CN107987766B - Method for preparing biomass adhesive by using formaldehyde residues - Google Patents
Method for preparing biomass adhesive by using formaldehyde residues Download PDFInfo
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- CN107987766B CN107987766B CN201711333708.9A CN201711333708A CN107987766B CN 107987766 B CN107987766 B CN 107987766B CN 201711333708 A CN201711333708 A CN 201711333708A CN 107987766 B CN107987766 B CN 107987766B
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- formaldehyde
- urea
- residues
- biomass adhesive
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
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- 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
- C08G12/40—Chemically modified polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to a method for preparing a modified biomass adhesive by using formaldehyde residues, belonging to the technical field of adhesives. The method comprises the steps of firstly, modifying lignin by using choline chloride-urea eutectic ionic liquid, regenerating and activating formaldehyde residues by using the ionic liquid-water as a medium, and then further copolymerizing with urea to form resin; finally, adding the condensed tannin and the chitin for modification and reducing free formaldehyde. The method can effectively and fully utilize the waste formaldehyde residues, is beneficial to environmental protection, and the prepared modified biomass adhesive has high viscosity, good toughness and low formaldehyde release amount, and can be widely applied to the production of high-grade household materials.
Description
Technical Field
The invention relates to a method for preparing an environment-friendly adhesive by using waste formaldehyde residues, belonging to the technical field of adhesives.
Technical Field
Formaldehyde is a large amount of important chemical raw materials in the chemical industry field of China, and the annual output is more than 3800 ten thousand tons. The formaldehyde is easy to polymerize by itself to form precipitate (commonly called formaldehyde residue) in the processes of storage and transportation, and the phenomenon of high-concentration formaldehyde is more prominent; the sediment is deposited at the bottom of a container and a pipeline, insoluble sediment is formed for a long time, and therefore the sediment needs to be cleaned regularly; according to incomplete statistics, the formaldehyde waste residue produced in China every year reaches about 100 million tons. The formaldehyde waste residue can be slowly decomposed in natural environment to release harmful gas formaldehyde again, so that once the formaldehyde waste residue is not properly treated, long-term regional environmental air pollution can be caused. In recent years, although many workshop-type factories use simple methods such as alkali liquor boiling to redissolve the formaldehyde residues to prepare formaldehyde solution, the production environment is severe, the pollution is serious, the product quality is unstable, and the market order is disturbed.
Disclosure of Invention
The invention aims to overcome the defects in the aspect of utilization of formaldehyde residues in the prior art, and provides a method for preparing a modified biomass adhesive by using waste formaldehyde residues.
Technical scheme
The invention aims to fully utilize the formaldehyde waste residue, rapidly activate the formaldehyde waste residue by adopting the eutectic ionic liquid, and further copolymerize the formaldehyde waste residue with urea and ionic liquid modified lignin to form resin with high viscosity and good toughness, and the condensed tannin and chitin can further improve the bonding performance of the resin and reduce the formaldehyde release amount.
The method comprises the steps of firstly, modifying lignin by using choline chloride-urea eutectic ionic liquid, regenerating and activating formaldehyde residues by using the ionic liquid-water as a medium, and then further copolymerizing with urea to form resin; finally, adding the condensed tannin and the chitin for modification and reducing free formaldehyde.
The specific scheme is as follows:
a method for preparing a modified biomass adhesive by using formaldehyde residues comprises the following steps:
(1) preparing choline chloride and a first part of urea into eutectic ionic liquid according to the mass ratio of 1:2, then adding lignin, heating to 85-90 ℃, and uniformly stirring;
(2) adding formaldehyde residue and water, heating to 70-80 ℃, and stirring for 30-60 min;
(3) adding a second part of urea, heating to 88-92 ℃ within 40-50 min, stirring for reacting for 15-20 min, cooling to 75 ℃, adjusting the pH value of the reaction solution to 4.6-5.3, heating to 90-92 ℃, and reacting for 90-120 min; adding a third part of urea, adjusting the pH value to 6.5-6.8, and reacting for 40-60 min; measuring the viscosity, and when the viscosity reaches 20-25 s/25 ℃ and 4 cups are coated, cooling to 55-65 ℃;
(4) adding condensed tannin and chitin, stirring for 20-60min at 55-65 ℃, adjusting the pH value to 7.5-7.8, then cooling to below 35 ℃, and discharging to obtain the modified biomass adhesive.
Furthermore, the mass ratio of the formaldehyde residue to the first part of urea to the second part of urea to the third part of urea is 100:50 (50-75) to (30-60).
Furthermore, the mass ratio of the formaldehyde residue to the condensed tannin to the chitin is 100 (0.05-10) to (0.05-2).
Further, in the step (1), the adding amount of the lignin is 10-20% of the total mass of the choline chloride and the first portion of urea.
Further, in the step (2), the mass ratio of the formaldehyde residue to the water is 1: 1-1.5.
The invention has the beneficial effects that: the method can effectively and fully utilize the waste formaldehyde residues, is beneficial to environmental protection, and the prepared modified biomass adhesive has high viscosity, good toughness and low formaldehyde release amount, and can be widely applied to the production of high-grade household materials.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
Firstly, 100kg of 75% choline chloride and 200kg of urea are added into a reaction kettle, stirred and heated to 90 ℃, 30kg of industrial lignin is added, and the stirring reaction is carried out for 10 min; adding 400kg of formaldehyde residue and 480kg of water, heating to 75 ℃, and stirring for reacting for 40 min; adding 260kg of second part of urea, heating to 90 ℃, reacting for 15min, cooling to 75 ℃, adjusting the pH value to 5.1 by formic acid, reacting for 100min at the temperature of 90 ℃, adding 160kg of third part of urea, stirring and adjusting the pH value to 6.5, reacting for 60min, detecting the viscosity, cooling to 60 ℃ when the viscosity reaches 22s/25 ℃ and coating-4 cups, adding 20kg of condensed tannin and 5kg of chitin, stirring for 30min, adding ammonia water to adjust the pH value to 7.8, cooling to 35 ℃, and discharging to obtain the modified biomass adhesive product.
The prepared biomass modified adhesive product has the following performance indexes: solid content: 65.4%, pH: 7.8, viscosity (25 ℃): 24s, free formaldehyde content: 0.05 percent. The bonding strength (class II) of the 7-layer eucalyptus poplar composite plywood produced by using the composite plywood is as follows: the average value is 1.24MPa, the minimum value is 0.96MPa, and the formaldehyde emission of the plywood is as follows: 0.17 mg/L.
Claims (3)
1. A method for preparing a modified biomass adhesive by using formaldehyde residues is characterized by comprising the following steps:
(1) preparing choline chloride and a first part of urea into eutectic ionic liquid according to the mass ratio of 1:2, then adding lignin, heating to 85-90 ℃, and uniformly stirring;
(2) adding formaldehyde residue and water, heating to 70-80 ℃, and stirring for 30-60 min;
(3) adding a second part of urea, heating to 88-92 ℃ within 40-50 min, stirring for reacting for 15-20 min, cooling to 75 ℃, adjusting the pH value of the reaction solution to 4.6-5.3, heating to 90-92 ℃, and reacting for 90-120 min; adding a third part of urea, adjusting the pH value to 6.5-6.8, and reacting for 40-60 min; measuring the viscosity, and when the viscosity reaches 20-25 s/25 ℃ and 4 cups are coated, cooling to 55-65 ℃;
(4) adding condensed tannin and chitin, stirring for 20-60min at 55-65 ℃, adjusting the pH value to 7.5-7.8, then cooling to below 35 ℃, and discharging to obtain the modified biomass adhesive;
the mass ratio of the formaldehyde residue to the first part of urea to the second part of urea to the third part of urea is 100:50 (50-75) to (30-60);
the mass ratio of the formaldehyde residue to the condensed tannin to the chitin is 100 (0.05-10) to (0.05-2).
2. The method for preparing the modified biomass adhesive by using the formaldehyde residue as claimed in claim 1, wherein in the step (1), the addition amount of the lignin is 10-20% of the total mass of the choline chloride and the first part of urea.
3. The method for preparing the modified biomass adhesive by using the formaldehyde residues as claimed in claim 1 or 2, wherein in the step (2), the mass ratio of the formaldehyde residues to the water is 1: 1-1.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711333708.9A CN107987766B (en) | 2017-12-14 | 2017-12-14 | Method for preparing biomass adhesive by using formaldehyde residues |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711333708.9A CN107987766B (en) | 2017-12-14 | 2017-12-14 | Method for preparing biomass adhesive by using formaldehyde residues |
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| Publication Number | Publication Date |
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| CN107987766A CN107987766A (en) | 2018-05-04 |
| CN107987766B true CN107987766B (en) | 2020-09-11 |
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| CN201711333708.9A Expired - Fee Related CN107987766B (en) | 2017-12-14 | 2017-12-14 | Method for preparing biomass adhesive by using formaldehyde residues |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170796B (en) * | 2020-02-22 | 2022-09-16 | 太尔化工（南京）有限公司 | Process for preparing agricultural slow-release nitrogen fertilizer by regenerating powdery amino resin |
| CN114231226A (en) * | 2021-12-27 | 2022-03-25 | 德华兔宝宝装饰新材股份有限公司 | Low-cost modified urea-formaldehyde resin adhesive |
Citations (8)
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|---|---|---|---|---|
| US4246152A (en) * | 1978-04-07 | 1981-01-20 | Patentes Y Novedades, S.A. | Urea/formaldehyde adhesives |
| CN1422928A (en) * | 2001-12-02 | 2003-06-11 | 杨文章 | Additive of applying condensed tannin extracts as adhesive for thermosetting wood |
| CN101684395A (en) * | 2008-09-28 | 2010-03-31 | 吴彩莲 | Additive composite for eliminating formaldehyde in adhesive and preparation method thereof |
| CN102120810A (en) * | 2011-01-25 | 2011-07-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high solid content expandable melamine modified urea resin |
| CN102241826A (en) * | 2011-05-09 | 2011-11-16 | 北京化工大学 | Modified lignin and urea-formaldehyde resin synthesized from same and preparation methods of modified lignin and urea-formaldehyde resin |
| CN104151513A (en) * | 2014-07-16 | 2014-11-19 | 常州大学 | Epoxy-modified urea-formaldehyde resin adhesive for artificial plates and preparation method of adhesive |
| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN107236500A (en) * | 2016-03-29 | 2017-10-10 | 中国林业科学研究院林产化学工业研究所 | The preparation method of lignin sulfonate modified urea-phenolic resin |
-
2017
- 2017-12-14 CN CN201711333708.9A patent/CN107987766B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4246152A (en) * | 1978-04-07 | 1981-01-20 | Patentes Y Novedades, S.A. | Urea/formaldehyde adhesives |
| CN1422928A (en) * | 2001-12-02 | 2003-06-11 | 杨文章 | Additive of applying condensed tannin extracts as adhesive for thermosetting wood |
| CN101684395A (en) * | 2008-09-28 | 2010-03-31 | 吴彩莲 | Additive composite for eliminating formaldehyde in adhesive and preparation method thereof |
| CN102120810A (en) * | 2011-01-25 | 2011-07-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of high solid content expandable melamine modified urea resin |
| CN102241826A (en) * | 2011-05-09 | 2011-11-16 | 北京化工大学 | Modified lignin and urea-formaldehyde resin synthesized from same and preparation methods of modified lignin and urea-formaldehyde resin |
| CN104151513A (en) * | 2014-07-16 | 2014-11-19 | 常州大学 | Epoxy-modified urea-formaldehyde resin adhesive for artificial plates and preparation method of adhesive |
| CN105504191A (en) * | 2016-01-22 | 2016-04-20 | 南京林业大学 | Preparation method of eutectic ionic liquid modified lignin-phenolic resin |
| CN107236500A (en) * | 2016-03-29 | 2017-10-10 | 中国林业科学研究院林产化学工业研究所 | The preparation method of lignin sulfonate modified urea-phenolic resin |
Non-Patent Citations (2)
| Title |
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| Synthesis of urea-formaldehyde resin by melt condensation polymerization;Ya-qing Liu;《Journal of Polymer Research》;20080429(第15期);第501-505页 * |
| 低共熔离子液活化木质素改性PF的制备及胶接性能研究;钟伟 等;《中国胶粘剂》;20160530;第25卷(第5期);第35页第1.3.1-1.3.2节 * |
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