CN100500723C - Environment friendly quaternarily copolymerized thermosetting copolymer resin for high pressure laminated decorative board - Google Patents
Environment friendly quaternarily copolymerized thermosetting copolymer resin for high pressure laminated decorative board Download PDFInfo
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- CN100500723C CN100500723C CNB2006100181553A CN200610018155A CN100500723C CN 100500723 C CN100500723 C CN 100500723C CN B2006100181553 A CNB2006100181553 A CN B2006100181553A CN 200610018155 A CN200610018155 A CN 200610018155A CN 100500723 C CN100500723 C CN 100500723C
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Abstract
The environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board is prepared through adding formaldehyde and phenol into reactor, regulating pH value with 30 % concentration sodium hydroxide aqua to 7.0-8.0, adding melamine and urea, heating to 85-95 deg.c and maintaining for 40-60 min, adding PVA via stirring for 10-20 min, regulating pH value with 30 % concentration formic acid solution to 4.6-6.0, adding urea and controlling the temperature in 60-75 deg.c, regulating pH value with 30 % concentration sodium hydroxide aqua to 7.5-8.0 after the viscosity reaches 14-16 s, adding urea via stirring, and discharging. The present invention has lowered molar ratio of formaldehyde to urea, added melamine and other measures to lower formaldehyde releasing amount, introduced phenol and PVA to raise the flexibility and water resistance of the resin, raised performance and simple production process.
Description
Technical field
The present invention relates to the resin dedicated and production method of widely used thermosetting resin impregnated paper high pressure laminated decorative board on the market, particularly a kind of environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board.
Background technology
Its production technique of thermosetting resin impregnated paper high pressure laminated decorative board (hereinafter to be referred as PLASTIC LAMINATED) is: sandwich layer selects for use kraft paper dipping oven dry back at the High Temperature High Pressure compacted under.Product acid and alkali-resistance, wearing and tearing, good flame resistance, ornamental strong are widely used in and decorate and furniture industry.It uses resol, but along with the raising of phenol price, cost rises too high.Existing PLASTIC LAMINATED factory adopts urea-formaldehyde resin more, and its main component is urea and formaldehyde, by the thermosetting resin that reactions such as addition, polycondensation form, has characteristics such as with low cost, easy to use, functional.But because the used urea-formaldehyde resin of PLASTIC LAMINATED factory is to revise a little to form on the basis of universal urea-formaldehyde resin prescription now, weak point is:
(1) the free formaldehyde volatile quantity exceeds standard, and does not meet the environmental requirement of country to finishing material.
(2) after the curing, the big and poor water resistance of the fragility of plate does not meet the service requirements and the provisions of the relevant regulations issued by the State.
(3) need dehydration, complex process causes the quality of PLASTIC LAMINATED to be difficult to stablize.
Have part producer to adopt urea-formaldehyde resin and resol to carry out physical mixed and use, but wherein the big cost of resol add-on is too high, add-on is little not to have effect, little at the PLASTIC LAMINATED quality improvement, and short easy layering storage period of mixed glue.
Have only the wood-based plate urea-formaldehyde resin on the existing market, but its viscosity is higher and need dehydration, is unsuitable for dipping, is not suitable for the production of PLASTIC LAMINATED, and most glue outward appearance is oyster white, transparent also inconsistent with PLASTIC LAMINATED with the resin requirement.
Summary of the invention
Purpose of the present invention will provide a kind of environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board exactly, it can overcome deficiency of the prior art, by reducing the mol ratio of urea formadehyde, measures such as interpolation trimeric cyanamide are up to state standards free formaldehyde release, on molecular chain, introduce snappiness and water tolerance that phenol ring and PVA chain have improved resin, make performance far above common urea-formaldehyde resin and the special-purpose resol of PLASTIC LAMINATED.The glue outward appearance is the incarnadine transparent liquid, and production technique is simple.
The object of the present invention is achieved like this: a kind of environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board, and the structural formula of resin is:
The structural formula of R1 is in the formula:
The structural formula of R2 is:
The structural formula of R3 is
N is less than 1500.
A kind of working method of environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board is add 4 parts-11 parts of 60 parts-100 parts in formaldehyde and phenol in reactor after, transfer PH to 7.0-8.0 with 30% aqueous sodium hydroxide solution, add 3 parts-10 parts of trimeric cyanamides, be warming up to 85 ℃-95 ℃ behind 10 parts-22 parts in the urea, added 1 part-4 parts of polyvinyl alcohol after being incubated 40 minutes-60 minutes, stirred 10 minutes-20 minutes, transfer PH to 4.6-6.0 with 30% formic acid solution, add 8 parts-17 parts in urea, temperature is controlled at 60 ℃-75 ℃, transfer PH to 7.5-8.0 with 30% aqueous sodium hydroxide solution when viscosity during to 14s-16s, add urea and stir for 3 parts-6 parts and be cooled to discharging behind the normal temperature in 10 minutes-15 minutes.
Another object of the present invention provides a kind of resin that is obtained by the working method of environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board.
The present invention is owing to adopt formaldehyde and urea adds phenol when carrying out hydroxymethylation in alkaline medium, phenol ring is introduced in the molecular chain, so increased reactive site on the one hand, reduced in the molecule-number of OH, condensation by phenolic hydroxyl group on the other hand, introduced flexible bigger-O-chain, improved the water tolerance and the fragility of cured article.Add the reaction of trimeric cyanamide and methylolurea simultaneously, reduce hydrophilic radical and introduce three nitrogen heterocyclics, improved water-fast and thermotolerance.Add polyvinyl alcohol in polycondensation phase, flexible chain is embedded in the macromole, improve the snappiness of urea-formaldehyde resin molecular chain.For guaranteeing the transparency of glue, at the strict control of acidic phase pH value.
Embodiment
Embodiment one
After in reactor, adding 7 parts of 84 parts in formaldehyde and phenol, transfer PH to 8.0 with 30% aqueous sodium hydroxide solution, add 7 parts of trimeric cyanamides, be warming up to 85 ℃-90 ℃ behind 17 parts in the urea, be incubated and add 2 parts of polyvinyl alcohol after 45 minutes, stirred 15 minutes, transfer PH to 5.4 with 30% formic acid solution, add 3 parts in urea, temperature is controlled at 70 ℃-75 ℃, viscosity is transferred PH to 8.0 with 30% aqueous sodium hydroxide solution during to 14s-16s, add urea stir for 3 parts be cooled to normal temperature in 15 minutes after discharging promptly get the environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board.
Embodiment two
After in reactor, adding 4 parts of 60 parts in formaldehyde and phenol, transfer PH to 7.0 with 30% aqueous sodium hydroxide solution, add 3 parts of trimeric cyanamides, be warming up to 80 ℃-85 ℃ behind 10 parts in the urea, be incubated and add 1 part of polyvinyl alcohol after 40 minutes, stirred 10 minutes, transfer PH to 4.6 with 30% formic acid solution, add 8 parts in urea, temperature is controlled at 60 ℃-70 ℃, viscosity is transferred PH to 8.0 with 30% aqueous sodium hydroxide solution during to 14s-16s, add urea stir for 4 parts be cooled to normal temperature in 10 minutes after discharging promptly get the environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board.
Embodiment three
After in reactor, adding 11 parts of 100 parts in formaldehyde and phenol, transfer PH to 7.5 with 30% aqueous sodium hydroxide solution, add 10 parts of trimeric cyanamides, be warming up to 90 ℃-95 ℃ behind 22 parts in the urea, be incubated and add 4 parts of polyvinyl alcohol after 60 minutes, stirred 20 minutes, transfer PH to 6.0 with 30% formic acid solution, add 17 parts in urea, temperature is controlled at 60 ℃-70 ℃, viscosity is transferred PH to 7.5 with 30% aqueous sodium hydroxide solution during to 14s-16s, add urea stir for 6 parts be cooled to normal temperature in 13 minutes after discharging promptly get the environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board.
The performance index of the final resin that embodiment one, embodiment two and embodiment three obtain are:
Viscosity: 15-16s (being coated with-4 glasss)
Density: 1.155-1.165g/cm
3
Solid content: 42-44%
PH：8.5
Free formaldehyde :≤1.2mg/L
Chemical equation in embodiment one, embodiment two and the embodiment three production processes is as follows:
Polyvinyl alcohol and formaldehyde reaction generate polyvinyl formal
Polyvinyl alcohol and dimethylolpropionic urea effect form following crosslinking structure
Trimeric cyanamide and methylolurea reaction
Polyreaction
Claims (2)
1, a kind of working method of environment friendly quaternary thermosetting copolymer resin for high pressure laminated decorative board, it is characterized in that: after in reactor, adding 4 parts-11 parts of 60 parts-100 parts in formaldehyde and phenol, transfer PH to 7.0-8.0 with 30% aqueous sodium hydroxide solution, add 3 parts-10 parts of trimeric cyanamides, be warming up to 85 ℃-95 ℃ behind 10 parts-22 parts in the urea, added 1 part-4 parts of polyvinyl alcohol after being incubated 40 minutes-60 minutes, stirred 10 minutes-20 minutes, transfer PH to 4.6-6.0 with 30% formic acid solution, add 8 parts-17 parts in urea, temperature is controlled at 60 ℃-75 ℃, transfer PH to 7.5-8.0 with 30% aqueous sodium hydroxide solution when viscosity during to 14s-16s, add urea and stir for 3 parts-6 parts and be cooled to discharging behind the normal temperature in 10 minutes-15 minutes.
2, a kind of resin that obtains by the described method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100181553A CN100500723C (en) | 2006-01-10 | 2006-01-10 | Environment friendly quaternarily copolymerized thermosetting copolymer resin for high pressure laminated decorative board |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100181553A CN100500723C (en) | 2006-01-10 | 2006-01-10 | Environment friendly quaternarily copolymerized thermosetting copolymer resin for high pressure laminated decorative board |
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| CN1810845A CN1810845A (en) | 2006-08-02 |
| CN100500723C true CN100500723C (en) | 2009-06-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955745B (en) * | 2009-12-25 | 2011-12-21 | 湖北康欣木制品有限公司 | Quaternary resin adhesive for manufacturing plywood board for bottom board of container |
| CN102250302B (en) * | 2011-06-02 | 2012-07-11 | 中南林业科技大学 | Intermediate-temperature curing type phenolic resin for artificial board and preparation method thereof |
| CN108178820A (en) * | 2017-12-26 | 2018-06-19 | 东营正和木业有限公司 | A kind of PMUF multi-copolymerization resins and preparation method thereof, application process |
| CN108102057A (en) * | 2017-12-26 | 2018-06-01 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of outdoor stages environment-friendlymedium-density medium-density fiberboard adhesive |
| CN110091407A (en) * | 2018-01-29 | 2019-08-06 | 东营正和木业有限公司 | A kind of outdoor use furniture type fiberboard production processes |
| CN109487569A (en) * | 2018-11-20 | 2019-03-19 | 苏州宏久航空防热材料科技有限公司 | A kind of carbon fiber/graphene oxide phenol-formaldehyde resin modified heating film and preparation method thereof |
| CN111763492A (en) * | 2020-07-13 | 2020-10-13 | 福建隆达竹业有限公司 | Modified melamine phenolic resin adhesive |
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