CN102010678A - Preparation method for biological oil-phenol-starch adhesive - Google Patents
Preparation method for biological oil-phenol-starch adhesive Download PDFInfo
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Abstract
The invention relates to a preparation method for a biological oil-phenol-starch adhesive, belonging to the technical field of artificial boards in the field of wood processing. The preparation method comprises the following steps of: firstly, making biological oil which partially replaces phenol react with oxidized starch acetate to prepare biological oil-phenol-starch resin; then preparing a starch-based cross-linking agent; and finally mixing the starch-based cross-linking agent and the biological oil-phenol-starch resin in a certain proportion and adding curing agent of isocyanate to prepare the biological oil-phenol-starch adhesive. The biological oil-phenol-starch adhesive has the advantages of no formaldehyde release, good water tolerance and the like, is biodegradable and can be used for the field of boards for family decoration.
Description
Technical field
The present invention relates to the preparation method of a kind of bio oil-phenol-starch adhesive, belong to the man-made board technology field in the wood working.
Technical background
In recent years, along with the appearance of national environmental protection rules and the enhancing of people's environmental consciousness, country is more and more stricter to free formaldehyde volatilization quantitative limitation in the tired tackiness agent of acetal, and major part all adopts urea aldehyde adhesive stick in the used sheet material of indoor furniture and upholstery, this type of tackiness agent formaldehyde volatile quantity is big, harm to human body and environment is bigger, therefore press for and develop the aldehyde-free cement that a kind of indoor furniture sheet material is used, this wherein the starch based tackiness agent have potentiality to be exploited most.
The starch based tackiness agent has been proposed various research both at home and abroad at present and improved one's methods.Syed H Imam etc. are primary standard with the polyvinyl alcohol, and adding W-Gum, melamine resin synthetic wood stick with glue agent, and this tackiness agent has good cementability and water resisting property, and the tool antibacterial ability.Schneider etc. utilize furfuryl alcohol, xylogen, maleic anhydride etc. to be mixed and made into the good wood adhesive of water resistance.Claus Felby etc. comes oxidative lignin to produce timber with oxydo-reductase to stick with glue agent, and this product can compare favourably with urea-formaldehyde resin.Bassi has invented the protein/starch paper coating, is used for the coating of kraft paper.Starch such as Syed, polyvinyl alcohol and hexamethoxymethyl melamine are as the glue crosslinking agent blend, researched and developed the cross-linking type wood adhesive that can be used for indoor plywood production, the methoxyl group of linking agent can by with starch, timber and polyvinyl alcohol molecule on the commentaries on classics etherification of hydroxyl realize various intermolecular crosslinked.Xue Guoqing is that oxygenant prepares coating with formaldehydeless environment-friendly type oxidized starch adhesive with chlorine under alkaline condition, and it has binding property and has good stability, adhesive power and the good premium properties of covering effect.Shi Junyous etc. have been studied with diprotic acid and W-Gum generation part esterification, under the condition that stablizer ethylene glycol exists, add carboxyl nitrile rubber latex and esterification starch mixing copolymerization, make starch adhesive host, with polyisocyanates make linking agent, POV barium is done filler, the modified starch adhesive of making meets the tackiness agent standard of glued board and core-board; Wu Yanbo etc. add an amount of emulsifying agent-polyvinyl alcohol at first with starch pasting, then under the initiation of initiator ammonium persulfate, add the mixture of vinyl-acetic ester and ethyl propenoate, make starch and two kinds of monomers preparation starch adhesive that reacts.
But above several water-resisting type starch-base timber adhesive is gone back more complicated from preparation technology; From the auxiliary of production usefulness, majority must by means of expensive, in use have the severe toxicity polyisocyanates; From the working conditions of tackiness agent, or hot pressing temperature height or the active phase is short or set time is long.
Summary of the invention
The objective of the invention is to propose the preparation method of a kind of bio oil-phenol-starch adhesive, overcome defective and problem that existing starch adhesive preparation method is faced, with bio oil and starch is main raw material, production environment-friendly type, excellent property, degradable starch class tackiness agent, to make full use of the natural resources, minimizing is to the pollution and the destruction of environment, and finally reduces cost.
The preparation method of bio oil-phenol-starch adhesive that the present invention proposes may further comprise the steps:
(1) preparation of dialdehyde starch acetic ester:
It is 35%～40% starch emulsion that starch and water are mixed with mass percent concentration, in starch emulsion, add sodium periodate solution, the mol ratio that adds is: starch: sodium periodate=1: 1.1, transferring the pH value of starch emulsion with hydrochloric acid is 1.2～1.5, is warming up to 35 ℃～40 ℃, insulation reaction 3 hours, obtain dialdehyde starch solution, dialdehyde starch solution is carried out suction filtration, washing, and 40 ℃ were descended dry 2～3 hours, and made dialdehyde starch;
The dialdehyde starch and the water that make are mixed with the dialdehyde starch emulsion that mass percent concentration is 40%-50%, add Glacial acetic acid, the mass ratio that adds is: dialdehyde starch: Glacial acetic acid=4: 1, mix and stirred 2 minutes, in 5 minutes, progressively join in the starch emulsion cold acetic anhydride, the mol ratio that adds is: dialdehyde starch: cold acetic anhydride=1: (1～1.2), methylsulfonic acid is diluted with Glacial acetic acid, the mol ratio of methylsulfonic acid and Glacial acetic acid is during dilution: methylsulfonic acid: Glacial acetic acid=1: 1, in 10 minutes, join in the dialdehyde starch, the mass ratio that adds is: dialdehyde starch: methylsulfonic acid=(16～14): 1, under constantly stirring, be warming up to 50 ℃～55 ℃, insulation reaction 1 hour, suction filtration, washing, drying is 1～2 hour under 50 ℃, obtains the dialdehyde starch acetic ester;
(2) preparation of bio oil-phenol-starch-resin:
It is 40%～45% starch acetate emulsion that the dialdehyde starch acetic ester of above-mentioned preparation and water are mixed with mass percent concentration, add phenol and bio oil, the mol ratio that adds is: starch acetate emulsion: phenol: bio oil=20: (0.9～1): 4, pH value with sodium hydrate regulator solution is 10～11, be warming up to 85 ℃～90 ℃ in 30 minutes, insulation reaction 1～1.5 hour, add silane coupling agent again, the ratio that adds is: silane coupling agent accounts for 2.5%～3% of dialdehyde starch acetic ester quality, insulation reaction 20～30 minutes, be cooled to 70 ℃～80 ℃, add borax, the add-on of borax accounts for 1.5%～2% of dialdehyde starch acetic ester quality, insulation reaction 15～20 minutes, with the salt acid for adjusting pH value is 7, and cooling discharge obtains bio oil-phenol-starch-resin;
(3) preparation of starch base linking agent:
(3-1) preparation of composite starch emulsion:
It is 35% starch emulsion that starch and water are mixed with mass percent concentration, pH value with hydrochloric acid conditioning solution is 1.2～2.1, add the Potassium Persulphate that accounts for starch quality 2%～2.25%, warming-in-water to 55 ℃, insulation reaction 1 hour, regulating the pH value with sodium hydroxide is 5～5.5, in 1.5 hours, add and account for the acrylamide that starch quality is 60%-65%, insulation reaction 1.5 hours, add sodium sulfite solution again, the mol ratio that adds is: Potassium Persulphate: sodium bisulfite=1: 1, and insulation reaction 10 minutes obtains the composite starch emulsion;
(3-2) preparation of the polyvinyl alcohol and the oxalic acid aqueous solution:
While stirring solid polyethylene alcohol is added to the water, the mass percent concentration that makes polyvinyl alcohol is 12%, by warming-in-water to 90 ℃, be incubated 1 hour, polyvinyl alcohol is dissolved fully, add the sodium laurylsulfonate account for polyvinyl alcohol quality 0.1% and the Xylo-Mucine that accounts for polyvinyl alcohol quality 3%, insulated and stirred is 20～30 minutes again, obtains mass percent and be 12% polyvinyl alcohol solution; The particulate state oxalic acid is added to the water, and the mass percent concentration that makes oxalic acid solution is 30%, and warming while stirring to 50 ℃ is incubated to oxalic acid and all dissolves, and it is standby to reduce to room temperature;
(3-3) preparation of starch base linking agent:
Under 50 ℃, in 30 minutes, in the composite starch emulsion that in above-mentioned steps (3-1), prepares, every 5 minutes, add the polyvinyl alcohol water solution and the oxalic acid of preparation in the step (3-2) at interval, the mass percent of adding is: composite starch emulsion: polyvinyl alcohol water solution: oxalic acid=(8.5～9): 1.5: 1, and polyvinyl alcohol water solution of every adding or oxalic acid, regulating the pH value with sodium hydroxide is 7, obtains the starch base linking agent;
(4) preparation of bio oil-phenol-starch adhesive:
The starch base linking agent of above-mentioned preparation is mixed with bio oil-phenol-starch-resin, blended quality proportioning is: the starch base linking agent: bio oil-phenol-starch-resin=3: 2, stirred 20～30 minutes at 40 ℃～50 ℃, add again that to account for mixture quality per-cent be 10% solidifying agent isocyanic ester, at room temperature, stir, obtain bio oil-phenol-starch adhesive.
The preparation method of bio oil-phenol-starch adhesive that the present invention proposes, its advantage is:
1, the bio oil that obtains of the inventive method employing agricultural residuum fast pyrogenation is a raw material, and the preparation tackiness agent makes that the forest waste resource is rationally utilized, and has reduced the dependence of adhesive raw materials to petroleum resources.
2, the inventive method prepares in the raw material of bio oil-phenol-modified starch adhesive, does not have formaldehyde, so do not contain formaldehyde in this tackiness agent, its environmental-protecting performance is superior.
3, preparation method's of the present invention technological process is simple, mature preparation process, and the reaction conditions gentleness, use equipment is easy to get, so the inventive method is implemented easily.
4, use the tackiness agent of the inventive method preparation, have good water-fast, heat-resisting, corrosion resistance nature, and biodegradable under certain conditions, little to environmental hazard.
Embodiment
The preparation method of bio oil-phenol-starch adhesive that the present invention proposes may further comprise the steps:
(1) preparation of dialdehyde starch acetic ester:
It is 35%～40% starch emulsion that starch and water are mixed with mass percent concentration, in starch emulsion, add sodium periodate solution, the mol ratio that adds is: starch: sodium periodate=1: 1.1, transferring the pH value of starch emulsion with hydrochloric acid is 1.2～1.5, is warming up to 35 ℃～40 ℃, insulation reaction 3 hours, obtain dialdehyde starch solution, dialdehyde starch solution is carried out suction filtration, washing, and 40 ℃ were descended dry 2～3 hours, and made dialdehyde starch;
The dialdehyde starch and the water that make are mixed with the dialdehyde starch emulsion that mass percent concentration is 40%-50%, add Glacial acetic acid, the mass ratio that adds is: dialdehyde starch: Glacial acetic acid=4: 1, mix and stirred 2 minutes, in 5 minutes, progressively join in the starch emulsion cold acetic anhydride, the mol ratio that adds is: dialdehyde starch: cold acetic anhydride=1: (1～1.2), methylsulfonic acid is diluted with Glacial acetic acid, the mol ratio of methylsulfonic acid and Glacial acetic acid is during dilution: methylsulfonic acid: Glacial acetic acid=1: 1, in 10 minutes, join in the dialdehyde starch, the mass ratio that adds is: dialdehyde starch: methylsulfonic acid=(16～14): 1, under constantly stirring, be warming up to 50 ℃～55 ℃, insulation reaction 1 hour, suction filtration, washing, drying is 1～2 hour under 50 ℃, obtains the dialdehyde starch acetic ester;
(2) preparation of bio oil-phenol-starch-resin:
It is 40%～45% starch acetate emulsion that the dialdehyde starch acetic ester of above-mentioned preparation and water are mixed with mass percent concentration, add phenol and bio oil, the mol ratio that adds is: starch acetate emulsion: phenol: bio oil=20: (0.9～1): 4, pH value with sodium hydrate regulator solution is 10～11, be warming up to 85 ℃～90 ℃ in 30 minutes, insulation reaction 1～1.5 hour, add silane coupling agent again, the ratio that adds is: silane coupling agent accounts for 2.5%～3% of dialdehyde starch acetic ester quality, insulation reaction 20～30 minutes, be cooled to 70 ℃～80 ℃, add borax, the add-on of borax accounts for 1.5%～2% of dialdehyde starch acetic ester quality, insulation reaction 15～20 minutes, with the salt acid for adjusting pH value is 7, and cooling discharge obtains bio oil-phenol-starch-resin;
(3) preparation of starch base linking agent:
(3-1) preparation of composite starch emulsion:
It is 35% starch emulsion that starch and water are mixed with mass percent concentration, pH value with hydrochloric acid conditioning solution is 1.2～2.1, add the Potassium Persulphate that accounts for starch quality 2%～2.25%, warming-in-water to 55 ℃, insulation reaction 1 hour, regulating the pH value with sodium hydroxide is 5～5.5, in 1.5 hours, add and account for the acrylamide that starch quality is 60%-65%, insulation reaction 1.5 hours, add sodium sulfite solution again, the mol ratio that adds is: Potassium Persulphate: sodium bisulfite=1: 1, and insulation reaction 10 minutes obtains the composite starch emulsion;
(3-2) preparation of the polyvinyl alcohol and the oxalic acid aqueous solution:
While stirring solid polyethylene alcohol is added to the water, the mass percent concentration that makes polyvinyl alcohol is 12%, by warming-in-water to 90 ℃, be incubated 1 hour, polyvinyl alcohol is dissolved fully, add the sodium laurylsulfonate account for polyvinyl alcohol quality 0.1% and the Xylo-Mucine that accounts for polyvinyl alcohol quality 3%, insulated and stirred is 20～30 minutes again, obtains mass percent and be 12% polyvinyl alcohol solution; The particulate state oxalic acid is added to the water, and the mass percent concentration that makes oxalic acid solution is 30%, and warming while stirring to 50 ℃ is incubated to oxalic acid and all dissolves, and it is standby to reduce to room temperature;
(3-3) preparation of starch base linking agent:
Under 50 ℃, in 30 minutes, in the composite starch emulsion that in above-mentioned steps (3-1), prepares, every 5 minutes, add the polyvinyl alcohol water solution and the oxalic acid of preparation in the step (3-2) at interval, the mass percent of adding is: composite starch emulsion: polyvinyl alcohol water solution: oxalic acid=(8.5～9): 1.5: 1, and polyvinyl alcohol water solution of every adding or oxalic acid, regulating the pH value with sodium hydroxide is 7, obtains the starch base linking agent;
(4) preparation of bio oil-phenol-starch adhesive:
The starch base linking agent of above-mentioned preparation is mixed with bio oil-phenol-starch-resin, blended quality proportioning is: the starch base linking agent: bio oil-phenol-starch-resin=3: 2, stirred 20～30 minutes at 40 ℃～50 ℃, add again that to account for mixture quality per-cent be 10% solidifying agent isocyanic ester, at room temperature, stir, obtain bio oil-phenol-starch adhesive.
Below introduce the embodiment of the inventive method:
Embodiment 1
(1) preparation of dialdehyde starch acetic ester:
It is 35% starch emulsion that starch and water are mixed with mass percent concentration, in starch emulsion, add sodium periodate solution, the mol ratio that adds is: starch: sodium periodate=1: 1.1, transferring the pH value of starch emulsion with hydrochloric acid is 1.4, is warming up to 37 ℃, insulation reaction 3 hours, obtain dialdehyde starch solution, dialdehyde starch solution is carried out suction filtration, washing, and 40 ℃ were descended dry 3 hours, and made dialdehyde starch;
It is 50% dialdehyde starch emulsion that the dialdehyde starch that makes and water are mixed with mass percent concentration, add Glacial acetic acid, the mass ratio that adds is: dialdehyde starch: Glacial acetic acid=4: 1, mix and stirred 2 minutes, in 5 minutes, progressively join in the starch emulsion cold acetic anhydride, the mol ratio that adds is: dialdehyde starch: cold acetic anhydride=1: 1, methylsulfonic acid is diluted with Glacial acetic acid, the mol ratio of methylsulfonic acid and Glacial acetic acid is during dilution: methylsulfonic acid: Glacial acetic acid=1: 1, in 10 minutes, join in the dialdehyde starch, the mass ratio that adds is: dialdehyde starch: methylsulfonic acid=16～: 1, under constantly stirring, be warming up to 50 ℃, insulation reaction 1 hour, suction filtration, washing, drying is 2 hours under 50 ℃, obtains the dialdehyde starch acetic ester;
(2) preparation of bio oil-phenol-starch-resin:
It is 40% starch acetate emulsion that the dialdehyde starch acetic ester of above-mentioned preparation and water are mixed with mass percent concentration, add phenol and bio oil, the mol ratio that adds is: starch acetate emulsion: phenol: bio oil=20: 1: 4, pH value with sodium hydrate regulator solution is 10, be warming up to 90 ℃ in 30 minutes, insulation reaction 1 hour, add silane coupling agent again, the ratio that adds is: silane coupling agent accounts for 2.5% of dialdehyde starch acetic ester quality, insulation reaction 30 minutes, be cooled to 70 ℃, add borax, the add-on of borax accounts for 1.5% of dialdehyde starch acetic ester quality, insulation reaction 15 minutes, with the salt acid for adjusting pH value is 7, and cooling discharge obtains bio oil-phenol-starch-resin;
(3) preparation of starch base linking agent:
(3-1) preparation of composite starch emulsion:
It is 35% starch emulsion that starch and water are mixed with mass percent concentration, pH value with hydrochloric acid conditioning solution is 2, add the Potassium Persulphate that accounts for starch quality 2.25%, warming-in-water to 55 ℃, insulation reaction 1 hour, regulating the pH value with sodium hydroxide is 5.5, add in 1.5 hours that to account for starch quality be 60% acrylamide, insulation reaction 1.5 hours, add sodium sulfite solution again, the mol ratio that adds is: Potassium Persulphate: sodium bisulfite=1: 1, and insulation reaction 10 minutes obtains the composite starch emulsion;
(3-2) preparation of the polyvinyl alcohol and the oxalic acid aqueous solution:
While stirring solid polyethylene alcohol is added to the water, the mass percent concentration that makes polyvinyl alcohol is 12%, by warming-in-water to 90 ℃, be incubated 1 hour, polyvinyl alcohol is dissolved fully, add the sodium laurylsulfonate account for polyvinyl alcohol quality 0.1% and the Xylo-Mucine that accounts for polyvinyl alcohol quality 3%, insulated and stirred is 30 minutes again, obtains mass percent and be 12% polyvinyl alcohol solution; The particulate state oxalic acid is added to the water, and the mass percent concentration that makes oxalic acid solution is 30%, and warming while stirring to 50 ℃ is incubated to oxalic acid and all dissolves, and it is standby to reduce to room temperature;
(3-3) preparation of starch base linking agent:
Under 50 ℃, in 30 minutes, in the composite starch emulsion that in above-mentioned steps (3-1), prepares, every 5 minutes, add the polyvinyl alcohol water solution and the oxalic acid of preparation in the step (3-2) at interval, the mass percent of adding is: composite starch emulsion: polyvinyl alcohol water solution: oxalic acid=9: 1.5: 1, polyvinyl alcohol water solution of every adding or oxalic acid, regulating the pH value with sodium hydroxide is 7, obtains the starch base linking agent;
(4) preparation of bio oil-phenol-starch adhesive:
The starch base linking agent of above-mentioned preparation is mixed with bio oil-phenol-starch-resin, blended quality proportioning is: the starch base linking agent: bio oil-phenol-starch-resin=3: 2, stirred 20 minutes at 40 ℃～50 ℃, add again that to account for mixture quality per-cent be 10% solidifying agent isocyanic ester, at room temperature, stir, obtain bio oil-phenol-starch adhesive.
Embodiment 2
(1) preparation of dialdehyde starch acetic ester:
It is 40% starch emulsion that starch and water are mixed with mass percent concentration, in starch emulsion, add sodium periodate solution, the mol ratio that adds is: starch: sodium periodate=1: 1.1, transferring the pH value of starch emulsion with hydrochloric acid is 1.4, is warming up to 37 ℃, insulation reaction 3 hours, obtain dialdehyde starch solution, dialdehyde starch solution is carried out suction filtration, washing, and 40 ℃ were descended dry 3 hours, and made dialdehyde starch;
It is 50% dialdehyde starch emulsion that the dialdehyde starch that makes and water are mixed with mass percent concentration, add Glacial acetic acid, the mass ratio that adds is: dialdehyde starch: Glacial acetic acid=4: 1, mix and stirred 2 minutes, in 5 minutes, progressively join in the starch emulsion cold acetic anhydride, the mol ratio that adds is: dialdehyde starch: cold acetic anhydride=1: 1, methylsulfonic acid is diluted with Glacial acetic acid, the mol ratio of methylsulfonic acid and Glacial acetic acid is during dilution: methylsulfonic acid: Glacial acetic acid=1: 1, in 10 minutes, join in the dialdehyde starch, the mass ratio that adds is: dialdehyde starch: methylsulfonic acid=16～: 1, under constantly stirring, be warming up to 50 ℃, insulation reaction 1 hour, suction filtration, washing, drying is 2 hours under 50 ℃, obtains the dialdehyde starch acetic ester;
(2) preparation of bio oil-phenol-starch-resin:
It is 40% starch acetate emulsion that the dialdehyde starch acetic ester of above-mentioned preparation and water are mixed with mass percent concentration, add phenol and bio oil, the mol ratio that adds is: starch acetate emulsion: phenol: bio oil=20: 1: 4, pH value with sodium hydrate regulator solution is 10, be warming up to 85 ℃ in 30 minutes, insulation reaction 1.5 hours, add silane coupling agent again, the ratio that adds is: silane coupling agent accounts for 2.5% of dialdehyde starch acetic ester quality, insulation reaction 30 minutes, be cooled to 70 ℃, add borax, the add-on of borax accounts for 1.5% of dialdehyde starch acetic ester quality, insulation reaction 15 minutes, with the salt acid for adjusting pH value is 7, and cooling discharge obtains bio oil-phenol-starch-resin;
(3) preparation of starch base linking agent:
(3-1) preparation of composite starch emulsion:
It is 35% starch emulsion that starch and water are mixed with mass percent concentration, pH value with hydrochloric acid conditioning solution is 2, add the Potassium Persulphate that accounts for starch quality 2.25%, warming-in-water to 55 ℃, insulation reaction 1 hour, regulating the pH value with sodium hydroxide is 5.5, add in 1.5 hours that to account for starch quality be 65% acrylamide, insulation reaction 1.5 hours, add sodium sulfite solution again, the mol ratio that adds is: Potassium Persulphate: sodium bisulfite=1: 1, and insulation reaction 10 minutes obtains the composite starch emulsion;
(3-2) preparation of the polyvinyl alcohol and the oxalic acid aqueous solution:
While stirring solid polyethylene alcohol is added to the water, the mass percent concentration that makes polyvinyl alcohol is 12%, by warming-in-water to 90 ℃, be incubated 1 hour, polyvinyl alcohol is dissolved fully, add the sodium laurylsulfonate account for polyvinyl alcohol quality 0.1% and the Xylo-Mucine that accounts for polyvinyl alcohol quality 3%, insulated and stirred is 30 minutes again, obtains mass percent and be 12% polyvinyl alcohol solution; The particulate state oxalic acid is added to the water, and the mass percent concentration that makes oxalic acid solution is 30%, and warming while stirring to 50 ℃ is incubated to oxalic acid and all dissolves, and it is standby to reduce to room temperature;
(3-3) preparation of starch base linking agent:
Under 50 ℃, in 30 minutes, in the composite starch emulsion that in above-mentioned steps (3-1), prepares, every 5 minutes, add the polyvinyl alcohol water solution and the oxalic acid of preparation in the step (3-2) at interval, the mass percent of adding is: composite starch emulsion: polyvinyl alcohol water solution: oxalic acid=9: 1.5: 1, polyvinyl alcohol water solution of every adding or oxalic acid, regulating the pH value with sodium hydroxide is 7, obtains the starch base linking agent;
(4) preparation of bio oil-phenol-starch adhesive:
The starch base linking agent of above-mentioned preparation is mixed with bio oil-phenol-starch-resin, blended quality proportioning is: the starch base linking agent: bio oil-phenol-starch-resin=3: 2, stirred 20 minutes at 40 ℃～50 ℃, add again that to account for mixture quality per-cent be 10% solidifying agent isocyanic ester, at room temperature, stir, obtain bio oil-phenol-starch adhesive.
Claims (1)
1. the preparation method of bio oil-phenol-starch adhesive is characterized in that this method may further comprise the steps:
(1) preparation of dialdehyde starch acetic ester:
It is 35%～40% starch emulsion that starch and water are mixed with mass percent concentration, in starch emulsion, add sodium periodate solution, the mol ratio that adds is: starch: sodium periodate=1: 1.1, transferring the pH value of starch emulsion with hydrochloric acid is 1.2～1.5, is warming up to 35 ℃～40 ℃, insulation reaction 3 hours, obtain dialdehyde starch solution, dialdehyde starch solution is carried out suction filtration, washing, and 40 ℃ were descended dry 2～3 hours, and made dialdehyde starch;
The dialdehyde starch and the water that make are mixed with the dialdehyde starch emulsion that mass percent concentration is 40%-50%, add Glacial acetic acid, the mass ratio that adds is: dialdehyde starch: Glacial acetic acid=4: 1, mix and stirred 2 minutes, in 5 minutes, progressively join in the starch emulsion cold acetic anhydride, the mol ratio that adds is: dialdehyde starch: cold acetic anhydride=1: (1～1.2), methylsulfonic acid is diluted with Glacial acetic acid, the mol ratio of methylsulfonic acid and Glacial acetic acid is during dilution: methylsulfonic acid: Glacial acetic acid=1: 1, in 10 minutes, join in the dialdehyde starch, the mass ratio that adds is: dialdehyde starch: methylsulfonic acid=(16～14): 1, under constantly stirring, be warming up to 50 ℃～55 ℃, insulation reaction 1 hour, suction filtration, washing, drying is 1～2 hour under 50 ℃, obtains the dialdehyde starch acetic ester;
(2) preparation of bio oil-phenol-starch-resin:
It is 40%～45% starch acetate emulsion that the dialdehyde starch acetic ester of above-mentioned preparation and water are mixed with mass percent concentration, add phenol and bio oil, the mol ratio that adds is: starch acetate emulsion: phenol: bio oil=20: (0.9～1): 4, pH value with sodium hydrate regulator solution is 10～11, be warming up to 85 ℃～90 ℃ in 30 minutes, insulation reaction 1～1.5 hour, add silane coupling agent again, the ratio that adds is: silane coupling agent accounts for 2.5%～3% of dialdehyde starch acetic ester quality, insulation reaction 20～30 minutes, be cooled to 70 ℃～80 ℃, add borax, the add-on of borax accounts for 1.5%～2% of dialdehyde starch acetic ester quality, insulation reaction 15～20 minutes, with the salt acid for adjusting pH value is 7, and cooling discharge obtains bio oil-phenol-starch-resin;
(3) preparation of starch base linking agent:
(3-1) preparation of composite starch emulsion:
It is 35% starch emulsion that starch and water are mixed with mass percent concentration, pH value with hydrochloric acid conditioning solution is 1.2～2.1, add the Potassium Persulphate that accounts for starch quality 2%～2.25%, warming-in-water to 55 ℃, insulation reaction 1 hour, regulating the pH value with sodium hydroxide is 5～5.5, in 1.5 hours, add and account for the acrylamide that starch quality is 60%-65%, insulation reaction 1.5 hours, add sodium sulfite solution again, the mol ratio that adds is: Potassium Persulphate: sodium bisulfite=1: 1, and insulation reaction 10 minutes obtains the composite starch emulsion;
(3-2) preparation of the polyvinyl alcohol and the oxalic acid aqueous solution:
While stirring solid polyethylene alcohol is added to the water, the mass percent concentration that makes polyvinyl alcohol is 12%, by warming-in-water to 90 ℃, be incubated 1 hour, polyvinyl alcohol is dissolved fully, add the sodium laurylsulfonate account for polyvinyl alcohol quality 0.1% and the Xylo-Mucine that accounts for polyvinyl alcohol quality 3%, insulated and stirred is 20～30 minutes again, obtains mass percent and be 12% polyvinyl alcohol solution; The particulate state oxalic acid is added to the water, and the mass percent concentration that makes oxalic acid solution is 30%, and warming while stirring to 50 ℃ is incubated to oxalic acid and all dissolves, and it is standby to reduce to room temperature;
(3-3) preparation of starch base linking agent:
Under 50 ℃, in 30 minutes, in the composite starch emulsion that in above-mentioned steps (3-1), prepares, every 5 minutes, add the polyvinyl alcohol water solution and the oxalic acid of preparation in the step (3-2) at interval, the mass percent of adding is: composite starch emulsion: polyvinyl alcohol water solution: oxalic acid=(8.5～9): 1.5: 1, and polyvinyl alcohol water solution of every adding or oxalic acid, regulating the pH value with sodium hydroxide is 7, obtains the starch base linking agent;
(4) preparation of bio oil-phenol-starch adhesive:
The starch base linking agent of above-mentioned preparation is mixed with bio oil-phenol-starch-resin, blended quality proportioning is: the starch base linking agent: bio oil-phenol-starch-resin=3: 2, stirred 20～30 minutes at 40 ℃～50 ℃, add again that to account for mixture quality per-cent be 10% solidifying agent isocyanic ester, at room temperature, stir, obtain bio oil-phenol-starch adhesive.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367367A (en) * | 2011-08-31 | 2012-03-07 | 华南理工大学 | Preparation method for environment-friendly starch-based binder |
| CN102634298A (en) * | 2012-05-03 | 2012-08-15 | 北京林业大学 | Biological oil-starch-glyoxal resin adhesive for artificial board and preparation method of biological oil-starch-glyoxal resin adhesive |
| CN102642222A (en) * | 2012-05-03 | 2012-08-22 | 北京林业大学 | Method for preparing aldehyde-free veneer boards by biological oil starch adhesives |
| US20130184381A1 (en) * | 2012-01-18 | 2013-07-18 | Rantec Corporation | Tackifier and modified starch formulation, system and method |
| CN103642147A (en) * | 2013-11-01 | 2014-03-19 | 界首市天翔塑料制品有限公司 | Composite wood plastic material |
| CN103665632A (en) * | 2013-11-01 | 2014-03-26 | 界首市佳通塑胶制品有限公司 | Wood-plastic composite material prepared from crop wastes |
| CN104119455A (en) * | 2014-07-14 | 2014-10-29 | 金东纸业（江苏）股份有限公司 | Cation modified starch, preparation method and applications thereof |
| CN105368352A (en) * | 2015-11-19 | 2016-03-02 | 太仓市金锚化工有限公司 | Preparation method of new starch adhesive used for artificial board bonding |
| CN105754516A (en) * | 2016-03-11 | 2016-07-13 | 中南林业科技大学 | Starch/phenolic resin composite adhesive and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102367367B (en) * | 2011-08-31 | 2013-02-13 | 华南理工大学 | Preparation method for environment-friendly starch-based binder |
| CN102367367A (en) * | 2011-08-31 | 2012-03-07 | 华南理工大学 | Preparation method for environment-friendly starch-based binder |
| US9150713B2 (en) * | 2012-01-18 | 2015-10-06 | Rantec Corporation | Tackifier and modified starch formulation, system and method |
| US20130184381A1 (en) * | 2012-01-18 | 2013-07-18 | Rantec Corporation | Tackifier and modified starch formulation, system and method |
| US20160002503A1 (en) * | 2012-01-18 | 2016-01-07 | Rantec Corporation | Tackifier and modified starch formulation, system and method |
| US9410061B2 (en) | 2012-01-18 | 2016-08-09 | Rantec Corporation | Tackifier and modified starch formulation, system and method |
| CN102642222A (en) * | 2012-05-03 | 2012-08-22 | 北京林业大学 | Method for preparing aldehyde-free veneer boards by biological oil starch adhesives |
| CN102642222B (en) * | 2012-05-03 | 2015-06-17 | 北京林业大学 | Method for preparing aldehyde-free veneer boards by biological oil starch adhesives |
| CN102634298A (en) * | 2012-05-03 | 2012-08-15 | 北京林业大学 | Biological oil-starch-glyoxal resin adhesive for artificial board and preparation method of biological oil-starch-glyoxal resin adhesive |
| CN103642147A (en) * | 2013-11-01 | 2014-03-19 | 界首市天翔塑料制品有限公司 | Composite wood plastic material |
| CN103665632A (en) * | 2013-11-01 | 2014-03-26 | 界首市佳通塑胶制品有限公司 | Wood-plastic composite material prepared from crop wastes |
| CN104119455A (en) * | 2014-07-14 | 2014-10-29 | 金东纸业（江苏）股份有限公司 | Cation modified starch, preparation method and applications thereof |
| CN105368352A (en) * | 2015-11-19 | 2016-03-02 | 太仓市金锚化工有限公司 | Preparation method of new starch adhesive used for artificial board bonding |
| CN105754516A (en) * | 2016-03-11 | 2016-07-13 | 中南林业科技大学 | Starch/phenolic resin composite adhesive and preparation method thereof |
| CN105754516B (en) * | 2016-03-11 | 2018-01-19 | 中南林业科技大学 | A kind of starch/phenolic resin composite adhesive and preparation method thereof |
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