CN109536126A - A kind of resistance to boiling water vegetable protein base based Wood Adhesives and its preparation method and application - Google Patents
A kind of resistance to boiling water vegetable protein base based Wood Adhesives and its preparation method and application Download PDFInfo
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- CN109536126A CN109536126A CN201810982006.1A CN201810982006A CN109536126A CN 109536126 A CN109536126 A CN 109536126A CN 201810982006 A CN201810982006 A CN 201810982006A CN 109536126 A CN109536126 A CN 109536126A
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- vegetable protein
- resistance
- boiling water
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- base based
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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
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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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
- C09J11/08—Macromolecular additives
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of vegetable protein of resistance to boiling water base based Wood Adhesives and its preparation method and application.The vegetable protein base based Wood Adhesives contain aqueous polyurethane adhesive, aqueous epoxy resins crosslinking agent；Wherein, the sum of the aqueous polyurethane adhesive and aqueous epoxy resins crosslinking agent quality account for the 5-15% of the vegetable protein of resistance to boiling water base based Wood Adhesives gross mass；It is preferred that 7-11%；Further preferred 10-11%.Vegetable protein base based Wood Adhesives of the present invention have solid content high, preparation process is simple, reactivity is strong, the advantages that glue-joint strength is high, solves common plant albumen base adhesive poor water resistance, the especially problem of boiling water resistance difference can satisfy the water-fast intensity requirement of outdoor wood-based plate adhesive.
Description
Technical field
The present invention relates to a kind of adhesive, in particular to a kind of wood-based plate vegetable protein of resistance to boiling water base based Wood Adhesives and
Preparation method and application.
Background technique
China is world's Wood-based Panel Production and consumption big country, wood-based plate total output, glued board yield, furniture yield, wooden
Floor yield occupies No. 1 in the world for years.The sustained and rapid development of industry of artificial boards is continuously increased timber industry gluing
The demand of agent.
Currently, three aldehydes adhesives (Lauxite, phenolic resin and melamine resin) dosage is still in based Wood Adhesives
It occupies an leading position in dosage, and the essence of poisonous and harmful substance and fossil resource that it is discharged in production and use process is not
It is disconnected to urge exploitation of the people for Environment-friendlyadhesive adhesive.Utilize the greenization of the renewable resources such as large agricultural product production environment-friendly type
Chemical product is that the exploitation of forest-friendly building timbers adhesive brings new opportunity.
The existing generally existing viscosity of vegetable protein base adhesive is big, curing rate is slow, solid content is low, higher cost, resistance to
It the problems such as aqueous poor, constructional difficulties, especially boiling water resistance difference outstanding problem, hinders vegetable protein base adhesive and further opens
Hair and popularization and application.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of wood-based plate vegetable protein of resistance to boiling water base based Wood Adhesives.
Present invention introduces aqueous polyurethane adhesives, aqueous epoxy resins crosslinking agent, and compound crosslinking system, energy are constructed between albumen substrate
Enough while greatly improving cured product crosslink density and water resistance, the solid content of albumen adhesive is significantly improved.It is real
Test the result shows that, the glued board bonding strength of modified adhesive preparation is fully able to meet II class glued board requirement in national standard.
Technical scheme is as follows.
A kind of resistance to boiling water vegetable protein base based Wood Adhesives are crosslinked containing aqueous polyurethane adhesive, aqueous epoxy resins
Agent；
Wherein, the sum of the aqueous polyurethane adhesive and aqueous epoxy resins crosslinking agent quality account for the vegetable protein of resistance to boiling water
The 5-15% of base based Wood Adhesives gross mass；It is preferred that 7-11%；Further preferred 10-11%.
The mass ratio of the aqueous polyurethane adhesive and aqueous epoxy resins crosslinking agent are as follows: (1-25): (1-20)；It is preferred that
(2-20): (2-15)；Further preferably (3-4): (1-2): or preferably (2-3): 1.
Wherein, it is poly- to can be selected from the standard aqueous that commercially available those skilled in the art are grasped for the aqueous polyurethane adhesive
Urethane adhesive, preferably makes by oneself with the following method in the present invention.
The Homemade method of the aqueous polyurethane adhesive is as follows:
(1) under nitrogen protection, catalyst action, isocyanates reacts 2-3 hours with polyalcohol in 70-80 DEG C；
(2) it is warming up to 80-90 DEG C, is added and contains hydrophilic radical chain extender, the reaction was continued 1-1.5 hours；
(3) 70 DEG C are cooled to, polyol chain extender is added, the reaction was continued 5-6 hours；
(4) under room temperature, neutralizer is added and reacts 0.5-1 hours, after high-speed stirred emulsification, aqueous polyurethane is made in discharging
Adhesive；
Wherein, the polyalcohol is selected from polytetramethylene glycol ether (PTMG), MDI or HDI, Isosorbide-5-Nitrae butanediol etc..
Wherein, the aqueous epoxy resins crosslinking agent is selected from glycidol ether, PAE (polyamine epichlorohydrin resin)
Deng.
As one of preferred embodiment for the present invention, the vegetable protein of the resistance to boiling water base based Wood Adhesives, including weigh as follows
Measure the component of part: 20-40 parts of the vegetable protein dregs of rice (powder), 1-25 parts of aqueous polyurethane adhesive, aqueous epoxy resins crosslinking agent 1-
20 parts, 60-80 parts of decentralized medium.
Preferably, the vegetable protein of the resistance to boiling water base based Wood Adhesives, the component including following parts by weight: the vegetable protein dregs of rice
25-35 parts of (powder), 2-20 parts of aqueous polyurethane adhesive, 2-15 parts of aqueous epoxy resins crosslinking agent, 65-75 parts of decentralized medium.
Further preferably, the vegetable protein of the resistance to boiling water base based Wood Adhesives, the component including following parts by weight: plant egg
White 25-35 parts of the dregs of rice (powder), 6-8 parts of aqueous polyurethane adhesive, 2-4 parts of aqueous epoxy resins crosslinking agent, decentralized medium 65-75
Part.
Still more preferably, the vegetable protein of the resistance to boiling water base based Wood Adhesives, the component including following parts by weight: plant
32-35 parts of the albumen dregs of rice (powder), 6-8 parts of aqueous polyurethane adhesive, 2-4 parts of aqueous epoxy resins crosslinking agent, decentralized medium 65-70
Part.
Wherein, the vegetable protein dregs of rice (powder) are selected from sunflower seed dregs powder, numb maple dregs of rice powder, peanut meal powder, the camellia oleosa seeds dregs of rice, castor
One or more of the numb dregs of rice, Cottonseed Meal powder, the vegetable seeds dregs of rice, corn germ cake, alcohol grain.
Wherein, the decentralized medium is softened water.
The present invention also provides the preparation methods of the above-mentioned vegetable protein of resistance to boiling water base based Wood Adhesives, comprising:
S1, the vegetable protein dregs of rice (powder) is added in decentralized medium, is stirred evenly；
S2, it is proportionally added into aqueous polyurethane adhesive, stirred evenly；
S3, aqueous epoxy resins crosslinking agent is added according to the ratio, homogenization obtains the vegetable protein of resistance to boiling water sill material gluing
Agent.
In above-mentioned S3, the pressure of homogenization is 20-40MPa.
The present invention also provides application of the above-mentioned vegetable protein of the resistance to boiling water base based Wood Adhesives in timber processing；It is preferred that described
Timber is wood-based plate.
The present invention also provides a kind of timber processed goods, contain the above-mentioned vegetable protein of resistance to boiling water base based Wood Adhesives.
What technical solution of the present invention obtained has the beneficial effect that:
The present invention is excellent using aqueous polyurethane adhesive has that reactivity is high, structure is adjustable and strength character is excellent
Point makes itself and aqueous epoxy resins crosslinker compounding, and fine and close molecule cross-link network is constructed between albumen substrate, thus significantly
Cured product crosslink density and water resistance are improved, while also significantly improving the solid content of vegetable protein base adhesive.Experiment
The result shows that being fully able to meet II class glue in national standard using the bonding strength of the glued board of adhesive of the present invention preparation
Plywood requirement.
The method of the present invention simple process, it is easy to operate, have many advantages, such as that manufacturing cost is low, renewable, it is environment friendly and pollution-free, it can
Reduce the harm generated in production, preparation and application process.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Without departing substantially from spirit of that invention
In the case where essence, to modifications or substitutions made by the method for the present invention, step or condition, all belong to the scope of the present invention.
If specializing, the conventional means that technological means used in embodiment is well known to those skilled in the art.
The percentage sign " % " being related in the present invention, if not specified, index finger mass percent；But the percentage of solution
Than unless otherwise specified, referring to and containing several grams of solute in solution 100ml；Percentage between liquid, capacity when referring to 20 DEG C
Ratio.
In following embodiments, the aqueous polyurethane adhesive by polytetramethylene glycol ether (PTMG), MDI or HDI,
The raw materials such as 1,4 butanediols are made by oneself using the above method.
The preparation of 1 vegetable protein of resistance to boiling water base based Wood Adhesives of embodiment
A kind of wood-based plate vegetable protein of resistance to boiling water base based Wood Adhesives, formula: softened water 65Kg, the vegetable protein dregs of rice
35Kg, aqueous polyurethane adhesive 8Kg, aqueous epoxy resins crosslinking agent (glycidol ether) 4Kg.
The preparation method of the above-mentioned vegetable protein of resistance to boiling water base based Wood Adhesives, comprising the following steps:
In the reaction kettle equipped with blender softened water is added according to the ratio, the vegetable protein dregs of rice stir evenly in S1；
Aqueous polyurethane adhesive is added according to the ratio and stirs evenly by S2；
Aqueous epoxy resins crosslinking agent (glycidol ether) is added according to the ratio and carries out homogenizer processing by S3, homogenization
Pressure is 25MPa.
Three batches of parallel samples are prepared with identical technique, and the performance quality index of obtained adhesive is shown in Table 1.
The preparation of 2 vegetable protein of resistance to boiling water base based Wood Adhesives of embodiment
A kind of wood-based plate vegetable protein of resistance to boiling water base based Wood Adhesives, formula: softened water 70Kg, the vegetable protein dregs of rice
30Kg, aqueous polyurethane adhesive 7Kg, aqueous epoxy resins crosslinking agent (PAE) 3Kg.
Preparation method is same as Example 1.
Three batches of parallel samples are prepared in the same way, and the performance quality index for the adhesive being made is shown in Table 1.
The preparation of 3 vegetable protein of resistance to boiling water base based Wood Adhesives of embodiment
A kind of wood-based plate vegetable protein of resistance to boiling water base based Wood Adhesives, formula: softened water 75Kg, the vegetable protein dregs of rice
25Kg, aqueous polyurethane adhesive 6Kg, aqueous epoxy resins crosslinking agent (PAE) 2Kg.
Preparation method is same as Example 1.
Three batches of parallel samples are prepared in the same way, and the performance quality index for the adhesive being made is shown in Table 1.
The performance indicator of 1 legumin adhesive of table
Reference examples 1
A kind of wood-based plate vegetable protein of resistance to boiling water base based Wood Adhesives, formula: softened water 75Kg, the vegetable protein dregs of rice
25Kg。
Preparation method is same as Example 1.
Reference examples 2
A kind of wood-based plate vegetable protein of resistance to boiling water base based Wood Adhesives, formula: softened water 75Kg, the vegetable protein dregs of rice
25Kg, aqueous polyurethane adhesive (with embodiment 1) 6Kg.
Preparation method is same as Example 1.
Reference examples 3
A kind of wood-based plate albumen of resistance to boiling water base adhesive, including following component: softened water 75Kg, the vegetable protein dregs of rice
25Kg, crosslinking agent (with embodiment 1) 2Kg.
Preparation method is same as Example 1.
Test example
Three layers of 450 × 450mm glued board of product manufacturing of 1-3 of the embodiment of the present invention and reference examples 1-3 are respectively adopted.
Board using poplar board: moisture content is dried to 6-14%；Thick 1.6mm；
Veneer adhesive is using the product of 1-3 of the embodiment of the present invention and the product of reference examples 1-3.
Glued board is prepared by following normal process:
Sizing: the two-sided sizing of core plate, glue-spread 300-360g/m2.
Aging and time: closure ageing, 10-30 minutes.
Preload pressure and time: precompressed 30 minutes, pressure 0.8MPa.
Hot pressing pressure: 1.2MPa, hot pressing temperature are 120 DEG C, hot pressing time 70s/mm.
By GB/T17657-1999 " wood-based plate and face artificial board physicochemical property experimental method " detection method to production
Plywood product carries out performance detection, and testing result is shown in Table 2.
The burst size of methanal and bonding strength of the splicing glued board of table 2
| Test specimen | Burst size of methanal (mg/L) | Bonding strength (MPa) |
| Embodiment 1 | 0.03 | 1.3±0.04 |
| Embodiment 2 | 0.04 | 1.1±0.05 |
| Embodiment 3 | 0.03 | 1.0±0.02 |
| Reference examples 1 | 0.06 | 0 (coming unglued) |
| Reference examples 2 | 0.06 | 0 (coming unglued) |
| Reference examples 3 | 0.05 | 0.6±0.03 |
The experimental results showed that the burst size of methanal of the glued board of present invention gained adhesive manufacture is all after hot-pressing processing
Very low (for timber ontology Form aldehyde release), the resistance to boiling water bonding strength of glued board reaches II class glued board standard (poplar in national standard
Wood >=0.70MPa).
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of vegetable protein of resistance to boiling water base based Wood Adhesives, which is characterized in that contain aqueous polyurethane adhesive, water-base epoxy
Resin cross-linking agent；
Wherein, the sum of the aqueous polyurethane adhesive and aqueous epoxy resins crosslinking agent quality account for the vegetable protein of resistance to boiling water sill
The 5-15% of material adhesive gross mass；It is preferred that 7-11%；Further preferred 10-11%.
2. the vegetable protein of resistance to boiling water base based Wood Adhesives according to claim 1, which is characterized in that the aqueous polyurethane
The mass ratio of adhesive and aqueous epoxy resins crosslinking agent are as follows: (1-25): (1-20)；It is preferred that (2-20): (2-15)；It is further excellent
It selects (3-4): (1-2): or preferably (2-3): 1.
3. the vegetable protein of resistance to boiling water base based Wood Adhesives according to claim 1 or 2, which is characterized in that described aqueous poly-
Urethane adhesive the preparation method is as follows:
(1) under nitrogen protection, catalyst action, isocyanates is reacted with polyalcohol in 70-80 DEG C；
(2) it is warming up to 80-90 DEG C, is added and contains hydrophilic radical chain extender, the reaction was continued；
(3) 70 DEG C are cooled to, polyol chain extender is added, the reaction was continued；
(4) under room temperature, neutralizer is added, after high-speed stirred emulsification, aqueous polyurethane adhesive is made in discharging.
4. the vegetable protein of resistance to boiling water base based Wood Adhesives according to claim 1 to 3, which is characterized in that described aqueous
Epoxy resin cross-linking agent is selected from glycidol ether, PAE.
5. the vegetable protein of resistance to boiling water base based Wood Adhesives according to claim 1 to 4, which is characterized in that including as follows
The component of parts by weight: 20-40 parts of the vegetable protein dregs of rice (powder), 1-25 parts of aqueous polyurethane adhesive, aqueous epoxy resins crosslinking agent
1-20 parts, 60-80 parts of decentralized medium；
Preferably, the vegetable protein of the resistance to boiling water base based Wood Adhesives, the component including following parts by weight: the vegetable protein dregs of rice (powder)
25-35 parts, 2-20 parts of aqueous polyurethane adhesive, 2-15 parts of aqueous epoxy resins crosslinking agent, 65-75 parts of decentralized medium；
Further preferably, the vegetable protein of the resistance to boiling water base based Wood Adhesives, the component including following parts by weight: the vegetable protein dregs of rice
25-35 parts of (powder), 6-8 parts of aqueous polyurethane adhesive, 2-4 parts of aqueous epoxy resins crosslinking agent, 65-75 parts of decentralized medium；
Still more preferably, the vegetable protein of the resistance to boiling water base based Wood Adhesives, the component including following parts by weight: vegetable protein
32-35 parts of the dregs of rice (powder), 6-8 parts of aqueous polyurethane adhesive, 2-4 parts of aqueous epoxy resins crosslinking agent, 65-70 parts of decentralized medium.
6. -5 any vegetable protein of resistance to boiling water base based Wood Adhesives according to claim 1, which is characterized in that the plant
The albumen dregs of rice (powder) be selected from sunflower seed dregs powder, numb maple dregs of rice powder, peanut meal powder, the camellia oleosa seeds dregs of rice, Castor seed Meal, Cottonseed Meal powder, the vegetable seeds dregs of rice,
One or more of corn germ cake, alcohol grain；
The decentralized medium is softened water.
7. a kind of preparation method of the vegetable protein of resistance to boiling water base based Wood Adhesives characterized by comprising
S1, the vegetable protein dregs of rice (powder) is added in decentralized medium, is stirred evenly；
S2, it is proportionally added into aqueous polyurethane adhesive, stirred evenly；
S3, aqueous epoxy resins crosslinking agent is added according to the ratio, homogenization obtains the vegetable protein of resistance to boiling water base based Wood Adhesives.
8. preparation method according to claim 7, which is characterized in that the pressure of homogenization is 20-40MPa.
9. application of any vegetable protein of the resistance to boiling water base based Wood Adhesives of claim 1-7 in timber processing；It is preferred that institute
Stating timber is wood-based plate.
10. a kind of timber processed goods, which is characterized in that contain any vegetable protein of the resistance to boiling water sill material of claim 1-7
Adhesive.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810982006.1A CN109536126A (en) | 2018-08-27 | 2018-08-27 | A kind of resistance to boiling water vegetable protein base based Wood Adhesives and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810982006.1A CN109536126A (en) | 2018-08-27 | 2018-08-27 | A kind of resistance to boiling water vegetable protein base based Wood Adhesives and its preparation method and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819276A (en) * | 2019-11-25 | 2020-02-21 | 浙江升华云峰新材股份有限公司 | High-strength low-formaldehyde glue and preparation method thereof |
| CN111171277A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Polyurethane elastic cross-linking agent, high-toughness vegetable protein adhesive and application |
| CN115477921A (en) * | 2022-09-27 | 2022-12-16 | 南京林业大学 | Plant meal-based adhesive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927757A (en) * | 2015-07-02 | 2015-09-23 | 青岛农业大学 | Preparation method of environment-friendly biomass adhesive |
| JP2017056715A (en) * | 2015-09-18 | 2017-03-23 | 王子ホールディングス株式会社 | Laminate |
-
2018
- 2018-08-27 CN CN201810982006.1A patent/CN109536126A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927757A (en) * | 2015-07-02 | 2015-09-23 | 青岛农业大学 | Preparation method of environment-friendly biomass adhesive |
| JP2017056715A (en) * | 2015-09-18 | 2017-03-23 | 王子ホールディングス株式会社 | Laminate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819276A (en) * | 2019-11-25 | 2020-02-21 | 浙江升华云峰新材股份有限公司 | High-strength low-formaldehyde glue and preparation method thereof |
| CN110819276B (en) * | 2019-11-25 | 2021-10-01 | 浙江升华云峰新材股份有限公司 | High-strength low-formaldehyde glue and preparation method thereof |
| CN111171277A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Polyurethane elastic cross-linking agent, high-toughness vegetable protein adhesive and application |
| CN111171277B (en) * | 2020-01-20 | 2024-04-19 | 北京林业大学 | Polyurethane elastic crosslinking agent, high-strength and high-toughness vegetable protein adhesive and application |
| CN115477921A (en) * | 2022-09-27 | 2022-12-16 | 南京林业大学 | Plant meal-based adhesive |
| CN115477921B (en) * | 2022-09-27 | 2024-03-19 | 南京林业大学 | Plant meal-based adhesive |
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