CN104193994A - Flame-retardant heat-resistant bismaleimide resin and preparation method thereof - Google Patents
Flame-retardant heat-resistant bismaleimide resin and preparation method thereof Download PDFInfo
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- CN104193994A CN104193994A CN201410435130.8A CN201410435130A CN104193994A CN 104193994 A CN104193994 A CN 104193994A CN 201410435130 A CN201410435130 A CN 201410435130A CN 104193994 A CN104193994 A CN 104193994A
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Abstract
The invention discloses flame-retardant heat-resistant bismaleimide resin and a preparation method thereof, belonging to the technical field of high performance thermosetting resin. According to the technical scheme, the flame-retardant heat-resistant bismaleimide resin is prepared from the following raw materials in parts by weight: 5-20 parts of phenylphosphonic dichloride, 21-52 parts of 1-amino-5-naphthol and 10-40 parts of maleic anhydride. The bismaleimide resin has a good molding technology and a cured product has high heat resistance and excellent flame retardance; the glass-transition temperature of the cured product reaches 370 DEG C, and the limit oxygen index reaches 48; benzyl di(5-amino) naphthoxy phosphonic acid is prepared by reaction between phenylphosphonic dichloride and excessive 1-amino-5-naphthol, and prepared benzyl di(5-amino) naphthoxy phosphonic acid is reacted with maleic anhydride to obtain the flame-retardant heat-resistant bismaleimide resin. The flame-retardant heat-resistant bismaleimide resin and the preparation method disclosed by the invention have the beneficial effects that the reaction is stable, the process condition is easy to control, unreacted raw materials can be recycled, and no three wastes are generated, so that the flame-retardant heat-resistant bismaleimide resin and the preparation method are suitable for industrialized production.
Description
Technical field
The present invention relates to bismaleimides and synthetic preparation field thereof, particularly a kind of flame-proof heat-resistant type bimaleimide resin and preparation method thereof.
Background technology
Bismaleimides (BMI) is the resinoid system being derived from by polyimide resin system, is to take the bifunctional compound that maleimide (MI) is active end group.Its resin use temperature is between epoxy resin and polyimide, bimaleimide resin base composite material has good high temperature resistant, radiation hardness, wet-heat resisting, good features such as manufacturability, is mainly used in the matrices of composite material in the fields such as aerospace, mechano-electronic, communications and transportation.
Under universal bimaleimide resin normal temperature, be generally solid, and solidification value is high, the time is long, flame retardant properties is general.For further improving the flame retardant properties of bimaleimide resin, carried out a large amount of research and developments both at home and abroad: by adding mineral filler, the flame retardant properties of mixing the raising bimaleimide resin that halogen system or phosphorus flame retardant can be to a certain degree.Yet, by the approach of outer addition, unavoidably can encounter the technical problem that additive and resin exist dispersed and consistency, these class methods often have to sacrifice bimaleimide resin processing characteristics, mechanical property is cost.In other words, when keeping original bimaleimide resin processing characteristics, dielectric properties, resistance toheat and mechanical property, the technical barrier of solution is needed in this field nowadays of effectively giving good flame retardant properties and be badly.
Using rigid radical as molecular resin skeleton main body, organophosphorus element is distributed in the middle of molecular backbone chain by chemical bonding, be expected to when improving bimaleimide resin patience, the synergistic effect by phosphorus-nitrogen element promotes its flame retardant properties.Therefore, by Molecular Structure Design and the modification of science, how by large-scale rigid group and organophosphorus structure assembly in molecular backbone chain, effectively comprehensive both constructional feature, heat-resisting flame-retardant bimaleimide resin and preparation method thereof the tool that obtains a kind of brand new is of great significance and using value.
Summary of the invention
The object of this invention is to provide a kind of heat-resisting, brand new bimaleimide resin that flame retardant properties is excellent, and a kind of step is simple, raw materials cost is low, without " three wastes ", the adjustable preparation method of viscosity.
To achieve these goals, the present invention adopts following technical scheme: a kind of flame-proof heat-resistant type bimaleimide resin, comprises the main raw material of following weight part:
Title component
Phenyl two chlorethoxyfos 5-20 parts
1-amino-5-naphthols 21-52 part
Maleic anhydride 10-40 part
Diallyl bisphenol 0-15 part
Further, it has following host molecule structure:
Further, described diallyl bisphenol is selected 4,4'-(1-methyl ethylidene) two [2-(2-propenyl)] phenol.
Further, the preparation method of described a kind of flame-proof heat-resistant type bimaleimide resin, comprises the following steps:
1, by 5-20 weight part phenyl two chlorethoxyfos, 21-52 weight part 1-amino-5-naphthols, hybrid reaction in 50-100 parts by weight solvent, 80 ℃-120 ℃ of temperature of reaction, reaction times 2-6h, reaction finishes the rear desolvation of cooling and unreacting material, obtains phenyl two (5-is amino) naphthyloxy oxygen phosphorus; Its reactive chemistry equation:
2, under inert atmosphere protection; by 20-35 weight part phenyl two (5-is amino) naphthyloxy oxygen phosphorus; 10-40 weight part maleic anhydride; 15-40 weight part solubility promoter; 0.5-3 weight part phase-transfer catalyst mixes; under 40 ℃ of-60 ℃ of conditions, react 4-6h; after reaction finishes; add 0-15 weight part diallyl bisphenol; 0-0.5 weight part radical initiator; stir 0.5-1h, underpressure distillation, except desolventizing, obtains the heat-resisting flame-retardant bimaleimide resin based on phenyl two (5-is amino) naphthyloxy oxygen phosphorus structure.
Further, described solvent is at least one in toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK).
Further, described solubility promoter is at least one in acetone, tetrahydrofuran (THF), methylene dichloride.
Further, described phase-transfer catalyst is selected at least one in benzyltrimethylammonium bromide, ethyl triphenyl brometo de amonio, ethyltriphenylphosphonium bromide.
Further, described initiator is selected at least one in peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, dicumyl peroxide.
The present invention has following beneficial effect: a kind of flame-proof heat-resistant type bimaleimide resin involved in the present invention, the contained naphthalene nucleus of molecular backbone chain structure, phenylphosphine oxide are rich in the two keys of aromatic nucleus planar conjugate, local arrangements is regular and be easy to pile up, can suppress sub-chain motion, there is good resistance toheat, organophosphorus atom is uniformly distributed in molecular skeleton simultaneously, with the contained nitrogen element of maleimide amine structure, forms the flame retardant properties that phosphorus-nitrogen synergistic effect promotes resin effectively.
The preparation method of a kind of flame-proof heat-resistant type bimaleimide resin involved in the present invention, adopts phenyl two chlorethoxyfos, 1-amino-5-naphthols, and maleic anhydride is main raw material, with low cost; In preparation feedback process, excessive 1-amino-5-naphthols raw material and solvent can reclaim again and react, and without carrying out separation of by-products, without " three wastes ", produce, and are applicable to suitability for industrialized production.
A kind of flame-proof heat-resistant type bimaleimide resin that the inventive method is prepared, viscosity can be low to moderate 0.5Pa.s at 90 ℃, and complete processing window is wide, has wide range of applications.The prepared resin solidification casting matrix of above-mentioned bimaleimide resin second-order transition temperature reaches more than 370 ℃, has good resistance toheat, and limiting oxygen index(LOI) 48 reaches UL94 V-0 level flame-retardant standard.
Embodiment
Embodiment 1:
In being equipped with the four-hole boiling flask of mechanical stirring, thermometer, reflux condensing tube and nitrogen gatherer, 250 mL add 32g 1-amino-5-naphthols and 90 g acetone, slow rising oil bath temperature to 80 ℃, after 1-amino-5-naphthols dissolves completely, 15 g phenyl two chlorethoxyfos are added drop-wise in reaction system, 0.5h is reinforced to be finished, temperature of reaction is controlled at 110 ℃, continues reaction 4h.Reaction finishes rear thickening filtration and removes unreacted 1-amino-5-naphthols, and 80 ℃ of deionized waters are washed 5 times, and underpressure distillation, except desolventizing and excessive moisture, obtains brown thick liquid.By gained brown thick liquid product 25g, 20g maleic anhydride epoxy chloropropane, 15g acetone mixed dissolution is in the 125 ml four-hole boiling flasks with stirring, reflux exchanger and thermometer, 45 ℃ of oil bath temperatures, 0.5g ethyltriphenylphosphonium bromide methanol solution is added to (wherein the weight percent concentration of ethyltriphenylphosphonium bromide is 70%) in reaction vessel, oil bath temperature is increased to 50 ℃, continue reaction 4h, reaction finishes, after rear desolvation, with methylene dichloride recrystallization, to obtain glassy yellow solid product.
Adopt the 100g bimaleimide resin of above-mentioned preparation according to 120 ℃ of 1h, 180 ℃ of 1h, 220 ℃ of 1h, obtain resin cured matter, 381.2 ℃ of second-order transition temperatures (DMA method), limiting oxygen index(LOI) 48.0, UL94-V0 flame-retardant standard after 280 ℃ of 1h solidify.
Embodiment 2:
In being equipped with the four-hole boiling flask of mechanical stirring, thermometer, reflux condensing tube and nitrogen gatherer, 250 mL add 32g 1-amino-5-naphthols and 90 g acetone, slow rising oil bath temperature to 80 ℃, after 1-amino-5-naphthols dissolves completely, 15 g phenyl two chlorethoxyfos are added drop-wise in reaction system, 0.5h is reinforced to be finished, temperature of reaction is controlled at 110 ℃, continues reaction 4h.Reaction finishes rear thickening filtration and removes unreacted 1-amino-5-naphthols, and 80 ℃ of deionized waters are washed 5 times, and underpressure distillation, except desolventizing and excessive moisture, obtains brown thick liquid.By gained brown thick liquid product 25g, 20g maleic anhydride epoxy chloropropane, 15g acetone mixed dissolution is in stirring, in 125 ml four-hole boiling flasks of reflux exchanger and thermometer, 45 ℃ of oil bath temperatures, 0.5g ethyltriphenylphosphonium bromide methanol solution is added to (wherein the weight percent concentration of ethyltriphenylphosphonium bromide is 70%) in reaction vessel, oil bath temperature is increased to 50 ℃, continue after reaction 4h, add 12g 4, 4 '-diallyl bisphenol and the reaction of 0.2g dicumyl peroxide finish after rear desolvation, obtain amber solid product, its 90 ℃ of melting viscosities are 0.75Pa.s.
Adopt 50g bimaleimide resin fusion-cast at 90 ℃ of above-mentioned preparation, according to 120 ℃ of 1h, 180 ℃ of 1h, 220 ℃ of 1h, obtain resin cured matter, 373.7 ℃ of second-order transition temperatures (DMA method) after 280 ℃ of 1h solidify, limiting oxygen index(LOI) 45.0, UL94-V0 flame-retardant standard.
Embodiment 3:
In being equipped with the four-hole boiling flask of mechanical stirring, thermometer, reflux condensing tube and nitrogen gatherer, 2500 mL add 600 g 1-amino-5-naphthols and 350 g acetone, slow rising oil bath temperature to 80 ℃, after 1-amino-5-naphthols dissolves completely, 500 g phenyl two chlorethoxyfos are added drop-wise in reaction system, 0.5h is reinforced to be finished, temperature of reaction is controlled at 115 ℃, continues reaction 4h.Reaction finishes rear thickening filtration and removes unreacted 1-amino-5-naphthols, and 80 ℃ of deionized waters are washed 3 times, and underpressure distillation, except desolventizing and excessive moisture, obtains brown thick liquid.By gained brown thick liquid product 500g, 400 g maleic anhydride epoxy chloropropane, 300 g acetone mixed dissolutions are in stirring, in 1500 ml four-hole boiling flasks of reflux exchanger and thermometer, 45 ℃ of oil bath temperatures, 10 g ethyltriphenylphosphonium bromide methanol solutions are added to (wherein the weight percent concentration of ethyltriphenylphosphonium bromide is 70%) in reaction vessel, oil bath temperature is increased to 50 ℃, continue after reaction 4h, add 280 g 4, 4 '-diallyl bisphenol and the reaction of 5 g dicumyl peroxides finish after rear desolvation, obtain amber solid product, its 90 ℃ of melting viscosities are 0.5Pa.s.
Adopt 100 g bimaleimide resins fusion-cast at 90 ℃ of above-mentioned preparation, according to 120 ℃ of 1h, 180 ℃ of 1h, 220 ℃ of 1h, obtain resin cured matter, 371.0 ℃ of second-order transition temperatures (DMA method) after 280 ℃ of 1h solidify, limiting oxygen index(LOI) 46.0, UL94-V0 flame-retardant standard.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, other modifications that those of ordinary skills make technical scheme of the present invention or be equal to replacement, only otherwise depart from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of claim scope of the present invention.
Claims (8)
1. a flame-proof heat-resistant type bimaleimide resin, is characterized in that, comprises the main raw material of following weight part:
Title component
Phenyl two chlorethoxyfos 5-20 parts;
1-amino-5-naphthols 21-52 part;
Maleic anhydride 10-40 part;
Diallyl bisphenol 0-15 part.
2. a kind of flame-proof heat-resistant type bimaleimide resin according to claim 1, is characterized in that, it has following host molecule structure:
。
3. a kind of flame-proof heat-resistant type bimaleimide resin according to claim 1, is characterized in that, described diallyl bisphenol is selected 4,4'-(1-methyl ethylidene) two [2-(2-propenyl)] phenol.
4. the preparation method of a kind of flame-proof heat-resistant type bimaleimide resin according to claim 1 and 2, is characterized in that, its preparation method comprises the following steps:
(1) by 5-20 weight part phenyl two chlorethoxyfos, 21-52 weight part 1-amino-5-naphthols, hybrid reaction in 50-100 parts by weight solvent, 80 ℃-120 ℃ of temperature of reaction, reaction times 2-6h, reaction finishes the rear desolvation of cooling and unreacting material, obtains phenyl two (5-is amino) naphthyloxy oxygen phosphorus;
(2) under inert atmosphere protection; by 20-35 weight part phenyl two (5-is amino) naphthyloxy oxygen phosphorus; 10-40 weight part maleic anhydride; 15-40 weight part solubility promoter; 0.5-3 weight part phase-transfer catalyst mixes; under 40 ℃ of-60 ℃ of conditions, react 4-6h; after reaction finishes; add 0-15 weight part diallyl bisphenol; 0-0.5 weight part radical initiator; stir 0.5-1h, underpressure distillation, except desolventizing, obtains the heat-resisting flame-retardant bimaleimide resin based on phenyl two (5-is amino) naphthyloxy oxygen phosphorus structure.
5. the preparation method of a kind of flame-proof heat-resistant type bimaleimide resin according to claim 4, is characterized in that, described solvent is at least one in toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK).
6. the preparation method of a kind of flame-proof heat-resistant type bimaleimide resin according to claim 4, is characterized in that, described solubility promoter is at least one in acetone, tetrahydrofuran (THF), methylene dichloride.
7. the preparation method of a kind of flame-proof heat-resistant type bimaleimide resin according to claim 4, is characterized in that, described phase-transfer catalyst is selected at least one in benzyltrimethylammonium bromide, ethyl triphenyl brometo de amonio, ethyltriphenylphosphonium bromide.
8. the preparation method of a kind of flame-proof heat-resistant type bimaleimide resin according to claim 4, is characterized in that, described initiator is selected at least one in peroxidized t-butyl perbenzoate, peroxide acid tert-amyl acetate, dicumyl peroxide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530430A (en) * | 2015-01-09 | 2015-04-22 | 西北工业大学 | High-tenacity flame-retardant bismaleimide resin and preparation method thereof |
| CN108129659A (en) * | 2017-12-25 | 2018-06-08 | 山东圣泉新材料股份有限公司 | A kind of bismaleimide amine composition and preparation method thereof |
| CN113174111A (en) * | 2021-05-26 | 2021-07-27 | 蔡顺光 | Modified ABS resin with good heat resistance and flame retardance and preparation method thereof |
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| US20090182116A1 (en) * | 2008-01-15 | 2009-07-16 | National Chung Hsing University | Manufacture of phosphorus-containing diamines and their derivatives |
| CN102167825A (en) * | 2011-03-11 | 2011-08-31 | 南京航空航天大学 | Bismaleimide resin for microdiameter pultrusion process and preparation method thereof |
| CN102276836A (en) * | 2011-06-03 | 2011-12-14 | 苏州大学 | Flame retardant bimaleimide resin and preparation method thereof |
| CN103059265A (en) * | 2013-01-20 | 2013-04-24 | 安徽善孚新材料科技有限公司 | Halogen-free flame retardant epoxy resin containing naphthalene ring structure and preparation method thereof |
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2014
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Patent Citations (5)
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|---|
| WEI-JYE SHU ET AL: "Phosphonate-Containing Bismaleimide Resins. II. Preparation and Characteristics of Reactive Blends of Phosphonate-Containing Bismaleimide and Epoxy", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530430A (en) * | 2015-01-09 | 2015-04-22 | 西北工业大学 | High-tenacity flame-retardant bismaleimide resin and preparation method thereof |
| CN108129659A (en) * | 2017-12-25 | 2018-06-08 | 山东圣泉新材料股份有限公司 | A kind of bismaleimide amine composition and preparation method thereof |
| CN108129659B (en) * | 2017-12-25 | 2020-11-10 | 山东圣泉新材料股份有限公司 | Bismaleimide composition and preparation method thereof |
| CN113174111A (en) * | 2021-05-26 | 2021-07-27 | 蔡顺光 | Modified ABS resin with good heat resistance and flame retardance and preparation method thereof |
| CN113174111B (en) * | 2021-05-26 | 2022-09-02 | 广州华邦电器工业有限公司 | Modified ABS resin with good heat resistance and flame retardance and preparation method thereof |
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