CN101892023B - Aldehyde-free adhesive and preparation method thereof - Google Patents
Aldehyde-free adhesive and preparation method thereof Download PDFInfo
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- CN101892023B CN101892023B CN2010102372956A CN201010237295A CN101892023B CN 101892023 B CN101892023 B CN 101892023B CN 2010102372956 A CN2010102372956 A CN 2010102372956A CN 201010237295 A CN201010237295 A CN 201010237295A CN 101892023 B CN101892023 B CN 101892023B
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Abstract
The invention discloses an aldehyde-free adhesive and a preparation method thereof. The preparation method comprises the following steps of: (1) oxidizing polyvinyl alcohol by using an oxidizing agent to obtain oxidized and modified polyvinyl alcohol, wherein the average degree of polymerization of the polyvinyl alcohol is between 1,000 and 2,500; (2) crosslinking the oxidized and modified polyvinyl alcohol by using a cross-linking agent to obtain cross-linked polyvinyl alcohol; and (3) adding a surfactant and fillers into solution of the cross-linked polyvinyl alcohol, and stirring uniformly to obtain the aldehyde-free adhesive. The aldehyde-free adhesive can replace white latex (polyvinyl acetate emulsion) completely in numerous application fields, and can be used as an adhesive for interior-wall building materials as well as interior-wall ceramic tiles, wall paper, wall cloth, carpets, office supplies and leather.
Description
Technical field
The present invention relates to a kind of adhesive without aldehyde and preparation method thereof, belong to field of fine chemical.
Background technology
China's timber industry in recent years, had become world's Wood-based Panel Production first big country through the fast development in more than 10 years, and wood adhesive output is the rank No. 1 in the world.The Wood-based Panel Production scale surpassed 100,000,000 m in 2009
3, produce the total value more than one hundred billion per year; Year, consumption glue amount reached more than 300 ten thousand tons, and the output value crosses 10,000,000,000.The wood-based plate that accounts for the absolute main body in market is to use urea-formaldehyde resin adhesive, Phenol aldehyde resin and melamine formaldehyde resin glue to make, and the burst size of methanal of this type of tackiness agent and splicing goods thereof is maximum problem always.All the more outstanding of sound along with the enhancing of people's environmental consciousness and national environmental protection rules, wood adhesive and the problem of environmental pollution that glueds joint goods thereof wants to avoid fully the generation of free formaldehyde thus, preferably uses formaldehyde binder to produce this series products.
Enterprise's development both at home and abroad or the adhesive without aldehyde of producing all are two component series tackiness agents of waterborne polymeric-isocyanic ester basically, be about to PVAC emulsion and fillers such as modified resin and lime carbonate and be mixed into host, be used by a certain percentage with the solidifying agent isocyanic ester.Formaldehyde-free wood tackiness agent such as " Chinese tackiness agent " 2000 (4) vinyl emulsion-isocyanic ester of being reported; " Chinese tackiness agent " 2000 (5) solid wooden floor boards of being reported then are to propose the PVA aqueous solution, rubber latex, treated starch, lime carbonate, zinc oxide and borax etc. are formed host with aldehyde-free cement research, thus again by with isocyanate-crosslinked formation formaldehyde binder.Also have EES-18 that the national starch company of the picture U.S. sells, PS-A that Switzerland Tylenol company sells and the deer board glue of Japan etc.These tackiness agents that host country is outer, all be with the vinyl acetate be main raw material synthetic resin as host, be the aqueous binder of solidifying agent again with carbimide.This class tackiness agent is because used host all is made up of multiple high molecular polymer, and generally all between 30-60%, along with the rise of petrochemical material, the price of these tackiness agents was more and more higher over the past two years for effective constituent.Because solid content is higher, and the viscosity of this class tackiness agent is all very high, exist the viscosity of tackiness agent bigger than normal when therefore producing in addition, mobile poor, hand brush and machine roll all difficult; The active phase short (less than 1 hour), use inconvenience, influence production efficiency etc.Still can't reach the degree of producer's satisfaction owing to the detection qualification rate of wood-based plate that above reason is produced.
United States Patent (USP) 4801631 has reported that the isocyanic ester that utilizes the solubility hydrolyzed starch to add an amount of flour in use as host and mix 15-30% is as producing multiple-plate adhesive without aldehyde.This method seems simply, in fact can not form production marketing.In order to reach the needed quality standard of wood-based plate, the amount of employed isocyanic ester is between 15-30%.Not only use cost is higher, and the work-ing life of product is short, not enough half an hour (can reach 1-2 hour) though be known as, and also glue-applying technique is unfavorable for the production of enterprise." timber industry " 2006,20 (6) have reported and have utilized the research of W-Gum for feedstock production API (waterborne polymeric-isocyanic ester) glue host, tell about the host that forms the API tackiness agent by the method that adds VEA emulsion and other high molecular polymers in the treated starch emulsion, composite about 10% isocyanic ester just can be produced qualified multi-ply wood when using.Though this technology is to say with starch as host, in fact in order to reach qualified bonding strength and necessary work-ing life, the amount of adding high molecular polymer is greater than contents of starch, therefore still higher on the cost, and the storage period of product is shorter, and up to the present this series products is not still seen on market sale.
Though some are also arranged is products of single component.Reported that such as " modern chemical industry " Japanese NK company utilizes the production glued board tackiness agent that does not contain formaldehyde of low-polyacrylate, PVAC emulsion, peroxide firming agent and the preparation of lime carbonate lightscreening agent.Chinese patent CN1712484 has then reported the wood-based plate formaldehyde binder of utilizing vinyl acetate-acrylic ester copolymerization emulsion, PVA, water-ground limestone, inorganic salt, starch, urea and water preparation.The something in common of this class tackiness agent is exactly in order to guarantee that the wood-based plate that uses this type of tackiness agent to produce can reach the standard of GB defined, except having used a large amount of high molecular polymers, also to have added the filler of more inorganic or organic class.Mostly the filler of mineral-type is lime carbonate, and mostly the filler of organic class is treated starch.Therefore the more foregoing two-component adhesive of price is higher.May seldom arrive assurance owing to the wood-based plate quality that this type of tackiness agent of use is produced, or price is higher and production technique is comparatively complicated, this type of tackiness agent yet there are no on market to be sold.
Summary of the invention
The purpose of this invention is to provide a kind of formaldehyde that do not contain, low price, stable performance and tackiness agent easy for operation and preparation method thereof on producing.
Tackiness agent provided by the present invention prepares according to the method that may further comprise the steps:
(1) with oxygenant polyvinyl alcohol is carried out oxide treatment and obtain the oxidation modification polyvinyl alcohol, the mean polymerisation degree of described polyvinyl alcohol is 1000-2500;
(2) make described oxidation modification polyvinyl alcohol carry out crosslinking reaction with linking agent and obtain cross-linking polyvinyl alcohol;
(3) in the solution of described cross-linking polyvinyl alcohol, add tensio-active agent and filler, stir and promptly get described adhesive without aldehyde.
Among the above-mentioned preparation method, the mean polymerisation degree of the described polyvinyl alcohol of step (1) specifically can be 1700-1850 or 2000-2150.
Among the above-mentioned preparation method, the described oxygenant of step (1) optional in potassium bichromate, hydrogen peroxide, Potassium Persulphate and ammonium persulphate any; The consumption of described oxygenant can be the 0.5%-4% of the quality of described polyvinyl alcohol, as 1%-2%, 1%-1.5% or 1.5%-2%.
Among the above-mentioned preparation method, the temperature of the described oxide treatment of step (1) is 30 ℃-80 ℃, preferred 40 ℃-60 ℃; The time of described oxide treatment is 1 hour-4 hours, preferred 2 hours.
Among the above-mentioned preparation method, the described linking agent of step (2) can be selected from following 1)-3) at least a:
1) inorganic salt; 2) organic acid or its salt; 3) isocyanic ester.
Above-mentioned inorganic salt can be the aluminium salt that contains polyvalent metal ion, preferably sulfuric acid aluminium; Above-mentioned organic acid or its salt are boric acid, borax, oxalic acid, fumaric acid, toxilic acid or citric acid; Above-mentioned isocyanic ester can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) or hexamethylene diisocyanate (HDI).
Among the above-mentioned preparation method, the ratio of quality and the number of copies of described linking agent of step (2) and described oxidation modification polyvinyl alcohol is (0.1-30): 100, and as (0.5-6): 100, (0.5-2): 100 or (2-6): 100.
Among the above-mentioned preparation method, the aqueous solution mass percentage concentration of the described polyvinyl alcohol of step (3) can be 5%-30%, as 10%-20%, 10%-15% or 15%-20%.
Among the above-mentioned preparation method, the described tensio-active agent of step (3) can be selected from following 1)-3) at least a:
1) anion surfactant; 2) cats product; 3) nonionogenic tenside.
Above-mentioned anion surfactant can be sodium lauryl sulphate (K12), sodium laurylsulfonate (DBS) or dioctyl sodium sulfosuccinate; Above-mentioned cats product is Dodecyl trimethyl ammonium chloride or cetalkonium chloride; Above-mentioned nonionogenic tenside can be selected from polyoxyethylene octylphenol ether (TX-10) or polyoxyethylene nonylphenol ether (OP-10).
Among the above-mentioned preparation method, the described filler of step (3) can be selected from wood powder, lime carbonate, starch and the flour any.
Among the above-mentioned preparation method, the ratio of quality and the number of copies of the described cross-linking polyvinyl alcohol of step (3), tensio-active agent and filler can be (100-200): (1-10): (50-80), and as (100-200): (2-4): (50-80), (100-150): (2-4): (50-80), (150-200): (2-4): (50-80), 100: 2: 50,200: 4: 50 or 150: 2: 80.
In the method for the present invention, the purpose of oxidation is that the polyvinyl alcohol macromole is become the moderate molecule of molecular weight, just make the part molecular rupture and import end carboxyl or aldehyde radical, like this by oxidation modification reaction, not only can reduce viscosity and increase mobile but also in molecular chain, introduce ketone group.These groups can join the agent effect with multiple friendship (idol), thereby improve sticking and the intensity and the water resistance of polyvinyl alcohol (PVA).
Method of the present invention is owing at PVA intramolecularly and the intermolecular acetal radical of introducing strong cementability, reduced the wetting ability free hydroxyl group.The carbonyl that oxidation modification is introduced in the PVA molecule under crosslinked condition simultaneously also can be formed with the ketal group of tackifying.Therefore tackify and the crosslinked action owing to ketal group not only further improves bond strength and glue-line water-repellancy, thereby but also owing to reduced the package stability that the generation of free hydroxyl group reduction hydrated gelization has further improved glue.
Adhesive without aldehyde of the present invention, except the tackiness agent of composite isocyanic ester as various wood-based plates, all right bonding all timber products, as Wood craft, wood furniture, cloth art furnishings, kitchen furniture, various wood-based plates; Adhesive without aldehyde of the present invention also can substitute white glue with vinyl (polyvinyl acetate emulsion) fully in many Application Areass; Can also and be used for the tackiness agent that inner-wall ceramic tile, wallpaper, wall paper, carpet, office appliance also have leather as the tackiness agent of interior wall material of construction.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
The preparation of embodiment 1, adhesive without aldehyde
The preparation mass percent is 10% water white transparency PVA1799 (mean polymerisation degree the is 1700-1850) aqueous solution 1000 grams, adds 2 gram Potassium Persulphates, under 50 ℃, stirs oxidation 2 hours.Add the alum liquor of 2 grams 20% afterwards, and the solution that contains 0.15 gram borax.The sodium lauryl sulphate that adds system gross weight 0.2% after stirring again, stirring cools to room temperature, adds the flour of system total mass 5% again, and the discharging that stirs promptly gets adhesive without aldehyde.
The preparation of embodiment 2, adhesive without aldehyde
Preparation concentration is 20% water white transparency PVA2099 (mean polymerisation degree the is 2000-2150) aqueous solution 1000 grams, adds 3 gram Ammonium Persulfate 98.5s, under 60 ℃, stirs oxidation down 2 hours.Add the OP-107 gram afterwards; Add 16 gram MDI afterwards again, reaction is 2 hours under 50 ℃ temperature.The dioctyl sodium sulfosuccinate that adds system gross weight 0.4% afterwards again, stirring cools to room temperature, adds the light calcium carbonate of system total mass 5% again, and the discharging that stirs promptly gets adhesive without aldehyde.
The preparation of embodiment 3, adhesive without aldehyde
The preparation mass percent is 15% water white transparency PVA1788 (mean polymerisation degree the is 1700-1850) aqueous solution 1000 grams, adds 1.5 gram Potassium Persulphates, under 40 ℃, stirs oxidation 1.5 hours.Add 1.5 gram TDI (bigization of Cangzhou 80/20) solution afterwards, and the solution that contains 0.15 gram borax.The sodium laurylsulfonate that adds system gross weight 0.2% after stirring again, stirring cools to room temperature, and the flour that the adds total system quality 8% again discharging that stirs promptly gets adhesive without aldehyde.
The application of the adhesive without aldehyde of embodiment 4, embodiment 1
Get 100 parts in the tackiness agent of embodiment 1 preparation, adds 12 parts of PMDI (gather diphenylmethanediisocyanate, Huntsman 5005), stir.Utilize this composite tackiness agent to produce the poplar three-layer glued board under the following conditions: the pressure 1.3MPa that colds pressing, 0.5 hour, hot pressing pressure 1MPa, 3-5 minute.The glued board of being produced after 3 hours, detects 7 prints at 63 ℃ of poach, and shearing resistance is 100% greater than the 0.7Mpa qualification rate all.
The application of the adhesive without aldehyde of embodiment 5, embodiment 2
Get 100 parts in the tackiness agent of embodiment 2 preparation, adds 8 parts of PMDI (gather diphenylmethanediisocyanate, Huntsman 5005), stir.Utilize this composite tackiness agent to produce the poplar three-layer glued board under the following conditions: the pressure 1.3MPa that colds pressing, 0.5 hour, hot pressing pressure 1MPa, 3-5 minute.The glued board of being produced after 3 hours, detects 7 prints at 63 ℃ of poach, and shearing resistance is 100% greater than the 0.7Mpa qualification rate all.
The application of the adhesive without aldehyde of embodiment 6, embodiment 3
Get 100 parts in the tackiness agent of embodiment 3 preparation, adds 10 parts of PMDI (gather diphenylmethanediisocyanate, Huntsman 5005), stir.Utilize this composite tackiness agent to produce the poplar three-layer glued board under the following conditions: the pressure 1.3MPa that colds pressing, 0.5 hour, hot pressing pressure 1MPa, 3-5 minute.The glued board of being produced after 3 hours, detects 7 prints at 63 ℃ of poach, and shearing resistance is 100% greater than the 0.7Mpa qualification rate all.
Claims (7)
1. the preparation method of an adhesive without aldehyde may further comprise the steps:
(1) with oxygenant polyvinyl alcohol is carried out oxide treatment and obtain the oxidation modification polyvinyl alcohol, the mean polymerisation degree of described polyvinyl alcohol is 1000-2500;
(2) make described oxidation modification polyvinyl alcohol carry out crosslinking reaction with linking agent and obtain cross-linking polyvinyl alcohol;
(3) in the solution of described cross-linking polyvinyl alcohol, add tensio-active agent and filler, stir and promptly get described adhesive without aldehyde;
In the step (1), described oxygenant is selected from potassium bichromate, hydrogen peroxide, Potassium Persulphate and the ammonium persulphate any; The consumption of described oxygenant is the 0.5%-4% of the quality of described polyvinyl alcohol; The temperature of the described oxide treatment of step (1) is 30 ℃-80 ℃; The time of described oxide treatment is 1 hour-4 hours;
In the step (2), described linking agent is selected from following 1)-3) at least a: 1) inorganic salt; 2) organic acid or its salt; 3) isocyanic ester; The ratio of quality and the number of copies of described linking agent of step (2) and described oxidation modification polyvinyl alcohol is (0.1-30): 100;
In the step (3), the ratio of quality and the number of copies of described cross-linking polyvinyl alcohol, tensio-active agent and filler is (100-200): (1-10): (50-80).
2. method according to claim 1 is characterized in that: described inorganic salt are the aluminium salt that contains polyvalent metal ion; Described organic acid or its salt are boric acid, borax, oxalic acid, fumaric acid, toxilic acid or citric acid; Described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate or hexamethylene diisocyanate.
3. method according to claim 2 is characterized in that: described inorganic salt are Tai-Ace S 150.
4. according to each described method among the claim 1-3, it is characterized in that: the described tensio-active agent of step (3) is selected from following 1)-3) at least a:
1) anion surfactant; 2) cats product; 3) nonionogenic tenside.
5. method according to claim 4 is characterized in that: described anion surfactant is sodium lauryl sulphate, sodium laurylsulfonate or dioctyl sodium sulfosuccinate; Described cats product is Dodecyl trimethyl ammonium chloride or cetalkonium chloride; Described nonionogenic tenside is polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol ether.
6. according to each described method among the claim 1-3, it is characterized in that: the described filler of step (3) is selected from wood powder, lime carbonate, starch and the flour any.
7. the adhesive without aldehyde of each described method preparation among the claim 1-6.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102372956A CN101892023B (en) | 2010-07-22 | 2010-07-22 | Aldehyde-free adhesive and preparation method thereof |
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| CN2010102372956A CN101892023B (en) | 2010-07-22 | 2010-07-22 | Aldehyde-free adhesive and preparation method thereof |
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| CN101892023B true CN101892023B (en) | 2011-11-16 |
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| CN113831863B (en) * | 2020-06-24 | 2022-09-20 | 万华化学集团股份有限公司 | Adhesive, preparation and application thereof |
| CN111890482B (en) * | 2020-08-18 | 2021-05-07 | 宁夏福宁木业有限公司 | Formaldehyde-free environment-friendly plywood and manufacturing method thereof |
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| CN101445710B (en) * | 2008-12-30 | 2010-08-11 | 陈利佳 | Cross linking modified PVA environment-friendly watertight label adhesive and manufacture method thereof |
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