CN103319670B - Bio-based phenolic resin and preparation method thereof - Google Patents
Bio-based phenolic resin and preparation method thereof Download PDFInfo
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- CN103319670B CN103319670B CN201310205185.5A CN201310205185A CN103319670B CN 103319670 B CN103319670 B CN 103319670B CN 201310205185 A CN201310205185 A CN 201310205185A CN 103319670 B CN103319670 B CN 103319670B
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- furfuryl alcohol
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Abstract
The invention relates to a bio-based phenolic resin and a preparation method thereof, wherein the bio-based phenolic resin is prepared by polymerizing furfuryl diphenolate, furfuryl gallate and furfural, an oxygen content is 19.7-28.8wt%, and molecular weight is between 3000-4000. The advantages reside in that: the raw materials come from agricultural waste biomass, are cheap and easily available, and the prepared bio-based phenolic resin has high oxygen content and molecular weight. The oxygen content is 19.7-28.8%, and is 1.3-1.9 times higher than that of a common phenolic resin. The molecular weight is between 3000-4000, and is twice higher than that of a common phenolic resin. The bio-based phenolic resin has excellent mechanical properties, electrical insulation property, chemical stability and heat stability, can replace metal to be used in vehicle and machine manufacturing industries, is suitable for key components of an internal combustion engine of high-end equipment, such as an engine inlet manifold assembly, a multilayer composite fuel tank, a petroleum pipeline, an engineering plastic charcoal tank, a resonant cavity type silencer, a radiator tank, a water pump, a fan and an electric appliance connector.
Description
Technical field
The present invention relates to a kind of bio-based resin, particularly relate to bio-based resol and preparation method thereof, belong to polymeric material field.
Background technology
Resol is the resin by phenolic compound and aldehyde compound polycondensation, phenolic compound used mainly phenol, the also mixture etc. of available cresols, mixture cresol, nonyl phenol, octyl phenol, xylenol, cardanol, aralkyl phenol, dihydroxyphenyl propane or several phenol; Aldehyde compound used mainly formaldehyde, the also mixture of available paraformaldehyde, furfural, acetaldehyde or several aldehyde.
Resol is as one of three large thermosetting resins, and wide application, amount are large, and developing history is long.Relative to other resins, resol has following characteristic: 1. cheap, the production technique of cost of material is simple and ripe, manufacture and processing units less investment, and forming process is easy; 2. heat-resisting, resistance to combustion, can go out certainly, and electrical insulation capability is good, but arc resistance is poor; 3. chemical stability is good, and acid resistance is strong, but not alkaline-resisting; 4. resin both can be mixed into mineral filler or plastics are made in organic filler, also impregnate fabric can make laminated product, can also foam; 5. product size is stablized.
At present, the preparation method of resol mainly contains following four kinds: weak acid catalysis method, prepares phenolic novolac, PVC modified phenolic resins, nbr modified phenolic resins, dimethylbenzene formaldehyde modified phenolic resins, phenolic aldehyde mould material; NH
3catalysis method, prepares the acidproof moulding compound of phenolic aldehyde asbestos, phenolic aldehyde cotton fibre moulding compound, aniline modified phenolic molding compound, phenolic aldehyde stratified plastics; NaOH catalysis method, prepares phenolic aldehyde asbestos moulding compound, phenolic aldehyde cloth waste moulding compound, phenol furfural moulding material; ZnO catalysis method, prepares high adjacent position phenolic resin, polyvinyl butyral resin, rapid shaping phenolaldehyde moulding compound.
Resol has high temperature resistant, shock-resistant, low being fuming and the feature such as chemical-resistant, cost be low, and this makes it have to develop faster.Be mainly used in varnish, sizing agent, coating, moulding compound, stratified plastics, porous plastics, protection against corrosion clay and the aspect such as ion exchange resin, ablation resistant material at present.Phenolic molded plastic has been widely used as the structured materials such as manufacturing machine part and gear; Phenolic aldehyde copper coated foil plate has been applied in the electronic industries such as wireless, televisor, computer; Resol, except being used as the sizing agent of emery wheel, brake facing, metal casting model, is also used as ablator etc.Resol can be predicted the continuous developing along with Application Areas is obtained manyly to develop faster.
Summary of the invention
The object of the invention is to be to provide one to have rich oxygen content and molecular weight, and there is bio-based resol of excellent mechanical property, electrical insulation capability, chemical stability and thermostability and preparation method thereof.
Bio-based resol of the present invention is obtained through polymerization by diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester and furfural, and its oxygen level is at 19.7-28.8wt%, and molecular weight is between 3000-4000, and its molecular formula is as follows:
Mol ratio A:B=0.1-1.
The preparation method of bio-based resol of the present invention is as follows:
1, diphenolic acid and furfuryl alcohol obtain diphenolic acid furfuryl alcohol ester through esterification technique;
With diphenolic acid and furfuryl alcohol for raw material, ZSM-5 molecular sieve is catalyzer, temperature of reaction 80 ~ 200 DEG C, under condition of normal pressure, carry out esterification, obtained diphenolic acid furfuryl alcohol ester, wherein: diphenolic acid/furfuryl alcohol is 1/1-4 in molar ratio, and catalyst levels is the 2-10wt% of diphenolic acid; Above-mentioned diphenolic acid transformation efficiency is more than 80%, and diphenolic acid furfuryl alcohol ester selectivity is 95%-100%, and molecular formula is as follows:
2, gallic acid and furfuryl alcohol obtain gallic acid furfuryl alcohol ester through esterification technique;
With gallic acid and furfuryl alcohol for raw material, ZSM-5 molecular sieve is catalyzer, temperature of reaction 80 ~ 200 DEG C, under condition of normal pressure, carry out esterification, obtained gallic acid furfuryl alcohol ester, wherein: gallic acid/furfuryl alcohol is 1/1-4 in molar ratio, and catalyst levels is the 2-10wt% of diphenolic acid; Above-mentioned diphenolic acid transformation efficiency is more than 80%, and gallic acid furfuryl alcohol ester selectivity is 90%-100%, and molecular formula is as follows:
3, the obtained bio-based resol of diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester and furfural polymerization;
By in order to the obtained diphenolic acid furfuryl alcohol ester of top method, the 1:0.1-1 mixing in molar ratio of gallic acid furfuryl alcohol ester, add in reactor, then to add with the total amount mol ratio of diphenolic acid and gallic acid be successively the furfural of 1-1.6, and catalysts and solvents;
Being polymerized catalyzer used is weak acid, as: oxalic acid, dilute hydrochloric acid, dilute sulphuric acid, acetic acid, boric acid, consumption is the 0.05-1wt% of the total amount of diphenolic acid and gallic acid; Solvent is the one in ethanol, propyl alcohol, butanols, acetone, and consumption is mol ratio solvent: the total amount of diphenolic acid and gallic acid adds furfural=4-8.
After abundant stirring, heat up.Polycondensation temperature is 80-100 DEG C, absolute pressure 0.1-1MPa, after reaction 30min-100min, carry out vacuum hydro-extraction, cooling discharging after dehydration, the obtained bio-based resol (mol ratio A:B=0.1-1) with following monomer, molecular weight is between 3000-4000.
The present invention's raw material used is all biomass derivatives, and comprise furfural, levulinic acid, phenol and gallic acid, wherein: furfural is obtained by hydrolysis of hemicellulose, levulinic acid is obtained by cellulose hydrolysis, and phenol is obtained by xylogen cracking; Gallic acid (Gallic Acid) is hydrolyzed obtained by Weibull.
Furfuryl alcohol is obtained by furfural hydrogenation; Diphenolic acid is obtained by levulinic acid and phenol condensation.Above product all can be obtained by the agricultural abandoned biomass of cheapness.
Compare with product with prior art, the present invention has the following advantages:
1, the raw material of the present invention's utilization is from agricultural abandoned biomass, cheap and easy to get.
2, develop a kind of new bio base resol, there is rich oxygen content and molecular weight.Its oxygen level, at 19.7-28.8%, improves 1.3-1.9 doubly than phenolic resin; Its molecular weight, between 3000-4000, improves more than 2 times than phenolic resin.This product has excellent mechanical property, electrical insulation capability, chemical stability and thermostability, alternative metal is used for automobile and machine building, be applicable to high-end equipment oil engine key part, as engine intake manifold assembly, MULTILAYER COMPOSITE fuel tank and transition pipeline, engineering plastics charcoal tank and resonant cavity type sourdine, radiator tank and water pump and fan, electric coupler etc.
Embodiment
Embodiment 1
Being equipped with agitator, temperature takes into account in the stainless steel cauldron of heating jacket, add diphenolic acid and furfuryl alcohol that mol ratio is 1:1, and the ZSM-5 molecular sieve catalyzer of 5%, 120 DEG C are raised to the temperature rise rate of 2 DEG C/min, open and stir, lower the temperature after reaction 30min, filter, be separated obtained diphenolic acid furfuryl alcohol ester.Diphenolic acid transformation efficiency is 85%, and diphenolic acid furfuryl alcohol ester selectivity is 95%.
In reactor, add gallic acid and furfuryl alcohol that mol ratio is 1:1, and the ZSM-5 molecular sieve catalyzer of 5%, be raised to 120 DEG C with the temperature rise rate of 2 DEG C/min, open and stir, lower the temperature after reaction 30min, filter, be separated obtained gallic acid furfuryl alcohol ester.Diphenolic acid transformation efficiency is 88%, and diphenolic acid furfuryl alcohol ester selectivity is 92%.
In reactor, add diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester, furfural and alcohol solvent that mol ratio is 1:0.1:1.3:12, and 0.5 wt%(accounts for the mass percent of mixed phenol (diphenolic acid and gallic acid)) Catalyzed by Oxalic Acid agent.Polycondensation temperature is 100 DEG C, pressure 0.8MPa, and after reaction 60min, carry out vacuum hydro-extraction, cooling discharging after dehydration, obtained molecular weight is the bio-based resol of 3850.
Embodiment 2
Being equipped with agitator, temperature takes into account in the stainless steel cauldron of heating jacket, add diphenolic acid and furfuryl alcohol that mol ratio is 1:2, and the ZSM-5 molecular sieve catalyzer of 5%, 120 DEG C are raised to the temperature rise rate of 2 DEG C/min, open and stir, lower the temperature after reaction 30min, filter, be separated obtained diphenolic acid furfuryl alcohol ester.Diphenolic acid transformation efficiency is 90%, and diphenolic acid furfuryl alcohol ester selectivity is 98%.
In reactor, add gallic acid and furfuryl alcohol that mol ratio is 1:3, and the ZSM-5 molecular sieve catalyzer of 5%, be raised to 120 DEG C with the temperature rise rate of 2 DEG C/min, open and stir, lower the temperature after reaction 30min, filter, be separated obtained gallic acid furfuryl alcohol ester.Diphenolic acid transformation efficiency is 92%, and diphenolic acid furfuryl alcohol ester selectivity is 95%.
In reactor, add diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester, furfural, ethanol that mol ratio is 1:1:1.3:16, and 0.5 wt%(accounts for the mass percent of mixed phenol) Catalyzed by Oxalic Acid agent.Polycondensation temperature is 100 DEG C, pressure 0.8MPa, and after reaction 60min, carry out vacuum hydro-extraction, cooling discharging after dehydration, obtained molecular weight is the bio-based resol of 3200.
Embodiment 3
Being equipped with agitator, temperature takes into account in the stainless steel cauldron of heating jacket, add diphenolic acid and furfuryl alcohol that mol ratio is 1:4, and the ZSM-5 molecular sieve catalyzer of 5%, 120 DEG C are raised to the temperature rise rate of 2 DEG C/min, open and stir, lower the temperature after reaction 30min, filter, be separated obtained diphenolic acid furfuryl alcohol ester.Diphenolic acid transformation efficiency is 96%, and diphenolic acid furfuryl alcohol ester selectivity is 100%.
In reactor, add gallic acid and furfuryl alcohol that mol ratio is 1:4, and the ZSM-5 molecular sieve catalyzer of 5%, be raised to 120 DEG C with the temperature rise rate of 2 DEG C/min, open and stir, lower the temperature after reaction 30min, filter, be separated obtained gallic acid furfuryl alcohol ester.Diphenolic acid transformation efficiency is 94%, and diphenolic acid furfuryl alcohol ester selectivity is 100%.
In reactor, add diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester, furfural and acetone that mol ratio is 1:0.5:1.3:14, and 0.1 wt%(accounts for the mass percent of mixed phenol) dilute sulphuric acid (10wt%) catalyzer.Polycondensation temperature is 100 DEG C, pressure 0.8MPa, and after reaction 60min, carry out vacuum hydro-extraction, cooling discharging after dehydration, obtained molecular weight is the bio-based resol of 3600.
Claims (4)
1. a bio-based resol, is characterized in that: obtained through polymerization by diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester and furfural, its oxygen level is at 19.7-28.8wt%, and molecular weight is between 3000-4000, and its molecular formula is as follows:
Mol ratio A:B=0.1-1.
2. the preparation method of a bio-based resol according to claim 1, it is characterized in that: with diphenolic acid and furfuryl alcohol for raw material, ZSM-5 molecular sieve is catalyzer, temperature of reaction 80 ~ 200 DEG C, under condition of normal pressure, carry out esterification, obtained diphenolic acid furfuryl alcohol ester, wherein: diphenolic acid/furfuryl alcohol is 1/1-4 in molar ratio, and catalyst levels is the 2-10wt% of diphenolic acid; With gallic acid and furfuryl alcohol for raw material, ZSM-5 molecular sieve is catalyzer, temperature of reaction 80 ~ 200 DEG C, under condition of normal pressure, carry out esterification, obtained gallic acid furfuryl alcohol ester, wherein: gallic acid/furfuryl alcohol is 1/1-4 in molar ratio, and catalyst levels is the 2-10wt% of diphenolic acid; By the 1:0.1-1 mixing in molar ratio of diphenolic acid furfuryl alcohol ester, gallic acid furfuryl alcohol ester, add in reactor, then to add with the total amount mol ratio of diphenolic acid and gallic acid be successively the furfural of 1-1.6, and catalysts and solvents; Described catalyzer is weak acid, and consumption is the 0.05-1wt% of the total amount of diphenolic acid and gallic acid; Described solvent is the one in ethanol, propyl alcohol, butanols, acetone, and consumption is mol ratio solvent: the total amount of diphenolic acid and gallic acid adds furfural=4-8; After abundant stirring, heat up, polycondensation temperature is 80-100 DEG C, absolute pressure 0.1-1MPa, after reaction 30min-100min, carries out vacuum hydro-extraction, cooling discharging after dehydration, obtained bio-based resol.
3. the preparation method of bio-based resol according to claim 2, is characterized in that: furfuryl alcohol is obtained by furfural hydrogenation; Diphenolic acid is obtained by levulinic acid and phenol condensation.
4. the preparation method of bio-based resol according to claim 3, is characterized in that: furfural is obtained by hydrolysis of hemicellulose.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092472A (en) * | 2007-07-27 | 2007-12-26 | 中国林业科学研究院林产化学工业研究所 | Phenol-formaldehyde resin of lignin and biomass oil in use for moulding plastic material, and preparation method |
| CN101367904A (en) * | 2008-10-10 | 2009-02-18 | 郑州大学 | Synthesis process of bisphenol acid type water soluble phenol resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092472A (en) * | 2007-07-27 | 2007-12-26 | 中国林业科学研究院林产化学工业研究所 | Phenol-formaldehyde resin of lignin and biomass oil in use for moulding plastic material, and preparation method |
| CN101367904A (en) * | 2008-10-10 | 2009-02-18 | 郑州大学 | Synthesis process of bisphenol acid type water soluble phenol resin |
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Address after: 014060 Wanshuiquan, Rare Earth High-tech Zone, Baotou City, Inner Mongolia Autonomous Region Patentee after: Pretty Oriental Bio Fuel Group Limited Address before: 014030 Jinjiao Industrial Park, Binhe New Area, Baotou Rare Earth High-tech Zone, Inner Mongolia Autonomous Region Patentee before: Jinjiao Special New Materials (Group) Co., Ltd. |
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