CN103320078B - Plant-based polyester polyol-chitosan adhesive, and preparation method and application thereof - Google Patents
Plant-based polyester polyol-chitosan adhesive, and preparation method and application thereof Download PDFInfo
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- CN103320078B CN103320078B CN201310194068.3A CN201310194068A CN103320078B CN 103320078 B CN103320078 B CN 103320078B CN 201310194068 A CN201310194068 A CN 201310194068A CN 103320078 B CN103320078 B CN 103320078B
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Abstract
The invention relates to a preparation method of a plant-based polyester polyol-chitosan adhesive, and an application of the adhesive, and belongs to the technical fields of chemical adhesives, resource utilization and composite materials. Plant-based polyester polyol is prepared through adopting agricultural wastes wheat straws, dihydric alcohol, a catalyst and maleic anhydride. The plant-based polyester polyol and an aqueous chitosan solution are blended to prepare a plant-based polyester polyol-chitosan aqueous emulsion, and the plant-based polyester polyol-chitosan aqueous emulsion and MDI which are individually packaged undergo room-temperature stirring mixing to prepare the plant-based polyester polyol-chitosan adhesive when used. The adhesive is used for adhering a decoration single board veneering artificial board.
Description
Technical field
The present invention relates to a kind of plant base polyesterols-chitosan gluing agent and its preparation method and application, belong to chemical sizing agent, resource utilization recycling and technical field of composite materials.
Background technology
Using natural polymers to prepare wood adhesive as soybean protein etc. has had very long history, but the shortcomings such as the low bonding strength of sheet material ubiquity of making and low water tolerance.And the three aldehyde adhesive made of synthetic resin that use in a large number at present, although have high-adhesive-strength and high water tolerance, the formaldehyde containing causes very large harm to human health.Along with the raising of people's quality of life and the enhancing of environmental consciousness, solve containing the pollution problem in aldehyde sizing agent and wood-based plate thereof, development of new non-formaldehyde wood sizing agent, eliminate the pollution of formaldehyde to environment, becoming the problem that based Wood Adhesives industry development need to solve, is also challenge and opportunity that chemist faces.The research and development of the based Wood Adhesives that the reproducible biomass high molecular polymer of take is raw material, have great importance.
Chitosan is the nitrogenous polysaccharose substance of a kind of natural polymer, the annual biosynthetic chitin of nature reaches 10,000,000,000 tons according to estimates, considerably beyond other glycosaminoglycan, chitosan is only second to Mierocrystalline cellulose in the output of occurring in nature, is one of organic natural macromolecular material the abundantest on the earth.That chitosan has is nontoxic, good biocompatibility, be easy to the features such as degraded.Seafood processing industry waste is one of source of chitin, utilizes these wastes to be hydrolyzed under alkaline condition, makes its deacetylation can make chitosan.Utilize chitosan for raw material, prepare the based Wood Adhesives of high performance-price ratio, both met the recycling economy development theory of waste reclaimation, can be again sizing agent industry development new thinking is provided.
At present, in published sizing agent preparation research, more used isocyanic ester.The sizing agent that the isocyanic ester of take is prepared as main raw material, normal temperature solidified, also heating curable, and easily produce crosslinking structure, heat-resisting, solvent resistance good, but that weak point is molecular weight is little, isocyanate group (NCO) content is high, glue-line after solidifying is hard and crisp, and isocyanic ester is expensive, has increased the production cost of sizing agent.Also the researchist that has attempts take chitosan and prepares sizing agent as main raw material, the glued board dry glue intensity of such sizing agent bonding, is better than traditional urea-formaldehyde resin, casein food grade and bean gum, and its water resistance is also better than casein food grade and bean gum, and this sizing agent also has effective preservative activity.But the complexity of chitosan concentration and gluing is to be difficult to the contradiction of balance in such sizing agent preparation technology, and, the sizing agent that the chitosan of take makes as raw material, resin added is larger, approximately 500～700g/m2 left and right.
Summary of the invention
One of technical assignment of the present invention is in order to make up the deficiencies in the prior art, a kind of plant base polyesterols-chitosan gluing agent that chitosan and agricultural wastes wheat stalk make as raw material of take is provided, this sizing agent raw materials cost is low, there is higher bonding strength and water tolerance, and environmentally safe.
Two of technical assignment of the present invention is to provide the preparation method of this plant base polyesterols-chitosan gluing agent, and this preparation technology is simple, easy to operate.
Three of technical assignment of the present invention is to provide the application of this plant base polyesterols-chitosan gluing agent, and this sizing agent is for timber gluing, high to timber bonding action.
1. plant base polyesterols-chitosan gluing agent, is characterized in that, this tackiness agent be by plant base polyester polyol-chitosan water miscible liquid and MDI-100 in mass ratio 100:3～8 stirring at room mix and make;
Described plant base polyester polyol-chitosan water miscible liquid be by plant base polyester polyol and chitosan aqueous solution in mass ratio 10～20:100 blend 30min make;
Described plant base polyester polyol is made by the raw material through chemical reaction of following mass parts:
Dibasic alcohol 100
Wheat stalk 30～40
Catalyzer 2～3
MALEIC ANHYDRIDE 20～30
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described wheat stalk is the drying wheat straw powder below 10 orders, and its water content massfraction is less than 1%;
It is one of following that described catalyzer is selected from: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid.
2. above-described plant base polyesterols-chitosan gluing agent preparation method, step is as follows:
(1) preparation of plant base polyester polyol
In the dibasic alcohol of 100 mass parts, under stirring, add wheat stalk powder 15～20 mass parts, catalyzer 2～3 mass parts below 10 orders, after blend evenly, be heated to 160～180 ℃, insulation 30min; Add again wheat stalk powder 15～20 mass parts below 10 orders, continue, at 160～180 ℃ of insulation 60～90min, to make plant base polyvalent alcohol; Add Succinic anhydried 20～30 mass parts, at 150 ℃, insulation 30min; Temperature is risen to 190～210 ℃, insulation 120～150min; Be cooled to normal temperature, make plant base polyester polyol.
(2) preparation of plant base polyesterols-chitosan water miscible liquid
In the water of 100 mass parts, add organic acid 1 mass parts, chitosan 2 mass parts, are heated to 30～50 ℃, are stirred to completely and dissolve and make chitosan aqueous solution; The plant base polyester polyol that chitosan aqueous solution and step (1) are made in mass ratio 100:5～10 blend 30min makes plant base polyesterols-chitosan water miscible liquid.
(3) while using, by plant base polyesterols-chitosan aqueous solution and MDI-100 in mass ratio 100:3～8 stirring at room mix, obtain the agent of plant base polyesterols-chitosan gluing.
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol;
Described wheat stalk is the drying wheat straw powder below 10 orders, and its water content massfraction is less than 1%;
It is one of following that described catalyzer is selected from: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid;
It is one of following that described organic acid is selected from: acetic acid, citric acid;
Described deacetylating degree of chitosan is 80%-90%, and molecular weight is 2 * 10
5～3 * 10
5;
Described MDI-100 is more than 98% MDI for containing 4,4'-diphenylmethanediisocyanate massfraction, its chromatic number≤30(platinum-cobalt), zero pour >=38.1 ℃, hexanaphthene insolubles≤0.3%, hydrolysis chlorine≤0.0050%.Be purchased from Yantai Wanhua Polyurethane Co., Ltd.
3. the plant base of above-described preparation polyesterols-chitosan gluing agent, is characterized in that, is applied to the gluing of wood single-plate overlaid wood based panel, and Amount of spread is 200g/m
2.
Bonding step carries out with reference to GB/T 15104-2006 < < Decorative veneered woodbased panel > >.One veneer test piece one side is coated with to the agent of plant base polyesterols-chitosan gluing as panel, and Amount of spread is 200g/m
2, dash board becomes sheet material with the vertical lamination of backboard fiber direction, after gluing first with the pressure of the 1.0MPa 20min that colds pressing, then, in thermocompressor, with the pressure of 1.0MPa, in 115 ℃ of even pressurization 3min, the sheet material room temperature ageing 24h after compacting.Sheet material after ageing is sawn into test specimen, surveys its surface bonding intensity.The white oak of take is that the test of examination material shows, surface bonding strength mean value is greater than 1.0 MPa, proves thus, and plant base polyesterols-chitosan gluing of the present invention agent has good gluing performance.
More than prepare and raw materials usedly all can buy from Chemical market.
Compared with prior art, plant base polyesterols-chitosan gluing agent outstanding feature of the present invention is:
(1) select agricultural wastes wheat stalk as preparing one of main raw material of plant base polyester polyol.Wheat stalk is under the condition of dibasic alcohol and catalyzer existence, and heating is liquefied and is depolymerized to low molecular polylol, and polyvalent alcohol and maleic acid anhydride reactant generate macromole polyester polyol.This preparation technology is new application approach and the field of having reclaimed useless straw Resource Supply, and the raw materials cost of synthesizing polyester alcohol is reduced, and added value of product increases, and also can save with part petroleum replacing chemical resource and prepare sizing agent.Therefore, the Sustainable development of the industrialization of this sizing agent to wheat stalk recycle and sizing agent industry, has great importance.
(2) select natural function polymer chitosan as another raw material of this sizing agent of preparation.As mentioned above, chitosan is by nature output, to be only second to cellulosic natural high molecular substance chitin to make.Above shrimp, the crab shells of tens million of tons that China discards are every year the important sources of producing chitosan.The Application Areas of chitosan has been widened in this invention, and the raw materials cost that makes sizing agent is reduced.The plant base polyester polyol that chitosan aqueous solution is prepared wheat stalk, has the feature of emulsify well, in addition, due to chitosan have nontoxic, be easy to the effects such as degraded and natural anticorrosion, this sizing agent also can carry out corrosionproof protection to timber.
(3) select 4,4'-diphenylmethanediisocyanate (MDI) as the linking agent of aqueous polymer dispersion.During hot pressing, 4,4'-diphenylmethanediisocyanate can be rapidly with the broad liquid of polymer-based polymkeric substance in activity hydroxy, moisture and timber in take the activity hydroxy generation crosslinking reaction that Mierocrystalline cellulose is main component, form the gluing point glueing joint with timber, after solidifying, form high bonding strength and water tolerance.
(4) preparation technology of this sizing agent is simple, easy to operate.Raw material sources are extensive, easily obtain, and cost are low, and industrialization economic and social benefit is remarkable.
Embodiment
For better, must understand the present invention, below in conjunction with embodiment, the invention will be further described, but content of the present invention is not only confined to the following examples.
Embodiment 1
(1) preparation of plant base polyester polyol: in the ethylene glycol of 200g, under stirring, add wheat stalk 30g, hydrochloric acid 4g below 10 orders, after blend evenly, be heated to 160 ℃, insulation 30min; Add again the wheat stalk powder 30g below 10 orders, continue, at 160 ℃ of insulation 60min, to make plant base polyvalent alcohol; Add Succinic anhydried 40g, at 150 ℃, insulation 30min; Temperature is risen to 190 ℃, insulation 150min; Be cooled to normal temperature, make plant base polyester polyol.
(2) preparation of plant base polyesterols-chitosan water miscible liquid: add acetic acid 2g in the water of 200g, chitosan 4g, is heated to 30 ℃, is stirred to completely and dissolves and make chitosan aqueous solution; The plant base polyester polyol that chitosan aqueous solution and step (1) are made in mass ratio 100:5 blend 30min makes plant base polyesterols-chitosan water miscible liquid.
(3) while using, by plant base polyesterols-chitosan water miscible liquid and MDI-100 in mass ratio 100:3 stirring at room mix, the agent of subbase polymkeric substance gluing secures satisfactory grades.
Embodiment 2
(1) preparation of plant base polyester polyol: in the propylene glycol of 200g, under stirring, add wheat stalk 36g, sulfuric acid 5g below 10 orders, after blend evenly, be heated to 170 ℃, insulation 30min; Add again the wheat stalk powder 36g below 10 orders, continue, at 170 ℃ of insulation 80min, to make plant base polyvalent alcohol; Add Succinic anhydried 50g, at 150 ℃, insulation 30min; Temperature is risen to 200 ℃, insulation 130min; Be cooled to normal temperature, make plant base polyester polyol.
(2) preparation of plant base polyesterols-chitosan water miscible liquid: add citric acid 2g in the water of 200g, chitosan 4g, is heated to 40 ℃, is stirred to completely and dissolves and make chitosan aqueous solution; The plant base polyester polyol that chitosan aqueous solution and step (1) are made in mass ratio 100:8 blend 30min makes plant base polyesterols-chitosan water miscible liquid.
(3) while using, by plant base polyesterols-chitosan water miscible liquid and MDI-100 in mass ratio 100:8 stirring at room mix, the agent of subbase polymkeric substance gluing secures satisfactory grades.
Embodiment 3
(1) preparation of plant base polyester polyol: in the tirethylene glycol of 200g, under stirring, add wheat stalk 40g, p-methyl benzenesulfonic acid 6g below 10 orders, after blend evenly, be heated to 180 ℃, insulation 30min; Add again the wheat stalk powder 40g below 10 orders, continue, at 180 ℃ of insulation 90min, to make plant base polyvalent alcohol; Temperature is chilled to 150 ℃, adds Succinic anhydried 60g, insulation 30min; Temperature is risen to 210 ℃, insulation 120min; Be cooled to normal temperature, make plant base polyester polyol.
(2) preparation of plant base polyesterols-chitosan water miscible liquid: add acetic acid 2g in the water of 200g, chitosan 4g, is heated to 50 ℃, is stirred to completely and dissolves and make chitosan aqueous solution; The plant base polyester polyol that chitosan aqueous solution and step (1) are made in mass ratio 100:10 blend 30min makes plant base polyesterols-chitosan water miscible liquid.
(3) while using, by plant base polyesterols-chitosan water miscible liquid and MDI-100 in mass ratio 100:6 stirring at room mix, the agent of subbase polymkeric substance gluing secures satisfactory grades.
Embodiment 4
The gluing that the plant base polyesterols-chitosan gluing agent making in embodiment 1, embodiment 2 and embodiment 3 is applied to respectively to wood single-plate veneered plywood, step is as follows:
One veneer test piece one side is coated with to the agent of plant base polyesterols-chitosan gluing as panel, and Amount of spread is 200g/m
2, dash board becomes test specimen with the vertical lamination of backboard fiber direction and central layer, after gluing first with the pressure of the 1.0MPa 20min that colds pressing.Then, in thermocompressor, with the pressure of 1.0MPa, in 115 ℃ of 3min that evenly pressurize, the sheet material room temperature ageing 24h after compacting.
Sheet material after ageing is sawn into test specimen, surveys its surface bonding intensity.The white oak of take shows as examination material test-results, and tensile shear strength average is all greater than 1.0 MPa, and veneer substrate interface destructive rate is greater than 95%, proof thus, and the plant base polyesterols-chitosan gluing agent making in three embodiment all has good gluing performance.
Claims (2)
1. a preparation method for plant base polyesterols-chitosan gluing agent, is characterized in that, preparation process is as follows:
(1) prepare plant base polyester polyol
In the dibasic alcohol of 100 mass parts, under stirring, add following dry wheat stalk 15～20 mass parts, catalyzer 2～3 mass parts of 10 orders, after blend evenly, be heated to 160～180 ℃, insulation 30min; Add again following dry wheat stalk powder 15～20 mass parts of 10 orders, continue, at 160～180 ℃ of insulation 60～90min, to make plant base polyvalent alcohol; Temperature is chilled to 150 ℃, adds MALEIC ANHYDRIDE 20～30 mass parts, insulation 30min; Temperature is risen to 190～210 ℃, insulation 120-150min; Be cooled to normal temperature, make plant base polyester polyol;
It is one of following that described dibasic alcohol is selected from: ethylene glycol, propylene glycol, butyleneglycol, neopentyl glycol, tirethylene glycol, triethylene Glycol; The following dry wheat stalk powder of described 10 orders, its water content massfraction is less than 1%;
It is one of following that described catalyzer is selected from: hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, Phenylsulfonic acid;
(2) prepare plant base polyesterols-chitosan water miscible liquid
In the water of 100 mass parts, add organic acid 1 mass parts, chitosan 2 mass parts, are heated to 30～50 ℃, are stirred to completely and dissolve and make chitosan aqueous solution;
The plant base polyester polyol that chitosan aqueous solution and step (1) are made is 100:3～8 blend 30min in mass ratio, makes plant base polyesterols-chitosan water miscible liquid;
It is one of following that described organic acid is selected from: acetic acid, citric acid;
Described deacetylating degree of chitosan massfraction is 80%-90%, and molecular weight is 2 * 10
5～3 * 10
5;
(3) while using, by plant base polyesterols-chitosan water miscible liquid and MDI-100 in mass ratio 100:5～10 stirring at room mix;
Described MDI-100 is more than 98% MDI for containing 4,4'-diphenylmethanediisocyanate massfraction.
2. plant base polyesterols-chitosan gluing agent that preparation method as claimed in claim 1 makes, is characterized in that, be applied to the gluing of wood single-plate veneered plywood, Amount of spread is 200g/m
2.
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| CN107400494A (en) * | 2016-05-19 | 2017-11-28 | 长沙市汇华胶粘剂科技有限公司 | A kind of wheat stalk-konjaku flour composite adhesive and preparation method thereof |
| CN107973892A (en) * | 2017-12-04 | 2018-05-01 | 昆山阿基里斯人造皮有限公司 | A kind of automobile polyester tack coat used for artificial leather and its preparation method and application |
| CN116478649B (en) * | 2023-01-04 | 2024-04-02 | 西南林业大学 | Wood adhesive based on biomass hyperbranched polyol-biomass polyacid, and preparation method and application thereof |
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| CN1888003A (en) * | 2006-07-12 | 2007-01-03 | 山东恒冠化工科技有限公司 | Waterproof sealing agent for wires, cables and terminals and its prepn |
| CN101265401A (en) * | 2008-04-23 | 2008-09-17 | 中国科学院广州化学研究所 | Method for preparing biomass polyurethane adhesive |
| CN101643513A (en) * | 2009-08-28 | 2010-02-10 | 华南理工大学 | Plant-fiber-base polyether ester polylol, and preparation method and applications thereof |
| CN102597105A (en) * | 2009-11-05 | 2012-07-18 | 诺瓦蒙特股份公司 | Mixtures of biodegradable polyesters with at least one polymer of natural origin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0345678A (en) * | 1989-07-14 | 1991-02-27 | Kuraray Co Ltd | Adhesive and glass base |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888003A (en) * | 2006-07-12 | 2007-01-03 | 山东恒冠化工科技有限公司 | Waterproof sealing agent for wires, cables and terminals and its prepn |
| CN101265401A (en) * | 2008-04-23 | 2008-09-17 | 中国科学院广州化学研究所 | Method for preparing biomass polyurethane adhesive |
| CN101643513A (en) * | 2009-08-28 | 2010-02-10 | 华南理工大学 | Plant-fiber-base polyether ester polylol, and preparation method and applications thereof |
| CN102597105A (en) * | 2009-11-05 | 2012-07-18 | 诺瓦蒙特股份公司 | Mixtures of biodegradable polyesters with at least one polymer of natural origin |
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| JP平3-45678A 1991.02.27 |
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