CN100516127C - Phenolic resin additive, phenolic resin with the additive and its preparation process - Google Patents
Phenolic resin additive, phenolic resin with the additive and its preparation process Download PDFInfo
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- CN100516127C CN100516127C CNB2007101057238A CN200710105723A CN100516127C CN 100516127 C CN100516127 C CN 100516127C CN B2007101057238 A CNB2007101057238 A CN B2007101057238A CN 200710105723 A CN200710105723 A CN 200710105723A CN 100516127 C CN100516127 C CN 100516127C
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- additive
- trigonella
- phenolic resin
- sodium carbonate
- carbonate solution
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Abstract
The phenolic resin adhesive additive is prepared through mixing 3-25 % concentration sodium carbonate solution in 70-80 weight portions and fenugreek slag powder in 20-30 weight portions, heating to 70-80 deg.c to react for 3-6 hr, cooling to 30 deg.c to obtain fenugreek adhesive with viscosity 200-400 mPa.s as the additive for phenolic resin adhesive. Alkaline water soluble phenolic resin and the fenugreek adhesive in the weight ratio of 50-90 to 10-50 are mixed to obtain the phenolic resin adhesive. The phenolic resin adhesive has low production cost, high adhesion strength and low formaldehyde releasing amount.
Description
Technical field
The present invention relates to a kind of tackiness agent additive, contain this additive based on tackiness agent of organic high molecular compound and preparation method thereof, particularly a kind of wood-based plate is with additive of resol and preparation method thereof.
Background technology
Along with the fast development of industries such as building, decorations, packing, the output of China's wood-based plate rapidly increases, and wood-based plate has obtained fast development with tackiness agent is also corresponding.China's wood-based plate uses the kind of tackiness agent with roughly the same abroad, and " three-aldehyde glue " commonly used comprises urea-formaldehyde resin, resol and terpolycyantoamino-formaldehyde resin tackiness agent, in occupation of dominant position.Wherein, resol is excellent performance in the wood adhesive, use glue kind widely, and resol be the tackiness agent of first-selection when producing weather-proof, heat-stable woodwork.But owing to phenol costs an arm and a leg, also according to height not down, price problem has limited the widespread use of aerodux to the aerodux price.
By in aerodux, adding low-cost material, reduce the cost of aerodux, for the purposes that enlarges aerodux, it is significant to improve the product benefit.Usually adopted in the past and waited the cost that reduces resol as bean powder, flour and urea.But the interpolation of these materials has not only consumed a large amount of edible resources, and usually brings such as shortcomings such as the reduction of aerodux curing speed, Joint strength reduction, workability reductions.
In addition, protein is more effective than common wheat flour as binder matrix, and it is not only water-fast, and the function of eliminating formaldehyde is arranged, and therefore is suitable as very much the filler of wood adhesive.But general proteinic price is higher and add-on usually influences the curing performance and the Joint strength of tackiness agent when too much, and these have all limited its use.At present, have the Semen Trigonellae of a kind of rich in proteins and glycan not to be fully utilized, only limit to medicinal and xanthan gum its utilization, and its utilization ratio probably the residuum residue about 30%, 70% go out of use and also be not utilized effectively.And rich in proteins and glycan in this residue of about 70%, wherein protein and glycan account for 41% and 14% of dry matter weight respectively, fully can be as the additive of aerodux.The trigonella residue has certain advantage as its low price of byproduct of the development and use of Semen Trigonellae as the aerodux additive.
Summary of the invention
At the problem that above prior art exists, an object of the present invention is to provide the additive of a kind of wood-based plate with resol.
Another object of the present invention provides the preparation method of a kind of wood-based plate with the additive of resol.
For realizing the purpose of the invention described above, the additive of resol provided by the invention adopts following weight ratio prescription: sodium carbonate solution 70-80 part of 3-25% concentration, trigonella residue powder 20-30 part.
Particularly, 75 parts of the weight ratio formula optimization sodium carbonate solutions of this additive, trigonella residue powder are 25 parts.
The additive of aerodux of the present invention adopts the following steps preparation: sodium carbonate solution 70-80 part, the trigonella residue powder 20-30 part of pressing 3-25% concentration; Sodium carbonate solution is added trigonella residue powder, stir; Be heated to 70 ℃-80 ℃, reacted 3-6 hour; Be cooled to 30 ℃, making viscosity is the even mucus of 200-400cP.
The present invention has the following advantages:
The trigonella residue is as a kind of reproducible disposability plant resources, the present invention handles the additive of back as resol to it, whole trigonella residues are fully utilized, turn waste into wealth, and can not reduce under aerodux curing speed, the bonding strength prerequisite in assurance, reduce the manufacturing cost of aerodux greatly, compare with the common aerodux that does not adopt the trigonella residue in the prior art, its manufacturing cost can reduce 8-40%;
In addition, because phenolic resin content descends in the aerodux of the inventive method preparation, therefore under the constant condition of Amount of spread, amount of resin reduces relatively, and contain the amino groups that to react with formaldehyde in the trigonella albumen, so burst size of methanal reduces.
Embodiment
Embodiment 1
1) compound concentration is 5% sodium carbonate solution, in the sodium carbonate solution of 75kg, adds 25kg trigonella residue powder, is heated with stirring to 70-80 ℃, reacts 3-6 hour, is cooled to 30 ℃, and making viscosity is the even trigonella residue mucus of 200-400cP.
2) be that 1: 2.1 alkaline water soluble phenol resin is that 30: 70 mixed is even by weight with the trigonella residue mucus of gained and phenol and formaldehyde mole ratio, make aerodux.
Wherein, the mucous performance index of trigonella residue are as follows:
Outward appearance: yellowish brown mucus
PH value: 9-11
Solids content: 25-30%
The quality index of tackiness agent is as follows:
Solids content 30-40%
PH value 10.0-11.0
Viscosity (20 ℃) 150-300mPas
Free formaldehyde content＜0.2%
Free phenol content＜0.2%
2-3 month storage period
The resol molar ratio range of above-mentioned alkaline water soluble phenol resin is: phenol: formaldehyde: sodium hydroxide=1: 1.8-2.3: 0.2-0, formaldehyde and sodium hydroxide add in the phenol at twice.
Concrete preparation process is as follows:
1, reactor is warming up to 50 ℃, adds preheating good 400 kilograms in 500 kilograms of phenol, water and concentration and be 250 kilograms of 40% sodium hydroxide solutions, start and stirred 10 minutes;
2, slowly adding concentration is 690 kilograms of 37% formaldehyde solutions, is warming up to 90 ± 2 ℃;
3,90 ± 2 ℃ of insulations 50 minutes, be cooled to 70 ℃;
4, slowly add 179 kilograms in formaldehyde in reactor, concentration is 50 kilograms of 40% sodium hydroxide solutions, is warming up to 92 ± 2 ℃ in 10 minutes, constantly viscosimetric;
5, react to viscosity: 20 ℃, be coated with-4 glasss of 30-32 after second, be cooled to 40 ℃ immediately, discharging.
The resol quality index:
Solids content 40-46%
Viscosity (20 ℃) 100-200mPas
Free formaldehyde content＜0.1%
Free-phenol content＜0.1%
Storage period＞February
The water soluble phenol resin that the present invention uses is not limited to above-mentioned technology synthetic resol, and various common resol and modified phenolic resins that factory generally adopts also all are suitable for.
Embodiment 2
1) compound concentration is 5% sodium carbonate solution, in 75kg solution, adds 25kg trigonella residue powder, is heated with stirring to 70-80 ℃, reacts 3-6 hour, is cooled to 30 ℃, and making viscosity is the even trigonella residue mucus of 200-400cP.
2) with the trigonella residue mucus of gained and the alkaline water soluble phenol resin identical, be that 50: 50 mixed is even by weight, make aerodux with embodiment 1.
This tackiness agent quality index:
Solids content 30-40%
PH value 9.5-10.5
Viscosity (20 ℃) 150-300mPas
Free formaldehyde content＜0.2%
Free phenol content＜0.2%
60-90 days storage period
Comparative example 1
Adopt with embodiment 1 and 2 in identical not adding the trigonella residue is mucous, mol ratio is 1: 2.1 alkaline water soluble phenol resin.
The tackiness agent quality index:
Solids content 35-45%
PH value 11.0-12.0
Viscosity (20 ℃) 150-200mPa.s
Free formaldehyde content＜0.2%
Free phenol content＜0.2%
60-90 days storage period
Comparative example 2
The trigonella residue powder that will be untreated is dispersed in the water, makes 25% aqueous dispersions, and the resol of itself and comparative example 1 is mixed by 20: 80 part by weight.
Experimental example
Utilize the resol of the embodiment of the invention 1,2 methods and comparative example 1 and the aerodux of comparative example 2 methods preparation to make seven layers of glued board respectively, adopt following preparation technology parameter:
Veneer: poplar, thick 1.6mm;
Impregnation: each glue kind adds flour by 10% of gross weight, is in harmonious proportion evenly;
Applying glue: central layer gluing, Amount of spread are 220～300g/m
2
Ageing: 10～30 minutes time;
Hot pressing: 130 ℃, 1.5MPa, 70s/mm.
The performance test results of seven layers of glued board making by above-mentioned technology is as shown in table 1, the regulation mensuration bonding strength of wherein press GB/T17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels ".
Table 1 glueds joint the burst size of methanal and the bonding strength of glued board
| Test specimen | Burst size of methanal (mg/L) | Bonding strength (MPa) |
| Embodiment 1 | 0.66 | 1.01 |
| Embodiment 2 | 0.49 | 0.87 |
| Comparative example 1 | 0.94 | 1.06 |
| Comparative example 2 | 0.76 | 0 (coming unglued) |
By table 1 as seen, to with the glued board of the aerodux preparation of the embodiment of the invention 1 and 2 methods preparation and adopt comparative example 1 method and the glued board of the tackiness agent preparation of comparative example 2 methods preparation detects, detected result shows: embodiment 1 and 2 burst size of methanal than comparative example 1 have descended 29.8% and 47.9% respectively; Embodiment 1 and 2 burst size of methanal than comparative example 2 have descended 16.7% and 35.5% respectively, therefore, when the trigonella residue liquid that process the inventive method is handled is used as the resol additive, can effectively reduce the burst size of methanal that glueds joint goods in the glue.
In addition, by it can also be seen that in the table 1, adopt trigonella residue mucus after handling through the inventive method, can obtain the bonding property aerodux suitable, can guarantee the bonding strength of glued board with common resol with after resol mixes; The aerodux of comparative example 2 methods preparation can cause delamination of plywood owing to be added with undressed trigonella residue powder when therefore glueing joint glued board with it.
By the test specimen detected result that adopts embodiment 2 tackiness agents as can be known, when the weight ratio of trigonella residue mucus and alkaline water soluble phenol resin is 50: 50, the content that is trigonella residue liquid in the aerodux reaches at 50% o'clock, bonding strength slightly descends, but still meets national standard (being not less than 0.7MPa).
Cost analysis:
At present, the phenol price is at 10000 yuan/ton, about 3000 yuan/ton of the cost of the PF resin glue of 40% solids content, and the trigonella residue is a processing byproduct, price has only 1600 yuan/ton (dry-matteies), and the cost of trigonella residue liquid (solids content 25-30%) is about 500 yuan/ton.Therefore, can calculate the cost of various mixed solutions as shown in table 2.
The cost of table 2 trigonella residue liquid (25%) and resol mixed glue solution
As shown in Table 2, aerodux of the present invention is compared with common pure phenolic resin tackiness agent, and cost value can reduce significantly, and 8-40% has descended.
Claims (6)
1, a kind of additive of resol is characterized in that making by following steps:
A) get the raw materials ready by sodium carbonate solution 70-80 weight part, the trigonella residue powder 20-30 weight part of 3-25% concentration;
B) described sodium carbonate solution is added trigonella residue powder, stir;
C) be heated to 70 ℃-80 ℃, reacted 3-6 hour;
D) be cooled to 30 ℃, making viscosity is the even mucus of 200-400cP.
2, additive as claimed in claim 1 is characterized in that: described sodium carbonate solution is 75 weight parts, and described trigonella residue powder is 25 weight parts.
3, additive as claimed in claim 1 or 2 is characterized in that: the concentration of described sodium carbonate solution is 5%.
4, a kind of preparation method of additive of resol is characterized in that may further comprise the steps:
A) get the raw materials ready by sodium carbonate solution 70-80 weight part, the trigonella residue powder 20-30 weight part of 3-25% concentration;
B) sodium carbonate solution is added trigonella residue powder, stir;
C) be heated to 70 ℃-80 ℃, reacted 3-6 hour;
D) be cooled to 30 ℃, making viscosity is the even mucus of 200-400cP.
5, the preparation method of additive as claimed in claim 4 is characterized in that:
Described sodium carbonate solution is 75 weight parts, and described trigonella residue powder is 25 weight parts.
6, as the preparation method of claim 4 or 5 described additives, it is characterized in that:
The concentration of described sodium carbonate solution is 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101057238A CN100516127C (en) | 2006-03-22 | 2006-03-22 | Phenolic resin additive, phenolic resin with the additive and its preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101057238A CN100516127C (en) | 2006-03-22 | 2006-03-22 | Phenolic resin additive, phenolic resin with the additive and its preparation process |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100655780A Division CN100352879C (en) | 2006-03-22 | 2006-03-22 | Additive of phenolic resin, phenolic resin therewith and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101089034A CN101089034A (en) | 2007-12-19 |
| CN100516127C true CN100516127C (en) | 2009-07-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2007101057238A Expired - Fee Related CN100516127C (en) | 2006-03-22 | 2006-03-22 | Phenolic resin additive, phenolic resin with the additive and its preparation process |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177505B (en) * | 2007-12-11 | 2010-06-09 | 北京林业大学 | Phenolic resin additive, phenolic resin containing the same and preparation method thereof |
| CN102002139B (en) * | 2010-10-22 | 2012-06-20 | 兰州石化职业技术学院 | Method for preparing modified phenolic resin for coating with cresol residue |
-
2006
- 2006-03-22 CN CNB2007101057238A patent/CN100516127C/en not_active Expired - Fee Related
Non-Patent Citations (7)
| Title |
|---|
| Applicationofcure-acceleratedphenol-formaldehyde(PF)adhesivesforthree-layer mediumdensity fiberboard(MDF)manufacture. B D Park et al.Wood Science and Technology,Vol.35 . 2001 |
| Applicationofcure-acceleratedphenol-formaldehyde(PF)adhesivesforthree-layer mediumdensity fiberboard(MDF)manufacture. B D Park et al.Wood Science and Technology,Vol.35. 2001 * |
| 改性葫芦巴蛋白质降低酚醛树脂胶粘剂成本的研究. 李建章等.中国胶粘剂，第15卷第2期. 2006 |
| 改性葫芦巴蛋白质降低酚醛树脂胶粘剂成本的研究. 李建章等.中国胶粘剂，第15卷第2期. 2006 * |
| 木材工业用酚醛树脂胶粘剂的快速固化研究. 李建章等.中国胶粘剂，第12卷第6期. 2003 |
| 胡芦巴湿渣用作脲醛树脂增量剂的研究. 蒋建新等.中国野生植物资源，第22卷第5期. 2003 |
| 胡芦巴湿渣用作脲醛树脂增量剂的研究. 蒋建新等.中国野生植物资源，第22卷第5期. 2003 * |
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| CN101089034A (en) | 2007-12-19 |
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Granted publication date: 20090722 Termination date: 20130322 |