminum adhesive with ferric oxide (3.3 percent of the mass of the adhesive), and then applying 220g/m of adhesive according to the double-sided adhesive application amount2And coating on the surface of the veneer. The veneer is hot-pressed (the hot-pressing temperature is 170 ℃, the hot-pressing time is 1.8 min/mm, and the hot-pressing pressure is 1.3 MPa) to prepare the plywood.
Respectively measuring the oxygen index, the mechanical property and the mildew-proof property of the sample according to the Chinese national standards GB/T8924-2005, GB/T17657-2013 and GB/T18261-2013; the oxygen index is 32.8 percent, the bonding strength is 2.4 MPa, the elastic modulus is 3000 MPa, the static bending strength is 43 MPa, and the mould control efficiency is 88 percent.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a phosphorus-aluminum formaldehyde-free adhesive for artificial boards is characterized by comprising the following steps: the method comprises the following steps:
(1) taking phosphoric acid solution or hydrogen phosphate solution with certain concentration and an aluminum compound as raw materials, wherein phosphorus and aluminum elements form a certain phosphorus-aluminum ratio, and the solid content of the adhesive is designed;
(2) heating a phosphoric acid solution or a hydrogen phosphate solution in water bath, and then adding an aluminum compound to react for a period of time;
(3) and adding a polyvalent metal salt or a polyvalent metal oxide and a boride into the solution, continuously reacting for a period of time, and cooling to obtain the phosphorus-aluminum formaldehyde-free adhesive for the artificial board.
2. The preparation method of the phosphorus-aluminum aldehyde-free adhesive for the artificial board according to claim 1, wherein the preparation method comprises the following steps: the hydrogen phosphate in the step (1) comprises one of soluble dihydrogen phosphate and soluble monohydrogen phosphate; the aluminum compound comprises one of aluminum hydroxide, aluminum oxide and aluminum nitride; the phosphorus-aluminum ratio is the molar ratio of phosphorus element to aluminum element, and ranges from 2.0:1 to 4.0: 1; the solid content of the adhesive is 40-85%.
3. The preparation method of the phosphorus-aluminum aldehyde-free adhesive for the artificial board according to claim 1, wherein the preparation method comprises the following steps: the water bath temperature in the step (2) is 50-150 ℃, and the reaction time is 20-300 min.
4. The preparation method of the phosphorus aluminum adhesive for artificial boards according to claim 1, which is characterized in that: the polyvalent metal salt and the polyvalent metal oxide in the step (3) are salts and oxides consisting of Zn, Mg, Fe, Cu and Cr; the boride is borax or boric acid; the reaction time is 20-120 min.
5. The phosphorus-aluminum aldehyde-free adhesive for artificial boards prepared by the preparation method according to claim 1, which is characterized in that: the viscosity of the phosphorus-aluminum formaldehyde-free adhesive for the artificial board is 30-600 mPa.S.
6. A method for preparing artificial boards by using the phosphorus-aluminum aldehyde-free adhesive for artificial boards according to claim 5, which is characterized by comprising the following steps: uniformly mixing a phosphorus-aluminum formaldehyde-free adhesive for the artificial board and a curing agent, and spraying the mixture on the surfaces of wood shavings or fibers or coating the mixture on the surfaces of veneers according to a certain proportion; and then hot-pressing the glued fibers, shavings or veneers according to certain hot-pressing conditions to form the artificial board.
7. The method for preparing artificial board by using the phosphorus-aluminum aldehyde-free adhesive for artificial board according to claim 6, wherein the method comprises the following steps: the curing agent is magnesium oxide, aluminum oxide, copper oxide, zinc oxide, iron oxide or aluminum nitride.
8. The method for preparing artificial board by using the phosphorus-aluminum aldehyde-free adhesive for artificial board according to claim 6, wherein the method comprises the following steps: the glue application amount of the fiber and the wood shavings is 8-30% of the absolute dry mass of the prepared artificial board, and the veneer is 300g/m of 100-2And (4) performing double-sided sizing.
9. The method for preparing artificial board by using the phosphorus-aluminum aldehyde-free adhesive for artificial board according to claim 6, wherein the method comprises the following steps: the hot pressing temperature of the fiber and the wood shavings 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.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910962562.7A CN110591567A (en) | 2019-10-11 | 2019-10-11 | Preparation method of phosphorus-aluminum formaldehyde-free adhesive for artificial board |
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| CN201910962562.7A CN110591567A (en) | 2019-10-11 | 2019-10-11 | Preparation method of phosphorus-aluminum formaldehyde-free adhesive for artificial board |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5443231A (en) * | 1977-09-13 | 1979-04-05 | Nippon Chemical Ind | Inorganic paste composition |
| CN101724352A (en) * | 2009-12-11 | 2010-06-09 | 北京工业大学 | Inorganic adhesive for artificial board and preparation method thereof |
| CN103468154A (en) * | 2013-08-27 | 2013-12-25 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant room temperature curing phosphate adhesive and preparation method thereof |
-
2019
- 2019-10-11 CN CN201910962562.7A patent/CN110591567A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5443231A (en) * | 1977-09-13 | 1979-04-05 | Nippon Chemical Ind | Inorganic paste composition |
| CN101724352A (en) * | 2009-12-11 | 2010-06-09 | 北京工业大学 | Inorganic adhesive for artificial board and preparation method thereof |
| CN103468154A (en) * | 2013-08-27 | 2013-12-25 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant room temperature curing phosphate adhesive and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| TINGJIE CHEN 等: "Hierarchical Lamellar Aluminophosphate Materials with Porosity as Ecofriendly Inorganic Adhesive for Wood-Based Boards", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
| 杨闵敏 等: "《建筑装饰材料》", 31 August 2017, 北京希望电子出版社 * |
| 黄世强 等: "《环保胶黏剂》", 31 October 2003, 化学工业出版社 * |
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Application publication date: 20191220 |
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