CN106336840A - Anticorrosion compound urea resin and production method thereof - Google Patents

Anticorrosion compound urea resin and production method thereof Download PDF

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CN106336840A
CN106336840A CN201610746799.8A CN201610746799A CN106336840A CN 106336840 A CN106336840 A CN 106336840A CN 201610746799 A CN201610746799 A CN 201610746799A CN 106336840 A CN106336840 A CN 106336840A
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parts
weight
formaldehyde resin
resin
preservative
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王飞虎
胡海强
李宁
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Nanning Chuang Chuang Plywood Co Ltd
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Nanning Chuang Chuang Plywood Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/32Modified amine-aldehyde condensates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00Preparation of derivatives of starch
    • C08B31/18Oxidised starch
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The invention discloses anticorrosion compound urea resin and a production method thereof. The anticorrosion compound urea resin is prepared from melamine modified urea-formaldehyde resin, oxidized starch, polyvinyl alcohol, hydrogenated rosin, propylene glycol polyoxypropylene polyvinyl ether, polyisocyanate, isobutyltriethoxysilane, phenolated lignin, clear water and preservative. The production method includes the steps of putting clear water into a reaction still to be heated to 80-100 DEG C, adding hydrogenated rosin, isobutyltriethoxysilane and propylene glycol polyoxypropylene polyvinyl ether to be stirred, adding polyvinyl alcohol and phenolated lignin to be dissolved, then adding melamine modified urea-formaldehyde resin, oxidized starch and preservative for stirring reaction for 2-5 h at constant temperature of 80-90 DEG C, and adding polyisocyanate before use to be evenly mixed and stirred so as to use the anticorrosion compound urea resin. The anticorrosion compound urea resin is high in water resistance, high in bonding strength, low in formaldehyde residual amount and remarkable in anticorrosion effect, prolongs the service life of panels and has great popularization value.

Description

Anti-corrosion composite urea formaldehyde resin and its production method
Technical field
The invention belongs to adhesive production field, particularly a kind of anti-anti-corrosion composite urea formaldehyde resin and its production method.
Background technology
With the raising of the development of China's economic, living standards of the people, the requirement to house decoration also constantly improves.Wood Floor, because of its naturally graceful lines, good texture, becomes the preferred material of family's ground surface finishing.And solid wooden compound floor The shortcoming overcoming solid wooden floor board moisture expansion and drying shrinkage, has preferable dimensional stability, remains the natural wood of solid wooden floor board simultaneously Stricture of vagina and comfortable feel, thus becoming the important kind in floor, produce the Lauxite floor glue that solid wooden compound floor is used Consumption is also lifted therewith.Lauxite or the adhesive of modified urea-formaldehyde resin glue Nian Jishi China timber industry consumption maximum, account for More than the 60% of wood-processing industry adhesive total flow, account for the 90% about of wood-based plate glue consumption.Urea-formaldehyde resin adhesive has Have many advantages, such as, such as higher glue-joint strength, high resistance to cold water performance, the property fast rapidly, miscible with water that solidifies are good, and it is suitable easily to modulate Viscosity and concentration etc., but, current urea-formaldehyde resin adhesive or modified urea-formaldehyde resin glue stick in agent and all do not have antiseptic property, because This, with this adhesive, the particieboard being prepared from, density board do not have antiseptic property yet, and particieboard and density board are wooden systems Product, easily by biological attack such as bacterium, worm, the raw boring in sea worms, easily rot, so the decay resistance of particieboard and density board is not Height, pest-resistant poor performance is so as to somewhat limited in utilization.Therefore, in order to improve the corrosion resistance of particieboard and density board And insect resistance capacity, extend the service life of particieboard and density board, carrying out preservative treatment to particieboard and density board is to have very much Necessary.At present, people attach great importance to the research of particieboard and density board antiseptic property, and how to manufacture production have anti-corrosion Characteristic and the particieboard that environment is not polluted and density board, extend the service life of sheet material, are that people are badly in need of solving at present Problem certainly.
And cyanurotriamide modified urea resin is to be modified being obtained on the basis of Lauxite, Lauxite has former The advantages of material is cheap and easy to get, solidification temperature no strictly limits, but Lauxite boiling water resistance and ageing resistance are poor, because its solidification There is hydrophilic free methylol, they are easily combined with water in resin afterwards.And the tripolycyanamide with ring molecule is introduced urea In urea formaldehyde, form tridimensional network, enclose many hydrophilic groups, change resin backbone structure, promote resin and hand over Connection, thus having reached the purpose of the adhesion strength, resistance to water and weatherability improving resin, turn avoid simple tripolycyanamide simultaneously The relatively costly shortcoming of formaldehyde resin.
Therefore, how to apply the excellent specific property of cyanurotriamide modified urea resin, give full play to it former as adhesive master The effect of material, ensure that adhesive has antiseptical performance after particieboard and density board bonding is a worth research and pole simultaneously The problem that tool is worth.
Content of the invention
For above-mentioned technological deficiency, it is an object of the invention to provide a kind of anti-corrosion composite urea formaldehyde resin and its production Method, by biological attack such as bacterium, worm, the raw boring in sea worms, the problems such as easily rotting, exploitation is a kind of because easily to solve wooden product at present Resistance to water is strong, adhesion strength is high, residual formaldehyde amount is low, the composite urea formaldehyde resin of tool antiseptic property.
The technical solution used in the present invention is:
A kind of anti-corrosion composite urea formaldehyde resin adhesive, is made up of the raw material of following parts by weight:
50~100 parts of cyanurotriamide modified urea resin;
20~30 parts of Oxytarch;
1~3 part of polyvinyl alcohol;
3~8 parts of hydrogenated rosin;
2~3 parts of propanediol polyoxypropylene polyvinylether;
4~6 parts of polyisocyanate;
0.5~5 part of isobutyl triethoxy silane;
5~10 parts of phenolate lignin;
100~200 parts of clear water;
3.9~7.8 parts of preservative.
Described preservative is activated carbon powder, the mixture of bamboo charcoal powder, Calcium pyroborate and sodium benzoate, and its part by weight is successively For 4:5:2:2;Described activated carbon powder and bamboo charcoal powder all cross 300 mesh sieves.
Described activated carbon powder and bamboo charcoal powder all cross 300 mesh sieves.The specific surface area of activated carbon powder and bamboo charcoal powder is big, has super Strong moisture effect, with the moisture in absorption air, it is to avoid timber main body has that mouldy, the situation such as addle.Calcium pyroborate Stability Analysis of Structures, In addition to having disinsection efficiency, to domestomycetes, mycete and Coptotermes formosanus Shtrari. are to having preferable resistance.It is micro- that sodium benzoate is that a kind of wide spectrum resists Biological reagent, fine to mycete action effect.The mixture of activated carbon powder, bamboo charcoal powder, Calcium pyroborate and sodium benzoate is as anti-corrosion Agent is added in composite urea formaldehyde resin adhesive of the present invention, improves the decay resistance of wood-based plate, to domestomycetes, mycete and white Ant has preferable resistance, extends the service life of cupboard board, does not affect the bonding strength of adhesive, disperses in adhesive Uniformly, can with glue to wood internal permeate, make product reach long-effective corrosion function it is often more important that, this several material is equal Safe and efficient low toxicity.
The production method of above-mentioned anti-corrosion composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 80-100 DEG C, it is subsequently adding hydrogenated rosin, isobutyl triethoxy silane and the propanediol polyoxypropylene polyethylene of parts by weight Ether, stirs 10 minutes to 30 minutes, adds polyvinyl alcohol, the phenolate lignin of parts by weight, be allowed to dissolve, add weight The cyanurotriamide modified urea resin of number, Oxytarch and preservative, keep 80-90 DEG C of stirring reaction 2-5 hour, are using Front 10-20 minute adds the polyisocyanate of parts by weight, and mixing and stirring can use.
Cyanurotriamide modified urea resin of the present invention adopts Guangxi Nanning Green Park Beilin Wood Industry Co., Ltd. to study Cyanurotriamide modified urea resin, number of patent application: cn 201310353442.x;The applying date: 2013.08.14;Open (public Accuse) number: cn 103408711a;Application (patent right) people: Guangxi Nanning Green Park Beilin Wood Industry Co., Ltd., this tripolycyanamide changes Property Lauxite primary raw material be formaldehyde, tripolycyanamide and carbamide, add formaldehyde using disposable, add several times carbamide and The method of tripolycyanamide, controls reaction rate, it is to avoid the generation of gelatin phenomenon, promotes the reaction completely of formaldehyde.Repeatedly add urine Element, the carbamide adding every time is all different with the polymerization rate of formaldehyde and condition, after being divided into prepolymerization, polymerization and polymerization Phase three phases, the amount of each stage addition carbamide is different, and reaction temperature is also different, by this technique, it is to avoid The generation of polymerization process gelatin phenomenon, the Lauxite narrow molecular weight distribution of gained, residual formaldehyde is low, artificial for producing Plate, it is possible to decrease the burst size of methanal of wood-based plate.
Above-described anti-corrosion composite urea formaldehyde resin adhesive, the function of each raw material is as follows:
Cyanurotriamide modified urea resin, is adhesive major ingredient.Urea-formaldehyde resin adhesive is a kind of thermosetting polymer adhesive. Due to its process is simple, raw material is cheap, and adhesive strength is high, the advantages of water white transparency, be widely used in plywood, particieboard, The industries such as medium density fibre board (MDF), the production of artificial board and interior decoration, can buy in Market of Adhesives.Band ring molecule Tripolycyanamide be introduced in Lauxite, formed tridimensional network, enclose many hydrophilic groups, change resin matrix knot Structure, promotes resin crosslinks, thus having reached the purpose of the adhesion strength, resistance to water and ageing resistance improving resin, again simultaneously Avoid the relatively costly shortcoming of simple melamine resin.
Oxytarch is that starch is acted on oxidant in acid, alkali, neutral medium, makes a kind of obtained from starch oxidation change Property starch.Oxytarch product colour is pure white, pastes transparent, good film-forming property, and freeze-thaw resistance is good, is the thickening of low viscosity high concentration Agent, is widely used in weaving, papermaking, food and Fine Chemical.Oxytarch carries more aldehyde radical and carboxyl, can be multiple During closing Lauxite polymer reaction, generate acetal and hemiacetal structure, thus improving the ageing-resistant performance of Lauxite; Simultaneous oxidation starch can be combined with the free formaldehyde in cyanurotriamide modified urea resin, can reduce free formaldehyde content;Oxidation On the other hand starch, can reduce cyanurotriamide modified urea resin addition as viscosity complexing agent again, reduce and produce Cost.
Polyvinyl alcohol, is toughener so that the wood-based plate intensity produced increases.
Hydrogenated rosin, is antioxidant so that the wood-based plate produced does not allow perishable, prolongation life-span, anti-aging.
Propanediol polyoxypropylene polyvinylether, is defoamer, prevents adhesive from having bubble cavity to produce during using.
Polyisocyanate is firming agent, is characterized in thering is very high wearability, and stable chemical nature, and intensity is high, The crosslinked action itself having, can improve heat-resisting, water, the plasticizer of adhesive and the performance of solvent.
Bridging agent, from isobutyl triethoxy silane, its one end can be combined with Lauxite carbonyl, and the other end can be with The hydroxy combining of starch, strengthens its plank intensity.
Lignin molecular mass after phenolate reaction reduces, and increases reaction active groups, can eliminate part free formaldehyde. The preparation method of phenolate lignin is: will be placed in separation container using the black liquid of alkaline boiling method slurrying, is removed with screen cloth Undissolved float, settles 4 hours after stirring, discharge lower floor silt, takes upper strata to contain the black liquor vacuum drying of alkali lignin Machine carries out vacuum spray drying process, obtains powdery alkali lignin;Take powdery alkali lignin to put in acidifier, add 70wt% sulphuric acid, after stirring, is warming up to 140-160 DEG C, sulfonating reaction 1-2 hour;Through standard vertical-tubes evaporation Device, circulation rate is 0.4m/s-0.5m/s, and control discharging moisture is 30wt%, precipitation, through filtering, being dried to water content For 15wt%;By lignin: phenol weight than for 1:1 add phenol, control temperature 85-95 DEG C, insulation reaction 1 hour, Finally adjust ph to 6.5-7.0 with 30wt% sodium hydroxide and obtain final product phenolate lignin.
Sodium benzoate is mostly white particle, odorless or micro-strip Benzoinum abnormal smells from the patient, and taste is micro- sweet, has convergence;Soluble in water (room temperature), ph 8 about, is acid preservative, no sterilization, bacteriostasis in alkaline medium;Its anti-corrosion optimal ph is 2.5- 4.0.Sodium benzoate is a kind of broad spectrum antimicrobial reagent, fine to mycete action effect.Sodium benzoate preservative is with it not The molecule of dissociation is had an effect, and non-dissociated benzoic acid lipophile is strong, easily passes through cell membrane, enters intracellular, disturbs mycete With the permeability of the microbial cell films such as antibacterial, the absorption to aminoacid for the block cell film, enter intracellular benzoic acid molecule, It is acidified intracellular storage alkali, the activity of the breathing enzyme system in suppression microbial cell, thus play antisepsises.
The preparation of described Oxytarch:
(1), select glass apparatus and assemble synthesizer:
Jj600 electronic balance;Digital display thermostat water bath;Digital display constant speed stirrer;There-necked flask;Electric heating constant-temperature blowing drying box; Ndj-79 Rotary Viscosimeter.
(2) reagent chemicals:
Raw material: tapioca (moisture 13.8%);
Reagent: hydrogen peroxide (30%), Copper hydrate, copper sulfate, sodium sulfite (being ar).
(3) preparation principle:
Starch oxidant effect under, the hydroxyl on glucose unit oxidable become carboxyl (- cooh), it makes binding agent Stability be improved significantly.Oxidation decreases the quantity of hydroxyl in starch molecule, so that molecular association is obstructed, thus subtracting The weak binding ability of intermolecular hydrogen chain.Meanwhile, glucosides chain break, makes macromolecules degradation, and starch molecule amount reduces, thus increasing Dissolubility, mobility and caking property are added.In the presence of liquid caustic soda, with not oxidized hydroxy combining in starch, destroy part hydrogen Key, makes declines between macromole, thus easily swelling gelatinizing, give its caking property.
Preparation process is as follows:
Weigh 200g tapioca in 1000ml there-necked flask, add water and be tuned into the starch milk of 18~21 ° of b é, stir, slowly The sodium hydroxide solution of slow a certain amount of 5%~7% concentration of Deca.After water-bath rises to design temperature, add 0.01% copper sulfate.So After add a certain amount of hydrogen peroxide, after isothermal reaction certain time, add 0.4g sodium sulfite, stir 10min terminating reaction. After reaction terminates, it is 5.5~6.0 with dilute hydrochloric acid neutralization reaction liquid ph value.Sucking filtration is dehydrated, washes clean, places 40-50 in baking oven Dry at DEG C, pulverize, screening obtains final product product.The Oxytarch of above-mentioned use can be produced with jumbo reactor.
Compared with prior art, the positive effect of the present invention is:
1st, in the present invention, using cyanurotriamide modified urea resin as adhesive major ingredient, there is process is simple, raw material is honest and clean Valency, adhesive strength is high, the advantages of water white transparency, and the release of low formaldehyde gases, it is a kind of environmental type resin, urea can be improved The resistance to water of urea formaldehyde, and prevent from glue-line from shrinking reducing internal stress, improve ageing-resistant performance, increases glue solid content, viscosity and just Viscosity, extends working life.And using hydrogenated rosin for antioxidant so that the wood-based plate produced do not allow perishable, extend Life-span, anti-aging;Using polyvinyl alcohol for toughener so that the wood-based plate intensity produced increases;Using propylene glycol polyoxy Propylene polyvinylether, is defoamer, prevents adhesive from having bubble cavity to produce during using;It is solidification using polyisocyanate Agent;From isobutyl triethoxy silane as bridging agent, its one end can be combined with Lauxite carbonyl, other end energy and starch Hydroxy combining, strengthen its plank intensity;Contain a large amount of active groups in phenolate lignin, as formaldehyde catching agent, can disappear Except part free formaldehyde;Using Oxytarch, as viscosity complexing agent, cyanurotriamide modified urea resin can be reduced and add Amount, cost-effective;Activated carbon powder, the mixture of bamboo charcoal powder, Calcium pyroborate and benzenpropanoic acid sodium are added to the present invention again as preservative Close in urea-formaldehyde resin adhesive, improve the decay resistance of wood-based plate, to domestomycetes, mycete and Coptotermes formosanus Shtrari. have preferable opposing Power, extend wood-based plate service life, do not affect the bonding strength of adhesive, be uniformly dispersed in adhesive, can with glue to Wood internal permeate, make product reach long-effective corrosion function it is often more important that, all safe and efficient low toxicity of this several material.
2nd, in the present invention, activated carbon powder and the fine and closely woven porous of bamboo charcoal powder, has superpower moisture protection, in energy absorption air Moisture, it is to avoid timber main body has that mouldy, the phenomenon such as addle;Also have and decompose the function that abnormal flavour removes U.S. sterilization, if absorbing wood The harmful gass such as formaldehyde, benzene, dimethylbenzene, hydrogen in matter product.Calcium pyroborate Stability Analysis of Structures, in addition to there is disinsection efficiency, rotten to wood Bacterium, mycete and Coptotermes formosanus Shtrari. are to having preferable resistance.Sodium benzoate is a kind of broad spectrum antimicrobial reagent, to mycete action effect Very well.The mixture of activated carbon powder, bamboo charcoal powder, Calcium pyroborate and sodium benzoate is added to the present invention as preservative and is combined ureaformaldehyde tree In fat adhesive, improve the decay resistance of wood-based plate, to domestomycetes, mycete and Coptotermes formosanus Shtrari. have preferable resistance, extend The service life of cupboard board, does not affect the bonding strength of adhesive, is uniformly dispersed in adhesive, can be with glue to wood internal Infiltration, make product reach long-effective corrosion function it is often more important that, all safe and efficient low toxicity of this several material.
Specific embodiment
Embodiment 1
A kind of anti-corrosion composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
50 parts of cyanurotriamide modified urea resin;
20 parts of Oxytarch;
1 part of polyvinyl alcohol;
3 parts of hydrogenated rosin;
2 parts of propanediol polyoxypropylene polyvinylether;
4 parts of polyisocyanate;
0.5 part of isobutyl triethoxy silane;
5 parts of phenolate lignin;
100 parts of clear water;
3.9 parts of preservative.
Described preservative is activated carbon powder, the mixture of bamboo charcoal powder, Calcium pyroborate and sodium benzoate, and its part by weight is successively For 4:5:2:2;Wherein 1.2 parts of activated carbon powder, 1.5 parts of bamboo charcoal powder, 0.6 part of Calcium pyroborate, 0.6 part of sodium benzoate.Described activity Powdered carbon and bamboo charcoal powder all cross 300 mesh sieves.
The production method of above-mentioned anti-corrosion composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 80 DEG C, it is subsequently adding hydrogenated rosin, isobutyl triethoxy silane and the propanediol polyoxypropylene polyvinylether of parts by weight, stirs Mix 30 minutes, add polyvinyl alcohol, the phenolate lignin of parts by weight, be allowed to dissolve, add the melamine of parts by weight Amine modified urea-formaldehyde resin, Oxytarch, activated carbon powder, bamboo charcoal powder, Calcium pyroborate and sodium benzoate, keep 80 DEG C of stirring reactions 5 little When, 10-20 minute adds the polyisocyanate of parts by weight before use, and mixing and stirring can use.
Embodiment 2
A kind of anti-corrosion composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
70 parts of cyanurotriamide modified urea resin;
24 parts of Oxytarch;
1.8 parts of polyvinyl alcohol;
5 parts of hydrogenated rosin;
2.5 parts of propanediol polyoxypropylene polyvinylether;
5 parts of polyisocyanate;
3 parts of isobutyl triethoxy silane;
7 parts of phenolate lignin;
150 parts of clear water;
5.2 parts of preservative.
Described preservative is activated carbon powder, the mixture of bamboo charcoal powder, Calcium pyroborate and sodium benzoate, and its part by weight is successively For 4:5:2:2;Wherein 1.6 parts of activated carbon powder, 2.0 parts of bamboo charcoal powder, 0.8 part of Calcium pyroborate, 0.8 part of sodium benzoate.Described activity Powdered carbon and bamboo charcoal powder all cross 300 mesh sieves.
The production method of above-mentioned anti-corrosion composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 85 DEG C, it is subsequently adding hydrogenated rosin, isobutyl triethoxy silane and the propanediol polyoxypropylene polyvinylether of parts by weight, stirs Mix 20 minutes, add polyvinyl alcohol, the phenolate lignin of parts by weight, be allowed to dissolve, add the melamine of parts by weight Amine modified urea-formaldehyde resin, Oxytarch, activated carbon powder, bamboo charcoal powder, Calcium pyroborate and benzenpropanoic acid sodium, keep 85 DEG C of stirring reactions 3 little When, 10-20 minute adds the polyisocyanate of parts by weight before use, and mixing and stirring can use.
Embodiment 3
A kind of anti-corrosion composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
80 parts of cyanurotriamide modified urea resin;
28 parts of Oxytarch;
2 parts of polyvinyl alcohol;
6 parts of hydrogenated rosin;
3 parts of propanediol polyoxypropylene polyvinylether;
5 parts of polyisocyanate;
4 parts of isobutyl triethoxy silane;
8 parts of phenolate lignin;
180 parts of clear water;
6.5 parts of preservative.
Described preservative is activated carbon powder, the mixture of bamboo charcoal powder, Calcium pyroborate and sodium benzoate, and its part by weight is successively For 4:5:2:2;Wherein 2.0 parts of activated carbon powder, 2.5 parts of bamboo charcoal powder, 1.0 parts of Calcium pyroborate, 1.0 parts of sodium benzoate.Described activity Powdered carbon and bamboo charcoal powder all cross 300 mesh sieves.
The production method of above-mentioned anti-corrosion composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 90 DEG C, it is subsequently adding hydrogenated rosin, isobutyl triethoxy silane and the propanediol polyoxypropylene polyvinylether of parts by weight, stirs Mix 15 minutes, add polyvinyl alcohol, the phenolate lignin of parts by weight, be allowed to dissolve, add the melamine of parts by weight Amine modified urea-formaldehyde resin, Oxytarch, activated carbon powder, bamboo charcoal powder, Calcium pyroborate and sodium benzoate, keep 88 DEG C of stirring reactions 3 little When, 10-20 minute adds the polyisocyanate of parts by weight before use, and mixing and stirring can use.
Embodiment 4
A kind of anti-corrosion composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
100 parts of cyanurotriamide modified urea resin;
30 parts of Oxytarch;
3 parts of polyvinyl alcohol;
8 parts of hydrogenated rosin;
3 parts of propanediol polyoxypropylene polyvinylether;
6 parts of polyisocyanate;
5 parts of isobutyl triethoxy silane;
10 parts of phenolate lignin;
200 parts of clear water;
7.8 parts of preservative.
Described preservative is activated carbon powder, the mixture of bamboo charcoal powder, Calcium pyroborate and sodium benzoate, and its part by weight is successively For 4:5:2:2;Wherein 2.4 parts of activated carbon powder, 3.0 parts of bamboo charcoal powder, 1.2 parts of Calcium pyroborate, 1.2 parts of sodium benzoate.Described activity Powdered carbon and bamboo charcoal powder all cross 300 mesh sieves.
The production method of above-mentioned anti-corrosion composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 100 DEG C, it is subsequently adding hydrogenated rosin, isobutyl triethoxy silane and the propanediol polyoxypropylene polyvinylether of parts by weight, Stirring 10 minutes, adds polyvinyl alcohol, the phenolate lignin of parts by weight, is allowed to dissolve, adds the trimerization of parts by weight Cyanamide modified urea-formaldehyde resin, Oxytarch, activated carbon powder, bamboo charcoal powder, Calcium pyroborate and sodium benzoate, keep 90 DEG C of stirring reactions 2 Hour, 10-20 minute adds the polyisocyanate of parts by weight before use, and mixing and stirring can use.
Comparative example 4
A kind of composite urea formaldehyde resin, is made up of the raw material of following parts by weight:
100 parts of cyanurotriamide modified urea resin;
30 parts of Oxytarch;
3 parts of polyvinyl alcohol;
8 parts of hydrogenated rosin;
3 parts of propanediol polyoxypropylene polyvinylether;
6 parts of polyisocyanate;
5 parts of isobutyl triethoxy silane;
10 parts of phenolate lignin;
200 parts of clear water.
The production method of above-mentioned composite urea formaldehyde resin: first the clear water of parts by weight is put in reactor, is heated to 100 DEG C, it is subsequently adding hydrogenated rosin, isobutyl triethoxy silane and the propanediol polyoxypropylene polyvinylether of parts by weight, stirring 10 minutes, add polyvinyl alcohol, the phenolate lignin of parts by weight, be allowed to dissolve, add the tripolycyanamide of parts by weight Modified urea-formaldehyde resin and Oxytarch, keep 90 DEG C of stirring reactions 2 hours, and 10-20 minute adds parts by weight before use Polyisocyanate, mixing and stirring can use.
The compound urea that anti-corrosion composite urea formaldehyde resin adhesive obtained by embodiment 1-4 and comparative example 4 are obtained Urea formaldehyde carries out the mensure of the residual quantity of formaldehyde respectively, and according to the regulation detection in gb/t9846.1- 9846.8-2004 Bonding strength.Formaldehyde determination adopts acetylacetone,2,4-pentanedione spectrophotography, residual formaldehyde %=measured value/example weight × %, 25mm), Additionally, being divided with particieboard prepared by anti-corrosion composite urea formaldehyde resin adhesive and comparative example 4 composite urea formaldehyde resin of the present invention Size identical sample sizes are not taken to put in the culture dish that culture has equal number Coptotermes formosanus Shtrari., culture detected culture after 24 hours The survival number of Coptotermes formosanus Shtrari. calculate the mortality rate of Coptotermes formosanus Shtrari. in ware.Result is as shown in the table: result is as shown in the table:
The difference from comparative example 4 for the embodiment 4 is, embodiment 4 adds preservative;And comparative example 4 does not add Enter preservative.But both residual formaldehyde and bonding strength is can be seen that by the data of embodiment 4 and comparative example 4 Physical index change inconspicuous, but pest control and anticorrosion performance but distinguishes very big, the anti-corrosion composite urea formaldehyde resin of embodiment 4 preparation After adhesive sheet material insect protected is tested 24 hours, termite mortality 99.3% in culture dish, the compound ureaformaldehyde of comparative example 4 preparation After Resin adhesive sheet material insect protected is tested 24 hours, in culture dish, termite mortality is only 10.8%.In the present invention, activated carbon Powder, bamboo charcoal powder, the mixture of Fructus Capsici powder, Calcium pyroborate and bitter fruit leaf powder are added to composite urea formaldehyde resin of the present invention as preservative In adhesive, improve the decay resistance of wood-based plate, to domestomycetes, mycete and Coptotermes formosanus Shtrari. have preferable resistance, prolonged human Make the service life of plate, do not affect the bonding strength of adhesive, be uniformly dispersed in adhesive, can ooze to wood internal with glue Thoroughly, make product reach long-effective corrosion function it is often more important that, all safe and efficient low toxicity of this several material, also have certain Insect protected performance.
Compare with the urea-formaldehyde resin adhesive data market from the data of embodiment 1-4, find that the present invention's is anti-corrosion Composite urea formaldehyde resin adhesive residual formaldehyde is less than the urea-formaldehyde resin adhesive on market, and its bonding strength is also slightly better than market On urea-formaldehyde resin adhesive.
By upper table it can also be seen that the anti-corrosion composite urea formaldehyde resin residual formaldehyde of the present invention is below the ureaformaldehyde on market Resin, high using safety coefficient, bonding strength is also more excellent with respect to Lauxite;Meanwhile, the anti-corrosion compound ureaformaldehyde of the present invention Resin adhesive weather resistance is high compared with the Lauxite on market.It can be seen that, the anti-corrosion composite urea formaldehyde resin adhesive of the present invention is not Only have the advantages that bonding strength high, using safe, also thoroughly solve sheet material and be subject to wood, domestomycetes, mycete and Coptotermes formosanus Shtrari. and invade The problem of erosion, extends the service life of sheet material, and burst size of methanal is well below comparative example 4.

Claims (3)

1. a kind of anti-corrosion composite urea formaldehyde resin adhesive it is characterised in that: be made up of the raw material of following parts by weight:
50~100 parts of cyanurotriamide modified urea resin;
20~30 parts of Oxytarch;
1~3 part of polyvinyl alcohol;
3~8 parts of hydrogenated rosin;
2~3 parts of propanediol polyoxypropylene polyvinylether;
4~6 parts of polyisocyanate;
0.5~5 part of isobutyl triethoxy silane;
5~10 parts of phenolate lignin;
100~200 parts of clear water;
3.9~7.8 parts of preservative.
2. anti-corrosion composite urea formaldehyde resin adhesive according to claim 1 it is characterised in that: described preservative be activity The mixture of powdered carbon, bamboo charcoal powder, Calcium pyroborate and sodium benzoate, its part by weight is followed successively by 4:5:2:2;Described activated carbon powder and Bamboo charcoal powder all crosses 300 mesh sieves.
3. anti-corrosion composite urea formaldehyde resin adhesive according to claim 1 it is characterised in that: anti-corrosion composite urea formaldehyde resin Production method: first the clear water of parts by weight is put in reactor, is heated to 80-100 DEG C, be subsequently adding the hydrogenation of parts by weight Colophonium, isobutyl triethoxy silane and propanediol polyoxypropylene polyvinylether, stirring added weight to 30 minutes in 10 minutes The polyvinyl alcohol of number, phenolate lignin, are allowed to dissolve, and add cyanurotriamide modified urea resin, the oxidation of parts by weight Starch and preservative, keep 80-90 DEG C of stirring reaction 2-5 hour, and 10-20 minute adds the poly- isocyanide of parts by weight before use Acid esters, mixing and stirring can use.
CN201610746799.8A 2016-08-29 2016-08-29 Anticorrosion compound urea resin and production method thereof Pending CN106336840A (en)

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CN113249069A (en) * 2021-03-25 2021-08-13 广西贺州恒达板业股份有限公司 Anti-corrosion adhesive for finger-jointed board wood and preparation method thereof

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Application publication date: 20170118