CN110696131A - Preparation method of organic-inorganic hybrid modifier - Google Patents
Preparation method of organic-inorganic hybrid modifier Download PDFInfo
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- CN110696131A CN110696131A CN201911127762.7A CN201911127762A CN110696131A CN 110696131 A CN110696131 A CN 110696131A CN 201911127762 A CN201911127762 A CN 201911127762A CN 110696131 A CN110696131 A CN 110696131A
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- resin
- urea
- glyoxal
- stirring
- modifier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/005—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process employing compositions comprising microparticles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
- C08G12/36—Ureas; Thioureas
- C08G12/38—Ureas; Thioureas and melamines
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Forests & Forestry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
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.
Description
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.
Example 1
(1) 80g of a powder (500 mesh) having a silica content of 99% and 400g of a mixed solution (prepared by mixing a 10% sodium hydroxide aqueous solution and 0.1% lithium carbonate) were put into a high-temperature high-pressure reaction vessel, and the temperature was raised by turning on the stirring. Stirring at 200r/min, slowly raising the temperature to 300 ℃, reacting for 2h at 300 ℃, and then gradually cooling to 40 ℃ to obtain a sodium silicate aqueous solution;
(2) the preparation method of the GU resin is characterized by comprising the following steps: adding a certain amount of glyoxal into a reaction kettle, adjusting the pH value to 6 by using sodium hydroxide, then adding a part of urea, heating to 62 ℃, reacting for 50min under the condition of stirring, adding the rest urea, keeping the temperature at 62 ℃, reacting for 35min, cooling, discharging to obtain GU resin (the mass ratio of the two urea additions is 2: 1);
(3) respectively weighing 5% of GU, 20% of sodium silicate aqueous solution and 75% of distilled water according to the mass percentage, mixing, and magnetically stirring for 5min at room temperature to obtain the organic-inorganic hybrid modifier.
Example 2
(1) 80g of a powder (500 mesh) having a silica content of 99% and 400g of a mixed solution (prepared by mixing a 10% sodium hydroxide aqueous solution and 0.1% lithium carbonate) were put into a high-temperature high-pressure reaction vessel, and the temperature was raised by turning on the stirring. Stirring at 200r/min, slowly raising the temperature to 300 ℃, reacting for 2h at 300 ℃, and then gradually cooling to 40 ℃ to obtain a sodium silicate aqueous solution;
(2) the preparation method of the GU resin is characterized by comprising the following steps: adding a certain amount of glyoxal into a reaction kettle, adjusting the pH value to 6 by using sodium hydroxide, then adding a part of urea, heating to 60 ℃, reacting for 40min under the condition of stirring, adding the rest urea, keeping the temperature at 60 ℃, reacting for 30min, cooling, discharging to obtain GU resin (the mass ratio of the two urea additions is 3: 1);
(3) respectively weighing 5% of GU, 20% of sodium silicate aqueous solution and 75% of distilled water according to the mass percentage, mixing, and magnetically stirring for 5min at room temperature to obtain the organic-inorganic hybrid modifier.
Example 3
(1) 80g of a powder (500 mesh) having a silica content of 99% and 400g of a mixed solution (prepared by mixing a 10% sodium hydroxide aqueous solution and 0.1% lithium carbonate) were put into a high-temperature high-pressure reaction vessel, and the temperature was raised by turning on the stirring. Stirring at 200r/min, slowly raising the temperature to 300 ℃, reacting for 2h at 300 ℃, and then gradually cooling to 40 ℃ to obtain a sodium silicate aqueous solution;
(2) the preparation method of the GMUF resin is characterized by comprising the following steps: glyoxal: urea: formaldehyde: the molar ratio of melamine is 1: 1: 1.2: 0.08. adding a certain amount of formaldehyde and glyoxal into a reaction kettle, starting stirring, adjusting the pH to 6.0 by using sodium hydroxide, stopping stirring, adding melamine and urea, starting stirring, heating to 45 ℃, stopping heating, automatically heating to 70 ℃, keeping the temperature at 70 ℃ for reaction for 1h, slowly dropwise adding sodium hydroxide within 1h, controlling the pH to be 6.0, keeping the temperature at 70 ℃ for reaction for 150min, cooling, and discharging to obtain GMUF resin;
(3) 5 percent of GMUF, 20 percent of sodium silicate aqueous solution and 80 percent of distilled water are weighed according to the mass percent respectively, and are mixed and stirred magnetically for 5min at room temperature to obtain the organic-inorganic hybrid modifier.
Example 4
(1) 80g of a powder (500 mesh) having a silica content of 99% and 400g of a mixed solution (prepared by mixing a 10% sodium hydroxide aqueous solution and 0.1% lithium carbonate) were put into a high-temperature high-pressure reaction vessel, and the temperature was raised by turning on the stirring. Stirring at 200r/min, slowly raising the temperature to 300 ℃, reacting for 2h at 300 ℃, and then gradually cooling to 40 ℃ to obtain a sodium silicate aqueous solution;
(2) the preparation method of the GMUF resin is characterized by comprising the following steps: glyoxal: urea: formaldehyde: the molar ratio of melamine is 1: 1: 1.7: 0.08. adding a certain amount of formaldehyde and glyoxal into a reaction kettle, starting stirring, adjusting the pH to 6.0 by using sodium hydroxide, stopping stirring, adding melamine and urea, starting stirring, heating to 45 ℃, stopping heating, automatically heating to 70 ℃, keeping the temperature at 70 ℃ for reaction for 1h, slowly dropwise adding sodium hydroxide within 1h, controlling the pH to be 6.0, keeping the temperature at 70 ℃ for reaction for 150min, cooling, and discharging to obtain GMUF resin;
(3) 5 percent of GMUF, 20 percent of sodium silicate aqueous solution and 75 percent of distilled water are weighed according to the mass percent respectively, and are mixed and stirred magnetically for 5min at room temperature to obtain the organic-inorganic hybrid modifier.
The solid content of the organic-inorganic hybrid modifier is 40-50%, the storage period is more than 60 days, and the water solubility is more than 10.
The organic-inorganic hybrid modifier obtained by the invention is used for impregnating wood for performance test:
the density, hardness, mechanical properties and the like of the modified material are effectively improved, so that the overall dimensional stability and durability are improved. Formaldehyde release is less than or equal to 0.5mg/L, and surface moisture and heat resistance is as follows: no crack, no bubble, no discoloration, surface crack resistance: no crack, surface resistance to cold and heat cycles: no crack and no bubble.
The above-mentioned embodiments are only preferred embodiments of the present invention, and do not limit the scope of the present invention, but all the modifications made by the principles of the present invention and the non-inventive efforts based on the above-mentioned embodiments shall fall within the scope of the present invention.
Claims (10)
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.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196161A (en) * | 2021-12-17 | 2022-03-18 | 中国林业科学研究院木材工业研究所 | Formaldehyde-free low-molecular-weight amino resin modifier and preparation method and application thereof |
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| CN104311767A (en) * | 2014-10-10 | 2015-01-28 | 湖北省宏源药业科技股份有限公司 | Modified urea-formaldehyde resin adhesive and preparation method thereof |
| CN105666611A (en) * | 2016-01-29 | 2016-06-15 | 东营泰然材料科技股份有限公司 | Preparing method for fiberboard surface treating agent and application method of fiberboard surface treating agent |
| CN108705635A (en) * | 2018-05-21 | 2018-10-26 | 北华大学 | A kind of enhancing modified artificial forest wood preparation method |
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2019
- 2019-11-18 CN CN201911127762.7A patent/CN110696131B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2267092A1 (en) * | 2009-06-24 | 2010-12-29 | Forestry And Forest Products Research Institute | Adhesive compositions containing bond-strength enhancing agent and methods for producing wood composite using the adhesive compositions |
| CN103305168A (en) * | 2013-07-02 | 2013-09-18 | 西南林业大学 | Resin adhesive free from formaldehyde release as well as preparation method and application thereof |
| CN103964451A (en) * | 2014-04-29 | 2014-08-06 | 深圳市国大长兴科技有限公司 | Method for preparing silicate aqueous solution by using polished quartz stone waste powder |
| CN104311767A (en) * | 2014-10-10 | 2015-01-28 | 湖北省宏源药业科技股份有限公司 | Modified urea-formaldehyde resin adhesive and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114196161A (en) * | 2021-12-17 | 2022-03-18 | 中国林业科学研究院木材工业研究所 | Formaldehyde-free low-molecular-weight amino resin modifier and preparation method and application thereof |
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