CN103554396A - Preparation method of lignin modified phenolic resin for molding compound - Google Patents
Preparation method of lignin modified phenolic resin for molding compound Download PDFInfo
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- CN103554396A CN103554396A CN201310477170.4A CN201310477170A CN103554396A CN 103554396 A CN103554396 A CN 103554396A CN 201310477170 A CN201310477170 A CN 201310477170A CN 103554396 A CN103554396 A CN 103554396A
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Abstract
The invention discloses a lignin modified phenolic resin for molding compound. The lignin modified phenolic resin can be prepared by the following method: mixing phenol, an acid catalyst and enzymolysis lignin, heating to 90 DEG C-160 DEG C, liquefying for 1-3 h, cooling to 70 DEG C, then adding formaldehyde into the reaction system, heating to 90-120 DEG C, reacting for 2-4 h, and carrying out vacuum distillation to obtain the lignin modified phenolic resin. The invention uses enzymolysis lignin in rich resource to partially substitute phenol to prepare phenolic resin, so as to obviously reduce cost. The lignin modified phenolic resin provided by the invention can be used for preparing molding compound, and has high mechanical properties, heat resistance and insulation.
Description
Technical field
The present invention relates to a kind of resol and preparation method thereof, relate in particular to a kind of lignin modification resol for moulding compound and preparation method thereof.
Background technology
Xylogen (lignin) is in the unique non-oil resource ，Shi vegitabilia that renewable aryl compound can be provided of nature, to be only second to cellulosic the second abundant natural polymer.Lignin molecule has numerous different types of active groups, has renewable, degradable, the advantage such as nontoxic concurrently.Enzymolysis xylogen (Enzymatic Hydrolysis Lignin is called for short EHL) is the Novel wooden quality of extracting in the residue of preparing alcohol fuel by fermentation of plant straws.At present; most enzymolysis xylogen is for burning; not only its composition is not utilized effectively; and contaminate environment; China produces 6,700,000,000 tons of maize straws now per year, and the residue that alcohol fuel is prepared in every 1 ton of maize straw fermentation can obtain the xylogen of 300 kilograms of left and right, the resource rational utilization that therefore efficiently utilizes enzymolysis xylogen not only can do; again can petroleum replacing Chemicals, protection of the environment.In the present invention, xylogen used derives from the residue that the agricultural wastes such as corn cob, maize straw are produced alcohol fuel or butanols.
Phenolaldehyde moulding compound is a kind of material with excellent thermotolerance and good cost performance, and its main component is resol.Resol by phenolic compound and the aldehyde compound resol that polycondensation forms under catalyst action because cheap, heat-resisting, resistance to ablation, fire-retardant, burning fuming is few etc. is widely used in sizing agent, coating, moulding compound, stratified plastics, porous plastics and ion exchange resin etc.The production of resol and the meeting of use consume bulk petroleum Chemicals, and bring pollution to a certain degree to environment, affect the whole ecosystem.For the production of the phenol of the main petrochemicals of resol,, the price of formaldehyde improves constantly, cause China's resol relevant industries profit sharply to decline, have a strong impact on the development of resol industry.
Utilize natural biomass the Study on Resources exploitation phenolaldehyde moulding compound to there is particularly important meaning.Cheng Xian Sue etc. adopt method separating-purifying from the residue of microorganism enzymolysis corn stalk that organic solvent extraction and inorganic chemical are processed to obtain enzymolysis xylogen, and prepare bio-modification hot melt type phenolic resin, and this method has increased production cost.
Summary of the invention
The object of this invention is to provide a kind of environmental protection, low cost, good combination property, the lignin modification preparation method of phenolic resin for the preparation of moulding compound that yield is higher, preparation method is simple, effectively utilized the residue that biomass fuel ethanol or butanols preparation process produce, cost is low, moulding compound mechanical property, the good insulation preformance with this raw material, prepared, cost is low.
The present invention adopts following technical scheme: a kind of preparation method of the lignin modification resol for moulding compound, prepare by the following method: phenol, acid catalyst and xylogen are mixed, be heated to 90 ℃-160 ℃, reaction 1-3h, is cooled to 70 ℃, then formaldehyde is added drop-wise in reaction system, be heated to 90 ℃-120 ℃ reaction 2-4h, underpressure distillation, makes lignin modification resol, 90 ℃-105 ℃ of softening temperatures; Wherein, acid catalyst used is oxalic acid.
Xylogen used is for preparing bio-ethanol or biological butanol by product enzymolysis xylogen.
Acid catalyst is the 1-7% of phenol quality.
The mass ratio of xylogen and phenol is 10-50:100.
Described phenol and the mol ratio of formaldehyde are 1:0.81-0.87.
Formaldehyde used is that mass percent concentration is the formaldehyde of 37-40%.
Beneficial effect:
1. because energy problem is becoming tight day, the research and development of biofuel ethanol or butanols are promoted and are come into one's own, and therefore effectively utilize enzymolysis xylogen, can reduce the cost of biofuel enterprise, promote the development of China's biofuel cause.The raw materials used xylogen of the present invention, without purification processes, is directly used the by product of biofuel ethanol or butanols, has not only reduced production cost, has also avoided the use pollution on the environment of organic solvent.
2. the present invention be take product that enzymolysis xylogen Liquefaction Products in Phenol obtains partly to substitute phenol and formaldehyde is basic raw material, under catalyst action, reacts, and obtains having low cost, the resol product of hypotoxicity (reduction of free phenol content).Lignin phenol liquefied product molecular weight reduces, and containing phenol structural content, increases, and with respect to xylogen macromole, it is high that it has reactive behavior, and speed of response is fast, the feature that production efficiency is high.
3. the yield of enzymatic hydrolysis (EH) lignin modified resol (64-70%) will be higher than the yield (61-63%) of pure phenolic resin.
Embodiment
A kind of lignin modification resol for moulding compound, softening temperature is 90 ℃-105 ℃, trickling degree is 1-7cm, polymerization velocity is 60-100s, viscosity is 12-18mPa.s, can make by the following method: by phenol, acid catalyst and enzymolysis xylogen mix, the mass ratio of xylogen and phenol is 10-50:100, by changing the add-on of acid catalyst, regulate the Ph value of above-mentioned reaction system to 1-3, reheat 90 ℃-160 ℃, reaction 1-3h, be cooled to 70 ℃, then add formaldehyde, the mol ratio of phenol and aldehyde is 1:0.81-0.87, regulate temperature of reaction to 90 ℃-120 ℃, reaction 2-4h, underpressure distillation, by the moisture in system and residual phenol, formaldehyde steams, obtain lignin modification resol.
Described xylogen is maize straw fermenting and preparing biological ethanol or biological butanol by product enzymolysis xylogen.
Described acid catalyst is oxalic acid.
Described catalyst levels is the 1%-7% of phenol quality.
Described aldehyde is that concentration is the formaldehyde of 37-40%.
Described resol is to prepare the novolac resin that moulding compound is used.
Embodiment 1
A kind of lignin modification resol for moulding compound, softening point temperature is 90 ℃-105 ℃, can prepare with the following method: phenol, acid catalyst and xylogen are mixed, be heated to 90 ℃-160 ℃, reaction 1-3h, is cooled to 70 ℃, again formaldehyde is added drop-wise in reaction system, be heated to 90 ℃-120 ℃ reaction 2-4h, underpressure distillation, makes lignin modification resol.Make lignin modification resol.The xylogen of participating in this reaction is enzymolysis xylogen, the residue that by product of biofuel ethanol or production of butanol namely produces.
Embodiment 2
A certain amount of phenol, enzymolysis xylogen (phenol quality 33%) and oxalic acid (phenol quality 1%) are added in reactor, 95 ℃ of temperature of reaction, reaction times 2h, be cooled to 70 ℃, adding formaldehyde (phenolic aldehyde mol ratio is 1:0.85), temperature of reaction is 100 ℃ again, reaction times 2h, underpressure distillation, makes lignin modification resol.93 ℃ of softening temperatures, trickling degree 4.5cm, polymerization velocity 70s, free phenol content 4%.
Embodiment 3
A certain amount of phenol, enzymolysis xylogen (phenol quality 33%) and Catalyzed by Oxalic Acid agent (phenol quality 3%) are added in reactor, 130 ℃ of temperature of reaction, reaction times 2h, be cooled to 70 ℃, adding formaldehyde (phenolic aldehyde mol ratio is 1:0.85), temperature of reaction is 110 ℃ again, reaction times 2h, underpressure distillation, makes lignin modification resol.96 ℃ of softening temperatures, trickling degree 4.3cm, polymerization velocity 63s, free phenol content 3.7%.
Embodiment 4
A certain amount of phenol, enzymolysis xylogen (phenol quality 10%) and Catalyzed by Oxalic Acid agent (phenol quality 7%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, be cooled to 70 ℃, adding formaldehyde (phenolic aldehyde mol ratio is 1:0.85), temperature of reaction is 120 ℃ again, reaction times 2h, underpressure distillation, makes lignin modification resol.98.5 ℃ of softening temperatures, trickling degree 4.0cm, polymerization velocity 60s, free phenol content 3.8%.
Embodiment 5
A certain amount of phenol, enzymolysis xylogen (phenol quality 33%) and Catalyzed by Oxalic Acid agent (phenol quality 3%) are added in reactor, 155 ℃ of temperature of reaction, reaction times 2h, be cooled to 70 ℃, adding formaldehyde (phenolic aldehyde mol ratio is 1:0.85), temperature of reaction is 100 ℃ again, reaction times 2h, underpressure distillation, makes lignin modification resol.95 ℃ of softening temperatures, trickling degree 4.1cm, polymerization velocity 62s, free phenol content 3.7%.
Embodiment 6
A certain amount of phenol, enzymolysis xylogen (phenol quality 25%) and Catalyzed by Oxalic Acid agent (phenol quality 5%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, be cooled to 70 ℃, adding formaldehyde (phenolic aldehyde mol ratio is 1:0.85), temperature of reaction is 120 ℃ again, reaction times 2h, first normal pressure pressurizes and sloughs moisture and residue phenol, makes lignin modification resol.94 ℃ of softening temperatures, trickling degree 5.1cm, polymerization velocity 69s, free phenol content 4.2%.
Embodiment 7
A certain amount of phenol, enzymolysis xylogen (phenol quality 50%) and Catalyzed by Oxalic Acid agent (phenol quality 5%) are added in reactor, 135 ℃ of temperature of reaction, reaction times 2h, be cooled to 70 ℃, adding formaldehyde (phenolic aldehyde mol ratio is 1:0.85), temperature of reaction is 115 ℃ again, reaction times 2h, first normal pressure pressurizes and sloughs moisture and residue phenol, makes lignin modification resol.105 ℃ of softening temperatures, trickling degree 3.8cm, polymerization velocity 89s, free phenol content 3.1%.
Note: the national standard of each index reference
The mensuration of HG/T 2753-1996 resol mobile distance on sheet glass
HG 5-1338-80 resol polymerization velocity experimental technique
GB/T 8146-2003 Test methods of rosin (softening temperature).
Claims (6)
1. the preparation method for the lignin modification resol of moulding compound, it is characterized in that, prepare by the following method: phenol, acid catalyst and xylogen are mixed, be heated to 90 ℃-160 ℃, reaction 1-3h, be cooled to 70 ℃, again formaldehyde is added drop-wise in reaction system, is heated to 90 ℃-120 ℃ reaction 2-4h, underpressure distillation, make lignin modification resol, 90 ℃-105 ℃ of softening temperatures; Wherein, acid catalyst used is oxalic acid.
2. the preparation method of the lignin modification resol for moulding compound according to claim 1, is characterized in that: xylogen used is for preparing bio-ethanol or biological butanol by product enzymolysis xylogen.
3. the preparation method of the lignin modification resol for moulding compound according to claim 1, is characterized in that: acid catalyst is the 1-7% of phenol quality.
4. the preparation method of the lignin modification resol for moulding compound according to claim 1, is characterized in that: the mass ratio of xylogen and phenol is 10-50:100.
5. the preparation method of the lignin modification resol for moulding compound according to claim 1, is characterized in that: described phenol and the mol ratio of formaldehyde are 1:0.81-0.87.
6. the preparation method of the lignin modification resol for moulding compound according to claim 1, is characterized in that: formaldehyde used is that mass percent concentration is the formaldehyde of 37-40%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817667A (en) * | 2015-05-07 | 2015-08-05 | 江苏乾翔新材料科技有限公司 | Process of making phenolic foam with calcium lignosulphonate |
| CN106380887A (en) * | 2016-09-27 | 2017-02-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-base phenolic aldehyde molding compound |
| CN110802700A (en) * | 2019-11-04 | 2020-02-18 | 南京林业大学 | Preparation method of impregnated smoked carbonized wood |
| CN110914341A (en) * | 2017-08-10 | 2020-03-24 | 出光兴产株式会社 | Method for producing modified lignin, and resin composition material containing modified lignin |
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| RU1786042C (en) * | 1990-10-30 | 1993-01-07 | Братский Индустриальный Институт | Method of modified phenolformaldehyde resin production |
| 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 |
| WO2013072047A1 (en) * | 2011-11-18 | 2013-05-23 | Momentive Specialty Chemicals Gmbh | Foam material on the basis on phenolic resin |
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| RU1786042C (en) * | 1990-10-30 | 1993-01-07 | Братский Индустриальный Институт | Method of modified phenolformaldehyde resin production |
| 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 |
| WO2013072047A1 (en) * | 2011-11-18 | 2013-05-23 | Momentive Specialty Chemicals Gmbh | Foam material on the basis on phenolic resin |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817667A (en) * | 2015-05-07 | 2015-08-05 | 江苏乾翔新材料科技有限公司 | Process of making phenolic foam with calcium lignosulphonate |
| CN106380887A (en) * | 2016-09-27 | 2017-02-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of lignin-base phenolic aldehyde molding compound |
| CN110914341A (en) * | 2017-08-10 | 2020-03-24 | 出光兴产株式会社 | Method for producing modified lignin, and resin composition material containing modified lignin |
| US11505655B2 (en) | 2017-08-10 | 2022-11-22 | Idemitsu Kosan Co., Ltd. | Modified lignin manufacturing method, modified lignin, and modified lignin-including resin composition material |
| CN110914341B (en) * | 2017-08-10 | 2023-02-21 | 出光兴产株式会社 | Method for producing modified lignin, and resin composition material containing modified lignin |
| CN110802700A (en) * | 2019-11-04 | 2020-02-18 | 南京林业大学 | Preparation method of impregnated smoked carbonized wood |
| CN110802700B (en) * | 2019-11-04 | 2021-04-06 | 南京林业大学 | Preparation method of impregnated smoked carbonized wood |
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Application publication date: 20140205 |