阅读说明：本技术 一种有机无机杂化改性剂的制备方法 (Preparation method of organic-inorganic hybrid modifier ) 是由 柴宇博 平立娟 孙柏玲 刘君良 吕文华 倪林 胡极航 王小青 于 2019-11-18 设计创作，主要内容包括：本发明公开了一种有机无机杂化改性剂,由5％～15％的树脂,5％～20％的硅酸钠水溶液,余量为蒸馏水混合后,在室温下磁力搅拌10min后制得。所述树脂可以选择GU树脂或GMUF树脂。向硅粉中加入4倍量10％氢氧化钠水溶液和0.1％的碳酸锂,随后在高温高压反应釜中反应,制得硅酸钠水溶液；将乙二醛和尿素,或乙二醛、尿素、三聚氰胺和甲醛加入反应釜,控制反应温度,反应时间和pH值,制得乙二醛-尿素(GU)树脂或乙二醛-三聚氰胺-尿素-甲醛(GMUF)树脂。本发明简单易行,得到的改性剂稳定性较好,其固含量在40～50％,水溶倍数>10,分子量为A,贮存期在60天以上,对木材的渗透性较好,采用乙二醛部分或全部代替甲醛,对环境友好,属于环保型改性剂。(The invention discloses an organic-inorganic hybrid modifier, which is prepared by mixing 5-15% of resin, 5-20% of sodium silicate aqueous solution and the balance of distilled water, and then magnetically stirring for 10min at room temperature. The resin may be selected from GU resin or GMUF resin. Adding 4 times of 10% sodium hydroxide aqueous solution and 0.1% lithium carbonate into the silicon powder, and then reacting in a high-temperature high-pressure reaction kettle to obtain sodium silicate aqueous solution; adding glyoxal and urea or glyoxal, urea, melamine and formaldehyde into a reaction kettle, and controlling the reaction temperature, the reaction time and the pH value to prepare glyoxal-urea (GU) resin or glyoxal-melamine-urea-formaldehyde (GMUF) resin. The method is simple and easy to implement, the obtained modifier has good stability, the solid content is 40-50%, the water solubility is greater than 10, the molecular weight is A, the storage period is more than 60 days, the permeability to wood is good, formaldehyde is partially or completely replaced by glyoxal, and the method is environment-friendly and belongs to an environment-friendly modifier.)

1. The preparation method of the organic-inorganic hybrid modifier is characterized in that the modifier is prepared from the following raw materials in percentage by mass: 5 to 15 percent of resin, 5 to 20 percent of sodium silicate solution and the balance of distilled water.

2. The method for preparing the organic-inorganic hybrid modifier according to claim 1, wherein the method comprises the following steps: mixing the resin, the sodium silicate aqueous solution and the distilled water, and magnetically stirring at room temperature for 10min to obtain the organic-inorganic hybrid modifier.

3. The method according to claim 2, wherein the resin is selected from any one of GU resin and GMUF resin.

4. The method of claim 2, wherein the aqueous sodium silicate solution is prepared by: adding 500-mesh silicon dioxide powder, 10% sodium hydroxide aqueous solution and 0.1% lithium carbonate into a high-temperature high-pressure reaction kettle, heating to 300 ℃ while stirring, reacting for 2 hours at the temperature of 300 ℃, and then gradually cooling to 40 ℃ to obtain sodium silicate aqueous solution for later use.

5. A method of preparation according to claim 3 wherein the GU resin is prepared by: adding glyoxal into a reaction kettle, adjusting the pH value to 6-7 with sodium hydroxide, adding part of urea, heating to 60-65 ℃, reacting for 40-60 min under the condition of stirring, adding the rest urea, keeping the temperature at 60-65 ℃, reacting for 30-40 min, cooling, discharging, and obtaining GU resin for later use.

6. The method of claim 3, wherein the GMUF resin is prepared by: adding formaldehyde and glyoxal into a reaction kettle, uniformly stirring, adjusting the pH value to 5.5-6.0, stopping stirring, adding melamine and urea, continuously stirring, heating to 40-45 ℃, stopping heating, maintaining the exothermic reaction for 1h, slowly dropwise adding sodium hydroxide during the exothermic reaction to adjust the pH value to 5.5-6.0, maintaining the temperature of 70 ℃, reacting for 2-3 h, cooling, and discharging to obtain the GMUF resin for later use.

7. The method according to claim 4, wherein the silica powder has a purity of 99%; the adding mass of the sodium hydroxide aqueous solution and the lithium carbonate is 4 times of that of the silicon dioxide; the stirring speed is 200 r/min.

8. The method according to claim 5, wherein the concentration of glyoxal is 40% by mass; the molar ratio of the glyoxal to the urea is 1.6: 1; the mass ratio of the urea added twice in sequence is 2-3: 1.

9. The method according to claim 6, wherein the ratio of glyoxal: urea: formaldehyde: the molar ratio of melamine is 1: 1: (1.2-1.7): 0.08.

10. an organic-inorganic hybrid modifier prepared by the preparation method of any one of claims 2 to 9.

Technical Field

The invention relates to the technical field of wood processing production, in particular to a preparation method of an organic-inorganic hybrid modifier and the organic-inorganic hybrid modifier prepared by the preparation method.

Background

Over millions of years of evolution, wood has developed microstructures and material compositions that can meet a variety of functional requirements and withstand various environmental stresses. More importantly, wood has a hierarchical pore structure characterized by a cellular pore structure, a form that is not possible with the prior art. However, wood, particularly plantation wood, has low density, low mechanical strength, low surface hardness, poor wear resistance, flammability, perishability, and poor biological durability. Therefore, according to the unique chemical composition, microstructure and porous structure system of wood, the high-performance and functional modification of wood becomes an important research subject of the wood processing industry, and a lot of experiments and theoretical exploration are carried out on scientists in various countries.

With the progress of science and technology and the development of human civilization, people are paying more and more attention to environmental problems, and especially in the 21 st century, the reduction of carbon emission becomes a significant problem related to the development of human survival. Most studies indicate that increasing the use of wood is one of the simple and feasible methods for slowing down climate change and improving the carbon balance of the earth's atmosphere. The concrete measures include increasing the utilization ratio of the wood, prolonging the service life of the wood products as far as possible, expanding the recycling and the cyclic utilization of the wood and the wood products and the like.

The main components of the existing wood modifier are urea-formaldehyde resin or phenolic resin, the prepared product has high formaldehyde release amount and is not environment-friendly, and the urea-formaldehyde resin or the phenolic resin also has the defects of short storage, poor reusability (gradual self-polymerization and solidification), high production cost and the like. In addition, the wood modifier needs to be dried (the water content is lower than 20%) before impregnation processing is carried out, so that the energy consumption and the production cost are high.

Disclosure of Invention

The invention aims to provide a preparation technology of an organic-inorganic modifier, which is simple and feasible, has little or no formaldehyde release, good water solubility and good storage stability.

The invention is realized by adopting the following technical scheme:

an organic-inorganic hybrid modifier is prepared from the following raw materials in percentage by mass: 5 to 15 percent of resin, 5 to 20 percent of sodium silicate solution and the balance of distilled water.

The invention also discloses a preparation method of the organic-inorganic hybrid modifier, which comprises the following steps: mixing the resin, the sodium silicate aqueous solution and the distilled water, and magnetically stirring at room temperature for 10min to obtain the organic-inorganic hybrid modifier.

Further, the resin is selected from any one of GU resin or GMUF resin.

Further, the sodium silicate aqueous solution is prepared by the following method: adding 500-mesh silicon dioxide powder, 10% sodium hydroxide aqueous solution and 0.1% lithium carbonate into a high-temperature high-pressure reaction kettle, heating to 300 ℃ while stirring, reacting for 2 hours at the temperature of 300 ℃, and then gradually cooling to 40 ℃ to obtain sodium silicate aqueous solution for later use.

Further, the purity of the silicon dioxide powder is 99%; the adding mass of the sodium hydroxide aqueous solution and the lithium carbonate is 4 times of that of the silicon dioxide; the stirring speed is 200 r/min.

Further, the GU resin is prepared by the following method: adding glyoxal into a reaction kettle, adjusting the pH value to 6-7 with sodium hydroxide, adding part of urea, heating to 60-65 ℃, reacting for 40-60 min under the condition of stirring, adding the rest urea, keeping the temperature at 60-65 ℃, reacting for 30-40 min, cooling, discharging, and obtaining GU resin for later use.

Further, the mass percentage concentration of the glyoxal is 40%; the molar ratio of the glyoxal to the urea is 1.6: 1; the mass ratio of the urea added in the two times is 2-3: 1.

Further, the GMUF resin is prepared by the following method: adding formaldehyde and glyoxal into a reaction kettle, uniformly stirring, adjusting the pH value to 5.5-6.0, stopping stirring, adding melamine and urea, continuously stirring, heating to 40-45 ℃, stopping heating, maintaining the exothermic reaction for 1h, slowly dropwise adding sodium hydroxide during the exothermic reaction to adjust the pH value to 5.5-6.0, maintaining the temperature of 70 ℃, reacting for 2-3 h, cooling, and discharging to obtain the GMUF resin for later use.

Further, the glyoxal: urea: formaldehyde: the molar ratio of melamine is 1: 1: (1.2-1.7): 0.08.

the invention also discloses an organic and inorganic hybrid modifier prepared by any one of the preparation methods.

The invention has the beneficial effects that:

1. the invention is an organic-inorganic composite modifier, which can realize the modification of wood in a mode of one dose and multiple effects.

2. The method is simple and easy to implement, low in production cost and suitable for industrial production.

3. The modifier prepared by the method has good stability, the storage period is more than 60 days, the molecular weight is A, and the permeability to wood is good.

4. The invention has low content of free formaldehyde or no free formaldehyde, and belongs to an environment-friendly modifier.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples.

In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.