CN100384898C - Urea-formaldehyde resin and urea-formaldehyde resin glue and preparation method thereof - Google Patents
Urea-formaldehyde resin and urea-formaldehyde resin glue and preparation method thereof Download PDFInfo
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- CN100384898C CN100384898C CNB200610066710XA CN200610066710A CN100384898C CN 100384898 C CN100384898 C CN 100384898C CN B200610066710X A CNB200610066710X A CN B200610066710XA CN 200610066710 A CN200610066710 A CN 200610066710A CN 100384898 C CN100384898 C CN 100384898C
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- absorbent resin
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Abstract
The present invention provides urea-formaldehyde resin and a preparation method used for a veneer board. In the process that urea-formaldehyde resin is synthesized, super absorbent resin which is 0.01 to 1% of the gross weight of formaldehyde and urea is added, or in the process that urea-formaldehyde resin adhesive is prepared, super absorbent resin which is 0.01 to 1% of the gross weight of the urea-formaldehyde resin is added. Therefore, the phenomenon that in the process of the production of veneer boards, a single board coated with adhesive is excessively aged is effectively prevented. The method ensures that when a single board coated with adhesive is aged for a long time under the conditions of strong wind and low humidity, the phenomenon that the prepressing effect of a board blank is not good can be avoided, and after a veneer board is thermally pressed, the phenomenon that the tackless condition occurs can be avoided. The original synthesis and adhesive mixed technology can not be changed fundamentally, the operation is simple and feasible, and the cost is low.
Description
Technical field
The present invention relates to a kind of adhesion agent for artificial board and preparation method thereof, relate in particular to a kind of glued board urea-formaldehyde resin and preparation method thereof and urea-formaldehyde resin adhesive and modulator approach thereof.
Background technology
At present, the tackiness agent that adopts of most wood-based plate manufacturer is a urea-formaldehyde resin.The urea-formaldehyde resin that wherein most producers use is to adopt " weak base-weak acid-weak base " explained hereafter, main raw material is urea and formaldehyde, modification is added a certain amount of trimeric cyanamide often and is improved water tolerance and bonding strength, adds a small amount of polyvinyl alcohol and improve tack (precompressed), uses and goes to toward adding solidifying agent (ammonium chloride commonly used), filler (flour commonly used during plywood production) etc.
China has thousands of plywood production producers now, mats formation wherein by hand, the middle-size and small-size factory of assembly is in the great majority.Because the working condition restriction, a lot of midget plants adopt urea-formaldehyde resin adhesive in the plywood production process, and the digestion time of remaining silent of blanket glued veneer is often very long, and what have can reach several hrs.And simultaneously, the production space of these factories is generally little, and in order to reduce airborne concentration of formaldehyde, the door and window in workshop usually is open.Though in order to improve the tack of urea-formaldehyde resin adhesive, guarantee the precompressed effect, the flour that when the urea-formaldehyde resin impregnation, has all added 10-20%, but under the situation big at wind, that humidity is low, it is excessive that long ageing often makes the limit portion of blanket glued veneer ageing occur, cause slab precompressed effect bad, the situation of coming unglued also appears in glued board after the hot pressing often.
Summary of the invention
An object of the present invention is provides a kind of urea-formaldehyde resin that is used for glued board and preparation method thereof at above problem, this urea-formaldehyde resin has added super absorbent resin in building-up process, prevented that effectively the ageing of blanket glued veneer is excessive in the plywood production, even guarantee to carry out long ageing under blanket glued veneer is big at wind, humidity the is low situation, it is bad and the situation of coming unglued occurs behind plywood hot-pressing slab precompressed effect also can not occur.
Another object of the present invention provides a kind of urea-formaldehyde resin adhesive and modulator approach thereof that is used for glued board, in the impregnation process of this urea-formaldehyde resin adhesive, added super absorbent resin, prevented that effectively the ageing of blanket glued veneer is excessive in the plywood production, even guarantee to carry out long ageing under blanket glued veneer is big at wind, humidity the is low situation, it is bad and the situation of coming unglued occurs behind plywood hot-pressing slab precompressed effect also can not occur.
For achieving the above object, an aspect of of the present present invention provides a kind of method for preparing glued board with urea-formaldehyde resin, adds super absorbent resin in formaldehyde and urea condensation reaction process.
Wherein, the consumption of super absorbent resin is the 0.01-1% of formaldehyde and urea gross weight.
Particularly, urea divides at least two batches to add in the formaldehyde solution in the condensation reaction, super absorbent resin can together add formaldehyde solution with a collection of urea wherein, can add together with first urea as super absorbent resin, also can together add, also can gradation add with second batch, the 3rd batch or the 4th batch of urea.
Another aspect of the present invention provides the glued board urea-formaldehyde resin of method for preparing.
Another aspect of the present invention is provided for the modulator approach of the urea-formaldehyde resin adhesive of glued board, comprise following materials of weight proportions, 100 parts of urea-formaldehyde resins, filler 10-20 part, solidifying agent 0.2-1 part, super absorbent resin consumption are the 0.01-1% of urea-formaldehyde resin total amount, urea-formaldehyde resin is added in the Glue mixer, then super absorbent resin and filler, solidifying agent are together added, be stirred to each component and mix.
Wherein urea-formaldehyde resin can be urea-formaldehyde resin or the modified urea-formaldehyde resin that present factory generally uses, modified urea-formaldehyde resin can be trimeric cyanamide, isocyanic ester, phenol, polyvinyl alcohol, acid polyethylene vac emulsion, alcohols modified urea-formaldehyde resin, also can be modified urea-formaldehyde resins such as flour, starch, zein, nut-shell, spent pulping liquor.
Another aspect of the present invention provides aforesaid method synthetic glued board urea-formaldehyde resin adhesive.
Particularly, super absorbent resin can be the blend of natural polymer super absorbent resin or synthetic macromolecule super absorbent resin or natural polymer super absorbent resin and synthetic macromolecule high-hydroscopicity tree.
Particularly, the natural polymer super absorbent resin is selected from one or more in starch graft polyacrylate, starch grafted polyacrylamide, starch-grafted polyacrylonitrile hydrolyzed thing, starch-acrylic acid-acrylamide graft copolymer, starch carboxymethylation reaction thing, cellulose graft polyacrylate, cellulose graft polyacrylamide, the carboxymethyl cellulose reactant; The synthetic macromolecule super absorbent resin is selected from one or more in polyacrylate, polyacrylamide, acrylic acid-acrylamide copolymer, polyvinyl alcohol, the polyvinyl alcohol-acrylic acid graft copolymer.Every have the high moisture retention that absorbs and again adhesive solidification do not produced dysgenic super absorbent resin and can use.
Wherein filler is one or more in flour, starch, art powder or the shell powder, and preferred filler is 15 parts of flour; Solidifying agent is a kind of in ammonium chloride, ammonium sulfate, the formic acid, and the preferred consolidation agent is 0.1-1 part ammonium chloride.
Urea-formaldehyde resin and synthetic urea-formaldehyde resin adhesive by the present invention's preparation have the following advantages:
1, because the super absorbent resin that contains among the present invention has good water retention property, when therefore using urea-formaldehyde resin of the present invention or urea-formaldehyde resin adhesive to prepare glued board, even if surpass under 4 hours the situation at the blanket glued veneer digestion time, still has good precompressed after the slab precompressed, and prevent from the phenomenon of coming unglued after the hot pressing from therefore effectively to have prevented the excessive ageing problem in the glued board preparation process;
2, the inventive method is simple and easy to do, and additive super absorbent resin and arbitrary urea together add, and perhaps adds super absorbent resin when using the urea-formaldehyde resin impregnation, does not therefore change the preparation technology or the impregnation technology of original urea-formaldehyde resin substantially;
3, because the addition of additive super absorbent resin is very limited, only be the 0.01-1% of formaldehyde and urea total amount or the 0.01-1% of urea-formaldehyde resin total amount, the cost increase that therefore makes urea-formaldehyde resin or urea-formaldehyde resin adhesive seldom is very easy to popularization.
Embodiment
Embodiment 1
1, be that 1.2: 1, super absorbent resin are that 1% of formaldehyde and urea gross weight got the raw materials ready according to the mole proportioning of formaldehyde and urea.
2,37% formaldehyde solution is added in the reactor, stirring is 7.5-8.5 with the sodium hydroxide solution adjust pH down.
3, add first urea U1 and whole super absorbent resins, the mol ratio that makes formaldehyde and urea is 2.0: 1, in 30-60 minute, slowly be warmed up to 90 ± ℃, be incubated 40-60 minute;
4, be 4.2-4.8 with the formic acid adjust pH.React to viscosity for being coated with-4 glasss of 22-30 second (25 ℃);
5, be 7.0-7.5 with the sodium hydroxide solution adjust pH immediately, add second crowd of urea U2, the mol ratio that makes formaldehyde and urea is 1.6: 1, and 70-80 ℃ was reacted 30-60 minute;
6, add residual content urea U3,60-70 ℃ was reacted 30-60 minute;
7, cool to below 40 ℃ discharging.
The resin quality index:
Solids content 55-60%
PH value 7.0-7.5
Viscosity (20 ℃) 150-300mPas
Curing speed 60-90s
Free formaldehyde content＜0.2%
Working life＞4 hour
30-60 days storage period
Embodiment 2
1, be that 1.4: 1, super absorbent resin are that 0.5% of formaldehyde and urea gross weight got the raw materials ready according to the mole proportioning of formaldehyde and urea.
2,37% formaldehyde solution is added in the reactor, stirring is 7.5-8.5 with the sodium hydroxide solution adjust pH down;
3, add urea U1 for the first time, the mol ratio that makes formaldehyde and urea is 2.0: 1, in 30-60 minute, slowly be warmed up to 90 ± ℃, be incubated 40-60 minute;
4, be 4.2-4.8 with the formic acid adjust pH.React to viscosity for being coated with-4 glasss of 22-30 second (25 ℃);
5, be 7.0-7.5 with the sodium hydroxide solution adjust pH immediately, add urea U2 and whole super absorbent resins for the second time, the mol ratio that makes formaldehyde and urea is 1.6: 1, and 70-80 ℃ was reacted 30-60 minute;
6, add residual content urea U3, the mol ratio that makes formaldehyde and urea is 1.4: 1, and 60-70 ℃ was reacted 30-60 minute;
7, cool to below 40 ℃ discharging.
The resin quality index:
Solids content 50-56%
PH value 7.0-7.5
Viscosity (20 ℃) 150-300mPas
Curing speed 40-70s
Free formaldehyde content＜0.5%
Working life＞4 hour
30-60 days storage period
Embodiment 3
1, be that 1.8: 1, super absorbent resin are that 0.01% of formaldehyde and urea gross weight got the raw materials ready according to the mole proportioning of formaldehyde and urea.
2,37% formaldehyde solution is added in the reactor, stirring is 7.5-8.5 with the sodium hydroxide solution adjust pH down.
3, add urea U1 for the first time, the mol ratio that makes formaldehyde and urea is 2.0: 1, in 30-60 minute, slowly be warmed up to 90 ± ℃, be incubated 40-60 minute;
4, be 4.2-4.8 with the formic acid adjust pH, react to viscosity for being coated with-4 glasss of 22-30 second (25 ℃);
5, be 7.0-7.5 with the sodium hydroxide solution adjust pH immediately, add residual content urea U2 and super absorbent resin, the mol ratio that makes formaldehyde and urea is 1.8: 1, and 60-70 ℃ was reacted 30-60 minute.
6, cool to below 40 ℃ discharging.
The resin quality index:
Solids content 45-55%
PH value 7.0-7.5
Viscosity (20 ℃) 150-300mPas
Curing speed 30-60s
Free formaldehyde content＜1.2%
Working life＞4 hour
30-60 days storage period
Embodiment 4
1, be to get the raw materials ready at 1.2: 1 according to the mole proportioning of formaldehyde and urea.
2,37% formaldehyde solution is added in the reactor, stirring is 7.5-8.5 with the sodium hydroxide solution adjust pH down.
3, add urea U1 for the first time, the mol ratio that makes formaldehyde and urea is 2.0: 1, in 30-60 minute, slowly be warmed up to 90 ± ℃, be incubated 40-60 minute;
4, be 4.2-4.8 with the formic acid adjust pH.React to viscosity: be coated with-4 glasss of 22-30 second (25 ℃);
5, be 7.0-7.5 with the sodium hydroxide solution adjust pH immediately, add secondary urea U2, the mol ratio that makes formaldehyde and urea is 1.6: 1, and 70-80 ℃ was reacted 30-60 minute;
6, add residue urea, 60-70 ℃ was reacted 30-60 minute;
7, cool to below 40 ℃ discharging;
8, urea-formaldehyde resin 100 weight parts that step 7 is obtained add in the Glue mixer, add flour 15 weight parts, ammonium chloride 0.5 weight part, super absorbent resin 1 weight part then, stir 20 minutes.
Embodiment 5
1, be to get the raw materials ready at 1.4: 1 according to the mole proportioning of formaldehyde and urea.
2,37% formaldehyde solution is added in the reactor, stirring is 7.5-8.5 with the sodium hydroxide solution adjust pH down;
3, add urea U1 for the first time, the mol ratio that makes formaldehyde and urea is 2.0: 1, in 30-60 minute, slowly be warmed up to 90 ± ℃, be incubated 40-60 minute;
4, be 4.2-4.8 with the formic acid adjust pH, react to viscosity for being coated with-4 glasss of 22-30 second (25 ℃);
5, be 7.0-7.5 with oxychlorination sodium solution adjust pH immediately, add urea U2 for the second time, the mol ratio that makes formaldehyde and urea is 1.6: 1, and 70-80 ℃ was reacted 30-60 minute;
6, add residual content urea U3, the mol ratio that makes formaldehyde and urea is 1.4: 1, and 60-70 ℃ was reacted 30-60 minute;
7, cool to below 40 ℃ discharging;
8, urea-formaldehyde resin 100 weight parts that step 7 is obtained add in the Glue mixer, add flour 15 weight parts, ammonium chloride 0.5 weight part, super absorbent resin 0.5 weight part then, stir 20 minutes.
Embodiment 6
1, be to get the raw materials ready at 1.8: 1 according to the mole proportioning of formaldehyde and urea.
2,37% formaldehyde solution is added in the reactor, stirring is 7.5-8.5 with the sodium hydroxide solution adjust pH down.
3, add urea U1 for the first time, the mol ratio that makes formaldehyde and urea is 2.0: 1, in 30-60 minute, slowly be warmed up to 90 ± ℃, be incubated 40-60 minute;
4, be 4.2-4.8 with the formic acid adjust pH, react to viscosity for being coated with-4 glasss of 22-30 second (25 ℃);
5, be 7.0-7.5 with the sodium hydroxide solution adjust pH immediately, add residual content urea U2, the mol ratio that makes formaldehyde and urea is 1.8: 1, and 60-70 ℃ was reacted 30-60 minute.
6, cool to below 40 ℃ discharging.
7, urea-formaldehyde resin 100 weight parts that step 6 is obtained add in the Glue mixer, add flour 15 weight parts, ammonium chloride 0.5 weight part, super absorbent resin 0.01 weight part then, stir 20 minutes.
Comparative example 1-3
Prepare common urea-formaldehyde resin, except not adding the super absorbent resin, other are identical with embodiment 1-3 technology respectively.
Comparative example 4-6
Prepare common urea-formaldehyde resin adhesive, except not adding the super absorbent resin, other are identical with embodiment 4-6 technology respectively.
Experimental example
Adopt the urea-formaldehyde resin of embodiment of the invention 1-3 and comparative example 1-3 to carry out impregnation respectively, concrete steps comprise urea-formaldehyde resin 100 weight parts are added in the Glue mixer, add flour 15 weight parts, ammonium chloride 0.5 weight part then, stir 20 minutes.
The urea-formaldehyde resin adhesive that then uses above-mentioned each urea-formaldehyde resin adhesive that is modulated by embodiment 1-3 and comparative example 1-3 and embodiment 4-6 and comparative example 4-6 is by following processing condition and 3 layers of glued board of parameter preparation:
Applying glue: central layer gluing, Amount of spread are 220～280g/m
2
Ageing: 4 hours time;
Precompressed: pressure 0.5-1.0MPa, time 30min.
Hot pressing: temperature 100-115 ℃, pressure 1.0-1.5Mpa, time 60s/mm.
Contrast use these urea-formaldehyde resin adhesives apply veneers and ageing after 4 hours slab precompressed effect and the bonding property after the hot pressing, experimental result is as shown in table 1.
Bonding property after table 1 slab precompressed effect and the hot pressing
| Test specimen | The precompressed effect | Bonding property |
| Embodiment 1 | ○ | ○ |
| Embodiment 2 | ○ | ○ |
| Embodiment 3 | ○ | ○ |
| Embodiment 4 | ○ | ○ |
| Embodiment 5 | ○ | ○ |
| Embodiment 6 | ○ | ○ |
| Comparative example 1 | × | △ |
| Comparative example 2 | × | △ |
| Comparative example 3 | △ | ○ |
| Comparative example 4 | × | × |
| Comparative example 5 | × | △ |
| Comparative example 6 | △ | ○ |
Annotate: zero: good (the diffusing base of slab upset does not have the phenomenon of coming unglued)
△: general (the slab upset the slight base phenomenon of loosing occurs, the phenomenon of coming unglued is individually arranged);
*: bad (the slab upset the diffusing base phenomenon of big area occurs, comes unglued seriously).
Show thus, the glued board that adopts the present invention to contain the urea-formaldehyde resin adhesive preparation of the super absorbent resin base that can not loose, do not have the phenomenon of coming unglued, therefore effectively prevented the phenomenon of coming unglued that glued board occurs after the bad and hot pressing of the blanket glued veneer ageing excessively causes in the plywood production precompressed effect; In addition, the present invention does not change the production technique of existing urea-formaldehyde resin adhesive substantially, and is simple and easy to do, and because the consumption of additive super absorbent resin only is the 0.01-1% of formaldehyde and urea total amount or the 0.01-1% of urea-formaldehyde resin total amount, therefore the cost increase seldom is very easy to promote.
Claims (10)
1. a method for preparing glued board with urea-formaldehyde resin is characterized in that: add super absorbent resin in formaldehyde and urea condensation reaction process.
2. the method for preparing glued board with urea-formaldehyde resin as claimed in claim 1, it is characterized in that: the consumption of super absorbent resin is the 0.01-1% of formaldehyde and urea gross weight.
3. the method for preparing glued board with urea-formaldehyde resin as claimed in claim 1 or 2 is characterized in that: urea divides at least two batches to add in the formaldehyde solution in described condensation reaction, and super absorbent resin together adds formaldehyde solution with a collection of at least urea wherein.
4. the method for preparing glued board with urea-formaldehyde resin as claimed in claim 1 or 2 is characterized in that: super absorbent resin is selected from the blend of natural polymer super absorbent resin, synthetic macromolecule super absorbent resin or natural polymer super absorbent resin and synthetic macromolecule high-hydroscopicity tree.
5. the method for preparing glued board with urea-formaldehyde resin as claimed in claim 4, it is characterized in that: the natural polymer super absorbent resin is selected from one or more in starch graft polyacrylate, starch grafted polyacrylamide, starch-grafted polyacrylonitrile hydrolyzed thing, starch-acrylic acid-acrylamide graft copolymer, starch carboxymethylation reaction thing, cellulose graft polyacrylate, cellulose graft polyacrylamide, the carboxymethyl cellulose reactant; The synthetic macromolecule super absorbent resin is selected from one or more in polyacrylate, polyacrylamide, acrylic acid-acrylamide copolymer, polyvinyl alcohol, the polyvinyl alcohol-acrylic acid graft copolymer.
6. a glued board urea-formaldehyde resin is prepared from by the arbitrary described method of claim 1 to 5.
7. a glued board is characterized in that may further comprise the steps with the modulator approach of urea-formaldehyde resin adhesive:
At first get the raw materials ready by following weight proportion: by 100 parts of urea-formaldehyde resins, filler 10-20 part, solidifying agent 0.2-1 part, super absorbent resin 0.01-1 part that formaldehyde and urea condensation reaction are made, described filler is one or more in flour, starch, wood powder and the shell powder;
Then urea-formaldehyde resin is added in the Glue mixer, then super absorbent resin and filler, solidifying agent are together added, be stirred to each component and mix.
8. glued board as claimed in claim 7 is characterized in that with the modulator approach of urea-formaldehyde resin adhesive super absorbent resin is selected from the blend of natural polymer super absorbent resin, synthetic macromolecule super absorbent resin and natural polymer super absorbent resin and synthetic macromolecule high-hydroscopicity tree.
9. the glued board as claimed in claim 8 modulator approach of urea-formaldehyde resin adhesive, it is characterized in that: the natural polymer super absorbent resin is selected from one or more in starch graft polyacrylate, starch grafted polyacrylamide, starch-grafted polyacrylonitrile hydrolyzed thing, starch-acrylic acid-acrylamide graft copolymer, starch carboxymethylation reaction thing, cellulose graft polyacrylate, cellulose graft polyacrylamide, the carboxymethyl cellulose reactant; The synthetic macromolecule super absorbent resin is selected from one or more in polyacrylate, polyacrylamide, acrylic acid-acrylamide copolymer, polyvinyl alcohol, the polyvinyl alcohol-acrylic acid graft copolymer.
10. a glued board urea-formaldehyde resin adhesive is formed by the arbitrary described method modulation of claim 7 to 9.
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| CNB200610066710XA CN100384898C (en) | 2006-04-05 | 2006-04-05 | Urea-formaldehyde resin and urea-formaldehyde resin glue and preparation method thereof |
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| CNB200610066710XA CN100384898C (en) | 2006-04-05 | 2006-04-05 | Urea-formaldehyde resin and urea-formaldehyde resin glue and preparation method thereof |
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| CN100384898C true CN100384898C (en) | 2008-04-30 |
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| CN102229773B (en) * | 2011-06-08 | 2013-01-09 | 赵玉文 | Flame retardant ground paint |
| CN102504156B (en) * | 2011-10-13 | 2013-03-20 | 江苏大江木业集团有限公司 | Urea-formaldehyde resin and preparation method thereof |
| CN102585129B (en) * | 2012-02-20 | 2014-07-09 | 常州大学 | Urea-formaldehyde resin for artificial board and modification modulation method thereof |
| CN102528861A (en) * | 2012-03-05 | 2012-07-04 | 辽宁久久木业有限责任公司 | Production method and manufacturing process for environmentally-friendly decorative board |
| CN103013406A (en) * | 2012-12-06 | 2013-04-03 | 青岛文创科技有限公司 | Environment-friendly plywood |
| CN103009691A (en) * | 2012-12-07 | 2013-04-03 | 青岛文创科技有限公司 | Plywood |
| CN103242740A (en) * | 2013-05-23 | 2013-08-14 | 苏州富通高新材料科技股份有限公司 | Flame-retardant coating for wood floors |
| CN103449924B (en) * | 2013-09-03 | 2014-11-26 | 广西大学 | Method for preparing slow-release fertilizer shell |
| CN105566591B (en) * | 2016-03-10 | 2018-01-02 | 广西南宁侨盛木业有限责任公司 | A kind of Lauxite of the cyanurotriamide modified solid wooden floor board base material of E1 levels |
| CN109514658A (en) * | 2018-10-23 | 2019-03-26 | 南京林业大学 | Inhale aldehyde type solid wooden compound floor plywood substrate and preparation method thereof |
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|---|---|---|---|---|
| JPS62283892A (en) * | 1986-06-02 | 1987-12-09 | 三菱油化株式会社 | Solidification prevention for urea grains or urea base resingrains |
| JPH07173371A (en) * | 1993-12-20 | 1995-07-11 | Matsushita Electric Works Ltd | Amino-based resin molding material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62283892A (en) * | 1986-06-02 | 1987-12-09 | 三菱油化株式会社 | Solidification prevention for urea grains or urea base resingrains |
| JPH07173371A (en) * | 1993-12-20 | 1995-07-11 | Matsushita Electric Works Ltd | Amino-based resin molding material |
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