CN101602838A - A kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate - Google Patents
A kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate Download PDFInfo
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- CN101602838A CN101602838A CNA2009100881728A CN200910088172A CN101602838A CN 101602838 A CN101602838 A CN 101602838A CN A2009100881728 A CNA2009100881728 A CN A2009100881728A CN 200910088172 A CN200910088172 A CN 200910088172A CN 101602838 A CN101602838 A CN 101602838A
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Abstract
The present invention relates to a kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate, belong to technical field of polymer materials.Raw material is phenol, formaldehyde, wood pyrolysis oil, glutaraldehyde or oxalic dialdehyde and composite catalyst, in part wood pyrolysis oil and glutaraldehyde or oxalic dialdehyde adding reactor, and adjust pH, heat up, insulation reaction adds phenol and composite catalyst, insulation reaction more successively, part formaldehyde is joined in the reactant, heat up, insulation reaction joins remaining formaldehyde and wood pyrolysis oil in the above-mentioned reactant, insulation reaction obtains wood pyrolysis oil modified phenolic resin.The resin free formaldehyde of the inventive method preparation is low, with low cost, good stability, storage period are long, and have good bonding strength and weathering resistance, can be used for the production of outdoor wood-base fibre and particle panel materials such as oriented wood chipboard, concrete form, container bottom board, bullet train compartment base plate.Wood pyrolysis oil need not realized 100% utilization through any purification in present method.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate, belong to technical field of polymer materials.
Background technology
Along with China's rapid economy development, building, carrier develop swift and violent, and outdoor wood-base fibre and particle panel material output such as oriented wood chipboard, concrete form, container bottom board, bullet train compartment base plate increase year by year.Because synvaren has Joint strength height, water-fast, weather-proof, heat-resisting, wear-resisting, chemical resistance corrosion and glueds joint advantages such as the goods burst size of methanal is low, therefore, usually uses synvaren in the manufacturing of outdoor wood-base fibre and particle panel material.But, in recent years because petroleum resources in short supply, produce one of main raw material phenol costliness of synvaren, make its price also high, and then caused its price of glueing joint goods higher relatively.Wood pyrolysis oil prepares resol as green chemical industry raw material substitution part phenol, not only reduced the cost of resin, also having reduced resin pollutes because of the wood-based plate phenol that the toxicity of raw material-phenol causes, the new source of low cost, high-performance, environmentally friendly phenol formaldehyde tackifier is provided for China outdoor wood-based panel industry, to become wood-based plate with resin adhesive to a low important directions that poisons development, become an integral part of renewable resources recovery energy.
Summary of the invention
The objective of the invention is to propose a kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate, wood-based plate is brought up to 40-60% with the substitution rate of the wood pyrolysis oil in the modified phenolic resins, and then reduction wood pyrolysis oil modified phenolic resin manufacturing cost, and the wood pyrolysis oil that is utilized is to be raw material with whole timber (comprising bark), can all utilize all components of wood pyrolysis oil, do not need to purify, solved processing cost height, complex process problem that wood pyrolysis oil produces because of purification.
The preparation method of the wood pyrolysis oil modified phenolic resin that is used for wood-based plate that the present invention proposes, the mass parts of each component is as follows in the raw material:
100 parts of phenol
Formaldehyde 150-250 part
Wood pyrolysis oil 100-200 part
Glutaraldehyde or oxalic dialdehyde 15-50 part,
Composite catalyst 5-15 part,
Its preparation method is as follows:
(1) wood pyrolysis oil with 60% in the wood pyrolysis oil of weighing according to the above ratio adds in the reactor with glutaraldehyde or oxalic dialdehyde, and adjust pH is 8.0-8.5, is warming up to 60-75 ℃, insulation reaction 20 minutes;
(2) add phenol and composite catalyst successively in above-mentioned reactant, reaction is 30-40 minute under 80-85 ℃ temperature;
(3) formaldehyde with 80% in the formaldehyde of weighing according to the above ratio joins in the reactant of above-mentioned steps (2), is warming up to 90-95 ℃, insulation reaction 30-40 minute;
20% formaldehyde that (4) will be left and remaining 40% wood pyrolysis oil join in the reactant of above-mentioned steps (3), continue reaction 20-30 minute in 80-85 ℃ temperature range;
(5) sampling is observed, when sample is cooled to 25 ℃, when viscosity reaches the 500-800 centipoise, obtains wood pyrolysis oil modified phenolic resin.
Among the above-mentioned preparation method, composite catalyst is mixed with sodium hydroxide by in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide or the yellow soda ash any one and forms, and the blended mass percent is: any one in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide or the yellow soda ash: sodium hydroxide=0.2-0.6: 1.
The preparation method of the wood pyrolysis oil modified phenolic resin that is used for wood-based plate that the present invention proposes, its advantage is:
(1) wood pyrolysis oil can be directly used in alternative phenol and prepare resol, reduce processing cost height, complex process problem that wood pyrolysis oil produces because of purification.
(2) the use composite catalyst solves wood pyrolysis oil solidification value height, speed is slow, realizes the low temperature fast setting of wood pyrolysis oil modified phenolic resin.
(3) bio oil is embedded in the resin structure preferably in the preparation wood pyrolysis oil modified phenolic resin, has improved water tolerance, the weathering resistance of resin.
Gained resin free formaldehyde of the present invention is low, with low cost, good stability, storage period are long, and have good bonding strength and weathering resistance, can be used for the production of outdoor wood-base fibre and particle panel materials such as oriented wood chipboard, concrete form, container bottom board, bullet train compartment base plate.Method of the present invention has the advantage that technology is succinct, processing condition are easy, cost is low, and wood pyrolysis oil need almost can not realized 100% utilization through any purification.
Embodiment
The preparation method of the wood pyrolysis oil modified phenolic resin that is used for wood-based plate that the present invention proposes, the mass parts of each component is as follows in the raw material:
100 parts of phenol
Formaldehyde 150-250 part
Wood pyrolysis oil 100-200 part
Glutaraldehyde or oxalic dialdehyde 15-50 part
Composite catalyst 5-15 part,
Its preparation method is as follows:
(1) wood pyrolysis oil with 60% in the wood pyrolysis oil of weighing according to the above ratio adds in the reactor with glutaraldehyde or oxalic dialdehyde, and adjust pH is 8.0-8.5, is warming up to 60-75 ℃, insulation reaction 20 minutes;
(2) add phenol and composite catalyst successively in above-mentioned reactant, reaction is 30-40 minute under 80-85 ℃ temperature;
(3) formaldehyde with 80% in the formaldehyde of weighing according to the above ratio joins in the reactant of above-mentioned steps (2), is warming up to 90-95 ℃, insulation reaction 30-40 minute;
20% formaldehyde that (4) will be left and remaining 40% wood pyrolysis oil join in the reactant of above-mentioned steps (3), continue reaction 20-30 minute in 80-85 ℃ temperature range;
(5) sampling is observed, when sample is cooled to 25 ℃, when viscosity reaches the 500-800 centipoise, obtains wood pyrolysis oil modified phenolic resin.
Composite catalyst in the aforesaid method, can be mixed with sodium hydroxide by in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide or the yellow soda ash any one and form, the blended mass percent is: any one in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide or the yellow soda ash: sodium hydroxide=0.2-0.6: 1.
The wood pyrolysis oil that uses among the preparation method of the present invention, by the preparation of wood materials scientific and engineering institute of Beijing Forestry University, its main component is 18% polyphenol, 39% aldose compounds, 43% moisture and other materials.
Below introduce embodiments of the invention.
Embodiment 1
Take by weighing phenol 100 gram, formaldehyde 150 grams, wood pyrolysis oil 200 grams, glutaraldehyde 15 grams, 10 gram composite catalysts (wherein sodium hydroxide 8.2 grams, zinc oxide 1.8 grams).
In the there-necked flask of 500mL, add 120 gram wood pyrolysis oils, 15 gram glutaraldehyde, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 60 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 10 gram composite catalysts successively, be warmed up to 80 ℃ again and carry out insulation reaction.React after 30 minutes, add 120 gram formaldehyde, in 10-15 minute, be warming up to 90 ℃ and insulation reaction 35 minutes.Be cooled to 75-80 ℃, add remaining 30 gram formaldehyde, remaining 80 gram wood pyrolysis oils.Carry out isothermal reaction after 20 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity reaches 500 centipoises, the cooling discharging of lowering the temperature immediately.
Embodiment 2
Take by weighing phenol 100 gram, formaldehyde 200 grams, wood pyrolysis oil 150 grams, oxalic dialdehyde 20 grams, 15 gram composite catalysts (wherein sodium hydroxide 10 grams, magnesium oxide 5 grams).
In the there-necked flask of 500mL, add 90 gram wood pyrolysis oils, 20 gram oxalic dialdehydes, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 75 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 15 gram composite catalysts successively, be warmed up to 85 ℃ again and carry out insulation reaction.React after 40 minutes, add 160 gram formaldehyde, be warming up to 90 ℃ and insulation reaction at 15 minutes 40 minutes.Be cooled to 75-80 ℃, add remaining 40 gram formaldehyde, remaining 60 gram wood pyrolysis oils.Carry out isothermal reaction after 30 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity (25 ℃) when reaching 700 centipoises, the cooling discharging of lowering the temperature immediately.
Embodiment 3
Take by weighing phenol 100 gram, formaldehyde 170 grams, wood pyrolysis oil 100 grams, oxalic dialdehyde 50 grams, 30 gram composite catalysts (wherein sodium hydroxide 24 grams, calcium hydroxide 6 grams).
In the there-necked flask of 500mL, add 60 gram wood pyrolysis oils, 50 gram oxalic dialdehydes, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 70 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 30 gram composite catalysts successively, be warmed up to 83 ℃ again and carry out insulation reaction.React after 40 minutes, add 136 gram formaldehyde, in 13 minutes, be warming up to 90 ℃ and insulation reaction 35 minutes.Be cooled to 75-80 ℃, add remaining 34 gram formaldehyde, remaining 40 gram wood pyrolysis oils.Carry out isothermal reaction after 25 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity (25 ℃) when reaching 800, the cooling discharging of lowering the temperature immediately.
Embodiment 4
Take by weighing phenol 100 gram, formaldehyde 170 grams, wood pyrolysis oil 100 grams, oxalic dialdehyde 50 grams, 40 gram composite catalysts (wherein sodium hydroxide 30 grams, calcium hydroxide 10 grams).
In the there-necked flask of 500mL, add 60 gram wood pyrolysis oils, 40 gram glutaraldehyde, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 75 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 40 gram composite catalysts successively, be warmed up to 80 ℃ again and carry out insulation reaction.React after 35 minutes, add 136 gram formaldehyde, in 10-15 minute, be warming up to 90 ℃ and insulation reaction 30 minutes.Be cooled to 75-80 ℃, add remaining 34 gram formaldehyde, remaining 40 gram wood pyrolysis oils.Carry out isothermal reaction after 20 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity (25 ℃) when reaching 700, the cooling discharging of lowering the temperature immediately.
Embodiment 5
Take by weighing phenol 100 gram, formaldehyde 250 grams, wood pyrolysis oil 180 grams, glutaraldehyde 35 grams, 5 gram composite catalysts (wherein sodium hydroxide 3 grams, hydrated barta 2 grams).
In the there-necked flask of 500mL, add 108 gram wood pyrolysis oils, 35 gram glutaraldehyde, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 75 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 5 gram composite catalysts successively, be warmed up to 84 ℃ again and carry out insulation reaction.React after 38 minutes, add 200 gram formaldehyde, in 10-15 minute, be warming up to 90 ℃ and insulation reaction 35 minutes.Be cooled to 75-80 ℃, add remaining 50 gram formaldehyde, remaining 72 gram wood pyrolysis oils.Carry out isothermal reaction after 30 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity (25 ℃) when reaching 550 centipoises, the cooling discharging of lowering the temperature immediately.
Embodiment 6
Take by weighing phenol 100 gram, formaldehyde 160 grams, wood pyrolysis oil 140 grams, oxalic dialdehyde 45 grams, 20 gram composite catalysts (wherein sodium hydroxide 14 grams, potassium hydroxide 6 grams).
In the there-necked flask of 500mL, add 84 gram wood pyrolysis oils, 45 gram oxalic dialdehydes, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 70 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 20 gram composite catalysts successively, be warmed up to 85 ℃ again and carry out insulation reaction.React after 35 minutes, add 128 gram formaldehyde, be warming up to 90 ℃ and insulation reaction at 15 minutes 40 minutes.Be cooled to 75-80 ℃, add remaining 32 gram formaldehyde, remaining 56 gram wood pyrolysis oils.Carry out isothermal reaction after 25 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity (25 ℃) when reaching 750 centipoises, the cooling discharging of lowering the temperature immediately
Embodiment 7
Take by weighing phenol 100 gram, formaldehyde 155 grams, wood pyrolysis oil 100 grams, oxalic dialdehyde 25 grams, 10 gram composite catalysts (wherein sodium hydroxide 8 grams, yellow soda ash 2 grams).
In the there-necked flask of 500mL, add 60 gram wood pyrolysis oils, 25 gram oxalic dialdehydes, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 65 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 10 gram composite catalysts successively, be warmed up to 85 ℃ again and carry out insulation reaction.React after 35 minutes, add 124 gram formaldehyde, in 10-15 minute, be warming up to 90 ℃ and insulation reaction 30 minutes.Be cooled to 75-80 ℃, add remaining 31 gram formaldehyde, remaining 40 gram wood pyrolysis oils.Carry out isothermal reaction after 25 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity (25 ℃) when reaching 700 centipoises, the cooling discharging of lowering the temperature immediately
Embodiment 8
Take by weighing phenol 100 gram, formaldehyde 160 grams, wood pyrolysis oil 100 grams, glutaraldehyde 20 grams, 40 gram composite catalysts (wherein sodium hydroxide 30 grams, zinc oxide 10 grams).
In the there-necked flask of 500mL, add 60 gram wood pyrolysis oils, 20 gram glutaraldehyde, after stirring, aqueous sodium hydroxide solution adjust pH with 30% is 8.0-8.5, be warmed up to 70 ℃, after the insulation reaction 20 minutes, add 100 gram phenol, 40 gram composite catalysts successively, be warmed up to 85 ℃ again and carry out insulation reaction.React after 40 minutes, add 128 gram formaldehyde, in 10-15 minute, be warming up to 90 ℃ and insulation reaction 30 minutes.Be cooled to 75-80 ℃, add remaining 32 gram formaldehyde, remaining 40 gram wood pyrolysis oils.Carry out isothermal reaction after 30 minutes at 80-85 ℃, sampling and testing viscosity frequently, when sample viscosity (25 ℃) when reaching 600 centipoises, the cooling discharging of lowering the temperature immediately
Utilize following evidence effect of the present invention, particular content is as follows:
Adopt the foregoing description 1, embodiment 2, embodiment 3, embodiment 4 method synthetic wood pyrolysis oil modified phenolic resin tackiness agent to produce three layers of poplar plywood respectively.Wherein, the flour that adds wood pyrolysis oil modified phenolic resin weight 15% during impregnation; Resin added is 280～300g/m
2(two-sided); Heat pressing process is: pressure 0.9-1.2MPa, 130～140 ℃ of temperature, time: 1.5min/mm.
The performance index of institute's synthetic wood pyrolysis oil modified phenolic resin see Table 1
| Index name | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The pH value | ??10.35 | ??10.14 | ??10.47 | ??10.52 |
| Solids content (%) | ??55～56 | ??55～56 | ??55～56 | ??55～56 |
| Viscosity (Pa.s) (25 ℃) | ??0.56 | ??0.61 | ??0.64 | ??0.59 |
| Storage period (d) | ??＞30 | ??＞30 | ??＞30 | ??＞30 |
| Working life (h) | ??＞8 | ??＞8 | ??＞8 | ??＞8 |
| Free formaldehyde (%) | ??＜0.1 | ??＜0.1 | ??＜0.1 | ??＜0.1 |
Measure the burst size of methanal of glued board with the moisture eliminator method, measure the anti-boiling water bonding strength of glued board according to the regulation of GB/T 17657-1999 " Test methods of evaluating the properties of woodbased panels and surface decorated woodbased panels ", burst size of methanal and bonding strength see Table 2.
| Sequence number | Burst size of methanal (mg/L) | Strength of Plywood (MPa) |
| Embodiment 1 | ??0.09 | ??0.78 |
| Embodiment 2 | ??0.21 | ??1.04 |
| Embodiment 3 | ??0.16 | ??0.93 |
| Embodiment 4 | ??0.11 | ??0.89 |
By table 2 as seen, utilize the inventive method synthetic wood pyrolysis oil modified phenolic resin tackiness agent to produce three layers of poplar plywood, the burst size of methanal of product can satisfy national E0 level (being not more than 0.5mg/L) standard, and bonding strength can satisfy I class glued board national standard (being not less than 0.70MPa).
Claims (2)
1, a kind of preparation method who is used for the wood pyrolysis oil modified phenolic resin of wood-based plate is characterized in that the mass parts of each component is as follows in the raw material:
100 parts of phenol
Formaldehyde 150-250 part
Wood pyrolysis oil 100-200 part
Glutaraldehyde or oxalic dialdehyde 15-50 part
Composite catalyst 5-15 part,
Its preparation method is as follows:
(1) wood pyrolysis oil with 60% in the wood pyrolysis oil of weighing according to the above ratio adds in the reactor with glutaraldehyde or oxalic dialdehyde, and adjust pH is 8.0-8.5, is warming up to 60-75 ℃, insulation reaction 20 minutes;
(2) add phenol and composite catalyst successively in above-mentioned reactant, reaction is 30-40 minute under 80-85 ℃ temperature;
(3) formaldehyde with 80% in the formaldehyde of weighing according to the above ratio joins in the reactant of above-mentioned steps (2), is warming up to 90-95 ℃, insulation reaction 30-40 minute;
20% formaldehyde that (4) will be left and remaining 40% wood pyrolysis oil join in the reactant of above-mentioned steps (3), continue reaction 20-30 minute in 80-85 ℃ temperature range;
(5) sampling is observed, when sample is cooled to 25 ℃, when viscosity reaches the 500-800 centipoise, obtains wood pyrolysis oil modified phenolic resin.
2, preparation method as claimed in claim 1, it is characterized in that wherein said composite catalyst is mixed with sodium hydroxide by in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide or the yellow soda ash any one forms, and the blended mass percent is: any one in zinc oxide, magnesium oxide, calcium hydroxide, hydrated barta, potassium hydroxide or the yellow soda ash: sodium hydroxide=0.2-0.6: 1.
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| CN2009100881728A CN101602838B (en) | 2009-07-10 | 2009-07-10 | Method for preparing wood pyrolysis oil modified phenolic resin for artificial board |
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| CN101602838B CN101602838B (en) | 2011-01-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265674A (en) * | 2013-05-11 | 2013-08-28 | 北京化工大学 | Phenol-polyaldehyde prepolymer modified environment-friendly phenolic resin and preparation method thereof |
| CN104031631A (en) * | 2014-06-16 | 2014-09-10 | 北京国海能源技术研究院 | Mud acid cross-linking agent and preparation method thereof |
| CN105131517A (en) * | 2015-07-16 | 2015-12-09 | 浙江杭摩合成材料有限公司 | Modified thermoplastic phenolic resin adhesive used in automobile brake pad and preparation method thereof |
| CN107099009A (en) * | 2017-05-15 | 2017-08-29 | 北京林业大学 | The preparation method of the common modified artificial plate thermosetting phenolic resin of boric acid/pyrolysis oil |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187369A (en) * | 1977-07-07 | 1980-02-05 | Farbshtein Jury G | Process for producing hydrocarbon-phenol-formaldehyde resin |
| CN100439411C (en) * | 2006-04-13 | 2008-12-03 | 华南理工大学 | Process for preparing phenolic resin by using waste circuit board pyrolytic oil |
| CN101328396A (en) * | 2007-06-22 | 2008-12-24 | 常建民 | Eastern larch bark rapid pyrolysis oil modified phenolic resin adhesive |
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2009
- 2009-07-10 CN CN2009100881728A patent/CN101602838B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265674A (en) * | 2013-05-11 | 2013-08-28 | 北京化工大学 | Phenol-polyaldehyde prepolymer modified environment-friendly phenolic resin and preparation method thereof |
| CN103265674B (en) * | 2013-05-11 | 2015-05-13 | 北京化工大学 | Phenol-polyaldehyde prepolymer modified environment-friendly phenolic resin and preparation method thereof |
| CN104031631A (en) * | 2014-06-16 | 2014-09-10 | 北京国海能源技术研究院 | Mud acid cross-linking agent and preparation method thereof |
| CN104031631B (en) * | 2014-06-16 | 2017-01-25 | 北京国海能源技术研究院 | Mud acid cross-linking agent and preparation method thereof |
| CN105131517A (en) * | 2015-07-16 | 2015-12-09 | 浙江杭摩合成材料有限公司 | Modified thermoplastic phenolic resin adhesive used in automobile brake pad and preparation method thereof |
| CN107099009A (en) * | 2017-05-15 | 2017-08-29 | 北京林业大学 | The preparation method of the common modified artificial plate thermosetting phenolic resin of boric acid/pyrolysis oil |
| CN107099009B (en) * | 2017-05-15 | 2019-01-25 | 北京林业大学 | Boric acid/pyrolysis oil is total to the preparation method of modified artificial plate thermosetting phenolic resin |
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