CN114133913B - Waste molasses-based high-strength environment-friendly formaldehyde-free adhesive and preparation method and application thereof - Google Patents
Waste molasses-based high-strength environment-friendly formaldehyde-free adhesive and preparation method and application thereof Download PDFInfo
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- CN114133913B CN114133913B CN202111597582.2A CN202111597582A CN114133913B CN 114133913 B CN114133913 B CN 114133913B CN 202111597582 A CN202111597582 A CN 202111597582A CN 114133913 B CN114133913 B CN 114133913B
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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
- C09J199/00—Adhesives based on natural macromolecular compounds or on derivatives thereof, not provided for in groups C09J101/00 -C09J107/00 or C09J189/00 - C09J197/00
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a waste molasses-based high-strength environment-friendly formaldehyde-free adhesive as well as a preparation method and application thereof, wherein the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive is composed of the following raw materials: 80-100 parts of waste molasses, 40-60 parts of wheat gluten protein, 4-5 parts of carbon nano tubes, 10-15 parts of graphene fibers, 5-10 parts of silica microspheres, 5-10 parts of KH560 silane coupling agent, 3-4 parts of sodium sulfite, 2-3 parts of polyacrylamide, 0.05-2 parts of phosphoric acid and 40-50 parts of water, wherein the waste molasses used in the invention is hydrolyzed under the catalytic action of phosphoric acid, and the hydrolysate is reacted with the wheat gluten protein under the action of the KH560 silane coupling agent to generate a high polymer, so that a cross-linked structure is more compact and stable, the adhesive formed after curing has good bonding strength and thermal stability, and the carbon nano tubes and the graphene fibers are added into the adhesive, so that the defect of poor thermal conductivity of the traditional adhesive is overcome, the thermal curing rate is improved, and further improves the bonding strength.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a waste molasses-based high-strength environment-friendly formaldehyde-free adhesive as well as a preparation method and application thereof.
Background
The plywood is an important board in the artificial board, and has the characteristics of small deformation, large breadth, inconvenient construction, difficult warping, large transverse grain tensile strength and the like, and is widely applied to furniture, carriages, shipbuilding, military industry, packaging and other industrial departments.
Meanwhile, the health and environmental protection problems are always paid attention by consumers, and the 'exceeding of formaldehyde' is also in the wind gap wave tip in the household decoration complaint field for a long time, so that the development of an environment-friendly wood adhesive made of renewable materials becomes a key topic of wood science.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a waste molasses-based high-strength environment-friendly formaldehyde-free adhesive as well as a preparation method and application thereof, and solve the technical problems of low thermal conductivity coefficient and poor bonding strength of the traditional adhesive.
In order to achieve the purpose, the invention adopts the following technical scheme:
the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive is prepared from the following raw materials in parts by weight: 80-100 parts of waste molasses, 40-60 parts of wheat gluten protein, 4-5 parts of carbon nano tube, 10-15 parts of graphene fiber, 5-10 parts of silicon dioxide microspheres, 5-10 parts of KH560 silane coupling agent, 3-4 parts of sodium sulfite, 2-3 parts of polyacrylamide, 0.05-2 parts of phosphoric acid and 40-50 parts of water.
Preferably, the thermal conductivity of the adhesive is 2.6-2.9W/(m.K).
Preferably, the viscosity of the adhesive is 445-736mPa · s.
The invention provides a preparation method of the waste molasses-based high-strength environment-friendly aldehyde-free adhesive, which comprises the following steps:
(1) uniformly mixing the waste molasses, the phosphoric acid and the water, and stirring at a low speed at a temperature of between 70 and 80 ℃ for reaction for 1 to 1.5 hours;
(2) adding wheat gluten protein, carbon nano tubes and graphene fibers into the reaction system in the step (1), and stirring at a low speed at the temperature of 60-80 ℃ for reaction for 1-2 hours;
(3) adding the silica microspheres and the KH560 silane coupling agent into the reaction system in the step (2), and stirring at a low speed at the temperature of 30-40 ℃ for reaction for 1-1.5 h;
(4) adding sodium sulfite into the reaction system in the step (3), and stirring at a high speed at a temperature of between 80 and 90 ℃ for reaction for 0.5 to 1 hour;
(5) and (5) after the temperature of the reaction system in the step (4) is reduced to room temperature, adding polyacrylamide into the reaction system, and stirring the mixture at a low speed for 0.5 to 1 hour to obtain the adhesive.
Preferably, the low-speed stirring rotation speed is 140-180r/min, and the high-speed stirring rotation speed is 380-400 r/min.
The invention provides an application of the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive in preparation of plywood.
Preferably, the method comprises the following steps: and (3) coating the adhesive on the single boards, assembling 3 layers of the plywood based on a vertical texture mode, and performing hot press molding to obtain the plywood.
Preferably, the dosage of the adhesive is 180-220g/m 2 。
Preferably, the hot-pressing temperature is 130-170 ℃, the pressure is 1-1.5MPa, and the hot-pressing time is 4-5 min.
The invention also provides a plywood which is formed by hot-pressing the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive and a veneer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste molasses used in the invention is hydrolyzed under the catalytic action of phosphoric acid, and the hydrolysate reacts with wheat gluten protein under the action of KH560 silane coupling agent to generate high molecular polymer, so that the cross-linked structure is more compact and stable, and the adhesive formed after curing has good bonding strength and thermal stability.
(2) According to the invention, the carbon nano tube and the graphene fiber are added into the adhesive, so that the defect of poor thermal conductivity of the traditional adhesive is overcome, the thermosetting rate is increased, and the bonding strength is further improved.
(3) The invention uses the waste molasses as the main raw material, no formaldehyde is added in the preparation process, no formaldehyde is released in the decomposition process, and the requirements of environmental protection can be met.
Detailed Description
The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.
It should be noted that the chemicals involved in the present invention are all purchased from commercial sources without specific reference.
Example 1
The preparation method of the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive comprises the following steps:
uniformly mixing 100g of waste molasses, 0.5g of phosphoric acid and 40g of water, stirring and reacting for 1h at the rotating speed of 70 ℃ and 160r/min, then adding 40g of wheat gluten, 4g of carbon nano tube and 10g of graphene fiber, stirring and reacting for 1h at the rotating speed of 60 ℃ and 160r/min, then adding 5g of silicon dioxide microspheres and 6gKH560 silane coupling agent, stirring and reacting for 1h at the rotating speed of 30 ℃ and 160r/min, then adding 3g of sodium sulfite, stirring and reacting for 1h at the rotating speed of 80 ℃ and 400r/min, then cooling to room temperature, adding 2g of polyacrylamide, stirring for 1h at the rotating speed of 160r/min, and obtaining the adhesive.
Example 2
The preparation method of the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive comprises the following steps:
uniformly mixing 80g of waste molasses, 1g of phosphoric acid and 45g of water, stirring and reacting for 1h at the rotating speed of 70 ℃ and 160r/min, then adding 50g of wheat gluten, 4g of carbon nano tube and 10g of graphene fiber, stirring and reacting for 1h at the rotating speed of 60 ℃ and 160r/min, then adding 8g of silicon dioxide microspheres and 8gKH560 silane coupling agent, stirring and reacting for 1h at the rotating speed of 30 ℃ and 160r/min, then adding 4g of sodium sulfite, stirring and reacting for 1h at the rotating speed of 80 ℃ and 400r/min, then cooling to room temperature, adding 3g of polyacrylamide, stirring for 1h at the rotating speed of 160r/min, and obtaining the adhesive.
Example 3
The preparation method of the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive comprises the following steps:
uniformly mixing 100g of waste molasses, 2g of phosphoric acid and 50g of water, stirring and reacting for 1h at the rotating speed of 70 ℃ and 160r/min, then adding 60g of wheat gluten, 5g of carbon nano tube and 12g of graphene fiber, stirring and reacting for 1h at the rotating speed of 60 ℃ and 160r/min, then adding 5g of silicon dioxide microspheres and 8gKH560 silane coupling agent, stirring and reacting for 1h at the rotating speed of 30 ℃ and 160r/min, then adding 4g of sodium sulfite, stirring and reacting for 1h at the rotating speed of 80 ℃ and 400r/min, then cooling to room temperature, adding 2g of polyacrylamide, stirring for 1h at the rotating speed of 160r/min, and obtaining the adhesive.
Comparative example 1
The preparation method of the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive comprises the following steps:
uniformly mixing 80g of waste molasses, 1g of phosphoric acid and 45g of water, stirring at 70 ℃ and 160r/min for reaction for 1h, then adding 4g of carbon nano tube and 10g of graphene fiber, stirring at 60 ℃ and 160r/min for reaction for 1h, then adding 8g of silicon dioxide microsphere and 8gKH560 silane coupling agent, stirring at 30 ℃ and 160r/min for reaction for 1h, then adding 4g of sodium sulfite, stirring at 80 ℃ and 400r/min for reaction for 1h, then cooling to room temperature, adding 3g of polyacrylamide, and stirring at 160r/min for 1h to obtain the adhesive.
Comparative example 2
The preparation method of the waste molasses-based high-strength environment-friendly formaldehyde-free adhesive comprises the following steps:
uniformly mixing 80g of waste molasses, 1g of phosphoric acid and 45g of water, stirring at 70 ℃ and 160r/min for reaction for 1h, then adding 50g of wheat gluten protein, stirring at 60 ℃ and 160r/min for reaction for 1h, then adding 8g of silicon dioxide microspheres and 8gKH560 silane coupling agent, stirring at 30 ℃ and 160r/min for reaction for 1h, then adding 4g of sodium sulfite, stirring at 80 ℃ and 400r/min for reaction for 1h, then cooling to room temperature, adding 3g of polyacrylamide, and stirring at 160r/min for 1h to obtain the adhesive.
The adhesives prepared in examples 1-3 and comparative examples 1-2 were tested for thermal conductivity and viscosity, and the results are shown in the following table:
the 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 a test piece is 300mm multiplied by 9mm, the adhesives prepared in the examples 1-3 and the comparative examples 1-2 are uniformly coated on poplar veneers in a manual painting mode, 3 layers of plywood are assembled based on a vertical texture mode, and the using amount of the adhesive is 200g/m 2 The hot pressing temperature is 145 ℃, and the pressure isThe force is 1.5MPa, and the hot pressing time is 4min, thus obtaining the plywood.
The plywood bonding strength is tested according to a type II plywood bonding strength test method specified in GB/T17657-2013 at 4.17, the formaldehyde emission is tested according to the GB18580-2017 standard, and the test results are shown in the following table:
| bonding Strength (MPa) | Formaldehyde emission (mg/m) 3 ) | |
| Example 1 | 1.16 | 0.006 |
| Example 2 | 1.25 | 0.004 |
| Example 3 | 1.19 | 0.005 |
| Comparative example 1 | 0.74 | 0.005 |
| Comparative example 2 | 0.95 | 0.006 |
| Class II plywood labelStandard value of | ≥0.70 | ≤0.124 |
Finally, it is to be noted that: the above examples do not limit the invention in any way. It will be apparent to those skilled in the art that various modifications and improvements can be made to the invention. Accordingly, any modification or improvement made without departing from the spirit of the present invention is within the scope of the claimed invention.
Claims (10)
1. The waste molasses-based high-strength environment-friendly formaldehyde-free adhesive is characterized by comprising the following raw materials in parts by weight: 80-100 parts of waste molasses, 40-60 parts of wheat gluten protein, 4-5 parts of carbon nano tube, 10-15 parts of graphene fiber, 5-10 parts of silica microsphere, 5-10 parts of KH560 silane coupling agent, 3-4 parts of sodium sulfite, 2-3 parts of polyacrylamide, 0.05-2 parts of phosphoric acid and 40-50 parts of water.
2. The molasses-based high-strength environment-friendly aldehyde-free adhesive as claimed in claim 1, wherein the thermal conductivity coefficient of the adhesive is 2.6-2.9W/(m.K).
3. The molasses-based high-strength environment-friendly aldehyde-free adhesive as claimed in claim 1, wherein the viscosity of the adhesive is 445-736 mPa-s.
4. The method for preparing the waste molasses-based high-strength environment-friendly aldehyde-free adhesive as claimed in any one of claims 1-3, characterized by comprising the following steps:
(1) uniformly mixing the waste molasses, the phosphoric acid and the water, and stirring at a low speed at a temperature of between 70 and 80 ℃ for reaction for 1 to 1.5 hours;
(2) adding wheat gluten protein, carbon nano tubes and graphene fibers into the reaction system in the step (1), and stirring at a low speed at a temperature of between 60 and 80 ℃ for reaction for 1 to 2 hours;
(3) adding the silica microspheres and the KH560 silane coupling agent into the reaction system in the step (2), and stirring at a low speed at the temperature of 30-40 ℃ for reaction for 1-1.5 h;
(4) adding sodium sulfite into the reaction system in the step (3), and stirring at a high speed at a temperature of between 80 and 90 ℃ for reaction for 0.5 to 1 hour;
(5) and (4) after the temperature of the reaction system in the step (4) is reduced to room temperature, adding polyacrylamide into the reaction system, and stirring the mixture at a low speed for 0.5 to 1 hour to obtain the adhesive.
5. The method for preparing the waste molasses-based high-strength environment-friendly aldehyde-free adhesive as claimed in claim 4, wherein the low-speed stirring rotation speed is 140-180r/min, and the high-speed stirring rotation speed is 380-400 r/min.
6. Use of the molasses-based high-strength environment-friendly aldehyde-free adhesive as claimed in any one of claims 1-3 in the preparation of plywood.
7. The use according to claim 6, comprising the steps of: and (3) coating the adhesive on the single boards, assembling 3 layers of the plywood based on a vertical texture mode, and performing hot press molding to obtain the plywood.
8. The use as claimed in claim 7, wherein the amount of the adhesive is 180- 2 。
9. The method as claimed in claim 7, wherein the hot-pressing temperature is 130-170 ℃, the pressure is 1-1.5MPa, and the hot-pressing time is 4-5 min.
10. A plywood formed by hot-pressing the high-strength environment-friendly waste molasses-based formaldehyde-free adhesive as claimed in any one of claims 1-3 with a veneer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111597582.2A CN114133913B (en) | 2021-12-24 | 2021-12-24 | Waste molasses-based high-strength environment-friendly formaldehyde-free adhesive and preparation method and application thereof |
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|---|---|---|---|
| CN202111597582.2A CN114133913B (en) | 2021-12-24 | 2021-12-24 | Waste molasses-based high-strength environment-friendly formaldehyde-free adhesive and preparation method and application thereof |
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| CN114133913A CN114133913A (en) | 2022-03-04 |
| CN114133913B true CN114133913B (en) | 2022-09-30 |
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| CN114854370B (en) * | 2022-05-27 | 2023-03-21 | 南京林业大学 | Biological purification waste molasses-based environment-friendly adhesive, plywood and preparation method and application thereof |
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| GB1469934A (en) * | 1974-02-22 | 1977-04-06 | Chemotherm Bonding Inc | Bonding of solid lignocellulosic material |
| CN85106931A (en) * | 1985-09-12 | 1987-03-11 | 叶禽择 | Adhesional crushed material boards by molasses glue |
| CN107903847A (en) * | 2017-11-20 | 2018-04-13 | 苏州甫众塑胶有限公司 | A kind of compound wooden case adhesive and preparation method thereof |
| WO2020032899A1 (en) * | 2018-08-07 | 2020-02-13 | T.C. Erciyes Universitesi | Molasses bio binder production and applications thereof |
| CN112778955A (en) * | 2021-01-11 | 2021-05-11 | 黄山学院 | Low-cost aqueous adhesive and preparation method thereof |
| WO2021101396A1 (en) * | 2019-11-19 | 2021-05-27 | Sestec Polska Sp. Z O.O. | Binding agent for cellulose containing materials and the product containing it |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2230222A1 (en) * | 2009-03-19 | 2010-09-22 | Rockwool International A/S | Aqueous binder composition for mineral fibres |
| ES2747394T3 (en) * | 2011-05-17 | 2020-03-10 | Construction Research & Technology Gmbh | Preparation procedure of additive for cementitious materials, additive and mixture comprising additive |
| EP3140361A2 (en) * | 2014-01-08 | 2017-03-15 | Cambond Limited | Bio-adhesives |
| JP6796938B2 (en) * | 2016-03-28 | 2020-12-09 | ヘンケルジャパン株式会社 | Water-based adhesive composition |
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- 2021-12-24 CN CN202111597582.2A patent/CN114133913B/en active Active
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| GB1469934A (en) * | 1974-02-22 | 1977-04-06 | Chemotherm Bonding Inc | Bonding of solid lignocellulosic material |
| CN85106931A (en) * | 1985-09-12 | 1987-03-11 | 叶禽择 | Adhesional crushed material boards by molasses glue |
| CN107903847A (en) * | 2017-11-20 | 2018-04-13 | 苏州甫众塑胶有限公司 | A kind of compound wooden case adhesive and preparation method thereof |
| WO2020032899A1 (en) * | 2018-08-07 | 2020-02-13 | T.C. Erciyes Universitesi | Molasses bio binder production and applications thereof |
| WO2021101396A1 (en) * | 2019-11-19 | 2021-05-27 | Sestec Polska Sp. Z O.O. | Binding agent for cellulose containing materials and the product containing it |
| CN112778955A (en) * | 2021-01-11 | 2021-05-11 | 黄山学院 | Low-cost aqueous adhesive and preparation method thereof |
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| Title |
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| 糖蜜胶粘剂及其特性;应向东;《化学建材》;19910630;第9-11页 * |
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