CN103709978A - Phenolic resin adhesive and preparation method thereof - Google Patents
Phenolic resin adhesive and preparation method thereof Download PDFInfo
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- CN103709978A CN103709978A CN201310714862.6A CN201310714862A CN103709978A CN 103709978 A CN103709978 A CN 103709978A CN 201310714862 A CN201310714862 A CN 201310714862A CN 103709978 A CN103709978 A CN 103709978A
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Abstract
The invention discloses a phenolic resin adhesive and a preparation method thereof. The phenolic resin adhesive comprises phenol, formaldehyde and a catalyst, and also comprises biomass briquette pyrolysis tar, wherein the ratio of a mixture of raw material phenol and biomass briquette pyrolysis tar to formaldehyde to the catalyst is 1: 1.5: 0.3, the catalyst is a composite catalyst of sodium hydroxide and potassium carbonate in a weight ratio of 2: (0.5-1.5), the raw material adopts the mixture of phenol and the biomass briquette pyrolysis tar, and the addition quantity of the biomass briquette pyrolysis tar is 30 to 50 percent. The product quality conforms to the national standard (GB/T14732-2006, GB/T9846-2004); the phenolic resin adhesive product has the advantage that the consumption of the phenol raw material is reduced, and has significance in promoting utilization of the biomass tar, reducing the environmental pollution in the production process of the biomass briquette, and lowering the preparation cost.
Description
Technical field
The present invention relates to a kind of phenolic resin adhesive and technology of preparing thereof, especially relate to a kind of phenol and biomass molding fuel pyrolytic tar mixture of utilizing and prepare the preparation method of phenolic resin adhesive for raw material.
Background technology
Phenol aldehyde resin has excellent Joint strength, good water tolerance, thermotolerance and chemical stability, is the main glue of using of wood-based plate for current indoor and outdoor.Its curing speed is slow, and solidification value is high, and cost is also higher.The present invention substitutes the higher phenol of price with the tar byproduct in biomass molding charcoal preparation process, special property for biomass molding fuel pyrolytic tar, adopt a kind of novel composite catalyst, the synthetic synvaren product that meets state quality standard, for the recycling of biomass molding fuel pyrolytic tar provides a kind of new approach.
Biomass molding fuel pyrolytic tar substitutes phenol and prepares the rare report of phenolic resin adhesive.Conventional biomass coke tar substitutes phenol to be prepared in phenolic resin adhesive preparation technology, general single sodium hydroxide, the hydrated bartas etc. of adopting are as catalyzer, in building-up reactions, the addition of biomass coke tar can not surpass 30%, otherwise storage period, the bonding strength that can shorten because product viscosity is excessive tackiness agent sharply decline and cause that product is defective or along with the increase of tar consumption, adhesive products Free-formaldehyde content rises and surpasses national standard.
Summary of the invention
The invention provides a kind of preparation method of environment amenable phenolic resin adhesive, the present invention has advantages of that biomass molding fuel pyrolytic tar substitutes phenol addition large (30%-50), the phenolic resin adhesive product making meets state quality standard, can the processing with wood-based plate for indoor and outdoor.
The present invention adopts following technical scheme: a kind of phenolic resin adhesive, comprise phenol, formaldehyde, basic catalyst, also comprise biomass molding fuel pyrolytic tar, form and count with the ratio of amount of substance: mixture material: formaldehyde: basic catalyst=1:1.5:0.3; Described basic catalyst is that sodium hydroxide and salt of wormwood are 2:(0.5-1.5 according to mass ratio) composite catalyst that is mixed to get, described mixture material is the mixture of phenol and biomass molding fuel pyrolytic tar, and wherein biomass molding fuel pyrolytic tar addition is the 30-50%wt of mixture material total mass.
Described biomass molding fuel pyrolytic tar is the biomass solid formed fuel tar that pyrolysis produces in can controlling oxygen-containing atmosphere.
Described biomass molding fuel pyrolytic tar is the liquid product producing in kahikatea wood shaped fuel pyrolytic process, and final pyrolysis temperature is 500 ℃.
The method of the phenolic resin adhesive that preparation is described, biomass molding fuel pyrolytic tar and phenol mix, progressively add composite catalyst, at 30 ℃-50 ℃, be uniformly mixed, then start to drip formaldehyde solution, in dropping process, pass through to control drop rate, hierarchy of control temperature is below 70 ℃, after dropwising, be increased to 75 ℃-85 ℃, then continue reaction 1.5-3 hour, discharging.
Compared with prior art, tool of the present invention has the following advantages:
The technology of the present invention is for the special property of biomass molding fuel pyrolytic tar, such as acid content wants high with respect to coal tar, sodium hydroxide, salt of wormwood composite catalyst (sodium hydroxide: salt of wormwood (weight ratio)=2:(0.5-1.5)) have been selected especially, greatly improved the addition of biomass molding fuel pyrolytic tar in building-up reactions (30%wt by common process is increased to 30%wt-50%wt below), biomass molding fuel pyrolytic tar utilization ratio is high; Reduced and used expensive and larger to environmental hazard phenol usage, avoided the waste of biomass molding fuel pyrolytic tar resource and the pollution that environment is brought, reduced the preparation cost of phenolic resin adhesive.
Because N, S content in the tar of the generation of pyrolysis in can controlling oxygen-containing atmosphere are very low, especially the content of sulphur is negligible, therefore more friendly to environment.
Accompanying drawing explanation
Fig. 1 resol is prepared setting drawing.
Wherein, 1. support; 2. agitator; 3. dropping funnel; 4. there-necked flask; 5. water-bath; 6 prolongs; 7. calrod; 8. sensor; 9. temp controlled meter; 10. power supply..
Embodiment
A kind of phenolic resin adhesive and preparation method thereof, according to mixture material (phenol+biomass molding fuel pyrolytic tar): formaldehyde: catalyzer (sodium hydroxide+salt of wormwood)=1:1.5:0.3 (mol ratio), catalyzer adopts sodium hydroxide, salt of wormwood composite catalyst (sodium hydroxide: salt of wormwood (weight ratio)=2:(0.5-1.5)), and raw material adopts the mixture (wherein biomass molding fuel pyrolytic tar addition is 30-50%) of phenol and biomass molding fuel pyrolytic tar.On tri-mouthfuls of round-bottomed flasks of 500ml, connect electric mixer, thermometer, reflux condensing tube, on reflux condensing tube, install separating funnel additional, first tar and phenol are placed in to 500ml round-bottomed flask (it is the total mass percentage ratio of tar phenol that tar substitutes amount), start agitator, progressively add composite catalyst, at about 45 ℃, stir 20min.Then start to drip formaldehyde solution, can control in 30min and dropwise, controlling time for adding is mainly in order to prevent that exothermic heat of reaction from making temperature of reaction too high, in other words, is also to prevent that by controlling drop rate system intensification is too high in dropping process.While dripping formaldehyde, temperature is controlled at below 70 ℃, is increased to corresponding temperature of reaction 75-85 ℃ after dropwising, then continues reaction 1.5-3 hour, till reacting while meeting the requirements to viscosity, and discharging.Can be made into the phenolic resin adhesive product that a kind of quality meets national standard (GB/T14732-2006, GB/T9846-2004).
Described biomass molding fuel pyrolytic tar is biomass solid formed fuel (comprising particulate state, the bar-shaped and block shaped fuel) tar that pyrolysis produces in can controlling oxygen-containing atmosphere.So long as the commercially available tar producing containing biomass solid formed fuel pyrolysis under oxygen condition is just fine.
The present invention's tar used is the liquid product producing in kahikatea wood shaped fuel pyrolytic process, and final pyrolysis temperature is 500 ℃, and for the Xiang Longtan of Dongning County, Heilongjiang Province industry, company limited provides.Specific performance can be referring to < < kahikatea wood shaped fuel pyrolytic tar performance and composition Study > > solar energy journal, 2013Vol.34No.(9): the analysis in 1509-1513.
1, a kind of phenolic resin adhesive and preparation method thereof, according to mixture material (phenol+biomass molding fuel pyrolytic tar): formaldehyde: catalyzer (sodium hydroxide+salt of wormwood)=1:1.5:0.3 (mol ratio), catalyzer adopts sodium hydroxide, salt of wormwood composite catalyst (sodium hydroxide: salt of wormwood (weight ratio)=2:(0.5-1.5)), and raw material adopts the mixture (wherein biomass molding fuel pyrolytic tar addition is 30-50%) of phenol and biomass molding fuel pyrolytic tar.On tri-mouthfuls of round-bottomed flasks of 500ml, connect electric mixer, thermometer, reflux condensing tube, on reflux condensing tube, install separating funnel additional, first tar and phenol are placed in to 500ml round-bottomed flask (it is the total mass percentage ratio of tar phenol that tar substitutes amount), start agitator, progressively add composite catalyst, at about 45 ℃, stir 20min.Then start to drip formaldehyde solution, in 30min, dropwise, in dropping process, control drop rate, prevent that system from heating up too high.While dripping formaldehyde, temperature is controlled at below 70 ℃, is increased to corresponding temperature of reaction 75-85 ℃ after dropwising, then continues reaction 1.5-3 hour, discharging.Can be made into the phenolic resin adhesive product that a kind of quality meets national standard (GB/T14732-2006, GB/T9846-2004).
A kind of phenolic resin adhesive and preparation method thereof, according to mixture material (phenol+biomass molding fuel pyrolytic tar): formaldehyde: catalyzer (sodium hydroxide+salt of wormwood)=1:1.5:0.3 (mol ratio), catalyzer adopts sodium hydroxide, salt of wormwood composite catalyst (sodium hydroxide: salt of wormwood (weight ratio)=2:0.5), raw material adopts the mixture (wherein biomass molding fuel pyrolytic tar addition is 30%) of phenol and biomass molding fuel pyrolytic tar.On tri-mouthfuls of round-bottomed flasks of 500ml, connect electric mixer, thermometer, reflux condensing tube, on reflux condensing tube, install separating funnel additional, first tar and phenol are placed in to 500ml round-bottomed flask (it is the total mass percentage ratio of tar phenol that tar substitutes amount), start agitator, progressively add composite catalyst, at about 45 ℃, stir 20min.Then start to drip formaldehyde solution, in 30min, dropwise, in dropping process, control drop rate, prevent that system from heating up too high.While dripping formaldehyde, temperature is controlled at below 70 ℃, is increased to 75 ℃ of corresponding temperature of reaction after dropwising, then continues reaction 1.5 hours, discharging.Can be made into the phenolic resin adhesive product that a kind of quality meets national standard (GB/T14732-2006, GB/T9846-2004).Synthetic phenolic resin adhesive performance is that free aldehyde amount is 0.193%; Free phenol content is 2.42%; Viscosity is 7120mP s; Solids content is 57.04%; PH is 10.78; Bonding strength is 1.79Mpa.
A kind of phenolic resin adhesive and preparation method thereof, according to mixture material (phenol+biomass molding fuel pyrolytic tar): formaldehyde: catalyzer (sodium hydroxide+salt of wormwood)=1:1.5:0.3 (mol ratio), catalyzer adopts sodium hydroxide, salt of wormwood composite catalyst (sodium hydroxide: salt of wormwood (weight ratio)=2:1), raw material adopts the mixture (wherein biomass molding fuel pyrolytic tar addition is 40%) of phenol and biomass molding fuel pyrolytic tar.On tri-mouthfuls of round-bottomed flasks of 500ml, connect electric mixer, thermometer, reflux condensing tube, on reflux condensing tube, install separating funnel additional, first tar and phenol are placed in to 500ml round-bottomed flask (it is the total mass percentage ratio of tar phenol that tar substitutes amount), start agitator, progressively add composite catalyst, at about 45 ℃, stir 20min.Then start to drip formaldehyde solution, in 30min, dropwise, in dropping process, control drop rate, prevent that system from heating up too high.While dripping formaldehyde, temperature is controlled at below 70 ℃, is increased to 80 ℃ of corresponding temperature of reaction after dropwising, then continues reaction 2 hours, discharging.Can be made into the phenolic resin adhesive product that a kind of quality meets national standard (GB/T14732-2006, GB/T9846-2004).Synthetic phenolic resin adhesive performance is that free aldehyde amount is 0.226%; Free phenol content is 3.58%; Viscosity is 8130mPs; Solids content is 68.07%; PH is 9.16; Bonding strength is 2.98Mpa.
A kind of phenolic resin adhesive and preparation method thereof, according to mixture material (phenol+biomass molding fuel pyrolytic tar): formaldehyde: catalyzer (sodium hydroxide+salt of wormwood)=1:1.5:0.3 (mol ratio), catalyzer adopts sodium hydroxide, salt of wormwood composite catalyst (sodium hydroxide: salt of wormwood (weight ratio)=2:1.5), raw material adopts the mixture (wherein biomass molding fuel pyrolytic tar addition is 50%) of phenol and biomass molding fuel pyrolytic tar.On tri-mouthfuls of round-bottomed flasks of 500ml, connect electric mixer, thermometer, reflux condensing tube, on reflux condensing tube, install separating funnel additional, first tar and phenol are placed in to 500ml round-bottomed flask (it is the total mass percentage ratio of tar phenol that tar substitutes amount), start agitator, progressively add composite catalyst, at about 45 ℃, stir 20min.Then start to drip formaldehyde solution, in 30min, dropwise, in dropping process, control drop rate, prevent that system from heating up too high.While dripping formaldehyde, temperature is controlled at below 70 ℃, is increased to 85 ℃ of corresponding temperature of reaction after dropwising, then continues reaction 3 hours, discharging.Can be made into the phenolic resin adhesive product that a kind of quality meets national standard (GB/T14732-2006, GB/T9846-2004).Synthetic phenolic resin adhesive performance is that free aldehyde amount is 0.281%; Free phenol content is 4.94%; Viscosity is 8720mPs; Solids content is 88.38%; PH is 8.53; Bonding strength is 3.23Mpa.
By embodiment, can find out that phenolic resin adhesive prepared by the present invention is along with the increase of the addition of tar, viscosity raises.
Claims (4)
1. a phenolic resin adhesive, comprises phenol, formaldehyde, basic catalyst, it is characterized in that, also comprises biomass molding fuel pyrolytic tar, forms and counts with the ratio of amount of substance: mixture material: formaldehyde: basic catalyst=1:1.5:0.3; Described basic catalyst is that sodium hydroxide and salt of wormwood are 2:(0.5-1.5 according to mass ratio) composite catalyst that is mixed to get, described mixture material is the mixture of phenol and biomass molding fuel pyrolytic tar, and wherein biomass molding fuel pyrolytic tar addition is the 30-50%wt of mixture material total mass.
2. phenolic resin adhesive as claimed in claim 1, is characterized in that, described biomass molding fuel pyrolytic tar is the biomass solid formed fuel tar that pyrolysis produces in can controlling oxygen-containing atmosphere.
3. phenolic resin adhesive as claimed in claim 1, is characterized in that, described biomass molding fuel pyrolytic tar is the liquid product producing in kahikatea wood shaped fuel pyrolytic process, and final pyrolysis temperature is 500 ℃.
4. the method for the phenolic resin adhesive of preparation described in claim 1 or 2, it is characterized in that, biomass molding fuel pyrolytic tar and phenol mix, and progressively add composite catalyst, at 30 ℃-50 ℃, are uniformly mixed, then start to drip formaldehyde solution, in dropping process, by controlling drop rate, hierarchy of control temperature, below 70 ℃, is increased to 75 ℃-85 ℃ after dropwising, continue again reaction 1.5-3 hour, discharging.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306043A (en) * | 2018-09-20 | 2019-02-05 | 吉林大学 | A kind of method that biomass power generation Sewage treatment containing phenolic tar utilizes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987948A (en) * | 2009-08-03 | 2011-03-23 | 北京化工大学 | Method for producing phenolic resin adhesive |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101987948A (en) * | 2009-08-03 | 2011-03-23 | 北京化工大学 | Method for producing phenolic resin adhesive |
Non-Patent Citations (2)
| Title |
|---|
| 边轶等: ""生物质热解焦油的性质与化学利用研究现状"", 《生物质化学工程》, vol. 45, no. 2, 31 March 2011 (2011-03-31), pages 51 - 55 * |
| 边轶等: ""白松木成型燃料热解焦油性能及成分研究"", 《太阳能学报》, vol. 34, no. 9, 30 September 2013 (2013-09-30), pages 1509 - 1513 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109306043A (en) * | 2018-09-20 | 2019-02-05 | 吉林大学 | A kind of method that biomass power generation Sewage treatment containing phenolic tar utilizes |
| CN109306043B (en) * | 2018-09-20 | 2021-01-12 | 吉林大学 | Method for recycling phenol-containing tar wastewater generated in biomass power generation |
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Application publication date: 20140409 |