CN110684484B - Environment-friendly adhesive with ultrahigh solid content for citric acid-based plywood, preparation method and application thereof - Google Patents
Environment-friendly adhesive with ultrahigh solid content for citric acid-based plywood, preparation method and application thereof Download PDFInfo
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- CN110684484B CN110684484B CN201911049953.6A CN201911049953A CN110684484B CN 110684484 B CN110684484 B CN 110684484B CN 201911049953 A CN201911049953 A CN 201911049953A CN 110684484 B CN110684484 B CN 110684484B
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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
- C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
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- 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
-
- 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
- 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
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Veneer Processing And Manufacture Of Plywood (AREA)
Abstract
The invention discloses an environment-friendly adhesive with ultrahigh solid content for citric acid-based plywood, which comprises the following components in percentage by weight: 100 parts of citric acid, 25-30 parts of cane sugar, 3-5 parts of copper chloride, 2-5 parts of calcium oxide, 10-15 parts of absolute ethyl alcohol and 15-28 parts of water; the solid content of the environment-friendly adhesive for the plywood is 75.1-84.8%, and the viscosity range is 277-537 mPa. Also discloses a preparation method thereof, application thereof in preparing plywood and the prepared plywood. The adhesive provided by the invention utilizes the catalytic action of citric acid on hydrolysis and conversion of sucrose to form a low molecular weight prepolymer, the viscosity of the adhesive is moderate, the solid content can reach 75.1-84.8%, the defect that the solid content cannot be increased due to overlarge viscosity of the traditional natural adhesive for plywood is overcome, the viscosity of the adhesive is adjusted by adopting an ethanol aqueous solution, the moisture content is reduced, the thermosetting efficiency is improved, and the thermosetting temperature is reduced.
Description
Technical Field
The invention relates to an environment-friendly adhesive with ultrahigh solid content for citric acid-based plywood, a preparation method and application thereof.
Background
Synthetic resin adhesives are generally prepared by taking petroleum extracts as main raw materials, and volatile organic compounds are released in the using process to pollute the environment; meanwhile, in consideration of the gradual shortage of petroleum resources, the development and application of environment-friendly adhesives taking renewable resources as main raw materials become key problems to be solved urgently in the wood adhesive industry; the traditional natural adhesive for the plywood is modified by adopting isolated soy protein or starch mostly, the solid content of the adhesive is low, the viscosity of the adhesive is high, the application process has the problems of high requirement on the flatness of materials, the need of adjusting the viscosity and the like, and the use is inconvenient, so that the development of the natural adhesive with ultrahigh solid content and low viscosity has important practical significance for expanding the application of the natural adhesive. The traditional citric acid-based adhesive adopts a sucrose adding mixing mode, the viscosity of the prepared adhesive is too low, the particle board can be prepared only in a spraying mode, and the preparation of the plywood cannot be carried out, so that the application field of a citric acid-sucrose bonding system can be expanded by developing the novel citric acid-based adhesive.
Disclosure of Invention
The invention aims to provide an environment-friendly adhesive with ultrahigh solid content for citric acid-based plywood.
The technical scheme of the invention is as follows:
the environment-friendly adhesive for the plywood with the ultrahigh solid content comprises the following components in percentage by weight:
100 parts of citric acid;
25-30 parts of cane sugar;
3-5 parts of copper chloride;
2-5 parts of calcium oxide;
10-15 parts of absolute ethyl alcohol;
15-28 parts of water;
the solid content of the environment-friendly adhesive for the plywood is 75.1-84.8%, and the viscosity range is 277-537 mPa.
The invention also discloses a preparation method of the environment-friendly adhesive for the plywood with the ultrahigh solid content, which comprises the following steps:
(1) mixing sucrose, copper chloride and water, and stirring at a low speed at a temperature of 70-80 ℃ for reaction for 1-1.5 hours;
(2) adding citric acid into the reaction system, and stirring at a low speed at 90-100 ℃ for reaction for 1-3 hours;
(3) adding absolute ethyl alcohol into the reaction system, and stirring at a high speed at a temperature of 80-90 ℃ for reaction for 0.5-1 hour;
(4) and after the temperature of the reaction system is reduced to room temperature, adding calcium oxide into the solution, and stirring at a low speed for 0.2-0.5 h.
Preferably, the low-speed stirring is 170-200 r/min, and the high-speed stirring is 350-370 r/min.
Preferably, the water is distilled water.
The invention also discloses an application of the environment-friendly adhesive for the plywood with the ultrahigh solid content in preparation of the plywood.
Preferably, the steps include: coating an environment-friendly adhesive for plywood on a single board, assembling a multi-layer plywood based on a vertical texture mode, and performing hot press molding, wherein the double-side adhesive applying amount is 160-200 g/m2The hot pressing temperature is 135-155 ℃, the pressure is 1-1.5 MPa, and the hot pressing time is 4-5 min.
Preferably, the multilayer plywood is 3-layer plywood
The invention also discloses a plywood which is formed by hot pressing the veneer and the environment-friendly adhesive for the plywood.
The invention has the following beneficial effects:
according to the adhesive disclosed by the invention, a low-molecular-weight prepolymer is formed by utilizing the catalytic action of citric acid and copper chloride on the caramelization reaction of sucrose, the defect that the solid content of the traditional natural adhesive for plywood cannot be increased due to overlarge viscosity is overcome, and the viscosity of the adhesive is prepared by adding absolute ethyl alcohol, so that the thermosetting speed and the bonding strength are increased.
The raw materials used in the invention have good water solubility, the viscosity of a saturated aqueous solution of the self-body is low, the solid content is low, and the self-body is not suitable for being used for the wood plywood, therefore, the invention enables sucrose to be subjected to hydrolysis reaction in a small amount of distilled water by improving the synthesis process, the solid content of the synthesized adhesive can reach 75.1-84.8%, and the viscosity range is 277-537 mPa.s.
Detailed Description
For better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1
The environment-friendly adhesive with ultrahigh solid content for the plywood comprises the following components in percentage by weight:
100 parts of citric acid;
30 parts of cane sugar;
5 parts of copper chloride;
5 parts of calcium oxide;
10 parts of absolute ethyl alcohol;
15 parts of water;
the preparation process of the adhesive comprises the following steps:
weighing corresponding raw material components in parts by weight, when the adhesive is prepared, firstly mixing sucrose, copper chloride and water, stirring at a low speed at 70 ℃ for reaction for 1.5 hours, then adding citric acid into a reaction system, stirring at a low speed at 90 ℃ for reaction for 3 hours, then adding absolute ethyl alcohol into the reaction system, stirring at a high speed at 80 ℃ for reaction for 1 hour, then closing a heating device, adding calcium oxide into the solution after the temperature of the reaction system is reduced to room temperature, and stirring at a low speed for 0.5 hour.
The solid content of the prepared adhesive is 84.8%.
The water is distilled water.
The low speed stirring is 170r/min and the higher speed stirring is 350 r/min.
The viscosity of the prepared adhesive is 537mPa & s at 25 ℃, and the testing method is a rotary viscometer.
Example 2
The environment-friendly adhesive with ultrahigh solid content for the plywood comprises the following components in percentage by weight:
100 parts of citric acid;
25 parts of cane sugar;
3 parts of copper chloride;
2 parts of calcium oxide;
15 parts of absolute ethyl alcohol;
28 parts of water;
the preparation process of the adhesive comprises the following steps:
weighing corresponding raw material components in parts by weight, when the adhesive is prepared, firstly mixing sucrose, copper chloride and water, stirring at a low speed at 75 ℃ for reaction for 1.2 hours, then adding citric acid into a reaction system, stirring at a low speed at 95 ℃ for reaction for 2 hours, then adding absolute ethyl alcohol into the reaction system, stirring at a high speed at 85 ℃ for reaction for 0.8 hour, then closing a heating device, adding calcium oxide into the solution after the temperature of the reaction system is reduced to room temperature, and stirring at a low speed for 0.4 hour.
The solid content of the prepared adhesive is 84.8%.
The water is distilled water.
The low speed stirring is 180r/min and the higher speed stirring is 360 r/min.
The viscosity of the prepared adhesive is 277mPa & s at 25 ℃, and the testing method is a rotary viscometer.
Example 3
The environment-friendly adhesive with ultrahigh solid content for the plywood comprises the following components in percentage by weight:
the environment-friendly adhesive with ultrahigh solid content for the plywood comprises the following components in percentage by weight:
100 parts of citric acid;
28 parts of cane sugar;
4 parts of copper chloride;
3 parts of calcium oxide;
13 parts of absolute ethyl alcohol;
22 parts of water;
the preparation process of the adhesive comprises the following steps:
weighing corresponding raw material components in parts by weight, when the adhesive is prepared, firstly mixing sucrose, copper chloride and water, stirring at a low speed at 80 ℃ for reaction for 1 hour, then adding citric acid into a reaction system, stirring at a low speed at 100 ℃ for reaction for 1 hour, then adding absolute ethyl alcohol into the reaction system, stirring at a high speed at 90 ℃ for reaction for 0.5 hour, then closing a heating device, adding calcium oxide into the solution after the temperature of the reaction system is reduced to room temperature, and stirring at a low speed for 0.2 hour.
The solid content of the prepared adhesive is 79.4%.
The water is distilled water.
The low speed stirring is 200r/min and the higher speed stirring is 370 r/min.
The viscosity of the prepared adhesive is 435mPa & s at 25 ℃, and the testing method is a rotary viscometer.
Comparative example 1: the only difference from example 1 is that sucrose is replaced by glucose.
Comparative example 2: the only difference from example 1 is that absolute ethanol was replaced with distilled water.
Comparative example 3: the only difference from example 1 is that calcium oxide is replaced by phosphorus pentoxide.
Example 4: plywood production
The poplar plywood is prepared by hot pressing according to the GB/T9846.7-2004 standard, and the technological parameters of the pressing plate are as follows: the size of the test piece is 300mm multiplied by 9mm, and the manual brushing mode is adopted to change the size of the test pieceThe adhesives prepared in the example 1 and the comparative example 1 are uniformly coated on poplar veneers, 3 layers of veneers are assembled based on a vertical texture mode, and the double-sided adhesive application amount is 200g/m2The hot pressing temperature is 145 ℃, the pressure is 1.5MPa, and the hot pressing time is 5 minutes.
Example 5: plywood production
The poplar plywood is prepared by hot pressing according to the GB/T9846.7-2004 standard, and the technological parameters of the pressing plate are as follows: the adhesive prepared in the example 2 and the comparative example 2 is uniformly coated on poplar veneers in a manual brushing mode, 3 layers of veneers are assembled based on a vertical texture mode, and the double-sided adhesive application amount is 160g/m2The hot pressing temperature is 135 ℃, the pressure is 1.2MPa, and the hot pressing time is 4.5 minutes.
Example 6: plywood production
The poplar plywood is prepared by hot pressing according to the GB/T9846.7-2004 standard, and the technological parameters of the pressing plate are as follows: the adhesive prepared in the example 3 and the comparative example 3 is uniformly coated on poplar veneers in a manual brushing mode, 3 layers of veneers are assembled based on a vertical texture mode, and the double-side adhesive application amount is 180g/m2The hot pressing temperature is 155 ℃, the pressure is 1.0MPa, and the hot pressing time is 4 minutes.
Performance testing and characterization
The related performance of the poplar plywood prepared by adopting the synthetic adhesive is tested according to a bonding strength test method of a II-type plywood specified in 4.17 in GB/T17657-2013, and the formaldehyde emission is tested according to the GB18580-2017 standard. The bonding strength of the product meets the relevant standard of national class II plywood,
table 1 shows the performance test results of poplar plywood prepared by the ultrahigh-solid-content adhesives of examples 1-3 and comparative examples 1-3 compared with the standard specified values (short for standard values) of GB/T9846-.
Table 1 performance test results of poplar plywood made with the ultra-high solid content adhesives of examples 1-3 and comparative examples 1-3
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (2)
1. The preparation method of the plywood is characterized by comprising the following steps: coating the citric acid-based plywood with ultrahigh solid content on a single board by using an environment-friendly adhesive, assembling 3 layers of plywood based on a vertical texture mode, and performing hot press molding, wherein the double-sided adhesive applying amount is 200g/m2Hot pressing temperature is 145 ℃, pressure is 1.5MPa, and hot pressing time is 5 min;
the environment-friendly adhesive for the citric acid-based plywood comprises the following components in percentage by weight: 100 parts of citric acid; 30 parts of cane sugar; 5 parts of copper chloride; 5 parts of calcium oxide; 10 parts of absolute ethyl alcohol; 15 parts of distilled water;
when the environment-friendly adhesive for the citric acid-based plywood is prepared, weighing corresponding raw material components in parts by weight, firstly mixing sucrose, copper chloride and distilled water, stirring at a low speed at 70 ℃ for reaction for 1.5 hours, then adding citric acid into a reaction system, stirring at a low speed at 90 ℃ for reaction for 3 hours, then adding absolute ethyl alcohol into the reaction system, stirring at a high speed at 80 ℃ for reaction for 1 hour, then closing a heating device, adding calcium oxide into a solution after the temperature of the reaction system is reduced to room temperature, and stirring at a low speed for 0.5 hour; the low-speed stirring is 170r/min, and the high-speed stirring is 350 r/min;
the solid content of the environment-friendly adhesive for the citric acid-based plywood is 84.8%, and the viscosity of the environment-friendly adhesive is 537 mPa.
2. Plywood produced according to the method of claim 1.
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| CN201911049953.6A CN110684484B (en) | 2019-10-30 | 2019-10-30 | Environment-friendly adhesive with ultrahigh solid content for citric acid-based plywood, preparation method and application thereof |
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| CN110366588A (en) * | 2017-02-24 | 2019-10-22 | 松下知识产权经营株式会社 | For hot-forming adhesive, wood based panel and its manufacturing method |
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Application publication date: 20200114 Assignee: NANJING DIOU FURNITURE CO.,LTD. Assignor: NANJING FORESTRY University Contract record no.: X2021980013336 Denomination of invention: Environmental friendly adhesive for citric acid based plywood with ultra-high solid content, preparation method and application thereof Granted publication date: 20210907 License type: Common License Record date: 20211125 |
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