CN114456759B - High-strength environment-friendly multilayer composite board and preparation method thereof - Google Patents
High-strength environment-friendly multilayer composite board and preparation method thereof Download PDFInfo
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- CN114456759B CN114456759B CN202210093516.XA CN202210093516A CN114456759B CN 114456759 B CN114456759 B CN 114456759B CN 202210093516 A CN202210093516 A CN 202210093516A CN 114456759 B CN114456759 B CN 114456759B
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Classifications
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
-
- 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
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a high-strength environment-friendly multilayer composite board and a preparation method thereof, wherein the high-strength environment-friendly multilayer composite board comprises a board core and a single board, the board core and the single board are connected through an adhesive, and the adhesive comprises the following components in parts by weight: 50-70 parts of epoxy resin, 20-30 parts of phenolic resin, 5-10 parts of lignin emulsifier, 0.2-2.4 parts of coupling agent and 0.5-1.5 parts of curing agent. The components of the application are matched with each other, the formed adhesive is suitable for adhesion of the multilayer composite board, the obtained composite board is environment-friendly, the VOC content is low, and the strength of the composite board is high.
Description
Technical Field
The application belongs to the field of plate manufacturing, and particularly relates to a high-strength environment-friendly multilayer composite plate and a preparation method thereof.
Background
The wood composite board is an artificial board with wood shavings or fiber material as board core and two sides glued with veneers. The composite board is mainly an artificial board with oriented strand board as a board core and a single board as a surface layer. Wood composite panels are laminated structural panels made by gluing two sheets Bao Biaoban to a thicker core layer by means of an adhesive.
With the improvement of environmental awareness, the existing adhesive mainly comprises polyurethane, soy protein, plant starch, polyvinyl acetate, polyacrylate, modified isocyanate and the like.
In order to protect the environment of the plate, lignin is currently researched to be added into the adhesive, the lignin is a natural adhesive for the plant body, but in the industry, due to the fact that the mechanical property of the lignin is insufficient, the lignin is not only used as the adhesive, but also added into the traditional phenolic resin, urea-formaldehyde resin and melamine formaldehyde resin, on one hand, the production cost of the adhesive can be reduced, and on the other hand, the property of the adhesive can be improved.
The lignin commonly used at present comprises alkali lignin, lignosulfonate, organic solvent lignin, enzymolysis lignin, bagasse lignin and biomass waste residues. The following problems exist in the preparation of adhesives from lignin: 1. the compounding property between lignin and other high polymer adhesives is poor; 2. the prepared adhesive has poor gluing effect in the gluing process, and the strength of the multilayer composite board is lower.
Disclosure of Invention
In order to solve the problems, the application provides a high-strength environment-friendly multilayer composite board and a preparation method thereof, wherein the high-strength environment-friendly multilayer composite board comprises a board core and a single board, the board core and the single board are connected through an adhesive, and the adhesive comprises the following components in parts by weight: 50-70 parts of epoxy resin, 20-30 parts of phenolic resin, 5-10 parts of lignin emulsifier, 0.2-2.4 parts of coupling agent and 0.5-1.5 parts of curing agent.
Preferably, the epoxy resin is bisphenol A type epoxy resin, the epoxy resin consists of E-51 and E-12, and the mass ratio of the E-51 to the E-12 is (3-6): 1.
preferably, the phenolic resin is composed of a high molecular weight phenolic resin having a molecular weight of 1200-2000 and a low molecular weight phenolic resin having a molecular weight of 300-800, and the mass ratio of the high molecular weight phenolic resin to the low molecular weight phenolic resin is (3-7): 1.
preferably, the coupling agent is a mixture of silane coupling agents KH560 and KH550, and the mass ratio of KH560 to KH550 is 1: (3-5).
Preferably, the curing agent is one or more of dicyandiamide, diaminodiphenylmethane and diaminodiphenyl sulfone.
Preferably, the preparation method of the lignin emulsifier comprises the following steps: adding a metal compound and an oxidant into a lignin solution with the pH value of 9-11, reacting for 2-3 hours at the temperature of 80-100 ℃ to obtain oxidized lignin, and then adding amine and formaldehyde, and reacting for 2-3 hours at the temperature of 80-100 ℃ to obtain the lignin emulsifier.
Preferably, the metal compound is one or more of ferric chloride, ferrous sulfate, copper sulfate, manganese dioxide and zinc sulfate, and the mass ratio of the metal compound to the lignin raw material is (0.001-0.004): 1, a step of;
preferably, the oxidant is one or more of hydrogen peroxide, potassium permanganate and sodium peroxide, and the mass ratio of the oxide to the lignin raw material is (0.01-0.05): 1, a step of;
preferably, the amine is one or more of diethanolamine, ethanolamine, diethylenetriamine and triethylenetetramine, and the mass ratio of the amine to the lignin raw material is (0.2-0.4): 1, a step of; the molar ratio of the amine to formaldehyde is 1: (1-3).
On the other hand, the invention discloses a preparation method of the high-strength environment-friendly multilayer composite board, which comprises the following steps:
(1) Adding epoxy resin and phenolic resin into a solvent, stirring, adding lignin emulsifier, and emulsifying and stirring to obtain a first adhesive, wherein the emulsifying temperature is 25-50 ℃ and the emulsifying time is 10-25min;
(2) Adding a coupling agent into the first adhesive, uniformly stirring, and reacting at 70-90 ℃ for 30-50min to obtain a second adhesive;
(3) Adding a curing agent into the second adhesive, and uniformly stirring;
(4) And uniformly coating the second adhesive on the single plate, pressing the single plate on the plate core, and aging, hot-pressing and cold-pressing to obtain the composite plate.
Preferably, the solvent in the step (1) is one or more of butanone, methanol, ethanol, n-propanol, isopropanol, propylene glycol, tetrahydrofuran, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monobutyl ether, propylene glycol monopropyl ether and ethyl acetate.
Preferably, the second adhesive in the step (3) is coated in an amount of 100-200g/m 2 。
The application can bring the following beneficial effects:
1. the components of the application are matched with each other, the formed adhesive is suitable for adhesion of the multilayer composite board, the obtained composite board is environment-friendly, the VOC content is low, and the strength of the composite board is high.
2. According to the preparation method, the lignin is added into the epoxy resin and the phenolic resin in the form of the emulsifier, the advantages of the three-dimensional network structure of the lignin are fully exerted, the epoxy resin and the phenolic resin are mutually combined in a co-emulsification mode, the compounding property among the three components is improved, and the adhesive strength is effectively improved.
3. According to the application, by adding the coupling agent, on the one hand, the structure of the hydrophilic-hydrophobic amphoteric group in the lignin is added, so that each component in the adhesive forms a cross-linked structure; on the other hand, the adhesiveness of the adhesive and the wood is improved, and the strength of the composite board is improved.
Detailed Description
Example 1:
the preparation method of the high-strength environment-friendly multilayer composite board in the embodiment is as follows:
s1: preparation of lignin emulsifier
Adding a metal compound and an oxidant into a lignin solution with the pH value of 9-11, reacting for 2-3 hours at the temperature of 80-100 ℃ to obtain oxidized lignin, and then adding amine and formaldehyde, reacting for 2-3 hours at the temperature of 80-100 ℃ to obtain a lignin emulsifier;
wherein the metal compound is one or more of ferric chloride, ferrous sulfate, copper sulfate, manganese dioxide and zinc sulfate, and the mass ratio of the metal compound to the lignin raw material is (0.001-0.004): 1, a step of;
the oxidant is one or more of hydrogen peroxide, potassium permanganate and sodium peroxide, and the mass ratio of the oxide to the lignin raw material is (0.01-0.05): 1, a step of;
the amine is one or more of diethanolamine, ethanolamine, diethylenetriamine and triethylenetetramine, and the mass ratio of the amine to the lignin raw material is (0.2-0.4): 1, a step of; the molar ratio of the amine to formaldehyde is 1: (1-3);
s2: adding epoxy resin and phenolic resin into a solvent, stirring, adding lignin emulsifier, and emulsifying and stirring to obtain a first adhesive, wherein the emulsifying temperature is 25-50 ℃ and the emulsifying time is 10-25min;
wherein the solvent is one or more of butanone, methanol, ethanol, n-propanol, isopropanol, propylene glycol, tetrahydrofuran, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monobutyl ether, propylene glycol monopropyl ether, and ethyl acetate
S3: adding a coupling agent into the first adhesive, uniformly stirring, and reacting at 70-90 ℃ for 30-50min to obtain a second adhesive;
s4: adding a curing agent into the second adhesive, and uniformly stirring;
s5: uniformly coating a second adhesive on the single plate, pressing the single plate on a plate core, and ageing, hot-pressing and cold-pressing to obtain a composite plate; the adhesive distribution amount of the second adhesive is 100-200g/m 2 。
It is understood that the ageing step comprises ageing on a cold press for 30 minutes at a pressure of 0.5-1.0MPa after gluing the plywood; the hot pressing temperature is 90-120 ℃, the hot pressing time is 20-40 min, and the cold pressing pressure is 1.2MPa; cold pressing for 30-40 min with cold pressing pressure of 0.2MPa.
The specific implementation conditions are as follows:
example 2: characterization of
The adhesive is characterized by comprising the following contents:
1. viscosity: according to GB1723-79 paint viscosity measurement method, a paint-4 cup viscometer (unit is S) is adopted, and the paint is converted into rotational viscosity after being tested;
2. free formaldehyde content, tested according to the method described in GB/T14074-2006;
3. the adhesive strength of the adhesive is characterized, and the adhesive is tested according to the method described in GB/T9846-2004, and the detailed operation is as follows: the adhesive prepared in each example and comparative example was used to prepare plywood having a poplar veneer size of 200mm by 2mm, a water content of 8% and a sizing amount of 100-200g/m in the pressing process 2 。
The pressing plate process is divided into:
(1) Aging: ageing the glued plywood on a cold press for 30min under the pressure of 0.5 MPa;
(2) Hot pressing: the hot pressing pressure is 1.2MPa, and the hot pressing is carried out for 6min;
(3) Cold pressing: the cold pressing pressure is 1.2MPa, and the hot pressing is carried out for 6min.
And (3) placing the test piece at room temperature for 72 hours, cutting the test piece into test pieces according to the standard, and placing the test pieces on an electronic universal testing machine for testing the bonding strength.
TABLE 1 adhesive Performance test results
| Sample numbering | Viscosity (mPas) | Free formaldehyde (%) | Bonding strength (MPa) | Glue penetration phenomenon |
| 1 | 108 | 0.063 | 1.12 | Without any means for |
| 2 | 112 | 0.058 | 1.15 | Without any means for |
| 3 | 123 | 0.049 | 1.26 | Without any means for |
| 4 | 129 | 0.051 | 0.98 | Without any means for |
| 5 | 102 | 0.048 | 0.81 | Without any means for |
| 6 | 98 | 0.053 | 0.85 | Without any means for |
| 7 | 131 | 0.049 | 0.91 | Without any means for |
| 8 | 122 | 0.047 | 1.03 | Without any means for |
| 9 | 123 | 0.046 | 0.98 | Without any means for |
| Comparative example 1 | - | - | 0.56 | Without any means for |
| Comparative example 2 | - | - | 0.61 | Without any means for |
| Comparative example 3 | 55 | - | 0.68 | Has the following components |
| Comparative example 4 | - | - | 0.81 | Without any means for |
| Comparative example 5 | - | - | 0.52 | Without any means for |
| Comparative example 6 | - | - | 0.70 | ### |
From the experimental results in table 1, it can be seen that: the adhesive obtained by the invention has moderate viscosity, lower formaldehyde content and higher bonding strength of the obtained composite board.
As can be seen from the comparison of examples 4-5 and example 3, the epoxy resin in the application is compounded by two components, namely E-51 and E-12, so that the bonding strength of the composite board is improved; as can be seen from examples 6 to 7 compared with example 3, the phenolic resin in the present application is compounded by the phenolic resin with low molecular weight and high molecular weight, which is beneficial to improving the bonding strength of the composite board; as can be seen from the comparison of examples 8 to 9 with example 3, the bonding strength of the composite board is improved by compounding the two components KH560 and KH 550.
From comparative example 1-comparative example 2 compared with example 7, the phenolic resin was replaced with another type of resin, which is not advantageous for the bonding strength of plywood, and from another point of view, it can be seen that the compounding effect between the epoxy resin, phenolic resin and lignin emulsifier of the present invention is the best;
compared with the comparative example 3, if the lignin emulsifier is replaced by other conventional emulsifiers, the adhesive effect of the adhesive cannot be achieved, and the viscosity of the obtained adhesive is too low, so that the adhesive penetration phenomenon occurs;
as can be seen from comparison of comparative example 4 with example 8, the addition of the coupling agent in the present invention is beneficial to improving the adhesive strength of the composite board;
as can be seen from the data of comparative examples 5-6, the effect of the invention is not as high as the adhesive strength of the composite board obtained by adding lignin in the invention after the lignin raw material or lignin is modified conventionally and then is directly compounded with epoxy resin and phenolic resin.
In this specification, each embodiment is described in a progressive manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments. In particular, for system embodiments, since they are substantially similar to method embodiments, the description is relatively simple, as relevant to see a section of the description of method embodiments.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various modifications and changes may be made to the present application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principles of the present application are intended to be included within the scope of the claims of the present application.
Claims (5)
1. The high-strength environment-friendly multilayer composite board is characterized by comprising a board core and a single board, wherein the board core and the single board are connected through an adhesive, and the adhesive comprises the following components in parts by weight: 50-70 parts of epoxy resin, 20-30 parts of phenolic resin, 5-10 parts of lignin emulsifier, 0.2-2.4 parts of coupling agent and 0.5-1.5 parts of curing agent;
the epoxy resin is bisphenol A type epoxy resin, the epoxy resin consists of E-51 and E-12, and the mass ratio of the E-51 to the E-12 is (3-6): 1, a step of;
the phenolic resin consists of high molecular weight phenolic resin with molecular weight of 1200-2000 and low molecular weight phenolic resin with molecular weight of 300-800, wherein the mass ratio of the high molecular weight phenolic resin to the low molecular weight phenolic resin is (3-7): 1, a step of;
the coupling agent is a mixture of silane coupling agents KH560 and KH550, and the mass ratio of KH560 to KH550 is 1: (3-5);
the preparation method of the lignin emulsifier comprises the following steps: adding a metal compound and an oxidant into a lignin solution with the pH value of 9-11, reacting for 2-3 hours at the temperature of 80-100 ℃ to obtain oxidized lignin, and then adding amine and formaldehyde, reacting for 2-3 hours at the temperature of 80-100 ℃ to obtain a lignin emulsifier;
the metal compound is one or more of ferric chloride, ferrous sulfate, copper sulfate, manganese dioxide and zinc sulfate, and the mass ratio of the metal compound to the lignin raw material is (0.001-0.004): 1, a step of;
the oxidant is one or more of hydrogen peroxide and sodium peroxide, and the mass ratio of the oxidant to the lignin raw material is (0.01-0.05): 1, a step of;
the amine is one or more of diethanolamine, ethanolamine, diethylenetriamine and triethylenetetramine, and the mass ratio of the amine to lignin raw materials is (0.2-0.4): 1, a step of; the molar ratio of the amine to formaldehyde is 1: (1-3).
2. The high strength, environmentally friendly multi-layer composite board of claim 1, wherein: the curing agent is one or more of dicyandiamide, diaminodiphenyl methane and diaminodiphenyl sulfone.
3. A method for preparing the high-strength environment-friendly multilayer composite board according to any one of claims 1-2, comprising the following steps:
(1) Adding epoxy resin and phenolic resin into a solvent, stirring, adding lignin emulsifier, and emulsifying and stirring to obtain a first adhesive, wherein the emulsifying temperature is 25-50 ℃ and the emulsifying time is 10-25min;
(2) Adding a coupling agent into the first adhesive, uniformly stirring, and reacting at 70-90 ℃ for 30-50min to obtain a second adhesive;
(3) Adding a curing agent into the second adhesive, and uniformly stirring;
(4) And uniformly coating the second adhesive on the single plate, pressing the single plate on the plate core, and aging, hot-pressing and cold-pressing to obtain the composite plate.
4. The method according to claim 3, wherein the solvent in the step (1) is one or more of butanone, methanol, ethanol, n-propanol, isopropanol, propylene glycol, tetrahydrofuran, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monobutyl ether, propylene glycol monopropyl ether, and ethyl acetate.
5. The method according to claim 3, wherein the second adhesive in the step (4) is applied in an amount of 100 to 200g/m 2 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992018557A1 (en) * | 1991-04-09 | 1992-10-29 | Repap Technologies Inc. | Improved lignin-based wood adhesives |
| CN102061141A (en) * | 2009-11-11 | 2011-05-18 | 青岛生物能源与过程研究所 | Method for preparing environmentally-friendly adhesive for lignin-based timber |
| CN102746516A (en) * | 2012-06-15 | 2012-10-24 | 江苏博特新材料有限公司 | Lignin asphalt emulsifier with high temperature tolerance, its preparation method and application |
| CN111361240A (en) * | 2020-02-28 | 2020-07-03 | 新沂市甜浩木业有限公司 | Anticorrosive flame-retardant plywood and manufacturing method thereof |
| CN112521623A (en) * | 2019-12-30 | 2021-03-19 | 济南圣泉集团股份有限公司 | Lignin emulsifier, asphalt emulsifier, preparation method of asphalt emulsifier and asphalt |
-
2022
- 2022-01-26 CN CN202210093516.XA patent/CN114456759B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992018557A1 (en) * | 1991-04-09 | 1992-10-29 | Repap Technologies Inc. | Improved lignin-based wood adhesives |
| CN102061141A (en) * | 2009-11-11 | 2011-05-18 | 青岛生物能源与过程研究所 | Method for preparing environmentally-friendly adhesive for lignin-based timber |
| CN102746516A (en) * | 2012-06-15 | 2012-10-24 | 江苏博特新材料有限公司 | Lignin asphalt emulsifier with high temperature tolerance, its preparation method and application |
| CN112521623A (en) * | 2019-12-30 | 2021-03-19 | 济南圣泉集团股份有限公司 | Lignin emulsifier, asphalt emulsifier, preparation method of asphalt emulsifier and asphalt |
| CN111361240A (en) * | 2020-02-28 | 2020-07-03 | 新沂市甜浩木业有限公司 | Anticorrosive flame-retardant plywood and manufacturing method thereof |
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