CN102977298B - Lignin and boronic acid modified phenolic resin and method for preparing same - Google Patents
Lignin and boronic acid modified phenolic resin and method for preparing same Download PDFInfo
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- CN102977298B CN102977298B CN201210492443.8A CN201210492443A CN102977298B CN 102977298 B CN102977298 B CN 102977298B CN 201210492443 A CN201210492443 A CN 201210492443A CN 102977298 B CN102977298 B CN 102977298B
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Abstract
The invention provides a method for preparing lignin and boronic acid modified phenolic resin, comprising the following steps of: (1) mixing phenol, a catalyst and boric acid, and enabling the materials to react for 2-4 hours; (2) adding lignin to the reaction mixture obtained in the step (1), and enabling the lignin and the reaction mixture to react at 105-115 DEG C for 1.5-2.5 hours; and (3) adding aldehyde into the reaction mixture obtained in the step (2), and enabling the aldehyde and the reaction mixture to be subjected to condensation reaction at 100-110 DEG C for 2-3 hours. According to the method, due to the double modification by the lignin and the boronic acid, the defect caused by single modification is overcome. The lignin is introduced into the resin, thus the brittleness of phenolic resin is effectively improved, and the degradation period of the phenolic resin is shortened. In addition, due to the introduction of the boron element, rub resistance, cutting resistance, high-temperature ablation resistance and water resistance of the lignin modified resin are improved greatly. The yield of the resin is improved by 10-45%, and the cost of the resin is reduced greatly.
Description
Technical field
The invention belongs to organic high molecular compound field, be specifically related to the preparation method of a kind of aldehyde of modification and the polycondensate of phenol and the product obtaining.
Background technology
Resin by phenolic compound and aldehyde compound polycondensation gained belongs to resol.Resol is synthetic conveniently, raw material is easy to get, and can meet many real requirements after resin solidification, is therefore used widely industrial.But the weak points such as solidification value is higher, fragility is larger, poor electrical performance that resol also has, therefore, various modified phenolic resinss arise at the historic moment.
Wood Adhesives from Biomass is the important directions of international bio matter industry development, the exhaustion of petrochemical industry resource, the development that pollution has promoted biomass macromolecular materials.Xylogen, as a kind of wide material sources, the huge natural organic high-molecular material of using value, has caused scientist's great interest very early.Its significant application value in industrial production, impels people to do a large amount of research to it, and has obtained successful Application.
Xylogen has been applied to resol industry with its distinctive thermoplastic structure, has substituted the use of part phenols, has reduced cost, has improved the fragility of resol.But this special construction also limits the further lifting of its usage quantity, the resol intensity of modification decreases, and water tolerance, high temperature resistant ablation, antidamping, rub resistance, resistance to cutting power weaken to some extent.The performance of the modified phenolic resins of this type need to improve.
Summary of the invention
For the deficiencies in the prior art part, the object of this invention is to provide the preparation method of a kind of xylogen and boric acid modified resol.Dual modified by xylogen, boric acid, has changed the part deficiency of single modified phenolic resins, makes its performance further perfect, cost.The modified phenolic resins rub resistance obtaining, resistance to cutting, high temperature resistant ablation, antidamping, water tolerance significantly improve.
Another object of the present invention is to propose the modified phenolic resins that described preparation method obtains.
The concrete technical scheme that realizes above-mentioned purpose of the present invention is:
A preparation method for xylogen and boric acid modified resol, comprises step:
1) phenol, catalyzer and boric acid are mixed to reaction 2-4h;
2) in step 1) gained reaction mixture, add xylogen, at temperature 105-115 DEG C, reaction 1.5-2.5h;
3) to step 2) add aldehyde in gained reaction mixture, at temperature 100-110 DEG C, carry out the condensation reaction of 2-3h.
Wherein, the molar ratio that described phenol, boric acid and aldehyde add is 1:0.05-0.35:0.5-0.85, the 5-50% of the quality that xylogen quality is phenol.
Wherein, described phenol is one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, cardanol; Preferably phenol.
Wherein, described xylogen is sulfonated lignin (sulfonated lignin), alkali lignin, acidolysis xylogen, acidolysis xylogen, high-boiling alcohol lignin etc.Xylogen is the complicated phenol polymer of one being formed by four kinds of alcohol monomers (to tonquinol, lubanol, 5-hydroxyl lubanol, sinapyl alcohol).Wherein, sulfonated lignin claims again sulfonated lignin, is the byproduct of sulphite process papermaking wood pulp, is linear polymer.Alkali lignin is the xylogen extracting from plant tissue with alkali.High-boiling alcohol lignin is the xylogen extracting from plant by the high alcohol method of boiling.The acidolysis such as sulfuric acid, hydrochloric acid xylogen is acidolysis xylogen.
Wherein, described aldehyde is one or more in formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde, trioxymethylene, preferably formaldehyde.
Taking reactant as formaldehyde, phenol is example, reaction scheme is suc as formula (1).
Wherein, Ligin represents various types of xylogen.
As shown in reaction scheme, this preparation method mainly contains four-step reaction: the first step, and phenol and boric acid pyroreaction generate boric acid phenol ester; Second step, the boric acid phenol ester of phenol or generation is combined with xylogen; The 3rd step, the intermediate of generation or unreacted phenol and formaldehyde addition reaction; The 4th step, rising system temperature, is condensed into the linear phenolic resin of macromolecule;
Lignin phenol contains many active function groups, can react separately with phenol.
Wherein, the catalyzer in described step 1) is one or more in formic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, thionamic acid; Preferably oxalic acid.
The 0.5-5% of the quality that wherein, described catalyst levels is phenol.
Wherein, described step 1) in, after mixing, phenol, catalyzer and boric acid first at 95-105 DEG C, reacts 0.9-1.1h, then at 140-160 DEG C, react 1-3h.In step 1), under reflux state, add successively phenol, catalyzer and boric acid.
Wherein, described step 2) in to add the temperature of xylogen be 75-85 DEG C.Be specially, step 1) gained reaction mixture is cooled to 75-85 DEG C, add xylogen, be then warming up to temperature 105-115 DEG C, react.
In step 3), to step 2) add after aldehyde in gained reaction mixture, reflux and react.
After step 3) finishes, also comprise and be warming up to 130-150 DEG C, slough the step of moisture.Slough after moisture, continue to heat up, vacuumize, free phenol is removed, obtain product.
The modified phenolic resins that preparation method of the present invention prepares.
Beneficial effect of the present invention is:
The present invention, by two modifications of xylogen, boric acid, has improved the deficiency that single modification brings.In resin, introduce xylogen, effectively improved the fragility of resol, shortened the degradation cycle of common resol.In addition, the introducing of boron, has improved the rub resistance of modified lignin resin, resistance to cutting, high temperature resistance ablation, water repelling property effectively.Resin yield has improved 10 ~ 45%, greatly reduces resin cost.
Embodiment
Following examples are used for illustrating the present invention, but do not limit the scope of the invention.
Xylogen used is alkali lignin, and Shengquan Group Co. Ltd., Jinan produces.
Embodiment 1
5Kg phenol is dropped in four-hole boiling flask (four-hole boiling flask of the 10L of customization), under stirring and reflux state, throw successively boric acid 0.5Kg, oxalic acid 0.1Kg, be heated to 100 DEG C, reaction 1h, is warming up to 150 DEG C of reaction 1.5h; Be cooled to 80, throw 1Kg xylogen, be warming up to 110 DEG C of reaction 1.5h; Be cooled to 90 DEG C, the formaldehyde 3Kg that dropping concentration is 37%; After dropwising, be warming up to 100 DEG C of back flow reaction 2.5h.Heat up dehydration to 150 DEG C, vacuumize-0.098MPa, slough free phenol, make modified phenolic resin fat prod.
Modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 1874, and vapor phase process records free phenol 1.27, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 60.5%.
The present embodiment is proceeded from the reality, Lay Importance on Practical, and many factors considers, and selecting phenol, formaldehyde is raw material.This product can be used for resin wheel, takes into account cost and performance, and its excellent performance and raw materials cost are cheap.
Embodiment 2
2Kg phenol is dropped in four-hole boiling flask, stirs and the state that refluxes under, throw successively boric acid 0.3Kg, oxalic acid 0.04Kg, be heated to 100 DEG C and react 1h, be warming up to 150 DEG C and react 2h; Be cooled to 80 left and right, throw 0.32Kg xylogen, be warming up to 110 DEG C of reaction 1h; Be cooled to 90 DEG C, the formaldehyde 1.08Kg that dropping concentration is 37%; After dropwising, be warming up to 100 DEG C of back flow reaction 2h, heat up dehydration to 150 DEG C, vacuumize-0.098MPa sloughs free phenol, make modified phenolic resins, resin index: molecular weight (Mw) 1661, free phenol 1.03, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 65.2%.
Embodiment 3
0.8Kg phenol is dropped in four-hole boiling flask, under stirring reflux state, throw successively boric acid 0.08Kg, oxalic acid 0.024Kg, be heated to 100 DEG C of reaction 1h, be warming up to 150 DEG C of reaction 2h; Be cooled to 75 DEG C, throw 0.32Kg xylogen, be warming up to 110 DEG C of reaction 2h; Be cooled to 90 DEG C, the formaldehyde 0.432Kg that dropping concentration is 37%; After dropwising, be warming up to 100 DEG C of back flow reaction 2.5h, the dehydration that heats up is to 150 DEG C, and vacuumize-0.098MPa sloughs free phenol, makes modified phenolic resins.
Modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2042, and vapor phase process records free phenol 1.75, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 64.5%.
Embodiment 4
3Kg phenol is dropped in four-hole boiling flask, under whipped state, throw successively boric acid 0.6Kg, oxalic acid 0.09Kg, be heated to 100 DEG C of reaction 1h, be warming up to 150 DEG C of reaction 2.5h; Be cooled to 85 DEG C, throw 0.9Kg xylogen, be warming up to 110 DEG C of reaction 2h; Be cooled to 90 DEG C, the formaldehyde 1.44Kg that dropping concentration is 37%; After dropwising, be warming up to 100 DEG C of back flow reaction 2.5h, the dehydration that heats up, to 150 DEG C, is carried vacuum-0.098MPa and is sloughed free phenol, makes modified phenolic resins.
Modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2278, and vapor phase process records free phenol 2.01, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 68.7%.
Embodiment 5
500g phenol is dropped in four-hole boiling flask, stirs and the state that refluxes under, throw boric acid 25g, oxalic acid 20g, be heated to 100 DEG C and react 1h, be warming up to 150 DEG C and react 2h; Be cooled to 80 left and right, throw 225g xylogen, be warming up to 110 DEG C of reaction 2.5h; Be cooled to 90 DEG C, the formaldehyde 220g that dropping concentration is 37%; After dropwising, be warming up to 100 DEG C of back flow reaction 2h, the dehydration that heats up is to 150 DEG C, and vacuumize-0.098MPa sloughs free phenol, makes modified phenolic resins.
Modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2199, and Meteorological Act records free phenol 2.33, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 59.1%.
Embodiment 6
300g phenol, 60g Resorcinol are dropped in four-hole boiling flask, stirs and the state that refluxes under, throw boric acid 70g, oxalic acid 7g, be heated to 100 DEG C and react 1h, be warming up to 150 DEG C and react 1.5h; Be cooled to 80 left and right, throw 210g xylogen, be warming up to 110 DEG C of reaction 1.5h; Be cooled to 80 DEG C, add paraformaldehyde 81.4g; 95 DEG C of reaction 30min, are warming up to 100 DEG C of back flow reaction 2h, and the dehydration that heats up, to 150 DEG C, is carried vacuum-0.098MPa and sloughed free phenol, makes modified phenolic resins.
Modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2706, and Meteorological Act records free phenol 1.25, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 70.5%.
Embodiment 7
500g phenol, 50g cresols are dropped in four-hole boiling flask, stirs and the state that refluxes under, throw boric acid 55g, tosic acid 8.5g, be heated to 100 DEG C and react 1h, be warming up to 150 DEG C and react 1.5h; Be cooled to 80 left and right, throw 55g xylogen, be warming up to 110 DEG C of reaction 1.5h; Be cooled to 80 DEG C, add butyraldehyde 312.7g; 95 DEG C of reaction 30min, are warming up to 100 DEG C of back flow reaction 1.5h, and the dehydration that heats up, to 150 DEG C, is carried vacuum-0.098MPa and sloughed free phenol, makes modified phenolic resins.
Modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 3200, and Meteorological Act records free phenol 2.15, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 63.7%.
Embodiment 8
150g phenol, 40g cardanol are dropped in four-hole boiling flask, stirs and the state that refluxes under, throw boric acid 55g, phosphatase 11 .5g, be heated to 100 DEG C and react 1h, be warming up to 150 DEG C and react 1.5h; Be cooled to 80 left and right, throw 50g xylogen, be warming up to 110 DEG C of reaction 1.5h; Be cooled to 90 DEG C, drip formaldehyde 100g; At a low price, be warming up to 100 DEG C of back flow reaction 1.5h, the dehydration that heats up, to 150 DEG C, is carried vacuum-0.098MPa and is sloughed free phenol, makes modified phenolic resins.
Modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2285, and Meteorological Act records free phenol 1.76, recording 800 DEG C of carbon residue rates with urotropine 2:8 mixing abrasive dust is 57.4%.
Performance test:
The resol 8% urotropine abrasive dust being made by embodiment 1-8, does 405*3.2*32 section with thermosetting resin PF-2550, does 10 cutter cutting experiments with 32mm six-edged steel, obtains cutting efficiency, cutting is as follows than parameter:
The resol 8% urotropine abrasive dust being made by embodiment 1-8, does 180*6*22 section with thermosetting resin PF-2550, does 5min grinding experiment, obtains grinding efficiency, grinding ratio parameter as table 1.
The performance test results of the modified resin that table 1. embodiment 1-8 makes
Can be found out by above-mentioned experimental result, the modified phenolic resins carbon residue rate that the present invention makes is higher, and the slicing product intensity of doing is high, and cutting efficiency is lower, cuts higher.Therefore the resin better mechanical property that the present invention makes, owing to having added a large amount of low price xylogen, resin cost advantage is obvious.
Below be only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (13)
1. a preparation method for xylogen and boric acid modified resol, comprises step:
1) phenol, catalyzer and boric acid are mixed to reaction 2-4h;
2) in step 1) gained reaction mixture, add xylogen, at temperature 105-115 DEG C, reaction 1.5-2.5h;
3) to step 2) add aldehyde in gained reaction mixture, at temperature 100-110 DEG C, carry out the condensation reaction of 2-3h.
2. preparation method according to claim 1, is characterized in that, the molar ratio that described phenol, boric acid and aldehyde add is 1:0.05-0.35:0.5-0.85, the 5-50% of the quality that xylogen quality is phenol.
3. preparation method according to claim 1 and 2, is characterized in that, described phenol is one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, cardanol.
4. preparation method according to claim 3, is characterized in that, described phenol is phenol.
5. preparation method according to claim 1 and 2, is characterized in that, described xylogen is the one in sulfonated lignin, alkali lignin, acidolysis xylogen, high-boiling alcohol lignin.
6. preparation method according to claim 1, is characterized in that, described aldehyde is one or more in formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde, trioxymethylene.
7. preparation method according to claim 6, is characterized in that, described aldehyde is formaldehyde.
8. preparation method according to claim 1, is characterized in that, the catalyzer in described step 1) is one or more in formic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, thionamic acid.
9. preparation method according to claim 8, is characterized in that, the catalyzer in described step 1) is oxalic acid.
10. according to the preparation method described in claim 1 or 6, it is characterized in that the 0.5-5% of the quality that described catalyst levels is phenol.
11. preparation methods according to claim 1, is characterized in that, described step 1) in, after mixing, phenol, catalyzer and boric acid first at 95-105 DEG C, reacts 0.9-1.1h, then at 140-160 DEG C, react 1-3h.
12. preparation methods according to claim 1, is characterized in that, described step 2) in to add the temperature of xylogen be 75-85 DEG C.
The modified phenolic resins that the arbitrary described preparation method of 13. claim 1-12 prepares.
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| CN103522209B (en) * | 2013-10-31 | 2016-07-27 | 山东圣泉新材料股份有限公司 | A kind of resin wheel |
| CN105754058B (en) * | 2016-03-04 | 2018-07-10 | 沙县宏盛塑料有限公司 | The preparation method of lignin and the dual modified phenolic resin of boron and phenolaldehyde moulding compound |
| CN107082859A (en) * | 2017-05-12 | 2017-08-22 | 浙江杭摩合成材料股份有限公司 | A kind of preparation method of the heat resistance modified phenolic resin of toughness reinforcing |
| CN107793698A (en) * | 2017-11-21 | 2018-03-13 | 南宁可煜能源科技有限公司 | A kind of flat-plate solar collector insulation material and preparation method thereof |
| CN108675801A (en) * | 2018-06-17 | 2018-10-19 | 刘玉清 | A kind of polymer ceramic liquefacient and preparation method thereof |
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| CN101284899A (en) * | 2008-06-03 | 2008-10-15 | 吉林大学 | Lignose and process for modifying phenolic resin with derivates thereof |
| CN101492522A (en) * | 2009-02-27 | 2009-07-29 | 中国林业科学研究院林产化学工业研究所 | Method of preparing alkali lignin modified phenolic resin |
| CN102010683A (en) * | 2010-10-27 | 2011-04-13 | 安徽格义清洁能源技术有限公司 | Method for controlling lignin-phenolic resin adhesive reaction end point |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284899A (en) * | 2008-06-03 | 2008-10-15 | 吉林大学 | Lignose and process for modifying phenolic resin with derivates thereof |
| CN101492522A (en) * | 2009-02-27 | 2009-07-29 | 中国林业科学研究院林产化学工业研究所 | Method of preparing alkali lignin modified phenolic resin |
| CN102010683A (en) * | 2010-10-27 | 2011-04-13 | 安徽格义清洁能源技术有限公司 | Method for controlling lignin-phenolic resin adhesive reaction end point |
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