CN116218416B - Modified chitosan-based wood adhesive and preparation method and application thereof - Google Patents
Modified chitosan-based wood adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN116218416B CN116218416B CN202310138383.8A CN202310138383A CN116218416B CN 116218416 B CN116218416 B CN 116218416B CN 202310138383 A CN202310138383 A CN 202310138383A CN 116218416 B CN116218416 B CN 116218416B
- Authority
- CN
- China
- Prior art keywords
- chitosan
- wood adhesive
- based wood
- modified chitosan
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 65
- 239000000853 adhesive Substances 0.000 title claims abstract description 47
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 47
- 239000002023 wood Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 16
- 239000008103 glucose Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 238000007112 amidation reaction Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011120 plywood Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 241000219000 Populus Species 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002303 glucose derivatives Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- 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
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
- C09J105/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a modified chitosan wood adhesive, which comprises the steps of firstly modifying Chitosan (CS) through Maleic Anhydride (MA) to obtain Carboxyl Chitosan (CCS), and further preparing the chitosan-based wood adhesive by taking the Carboxyl Chitosan (CCS) and alcohol compounds as raw materials through esterification reaction. The modified chitosan-based wood adhesive prepared by the method is environment-friendly, has no formaldehyde release, is used for three-layer plywood, and has high mechanical strength and good water resistance, and all indexes are superior to those of related national standards. The aim is to develop a novel chitosan-based wood adhesive to realize the conversion of chitosan resources to high-value utilization.
Description
Technical Field
The invention relates to the technical field of wood adhesive synthesis, in particular to a modified chitosan-based wood adhesive, and a preparation method and application thereof.
Background
China is a large country of artificial boards, however, most wood adhesives used in wood processing are mainly formaldehyde-based adhesives, and the formaldehyde-based adhesives account for more than 80% of the total yield of the adhesives in China. The preparation of formaldehyde-based adhesives not only consumes petroleum resources, but also inevitably releases formaldehyde during the preparation and use. In recent years, with the concern of non-renewable fossil resources and the pursuit of ecological environment by human beings, sustainable development has attracted more and more attention, and research on environment-friendly wood adhesives using biomass as a raw material has been unprecedented.
Chitosan has many unique properties such as biodegradability, cell affinity and biocompatibility, and especially chitosan containing free amino groups is the only basic polysaccharide in natural polysaccharide. The characteristics enable chitosan to have excellent biological functions and to be subjected to chemical modification. The modified chitosan is applied to the wood adhesive, so that the waterproof strength of the adhesive can be greatly improved, the production cost can be reduced, and the added value can be improved.
Disclosure of Invention
The invention aims to provide an environment-friendly modified chitosan-based wood adhesive, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the modified chitosan-based wood adhesive is prepared from carboxyl chitosan CCS and glucose GL, and comprises the following steps:
(1) Under the stirring condition, adding maleic anhydride into a reactor, heating and melting, slowly adding chitosan, heating and stirring to perform amidation reaction, washing a mixture obtained after the reaction is finished by deionized water, and freeze-drying a precipitate to obtain carboxyl chitosan;
(2) Under the stirring condition, sequentially adding carboxyl chitosan, glucose GL and deionized water into a reactor, and heating to perform esterification reaction to obtain the modified chitosan-based wood adhesive.
Further, in the step (1), the reaction temperature is 90-100 ℃ and the reaction time is 6-8 h.
Further, in the step (2), the washing times are 2 to 4 times, and the drying time is 12 to 24 hours.
Preferably, in the step (1), the mass ratio of the maleic anhydride to the chitosan is 8-10:1.
further, in the step (2), the chemical structural formula of the carboxyl Chitosan (CS) is shown as the following formula:
further, in the step (2), the reaction temperature is 90 ℃ and the reaction time is 6-10h.
Further, in the step (2), the final solid content of the modified chitosan-based wood adhesive is 30% -50%.
Further, the mass ratio of the carboxyl chitosan to the glucose GL is 1:0.5-2.
The beneficial effects are that: the chitosan, maleic anhydride and glucose adopted by the invention are derived from biomass, and are renewable, wide in source and low in price. The modified chitosan-based wood adhesive prepared by the invention has no formaldehyde release, is environment-friendly, and avoids environmental pollution. The preparation method of the modified chitosan-based wood adhesive is simple, has low cost, is suitable for industrial production, and has good application prospect in the field of artificial board adhesives.
Drawings
FIG. 1 shows the chemical structure of the carboxychitosan (CCS) of the present invention.
FIG. 2 is a modified chitosan-based wood adhesive prepared by an esterification reaction according to the present invention.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are illustrative and exemplary of the present invention and are not intended to limit the scope of the present invention in any way.
Example 1
As shown in fig. 1 and 2, the preparation method of the modified chitosan-based wood adhesive of the embodiment includes the following steps:
(1) Under magnetic stirring, 48g of maleic anhydride MA is added into a reactor, the reactor is heated to 90 ℃, 6g of chitosan CS is slowly added after the maleic anhydride MA is melted, and stirring is continued for 8 hours at 90 ℃;
(2) After the reaction was completed, the mixture in step (1) was washed 3 times. Freeze-drying to obtain carboxyl chitosan CCS;
(3) Under magnetic stirring, 12g of deionized water, 5g of carboxyl chitosan CCS and 5g of glucose GL are sequentially added into a reactor, wherein the mass ratio of the carboxyl chitosan CCS to the glucose GL is 1:1, the solid content of the adhesive is 45%, the reaction condition is 90 ℃ and the reaction time is 6 hours, and the two are in synergistic copolymerization to prepare the modified chitosan-based wood adhesive.
The adhesive prepared in the step (3) is used for preparing plywood, and the sizing amount is 250g/m 2 The hot pressing temperature is 200 ℃, the hot pressing time is 6min,according to the requirements of national standard GB/T17657-2013 'artificial board and veneer artificial board physical and chemical Property experiment method', the plywood bonding strength and water resistance are tested.
Example 2
Example 2 differs from example 1 in that in step (3), 18g of deionized water, 5g of carboxyl chitosan CCS and 10g of glucose GL were sequentially added to the reactor under magnetic stirring, and the mass ratio of carboxyl chitosan CCS to glucose GL was 1:2, the solid content of the adhesive is 45%, the reaction condition is 90 ℃ and the reaction time is 6 hours, and the two are in synergistic copolymerization to prepare the modified chitosan-based wood adhesive.
Example 3
Example 3 differs from example 1 in that in step (3), 18g of deionized water, 10g of carboxyl chitosan CCS and 5g of glucose GL were sequentially added to the reactor under magnetic stirring, and the mass ratio of carboxyl chitosan CCS to glucose GL was 2:1, the solid content of the adhesive is 45%, the reaction condition is 90 ℃ and the reaction time is 6 hours, and the two are in synergistic copolymerization to prepare the modified chitosan-based wood adhesive.
Comparative example 1
12g of deionized water, 5g of chitosan CS and 5g of glucose GL are sequentially added into a reactor under magnetic stirring, wherein the mass ratio of the chitosan CS to the glucose GL is 1:1, the solid content of the adhesive is 45%, the reaction condition is 90 ℃ and the reaction time is 6 hours, and the two are in synergistic copolymerization to prepare the unmodified chitosan-based wood adhesive.
Comparative example 2
12g of deionized water, 5g of maleic anhydride MA and 5g of glucose GL are sequentially added into a reactor under magnetic stirring, wherein the mass ratio of the maleic anhydride MA to the glucose GL is 1:1, the solid content of the adhesive is 45%, the reaction condition is 90 ℃ and the reaction time is 6 hours, and the two are in synergistic copolymerization to prepare the unmodified glucose GL-based wood adhesive.
Application example
To verify the performance characteristics of the synthesized modified chitosan-based wood adhesives, the following tests were performed:
the modified chitosan-based wood adhesives prepared in each example and comparative example are used for pressing a three-layer plywood by using a poplar veneer with the thickness of 2mm, and the physical and mechanical properties of the board are tested according to the requirements of national standard GB/T17657-2013 for the physical and chemical properties test method of artificial boards and veneer artificial boards, and the water resistance of the board is mainly tested.
The method comprises the following specific steps: the synthesized modified chitosan-based wood adhesive is applied according to the sizing amount of 250g/m 2 The product is coated on a single-layer poplar board, hot pressed for 6 minutes at a hot pressing temperature of 200 ℃, and the dry strength, the wet strength (the test piece is soaked in water at 63 ℃ for 3 hours) and the water resistance of the test piece are respectively tested. The test piece is placed in boiling water for soaking for 3 hours, and the test results are shown in the following table 1, and according to the water resistance requirement of GB/T9846-2015 common plywood on class II plywood, each performance test data of the branched biomass-based wood adhesive is higher than the national standard requirement.
| Test piece | Dry Strength (MPa) | Soaking at 63 deg.c for 3 hr wet strength/MPa | Soaking wet 3h strength/MPa at 93 DEG C |
| Example 1 | 1.62 | 1.28 | 0.84 |
| Example 2 | 1.31 | 0.96 | 0.62 |
| Example 3 | 1.58 | 1.44 | 1.26 |
| Comparative example 1 | 0.83 | 0.72 | 0.55 |
| Comparative example 2 | 0.88 | 0.71 | 0.46 |
According to the water resistance requirement of GB/T9846-2015 common plywood on plywood, each item of data of the modified chitosan-based wood adhesive is higher than the national standard requirement.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or its scope as defined in the accompanying claims.
Claims (4)
1. The preparation method of the modified chitosan-based wood adhesive is characterized by comprising the following steps of:
(1) Under the stirring condition, adding maleic anhydride into a reactor, heating and melting, slowly adding chitosan, heating and stirring to perform amidation reaction, washing a mixture obtained after the reaction is finished by deionized water, and freeze-drying a precipitate to obtain carboxyl chitosan;
in the step (1), the mass ratio of the maleic anhydride to the chitosan is 8-10:1, a step of;
(2) Under the stirring condition, sequentially adding carboxyl chitosan, glucose GL and deionized water into a reactor, and heating to perform esterification reaction to obtain the modified chitosan-based wood adhesive;
in the step (2), the reaction temperature of the esterification reaction is 90-100 ℃ and the reaction time is 6-8h;
the mass ratio of the carboxyl chitosan to the glucose GL is 1:0.5-2.
2. The method for preparing the modified chitosan-based wood adhesive according to claim 1, wherein the method comprises the following steps: in the step (1), the reaction temperature of the amidation reaction is 90-100 ℃ and the reaction time is 6-8 h.
3. The method for preparing the modified chitosan-based wood adhesive according to claim 1, wherein the method comprises the following steps: in the step (1), the washing times are 2-4 times, and the drying time is 12-24 hours.
4. The method for preparing the modified chitosan-based wood adhesive according to claim 1, wherein the method comprises the following steps: in the step (2), the final solid content of the modified chitosan-based wood adhesive is 30% -50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310138383.8A CN116218416B (en) | 2023-02-20 | 2023-02-20 | Modified chitosan-based wood adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310138383.8A CN116218416B (en) | 2023-02-20 | 2023-02-20 | Modified chitosan-based wood adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116218416A CN116218416A (en) | 2023-06-06 |
| CN116218416B true CN116218416B (en) | 2024-01-16 |
Family
ID=86578131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310138383.8A Active CN116218416B (en) | 2023-02-20 | 2023-02-20 | Modified chitosan-based wood adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116218416B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011042610A1 (en) * | 2009-10-08 | 2011-04-14 | Upm-Kymmene Wood Oy | Bio-adhesive and wood board |
| CN103748124A (en) * | 2011-08-18 | 2014-04-23 | 巴斯夫欧洲公司 | Method for producing an aqueous binder system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2429598A2 (en) * | 2009-05-13 | 2012-03-21 | Kitozyme S.A. | Adhesive composition |
| ES2379329B1 (en) * | 2010-09-29 | 2013-03-20 | Instituto Científico Y Tecnológico De Navarra, S.A. | USE OF CARBOXIMETHYLQUITOSANS AS ADDITIVES IN CONGLOMERANT COMPOSITIONS. |
| CN112111022B (en) * | 2020-10-10 | 2021-06-04 | 山东一滕新材料股份有限公司 | Modified chitosan, preparation method thereof, ceramic tile glue additive and application thereof |
-
2023
- 2023-02-20 CN CN202310138383.8A patent/CN116218416B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011042610A1 (en) * | 2009-10-08 | 2011-04-14 | Upm-Kymmene Wood Oy | Bio-adhesive and wood board |
| CN103748124A (en) * | 2011-08-18 | 2014-04-23 | 巴斯夫欧洲公司 | Method for producing an aqueous binder system |
Non-Patent Citations (1)
| Title |
|---|
| Development of new natural polymer-based wood adhesives III: effects of glucose addition on properties of chitosan;Kenji Umemura等;《Journal of Wood Science》;第56卷;388, 392-393, 图9-10 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116218416A (en) | 2023-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110079270B (en) | Fiber modified soybean protein-based adhesive for artificial board and preparation method thereof | |
| CN109181585B (en) | Lignin-based formaldehyde-free adhesive and preparation method thereof | |
| CN105542710A (en) | Waterproof soybean meal adhesive and preparation method thereof | |
| CN114621705B (en) | Preparation method of starch-based adhesive based on aldehyde-amine crosslinking reaction | |
| CN112300756B (en) | Modified nano-cellulose reinforced soy protein adhesive and preparation method thereof | |
| Liu et al. | Activated wood surface and functionalized cellulose co-building strong chemical wood bonding performance | |
| CN108359407A (en) | A kind of modified vegetable protein adhesive and preparation method thereof | |
| Yang et al. | Development of high-performance sucrose-based adhesives with high density cross-linking network inspired by Maillard reaction or Cuisine chemistry | |
| CN116218416B (en) | Modified chitosan-based wood adhesive and preparation method and application thereof | |
| CN115584237B (en) | Biomass wood adhesive and preparation method and application thereof | |
| Feng et al. | Air oxidation and hyperbranched crosslinking approach for a boiling water-resistant sucrose-derived wood adhesive | |
| CN111234132B (en) | Water-based epoxy resin cross-linking agent, modified protein adhesive and application | |
| CN114316898B (en) | Preparation method of hyperbranched polyamine modified lignin adhesive | |
| CN113512399B (en) | Activated lignin modified formaldehyde-free soybean meal-based adhesive and preparation method and application thereof | |
| CN113913152A (en) | Spirulina protein adhesive and preparation method and application thereof | |
| CN111040728A (en) | Yeast protein adhesive and preparation method and application thereof | |
| CN109129798B (en) | High-performance structural material and preparation method thereof | |
| CN114196350B (en) | Waste molasses-based formaldehyde-free high-performance high-thermal-conductivity adhesive and preparation method and application thereof | |
| CN110964434B (en) | Aldehyde-free green environment-friendly adhesive and preparation method thereof | |
| CN115029102A (en) | High-initial-viscosity plant protein adhesive and preparation method and application thereof | |
| CN109401726B (en) | PEI-g-HBA prepolymer vegetable protein composite modified adhesive as well as preparation method and application thereof | |
| CN114292605A (en) | Formaldehyde-free antibacterial cellulose-based wood adhesive and preparation method thereof | |
| Zeng et al. | Preparation a novel high performance glucose-based wood adhesive with hyperbranched cross-linked network by air oxidation | |
| CN117402571B (en) | Biomass starch adhesive and preparation method and application thereof | |
| CN109180890B (en) | Method for preparing low-formaldehyde water-resistant copolycondensation resin adhesive from cellulosic ethanol fermentation residues |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |