CN103360557B - A kind of modified phenolic resins - Google Patents
A kind of modified phenolic resins Download PDFInfo
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- CN103360557B CN103360557B CN201310317417.6A CN201310317417A CN103360557B CN 103360557 B CN103360557 B CN 103360557B CN 201310317417 A CN201310317417 A CN 201310317417A CN 103360557 B CN103360557 B CN 103360557B
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- aldehyde
- phenolic resins
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- phenolic compound
- polyimide
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Abstract
The invention discloses a kind of modified phenolic resins, it is primarily of made by following component: phenolic compound, aldehyde and polyimide.The mol ratio of described phenolic compound and aldehyde is (1.2-1.7): 1.0, and described polyimide quality is 0.5-1 times of phenolic compound and aldehyde total mass.The present invention is relative to prior art, and the modified phenolic resins of gained, its thermotolerance and toughness improve all greatly, thus can be adapted to the needs of the high-technology fields such as automobile, electronics, Aeronautics and Astronautics and national defense industry.
Description
Technical field
The present invention relates to a kind of resin, be specifically related to a kind of modified phenolic resins, be widely used in the high-technology fields such as automobile, electronics, Aeronautics and Astronautics and national defense industry energy.
Background technology
Resol realizes industrialized synthetic resins the earliest in the world, so far the history of existing last 100 years.Because its raw material is easy to get, cheap, production technique and equipment simple, and product has excellent mechanicalness, thermotolerance, winter hardiness, electrical insulating property, dimensional stability, molding processibility, flame retardant resistance and smokiness, therefore it has become the indispensable material of industrial sector, and tool has been widely used.
But the weak link on phenolic resin structure is that phenolic hydroxyl group and methylene radical are easily oxidized, and thermotolerance is affected.And conventional unmodified resol fragility is large, poor toughness, limits the exploitation of high performance material to a great extent.In a lot of situation, the toughness of resol and the raising of thermotolerance are difficult to and deposit.Therefore, be the needs adapting to the high-technology fields such as automobile, electronics, Aeronautics and Astronautics and national defense industry, modification is carried out to resol, improve the developing direction that its toughness and thermotolerance are resol.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides a kind of modified phenolic resins.
Technical scheme: for achieving the above object, a kind of modified phenolic resins provided by the invention, it is primarily of made by following component: phenolic compound, aldehyde and polyimide, the mol ratio of described phenolic compound and aldehyde is (1.2-1.7): 1.0, and described polyimide quality is 0.5-1 times of phenolic compound and aldehyde total mass.
Preferably, described modified phenolic resins is primarily of made by following component: phenolic compound, aldehyde and polyimide, the mol ratio of described phenolic compound and aldehyde is (1.4-1.6): 1.0, and described polyimide quality is 0.6-0.8 times of phenolic compound and aldehyde total mass.
Preferably, described phenolic compound is selected from the one in phenol, cresylol, Resorcinol, bis-phenol, Phloroglucinol, alkylphenol, phenol ether and naphthols.
Preferably, described aldehyde is selected from the one in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, propenal, hexanaphthene two acetal, phenyl aldehyde, furfural, aryl aldehyde and heterocyclic aldehydes.
Preferably, described polyimide is bismaleimides.
The preparation method of above-mentioned modified phenolic resins, its preparation comprises the steps:
(1) take phenolic compound and aldehyde, drop in reaction vessel, stirring and evenly mixing, is heated to 70-100 DEG C.
(2) add catalyzer, stir, insulation reaction 2-7 hour.
(3) in the product of step (2) gained, polyimide is added, stirring and evenly mixing.
(4) 80-100 DEG C is adjusted the temperature to, insulation reaction 2-3 hour.
(5) be heated to 130-140 DEG C of dehydration 0.5-1 hour, cool to less than 50 DEG C, to obtain final product.
Beneficial effect: the present invention is relative to prior art, and the modified phenolic resins of gained, thermotolerance and toughness improve all greatly, can adapt to the needs of the high-technology fields such as automobile, electronics, Aeronautics and Astronautics and national defense industry.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1:
Modified phenolic resins prescription: the mol ratio of phenol and formaldehyde is 1.5:1.0, bismaleimides quality is 0.7 times of phenol and formaldehyde total mass.
The preparation method of above-mentioned modified phenolic resins, its preparation comprises the steps:
(1) take feed composition by prescription proportioning, phenol and formaldehyde are dropped in reactor, after both stirring and evenly mixings, is heated to 80 DEG C.
(2) add catalyzer, and constantly stir, insulation reaction 5 hours.
(3) in the product of step (2) gained, the bismaleimides of prescription amount is added, limit edged stirring and evenly mixing.
(4) 80 DEG C are adjusted the temperature to, insulation reaction 2 hours.
(5) be heated to 130 DEG C and carry out dehydration 0.5 hour, cool to less than 50 DEG C, to obtain final product.
Modified phenolic resins shock strength obtained in the present embodiment is 12.6kJ/m
2, maximum decomposition temperature is 467 DEG C, common resol of comparing, and shock strength and maximum decomposition temperature improve all greatly.
Embodiment 2:
Modified phenolic resins prescription: the mol ratio of cresylol and butyraldehyde is 1.2:1.0, bismaleimides quality is 0.5 times of cresylol and butyraldehyde total mass.
The preparation method of above-mentioned modified phenolic resins, its preparation comprises the steps:
(1) take feed composition by prescription proportioning, cresylol and butyraldehyde are dropped in reactor, after both stirring and evenly mixings, is heated to 70 DEG C.
(2) add catalyzer, and constantly stir, insulation reaction 3 hours.
(3) in the product of step (2) gained, the bismaleimides of prescription amount is added, limit edged stirring and evenly mixing.
(4) 80 DEG C are adjusted the temperature to, insulation reaction 3 hours.
(5) be heated to 140 DEG C and carry out dehydration 1 hour, cool to less than 50 DEG C, to obtain final product.
Modified phenolic resins shock strength obtained in the present embodiment is 12.2kJ/m
2, maximum decomposition temperature is 462 DEG C, common resol of comparing, and shock strength and maximum decomposition temperature improve all greatly.
Embodiment 3:
Modified phenolic resins prescription: the mol ratio of bis-phenol and propenal is 1.7:1.0, bismaleimides quality is 1 times of bis-phenol and propenal total mass.
The preparation method of above-mentioned modified phenolic resins, its preparation comprises the steps:
(1) take feed composition by prescription proportioning, bis-phenol and propenal are dropped in reactor, after both stirring and evenly mixings, is heated to 100 DEG C.
(2) add catalyzer, and constantly stir, insulation reaction 7 hours.
(3) in the product of step (2) gained, the bismaleimides of prescription amount is added, limit edged stirring and evenly mixing.
(4) 80 DEG C are adjusted the temperature to, insulation reaction 2 hours.
(5) be heated to 130 DEG C and carry out dehydration 0.8 hour, cool to less than 50 DEG C, to obtain final product.
Modified phenolic resins shock strength obtained in the present embodiment is 12.9kJ/m
2, maximum decomposition temperature is 460 DEG C, common resol of comparing, and shock strength and maximum decomposition temperature improve all greatly.
Embodiment 4:
Modified phenolic resins prescription: the mol ratio of Resorcinol and formaldehyde is 1.4:1.0, bismaleimides quality is 0.6 times of Resorcinol and formaldehyde total mass.
The preparation method of above-mentioned modified phenolic resins, its preparation comprises the steps:
(1) take feed composition by prescription proportioning, Resorcinol and formaldehyde are dropped in reactor, after both stirring and evenly mixings, is heated to 90 DEG C.
(2) add catalyzer, and constantly stir, insulation reaction 4 hours.
(3) in the product of step (2) gained, the bismaleimides of prescription amount is added, limit edged stirring and evenly mixing.
(4) 85 DEG C are adjusted the temperature to, insulation reaction 2.5 hours.
(5) be heated to 135 DEG C and carry out dehydration 1 hour, cool to less than 50 DEG C, to obtain final product.
Modified phenolic resins shock strength obtained in the present embodiment is 11.8kJ/m
2, maximum decomposition temperature is 463 DEG C, common resol of comparing, and shock strength and maximum decomposition temperature improve all greatly.
Embodiment 5:
Modified phenolic resins prescription: the mol ratio of phenol and butyraldehyde is 1.6:1.0, bismaleimides quality is 0.8 times of phenol and butyraldehyde total mass.
The preparation method of above-mentioned modified phenolic resins, its preparation comprises the steps:
(1) take feed composition by prescription proportioning, phenol and butyraldehyde are dropped in reactor, after both stirring and evenly mixings, is heated to 95 DEG C.
(2) add catalyzer, and constantly stir, insulation reaction 6 hours.
(3) in the product of step (2) gained, the bismaleimides of prescription amount is added, limit edged stirring and evenly mixing.
(4) 90 DEG C are adjusted the temperature to, insulation reaction 2 hours.
(5) be heated to 140 DEG C and carry out dehydration 0.5 hour, cool to less than 50 DEG C, to obtain final product.
Modified phenolic resins shock strength obtained in the present embodiment is 12.9kJ/m
2, maximum decomposition temperature is 458 DEG C, common resol of comparing, and shock strength and maximum decomposition temperature improve all greatly.
The above is only the preferred embodiment of the present invention; be noted 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 (4)
1. a modified phenolic resins, it is characterized in that, it is primarily of made by following component: phenolic compound, aldehyde and polyimide, the mol ratio of described phenolic compound and aldehyde is (1.2-1.7): 1.0, and described polyimide quality is 0.6-0.8 times of phenolic compound and aldehyde total mass;
The preparation method of described modified phenolic resins is as follows:
(1) take phenolic compound and aldehyde, drop in reaction vessel, stirring and evenly mixing, is heated to 70-100 DEG C;
(2) add catalyzer, stir, insulation reaction 2-7 hour;
(3) in the product of step (2) gained, polyimide is added, stirring and evenly mixing;
(4) 80-100 DEG C is adjusted the temperature to, insulation reaction 2-3 hour;
(5) be heated to 130-140 DEG C of dehydration 0.5-1 hour, cool to less than 50 DEG C, to obtain final product.
2. a kind of modified phenolic resins according to claim 1, is characterized in that, it is primarily of made by following component: phenolic compound, aldehyde and polyimide, the mol ratio of described phenolic compound and aldehyde is (1.4-1.6): 1.0.
3. a kind of modified phenolic resins according to claim 1, is characterized in that: described phenolic compound is selected from the one in phenol, cresylol, Resorcinol, bis-phenol, Phloroglucinol, phenol ether and naphthols.
4. a kind of modified phenolic resins according to claim 1, is characterized in that: described aldehyde is selected from the one in formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, propenal, phenyl aldehyde and furfural.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310317417.6A CN103360557B (en) | 2013-07-25 | 2013-07-25 | A kind of modified phenolic resins |
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| CN201310317417.6A CN103360557B (en) | 2013-07-25 | 2013-07-25 | A kind of modified phenolic resins |
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| CN103360557A CN103360557A (en) | 2013-10-23 |
| CN103360557B true CN103360557B (en) | 2015-11-11 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104655A (en) * | 2006-07-10 | 2008-01-16 | 中国科学院化学研究所 | Heat convertible resin composition and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101104655A (en) * | 2006-07-10 | 2008-01-16 | 中国科学院化学研究所 | Heat convertible resin composition and its preparing process |
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