CN102977298A - 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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- CN102977298A CN102977298A CN2012104924438A CN201210492443A CN102977298A CN 102977298 A CN102977298 A CN 102977298A CN 2012104924438 A CN2012104924438 A CN 2012104924438A CN 201210492443 A CN201210492443 A CN 201210492443A CN 102977298 A CN102977298 A CN 102977298A
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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 the organic high molecular compound field, be specifically related to the preparation method of polycondensate of a kind of aldehyde of modification and phenol and the product that obtains.
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 satisfy many real requirements behind the resin solidification, therefore is 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, and the exhaustion of petrochemical industry resource, pollution have promoted the development of biomass macromolecular materials.Xylogen has caused scientist's great interest very early as a kind of wide material sources, the huge natural organic high-molecular material of using value.Its significant application value on industrial production is impelled people that it has been done a large amount of research, and has been obtained successful Application.
Xylogen has been applied to the resol industry with its distinctive thermoplastic structure, has substituted the use of part phenols, has reduced cost, has improved the fragility of resol.Yet this special construction also limits the further lifting of its usage quantity, and the resol intensity of modification decreases, and water tolerance, high temperature resistant ablation, antidamping, rub resistance, anti-cutting power weaken to some extent.The performance of the modified phenolic resins of this type is still waiting to improve.
Summary of the invention
For the deficiencies in the prior art part, the purpose 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, the part that has changed single modified phenolic resins is not enough, makes its performance further perfect, cost.Resulting modified phenolic resins rub resistance, anti-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:
The preparation method of a kind of xylogen and boric acid modified resol comprises step:
1) phenol, catalyzer and boric acid are mixed reaction 2-4h;
2) in step 1) gained reaction mixture, add xylogen, under temperature 105-115 ℃, reaction 1.5-2.5h;
3) to step 2) add aldehyde in the gained reaction mixture, under temperature 100-110 ℃, 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, and the xylogen quality is the 5-50% of the quality of phenol.
Wherein, described phenol is one or more in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol, the cardanol; Preferred phenol.
Wherein, described xylogen is sulfonated lignin (sulfonated lignin), alkali lignin, acidolysis xylogen, acidolysis xylogen, high-boiling alcohol lignin etc.Xylogen is a kind of complicated phenol polymer that is 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 that extracts from plant tissue with alkali.High-boiling alcohol lignin is the xylogen that extracts from plant with the high pure method of boiling.The acidolysis such as sulfuric acid, hydrochloric acid xylogen is the acidolysis xylogen.
Wherein, described aldehyde is one or more in formaldehyde, acetaldehyde, butyraldehyde, Paraformaldehyde 96, the trioxymethylene, preferred formaldehyde.
Take reactant as formaldehyde, phenol is example, reaction scheme is suc as formula (1).
Wherein, Ligin represents various types of xylogen.
Shown in reaction scheme, this preparation method mainly contains four-step reaction: the first step, and phenol and boric acid pyroreaction generate the 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; In the 4th step, the 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 the described step 1) is one or more in formic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, the thionamic acid; Preferred oxalic acid.
Wherein, described catalyst levels is the 0.5-5% of the quality of phenol.
Wherein, described step 1) in, after mixing, phenol, catalyzer and boric acid under 95-105 ℃, reacts first 0.9-1.1h, then at 140-160 ℃ of lower reaction 1-3h.In the step 1), under reflux state, add successively phenol, catalyzer and boric acid.
Wherein, the temperature that adds xylogen described step 2) is 75-85 ℃.Be specially, step 1) gained reaction mixture is cooled to 75-85 ℃, add xylogen, then be warming up to temperature 105-115 ℃, react.
In the step 3), to step 2) add aldehyde in the gained reaction mixture after, reflux and react.
Step 3) also comprises being warming up to 130-150 ℃ after finishing, sloughs the step of moisture.After sloughing moisture, continue to heat up, vacuumize, free phenol is removed, namely obtain product.
The modified phenolic resins that preparation method of the present invention prepares.
Beneficial effect of the present invention is:
The present invention has improved the deficiency that single modification brings by two modifications of xylogen, boric acid.Introduce xylogen in the resin, 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, anti-cutting, high temperature resistance ablation, water repelling property effectively.The resin yield has improved 10 ~ 45%, greatly reduces the resin cost.
Embodiment
Following examples are used for explanation the present invention, but do not limit the scope of the invention.
Used xylogen is alkali lignin, and Shengquan Group Co. Ltd., Jinan produces.
Embodiment 1
5Kg phenol is dropped in the four-hole boiling flask (four-hole boiling flask of the 10L of customization), under stirring and the reflux state, throw successively boric acid 0.5Kg, oxalic acid 0.1Kg, be heated to 100 ℃, reaction 1h is warming up to 150 ℃ of reaction 1.5h; Be cooled to 80, throw the 1Kg xylogen, be warming up to 110 ℃ of reaction 1.5h; Be cooled to 90 ℃, dropping concentration is 37% formaldehyde 3Kg; After dropwising, be warming up to 100 ℃ of back flow reaction 2.5h.Heat up dehydration to 150 ℃, vacuumize-0.098MPa, slough free phenol, make the modified phenolic resin fat prod.
The modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 1874, and vapor phase process records free phenol 1.27, and recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 60.5%.
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 the four-hole boiling flask, under the state of stirring and backflow, throw successively boric acid 0.3Kg, oxalic acid 0.04Kg, be heated to 100 ℃ of reaction 1h, be warming up to 150 ℃ of reaction 2h; Be cooled to about 80, throw the 0.32Kg xylogen, be warming up to 110 ℃ of reaction 1h; Be cooled to 90 ℃, dropping concentration is 37% formaldehyde 1.08Kg; After dropwising, be warming up to 100 ℃ of back flow reaction 2h, heat up dehydration to 150 ℃, vacuumize-0.098MPa sloughs free phenol, make modified phenolic resins, the resin index: molecular weight (Mw) 1661, free phenol 1.03, recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 65.2%.
Embodiment 3
0.8Kg phenol is dropped in the four-hole boiling flask, under stirring and the reflux state, throw successively boric acid 0.08Kg, oxalic acid 0.024Kg, be heated to 100 ℃ of reaction 1h, be warming up to 150 ℃ of reaction 2h; Be cooled to 75 ℃, throw the 0.32Kg xylogen, be warming up to 110 ℃ of reaction 2h; Be cooled to 90 ℃, dropping concentration is 37% formaldehyde 0.432Kg; After dropwising, be warming up to 100 ℃ of back flow reaction 2.5h, the dehydration that heats up is to 150 ℃, vacuumize-0.098MPa sloughs free phenol, makes modified phenolic resins.
The modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2042, and vapor phase process records free phenol 1.75, and recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 64.5%.
Embodiment 4
3Kg phenol is dropped in the four-hole boiling flask, under the whipped state, throw successively boric acid 0.6Kg, oxalic acid 0.09Kg, be heated to 100 ℃ of reaction 1h, be warming up to 150 ℃ of reaction 2.5h; Be cooled to 85 ℃, throw the 0.9Kg xylogen, be warming up to 110 ℃ of reaction 2h; Be cooled to 90 ℃, dropping concentration is 37% formaldehyde 1.44Kg; After dropwising, be warming up to 100 ℃ of back flow reaction 2.5h, the dehydration that heats up is carried vacuum-0.098MPa and is sloughed free phenol to 150 ℃, makes modified phenolic resins.
The modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2278, and vapor phase process records free phenol 2.01, and recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 68.7%.
Embodiment 5
500g phenol is dropped in the four-hole boiling flask, under the state of stirring and backflow, throw boric acid 25g, oxalic acid 20g, be heated to 100 ℃ of reaction 1h, be warming up to 150 ℃ of reaction 2h; Be cooled to about 80, throw the 225g xylogen, be warming up to 110 ℃ of reaction 2.5h; Be cooled to 90 ℃, dropping concentration is 37% formaldehyde 220g; After dropwising, be warming up to 100 ℃ of back flow reaction 2h, the dehydration that heats up is to 150 ℃, vacuumize-0.098MPa sloughs free phenol, makes modified phenolic resins.
The modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2199, and Meteorological Act records free phenol 2.33, and recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 59.1%.
Embodiment 6
300g phenol, 60g Resorcinol are dropped in the four-hole boiling flask, under the state of stirring and backflow, throw boric acid 70g, oxalic acid 7g, be heated to 100 ℃ of reaction 1h, be warming up to 150 ℃ of reaction 1.5h; Be cooled to about 80, throw the 210g xylogen, be warming up to 110 ℃ of reaction 1.5h; Be cooled to 80 ℃, add Paraformaldehyde 96 81.4g; 95 ℃ of reaction 30min are warming up to 100 ℃ of back flow reaction 2h, and the dehydration that heats up is carried vacuum-0.098MPa and sloughed free phenol to 150 ℃, makes modified phenolic resins.
The modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2706, and Meteorological Act records free phenol 1.25, and recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 70.5%.
Embodiment 7
500g phenol, 50g cresols are dropped in the four-hole boiling flask, under the state of stirring and backflow, throw boric acid 55g, tosic acid 8.5g, be heated to 100 ℃ of reaction 1h, be warming up to 150 ℃ of reaction 1.5h; Be cooled to about 80, throw the 55g xylogen, be warming up to 110 ℃ of reaction 1.5h; Be cooled to 80 ℃, add butyraldehyde 312.7g; 95 ℃ of reaction 30min are warming up to 100 ℃ of back flow reaction 1.5h, and the dehydration that heats up is carried vacuum-0.098MPa and sloughed free phenol to 150 ℃, makes modified phenolic resins.
The modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 3200, and Meteorological Act records free phenol 2.15, and recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 63.7%.
Embodiment 8
150g phenol, 40g cardanol are dropped in the four-hole boiling flask, under the state of stirring and backflow, throw boric acid 55g, phosphatase 11 .5g, be heated to 100 ℃ of reaction 1h, be warming up to 150 ℃ of reaction 1.5h; Be cooled to about 80, throw the 50g xylogen, be warming up to 110 ℃ of reaction 1.5h; Be cooled to 90 ℃, drip formaldehyde 100g; After low price is complete, be warming up to 100 ℃ of back flow reaction 1.5h, the dehydration that heats up is carried vacuum-0.098MPa and is sloughed free phenol to 150 ℃, makes modified phenolic resins.
The modified phenolic resin fat indicators: gel chromatography records molecular weight (Mw) 2285, and Meteorological Act records free phenol 1.76, and recording 800 ℃ of carbon residue rates with urotropine 2:8 mixing abrasive dust is 57.4%.
Performance test:
The resol 8% urotropine abrasive dust that is made by embodiment 1-8 is done the 405*3.2*32 section with thermosetting resin PF-2550, does 10 cutter cutting experiments with the 32mm six-edged steel, gets cutting efficiency, cutting is as follows than parameter:
By the resol 8% urotropine abrasive dust that embodiment 1-8 makes, do the 180*6*22 section with thermosetting resin PF-2550, do the 5min grinding experiment, get grinding efficiency, grinding ratio parameter such as table 1.
The performance test results of the modified resin that table 1. embodiment 1-8 makes
Can be found out that by above-mentioned experimental result the modified phenolic resins carbon residue rate that the present invention makes is higher, the slicing product intensity of doing is high, and cutting efficiency is lower, cuts higher.Therefore the resin better mechanical property that makes of the present invention, owing to added a large amount of low price xylogen, the resin cost advantage is obvious.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (10)
1. the preparation method of an xylogen and boric acid modified resol comprises step:
1) phenol, catalyzer and boric acid are mixed reaction 2-4h;
2) in step 1) gained reaction mixture, add xylogen, under temperature 105-115 ℃, reaction 1.5-2.5h;
3) to step 2) add aldehyde in the gained reaction mixture, under temperature 100-110 ℃, 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, and the xylogen quality is the 5-50% of the quality of 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, the cardanol; Preferred phenol.
4. preparation method according to claim 1 and 2 is characterized in that, described xylogen is a kind of in sulfonated lignin, alkali lignin, acidolysis xylogen, the high-boiling alcohol lignin.
5. preparation method according to claim 1 is characterized in that, described aldehyde is one or more in formaldehyde, acetaldehyde, butyraldehyde, Paraformaldehyde 96, the trioxymethylene, preferred formaldehyde.
6. according to preparation method claimed in claim 1, it is characterized in that the catalyzer in the described step 1) is one or more in formic acid, oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, tosic acid, the thionamic acid; Preferred oxalic acid.
7. according to claim 1 or 6 described preparation methods, it is characterized in that described catalyst levels is the 0.5-5% of the quality of phenol.
8. preparation method according to claim 1 is characterized in that, described step 1) in, after mixing, phenol, catalyzer and boric acid under 95-105 ℃, reacts first 0.9-1.1h, then at 140-160 ℃ of lower reaction 1-3h.
9. preparation method according to claim 1 is characterized in that, described step 2) in add xylogen temperature be 75-85 ℃.
10. the modified phenolic resins for preparing of the arbitrary described preparation method of claim 1-9.
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Cited By (5)
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| CN103522209A (en) * | 2013-10-31 | 2014-01-22 | 山东圣泉化工股份有限公司 | Resin grinding wheel |
| CN105754058A (en) * | 2016-03-04 | 2016-07-13 | 沙县宏盛塑料有限公司 | Preparation method of lignin and boron dual-modified phenolic resin and phenolic moulding plastic |
| 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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| CN101284899A (en) * | 2008-06-03 | 2008-10-15 | 吉林大学 | Lignose and process for modifying phenolic resin with derivates thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103522209A (en) * | 2013-10-31 | 2014-01-22 | 山东圣泉化工股份有限公司 | Resin grinding wheel |
| 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 |
| CN105754058A (en) * | 2016-03-04 | 2016-07-13 | 沙县宏盛塑料有限公司 | Preparation method of lignin and boron dual-modified phenolic resin and phenolic moulding plastic |
| 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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