阅读说明：本技术 一种多功能木材仿生硅化改性剂及其制备应用方法 (Multifunctional wood bionic silicification modifier and preparation and application method thereof ) 是由 吕文华 石媛 刘强强 杜浩佳 倪林 柴宇博 刘君良 于 2019-09-11 设计创作，主要内容包括：本发明涉及一种多功能木材仿生硅化改性剂及其制备应用方法,它包括以下按重量份计的组分：20～50份硅石粉、5～15份固体强碱、2～8份引发剂、5～20份有机杂化剂、3～10份活化剂、0.1～3.0份染料、3～10份功能性助剂,在高温高压反应釜里将硅石粉充分液化并有机杂化后,再加入染料和其它功能性助剂,得到一种多功能木材仿生硅化改性剂。本发明的优点在于通过木竹材等生物质材料进行真空加压等浸渍改性处理,既可提高处理材密度、强度、硬度、阻燃和耐腐等性能,又可同时赋予其较好的耐湿性、尺寸稳定等性能,还能定制颜色赋予其良好的表面装饰特性；具有功能多、适用性广、成本低、工艺简单、节能、环保等特点,应用前景广阔。(The invention relates to a multifunctional wood bionic silicification modifier and a preparation and application method thereof, wherein the multifunctional wood bionic silicification modifier comprises the following components in parts by weight: 20-50 parts of silica powder, 5-15 parts of solid strong base, 2-8 parts of initiator, 5-20 parts of organic hybridization agent, 3-10 parts of activating agent, 0.1-3.0 parts of dye and 3-10 parts of functional auxiliary agent, wherein the silica powder is fully liquefied and organically hybridized in a high-temperature high-pressure reaction kettle, and then the dye and other functional auxiliary agents are added to obtain the multifunctional wood bionic silicification modifier. The invention has the advantages that the wood and bamboo biomass materials are subjected to impregnation modification treatment such as vacuum pressurization, so that the density, strength, hardness, flame retardance, corrosion resistance and other properties of the treated materials can be improved, better moisture resistance, stable size and other properties can be endowed, and the color can be customized to endow the treated materials with good surface decoration properties; the method has the characteristics of multiple functions, wide applicability, low cost, simple process, energy conservation, environmental protection and the like, and has wide application prospect.)

1. A multifunctional wood bionic silicification modifier is characterized by comprising the following raw materials in parts by weight:

20-50 parts of silica powder, 5-15 parts of solid strong base, 2-8 parts of initiator, 5-20 parts of organic hybridization agent, 3-10 parts of activating agent, 0.1-3.0 parts of dye and 3-10 parts of functional auxiliary agent.

2. The multifunctional wood bionic silicification modifier according to claim 1 is characterized by comprising the following raw materials in parts by weight:

30-10 parts of silica powder, 10-15 parts of solid strong base, 5-8 parts of initiator, 10-20 parts of organic hybridization agent, 5-10 parts of activating agent, 1-3.0 parts of dye and 5-10 parts of functional auxiliary agent.

3. The multifunctional wood bionic silicification modifier as claimed in claims 1 and 2, wherein the silica powder refers to commercially available quartz powder and silica micropowder with purity of more than 95% and mesh number of 20-600 meshes, preferably purity of more than 99%, preferably mesh number of 50-200 meshes.

4. The multifunctional wood bionic silicification modifier as claimed in claims 1 and 2, is characterized in that the solid strong base comprises one or more of solid sodium hydroxide, potassium hydroxide and lithium hydroxide and the combination thereof.

5. The multifunctional wood bionic silicification modifier as claimed in claims 1 and 2, characterized in that the initiator comprises one or more of benzoyl, sodium thiosulfate, copper sulfate, ferrous sulfate, sodium sulfite, ammonium persulfate, sodium persulfate and potassium persulfate and combination thereof.

6. The multifunctional wood bionic silicification modifier as claimed in claims 1 and 2, characterized in that the organic hybridization agent comprises one or more of glyoxal, n-butyraldehyde, dialdehyde starch, melamine, dicyandiamide, urea, polyvinyl alcohol, ethylene glycol, glucose, starch, vinyl acetate, ethyl acrylate, polyacrylamide, methyl triethoxysilane, dodecyl silicone oil and combination thereof.

7. The multifunctional wood bionic silicification modifier as claimed in claims 1 and 2, characterized in that the activating agent comprises one or more of ammonium alkyl benzene sulfonate, ammonium lignin sulfonate, sodium alkyl naphthalene sulfonate, alkylphenol ethoxylates, fatty alcohol polyoxyethylene ether, sodium dodecyl benzene sulfonate, N-dodecyl dimethylamine, sodium fatty alcohol sulfate, sodium lauryl polyoxyethylene ether sulfate, polyacrylic acid, sodium polyacrylate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, and combinations thereof.

8. The multifunctional wood bionic silicification modifier as claimed in claims 1 and 2, characterized in that the dye is a metal ion dye solution comprising one or more of copper sulfate, ferrous sulfate, ferric sulfate, copper nitrate, ferric nitrate, manganese nitrate and combinations thereof, or is a water-soluble acid dye comprising one or more of reactive dye, direct dye, basic dye and combinations thereof.

9. The multifunctional wood bionic silicification modifier as claimed in claims 1 and 2, characterized in that the auxiliary agent comprises one or more of boric acid, borax, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, low-polymerization-degree ammonium polyphosphate, nano titanium dioxide, nano zinc dioxide, nano silicon dioxide, nano montmorillonite and combination thereof.

10. A method for preparing the multifunctional wood bionic silicification modifier applied according to claim 1, characterized in that: it comprises the following steps:

(1) adding 20-50 parts by weight of silica powder and 5-15 parts by weight of solid strong base into a reaction kettle, heating and stirring to keep the temperature at 130-300 ℃, reacting for 2-6 hours, adding 20-80 parts by weight of water, and preparing into a silica powder liquefied solution with a certain concentration;

(2) adding 5-20 parts of organic hybridization agent into 2-8 parts of initiator solution by weight, adjusting the pH value to 8-10, heating to 50-90 ℃, continuing to react for 0.5-1 h after the solution becomes clear, adjusting the pH value to 3-6, keeping the temperature at 60-90 ℃, and reacting for 1-3 h;

(3) cooling to 40-50 ℃, adding 3-10 parts by weight of activator solution, adjusting the pH value to 8-10, adding the prepared silica liquefaction solution with a certain concentration, and fully stirring and mixing under a heating condition to obtain the organic hybrid silica powder liquefaction modifier;

(4) adding 0.1-3 parts by weight of the metal ion dye solution or dye aqueous solution, heating and stirring, and fully mixing to obtain an organic hybrid silica powder dyeing modifier;

(5) adding 3-10 parts of the flame-retardant, anti-corrosion and other functional additives, and fully stirring and mixing to obtain the multifunctional wood bionic silicification modifier;

(6) vacuum pressurization dipping treatment: putting the fast-growing wood-bamboo board into a treatment tank, vacuumizing to-0.08 to-1 MPa, keeping for 30 minutes, decompressing, pressurizing to 1.0 to 1.2MPa, treating for 2 hours, repeating the steps of vacuumizing, decompressing and pressurizing for 2 to 5 times, discharging, air-drying the board until the water content is below 50 percent, transferring the board into a drying box, manually drying by adopting a soft reference of gradual temperature rise, and drying until the water content of the board is 10 percent to obtain the modified wood board.

Technical Field

The invention relates to a multifunctional wood bionic silicification modifier and a preparation and application method thereof.

Background

At present, China has completely banned and fell natural forest wood, and fast growing wood is difficult to be directly used in the economic high-added-value fields of furniture, industrial manufacturing and the like due to fast growth, soft material, low strength and unstable size. China has the most abundant artificial forest resources and silica resources in the world, and through wood silicification modification, the artificial forest resources are efficiently utilized, so that the green ecological and sustainable development of the wood processing industry can be promoted, and the resource advantages in China are converted into economic advantages. Along with the enhancement of health and environmental protection consciousness of people, a novel nontoxic, green and multifunctional wood modifier becomes a research hotspot for developing green and ecological wood modification technology. The re-compounding property of organic and inorganic silicon and other assistants, the influence of the re-compounding process on the curing and crosslinking state of the re-compounded modifier in wood, and the final performance of the modified material remain the hot research point of wood modification.

Natural silicified wood is wood buried deeply, and inorganic minerals such as SiO2 around the wood undergo dissolution-deposition substitution for hundreds of millions of years, so that organic components of the wood are replaced on the basis of retaining the morphological structure of the wood, and finally, a woodstone is formed. One or more inorganic components or precursors thereof are immersed into the wood tissue and consolidated, so that the performances of flame retardance, wear resistance and the like of the wood can be effectively improved. The silicide involved in wood modification includes inorganic silicon compounds such as silicate, fluorosilicone compound, chlorosilicone compound, etc., and organic silicon compounds such as ethyl silicate, methyl triethoxy siloxane, etc. The organic silicon modifier has high cost and complex treatment process; the inorganic silicide has larger rigidity and can damage the toughness of the wood, which greatly limits the application and development of the wood silicification modification.

The sodium silicate is a general name of silicate aqueous solution, and the sodium silicate is environment-friendly, cheap and easy to obtain, and is widely applied to the fields of chemical production, mechanical manufacturing and the like. At present, the production of sodium silicate is divided into dry production and wet production. The dry production is that quartz sand and soda are mixed according to a certain proportion and then heated to about 1400 ℃ in a reverberatory furnace to generate molten sodium silicate, which has the problems of large energy consumption, large pollution and the like. In the wet production, quartzite powder and caustic soda are used as raw materials, liquid sodium silicate is directly generated in a high-pressure reaction kettle, and the problems of small modulus, poor water resistance and the like exist.

Disclosure of Invention

The invention aims to provide a multifunctional wood bionic silicification modifier and a preparation and application method thereof, the multifunctional wood bionic silicification modifier is free of formaldehyde hazard and good in water resistance, can remarkably improve the physical mechanics, flame retardance, corrosion resistance, mildew resistance, surface decoration and other properties of materials, and has the advantages of low modification cost, simple process, low equipment price and efficient utilization.

A multifunctional wood bionic silicification modifier comprises the following raw materials in parts by weight:

20-50 parts of silica powder, 5-15 parts of solid strong base, 2-8 parts of initiator, 5-20 parts of organic hybridization agent, 3-10 parts of activating agent, 0.1-3.0 parts of dye and 3-10 parts of functional auxiliary agent.

The preferable weight ratio of the raw materials is as follows:

30-10 parts of silica powder, 10-15 parts of solid strong base, 5-8 parts of initiator, 10-20 parts of organic hybridization agent, 5-10 parts of activating agent, 1-3.0 parts of dye and 5-10 parts of functional auxiliary agent.

The silica powder refers to commercially available quartz powder and silica micropowder with the purity of more than 95% and the mesh number of 20-600 meshes, preferably the purity is more than 99%, and preferably the mesh number is 50-200 meshes.

The solid strong base comprises one or more of solid sodium hydroxide, potassium hydroxide and lithium hydroxide and a combination thereof.

The initiator comprises one or more of benzoyl, sodium thiosulfate, copper sulfate, ferrous sulfate, sodium sulfite, ammonium persulfate, sodium persulfate and potassium persulfate and the combination thereof

The organic hybridization agent comprises one or more of glyoxal, n-butyl aldehyde, dialdehyde starch, melamine, dicyandiamide, urea, polyvinyl alcohol, glycol, glucose, starch, vinyl acetate, ethyl acrylate, polyacrylamide, methyl triethoxysilane, dodecyl silicone oil and a combination thereof.

The activating agent comprises one or more of ammonium alkyl benzene sulfonate, ammonium lignosulfonate, sodium alkyl naphthalene sulfonate, alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene ether, sodium dodecyl benzene sulfonate, N-dodecyl dimethylamine, sodium fatty alcohol sulfate, sodium lauryl alcohol polyoxyethylene ether sulfate, polyacrylic acid, sodium polyacrylate, dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and a combination thereof.

The dye is metal ion dye solution, which comprises one or more of copper sulfate, ferrous sulfate, ferric sulfate, copper nitrate, ferric nitrate and manganese nitrate and a combination thereof, or water-soluble acid dye, which comprises one or more of reactive dye, direct dye and basic dye and a combination thereof.

The auxiliary agent comprises one or more of boric acid, borax, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, low-polymerization-degree ammonium polyphosphate, nano titanium dioxide, nano zinc dioxide, nano silicon dioxide, nano montmorillonite and a combination thereof.

A method for preparing a multifunctional wood bionic silicification modifier comprises the following steps:

(1) adding 20-50 parts by weight of silica powder and 5-15 parts by weight of solid strong base into a reaction kettle, heating and stirring to keep the temperature at 130-300 ℃, reacting for 2-6 hours, and adding 20-80 parts by weight of water to prepare a silica powder liquefied solution with a certain concentration.

(2) Adding 5-20 parts of organic hybridization agent into 2-8 parts of initiator solution by weight, adjusting the pH value to 8-10, heating to 50-90 ℃, continuing to react for 0.5-1 h after the solution becomes clear, adjusting the pH value to 3-6, keeping the temperature at 60-90 ℃, and reacting for 1-3 h.

(3) Cooling to 40-50 ℃, adding 3-10 parts by weight of activator solution, adjusting the pH value to 8-10, adding the prepared silica liquefaction solution with a certain concentration, and fully stirring and mixing under a heating condition to obtain the organic hybrid silica powder liquefaction modifier.

(4) Adding 0.1-3 parts by weight of the metal ion dye solution or dye aqueous solution, heating and stirring, and fully mixing to obtain the organic hybrid silica powder dyeing modifier.

(5) And adding 3-10 parts of the flame-retardant, anticorrosive and other functional additives, and fully stirring and mixing to obtain the multifunctional wood bionic silicification modifier.

(6) Vacuum pressure impregnation treatment of the fast-growing wood bamboo board: and (4) stacking the fast-growing wood bamboo boards and placing the fast-growing wood bamboo boards into a treatment tank. Vacuumizing to-0.08 to-1 MPa, keeping for 30 minutes, relieving pressure, pressurizing to 1.0 to 1.2MPa, processing for 2 hours, repeating the vacuumizing, pressure relieving and pressurizing steps for 2 to 5 times, discharging, air-drying the board until the water content is below 50 percent, transferring the board into a drying box, manually drying by adopting a soft reference of gradual temperature rise until the water content of the board is 10 percent, and obtaining the modified wood board.

The invention provides a multifunctional wood bionic silicification modifier without formaldehyde hazard, with good water resistance, which can obviously improve the physical mechanics, flame retardance, corrosion resistance, mildew resistance, surface decoration and other properties of the material, and has the advantages of low modification cost, simple process, low equipment price and high efficiency utilization.

Compared with the prior art, the invention has the following advantages:

(1) the invention directly adopts the silica powder to carry out high-efficiency liquefaction, and can greatly reduce the cost.

(2) The invention does not use formaldehyde and has no environmental hazards such as micromolecule release and the like.

(3) The invention adopts inorganic-organic hybrid modifier, which can effectively improve the performance of wood.

(4) The multifunctional wood bionic silicification modifier can endow wood with good performances of dimensional stability, mechanical strength, flame retardance, corrosion resistance, mildew resistance and the like, and the color is adjustable.

(5) The multifunctional wood bionic silicification modifier has the advantages of simple production process, low equipment price and controllable product quality.

Detailed Description