CN101429172A - Fluorenyl di-benzoxazine monomer and method of preparing the same - Google Patents
Fluorenyl di-benzoxazine monomer and method of preparing the same Download PDFInfo
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- CN101429172A CN101429172A CNA2008102096380A CN200810209638A CN101429172A CN 101429172 A CN101429172 A CN 101429172A CN A2008102096380 A CNA2008102096380 A CN A2008102096380A CN 200810209638 A CN200810209638 A CN 200810209638A CN 101429172 A CN101429172 A CN 101429172A
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Abstract
The invention provides a flourenyl dibenzoxazine monomer and a preparation method thereof. Diamine fluorine is used as a raw material, and reacts with salicylic aldehyde to synthesize the flourenyl dibenzoxazine monomer through reduction and ring formation. The preparation method comprises the following steps: dissolving the diamine fluorine in amide solvent, dripping the salicylic aldehyde into the amide solvent within 1 to 3 hours at a temperature of between 15 and 35 DEG C, and making the mixture react for 2 to 5 hours to obtain an intermediate product 1 through filtering, water washing and drying; dissolving the intermediate product 1 in a mixture of ethanol and tetrahydro furan, and making the intermediate product react with borohydride reducer for 8 to 12 hours at a temperature of between 15 and 35 DEG C to obtain an intermediate product 2 through water washing, filtering and drying; and making the intermediate product 2 and formaldehyde react for 4 to 8 hours, heating the mixture to between 50 and 80 DEG C and making the mixture react continuously for 8 to 12 hours, and distilling the mixture and removing halohydrocarbon solvent to obtain the target product of flourenyl dibenzoxazine through water washing, filtering and drying. The flourenyl dibenzoxazine obtained by the method has favorable thermal stability and humidity resisting property.
Description
(1) technical field
What the present invention relates to is a kind of organic high molecular compound, the invention still further relates to a kind of preparation method of organic high molecular compound.Relate in particular to a kind of fluorenyl bi-benzoxazine monomer and preparation method thereof.
(2) background technology
Benzoxazine is a kind of novel phenolic resins monomer.It is to be the intermediate that raw material synthetic one class contains heterocycle structure with phenolic compound, aldehydes and aminated compounds, under heating and/or catalyst action ring-opening polymerization takes place, and generates the reticulation of nitrogenous similar resol, i.e. benzoxazine colophony.Benzoxazine colophony had both kept good thermotolerance of traditional resol and flame retardant resistance, also had some special performances: do not discharge as there is small molecules in the forming and hardening process; The goods porosity is low, shrinks near zero; The physical strength aspect, all on phenolic aldehyde, Resins, epoxy, stress is little, does not have tiny crack for the performance of aspects such as tensile modulus, tensile strength, elongation at break; The electrical property aspect, the benzoxazine colophony specific inductivity is very little with wavelength change, is almost constant; Water-intake rate is much smaller than Resins, epoxy and resol.Therefore, benzoxazine can be used as the body material of preparation matrix material, can also utilize active group and other resin reactions on its molecule, carries out various modifications.Benzoxazine colophony after the modification has more excellent comprehensive performances, has been widely used in fields such as electronics, aviations.
Since people such as Holly have reported to find benzoxazine compound in synthetic Mannich reaction product, all carried out correlative study both at home and abroad in succession.Miscellaneous phenol source, amine source provide greater flexibility for the molecular designing of modified benzoxazine.At paper " progress of novel phenolic resins---benzoxazine colophony " (" polymer material science and engineering " 2004 03 phase 2-5 pages or leaves) progress of benzoxazine monomer and resin thereof has been done special introduction to sea and Gu Yi.In paper " progress of high-performance benzoxazine colophony " (" insulating material " 2006 4 a phase 5-9 page or leaf) literary composition, introduced the Progress in Modification of high-performance benzoxazine colophony with people such as inferior jasmines.It is the phenol source with the bisphenol fluorene that people such as Wang Jun have introduced a kind of in Chinese patent " fluorenyl bi-benzoxazine monomer and preparation method thereof " (application number 200810137211.4), by carrying out the synthetic fluorenyl bi-benzoxazine monomer of annulation with formaldehyde and primary amine, the product structure that this method obtains is that the oxazine ring directly links to each other with bisphenol fluorene.
(3) summary of the invention
The object of the present invention is to provide a kind of the have good thermostability and the fluorenyl bi-benzoxazine monomer of wet-hot aging performance.The present invention also aims to provide a kind of preparation method of fluorenyl bi-benzoxazine monomer.
The object of the present invention is achieved like this:
Fluorenyl bi-benzoxazine monomer of the present invention has following structure:
In the formula, R and R
1Be respectively H, CH
3Or C
2H
5
The preparation method of fluorenyl bi-benzoxazine monomer is:
The first step: in reaction vessel, the diamine fluorenes is dissolved in the amide solvent, the concentration of diamine fluorenes is 100～200g/L, in 1～3 hour, drip salicylaldhyde under 15～35 ℃ of nitrogen protection conditions, the mol ratio of diamine fluorenes and salicylaldhyde is 1:1～1.2, continues stirring reaction 2～5 hours under this temperature, after reaction finishes, after filtration, washing, drying, intermediate product 1;
Second step: intermediate product 1 is dissolved in the mixture of ethanol that volume ratio is 1:1 and tetrahydrofuran (THF), strength of solution is 20～50g/L, add hydroborate down at 15～35 ℃, the mol ratio of hydroborate and intermediate product 1 is 4～6:1, under this temperature, continued stirring reaction 8～12 hours, through washing, filtration, drying, get intermediate product 2.
The 3rd step: intermediate product 2 is dissolved in the halohydrocarbon, concentration is 70～120g/L, the adding massfraction is 37% formaldehyde solution, the mol ratio of formaldehyde and intermediate product 2 is 2～3:1,15～35 ℃ of following stirring reactions 4～8 hours, be warming up to 50～80 ℃ and continue reaction 8～12 hours, halohydrocarbon is removed in distillation, through washing, filtration, drying, obtain the target product fluorenyl bi-benzoxazine.
The preparation method of fluorenyl bi-benzoxazine monomer of the present invention can also comprise:
1, described amide solvent is N, dinethylformamide or N,N-dimethylacetamide.
2, described diamine fluorenes is 9,9-pair-(4-amine phenyl) fluorenes, 9, and 9-pair-(3-methyl-4-amine phenyl) fluorenes, 9,9-pair-(3-ethyl-4-amine phenyl) fluorenes or 9,9-pair-(3,5-dimethyl-4-amine phenyl) fluorenes.
3, described hydroborate is sodium borohydride or POTASSIUM BOROHYDRIDE.
4, described halohydrocarbon is trichloromethane, tetracol phenixin, 1,1-ethylene dichloride or 1,2-ethylene dichloride.
The present invention adopts the diamine fluorenes as the amine source, by three-step reaction the benzoxazine ring is connected on the diamine fluorenes.The novel benzoxazine colophony of synthetic of the present invention is because fluorene structured introducing can improve the molecule chain rigidity, the second-order transition temperature of resin is improved, because of the nonpolar enhancing of molecule, reduced the water-absorbent of resin, thereby the wet-hot aging performance of this resin is greatly improved again.
(4) embodiment
For example the present invention is done in more detail below and describes:
Embodiment one:
Fluorenyl bi-benzoxazine monomer is made according to following three-step reaction:
The first step: in the reaction vessel that agitator, condenser, thermometer are housed; the diamine fluorenes is dissolved in the amide solvent; the concentration of diamine fluorenes is 100～200g/L; in 1～3 hour, drip salicylaldhyde under 15～35 ℃ of nitrogen protection conditions; the mol ratio of diamine fluorenes and salicylaldhyde is 1:1～1.2, continues stirring reaction 2～5 hours under this temperature, after reaction finishes; after filtration, washing, drying, intermediate product 1.
Second step: intermediate product 1 is dissolved in the complex solvent, strength of solution is 20～50g/L, complex solvent is the mixture of ethanol and tetrahydrofuran (THF), both volume ratios are 1:1, add borane reducing agent hydride down at 15～35 ℃, the mol ratio of hydroborate and intermediate product 1 is 4～6:1, continues stirring reaction 8～12 hours under this temperature, through washing, filtration, drying, get intermediate product 2.
The 3rd step: intermediate product 2 is dissolved in the halohydrocarbon, concentration is 70～120g/L, add 37% (massfraction) formaldehyde solution, the mol ratio of formaldehyde and intermediate product 2 is 2～3:1,15～35 ℃ of following stirring reactions 4～8 hours, be warming up to 50～80 ℃ and continue reaction 8～12 hours, halohydrocarbon is removed in distillation, through washing, filtration, drying, obtain the target product fluorenyl bi-benzoxazine.
Wherein: amide solvent is N, dinethylformamide or N,N-dimethylacetamide.
Raw material diamine fluorenes is 9,9-pair-(4-amine phenyl) fluorenes, 9, and 9-pair-(3-methyl-4-amine phenyl) fluorenes, 9,9-pair-(3-ethyl-4-amine phenyl) fluorenes or 9,9-pair-(3,5-dimethyl-4-amine phenyl) fluorenes.
Reductive agent is sodium borohydride or POTASSIUM BOROHYDRIDE.
Halohydrocarbon is trichloromethane, tetracol phenixin, 1,1-ethylene dichloride or 1,2-ethylene dichloride.
Embodiment two:
The first step: in the 250mL there-necked flask of agitator, prolong, thermometer is housed; add 20mL and be dissolved with 3.48g 9; the N of 9-pair-(4-amine phenyl) fluorenes; dinethylformamide, nitrogen protection slowly drip 2.45g salicylaldhyde, stirring reaction 3h under the normal temperature down; after reaction finishes; after filtration, washing, drying, glassy yellow intermediate product 1, product 1 yield reaches 86.0%.
Second step: in the 250mL there-necked flask of agitator, prolong, thermometer is housed, add the complex solvent solution 90mL that contains 2.8g intermediate product 1, the volume ratio of ethanol and tetrahydrofuran (THF) is 1:1 in the complex solvent, and normal temperature adds 0.9g sodium borohydride, stirring reaction 10h down.After reaction finishes, through stirring washing, filtration, washing, drying, get yellow intermediate product 2, product yield reaches 75.2%.
The 3rd step: in the 250mL there-necked flask of agitator, prolong, thermometer is housed, adding 15mL is dissolved with the chloroform soln of 1.36g intermediate product 2, slowly drip 0.5g 37% (massfraction) formaldehyde solution, behind the stirring reaction 6h, be warming up to 60 ℃ of reaction 9h under the normal temperature.Reaction removes organic solvent under reduced pressure after finishing, and through washing, filtration, drying, gets faint yellow benzoxazine, is final product, and yield reaches 89.3%.
Embodiment three:
The first step: in the 250mL there-necked flask of agitator, prolong, thermometer is housed; add 40mL and be dissolved with 6.96g 9; the N of 9-pair-(3-methyl-4-amine phenyl) fluorenes; N-dimethylacetamide solution, nitrogen protection slowly drip 4.89g salicylaldhyde, stirring reaction 4h under the normal temperature down; after reaction finishes; after filtration, washing, drying, glassy yellow intermediate product 1, product 1 yield reaches 92.0%.
Second step: in the 250mL there-necked flask of agitator, prolong, thermometer is housed, add the complex solvent solution 90mL that contains 2.8g intermediate product 1, the volume ratio of ethanol and tetrahydrofuran (THF) is 1:1 in the complex solvent, and normal temperature adds 2.6g sodium borohydride, stirring reaction 10h down.After reaction finishes, through stirring washing, filtration, washing, drying, get yellow intermediate product 2, product yield reaches 78.2%.
The 3rd step: in the 250mL there-necked flask of agitator, prolong, thermometer is housed, add 10mL and be dissolved with 1 of 1.36g intermediate product 2, the 2-dichloroethane solution slowly drips 0.5g 37% (massfraction) formaldehyde solution, behind the stirring reaction 6h, be warming up to 75 ℃ of reaction 9h under the normal temperature.Reaction removes organic solvent under reduced pressure after finishing, and through washing, filtration, drying, gets faint yellow benzoxazine, is final product, and yield reaches 93.1%.
Claims (10)
1, a kind of fluorenyl bi-benzoxazine monomer is characterized in that: its structural formula is
In the formula, R and R
1Be respectively H, CH
3Or C
2H
5
2, a kind of preparation method of fluorenyl bi-benzoxazine monomer of the structural formula with claim 1 is characterized in that:
The first step: in reaction vessel, the diamine fluorenes is dissolved in the amide solvent, the concentration of diamine fluorenes is 100～200g/L, in 1～3 hour, drip salicylaldhyde under 15～35 ℃ of nitrogen protection conditions, the mol ratio of diamine fluorenes and salicylaldhyde is 1:1～1.2, continues stirring reaction 2～5 hours under this temperature, after reaction finishes, after filtration, washing, drying, intermediate product 1;
Second step: intermediate product 1 is dissolved in the mixture of ethanol that volume ratio is 1:1 and tetrahydrofuran (THF), strength of solution is 20～50g/L, add hydroborate down at 15～35 ℃, the mol ratio of hydroborate and intermediate product 1 is 4～6:1, under this temperature, continued stirring reaction 8～12 hours, through washing, filtration, drying, get intermediate product 2.
The 3rd step: intermediate product 2 is dissolved in the halohydrocarbon, concentration is 70～120g/L, the adding massfraction is 37% formaldehyde solution, the mol ratio of formaldehyde and intermediate product 2 is 2～3:1,15～35 ℃ of following stirring reactions 4～8 hours, be warming up to 50～80 ℃ and continue reaction 8～12 hours, halohydrocarbon is removed in distillation, through washing, filtration, drying, obtain the target product fluorenyl bi-benzoxazine.
3, the preparation method of fluorenyl bi-benzoxazine monomer according to claim 2 is characterized in that: described amide solvent is N, dinethylformamide or N,N-dimethylacetamide.
4, according to the preparation method of claim 2 or 3 described fluorenyl bi-benzoxazine monomers, it is characterized in that: described diamine fluorenes is 9,9-pair-(4-amine phenyl) fluorenes, 9,9-pair-(3-methyl-4-amine phenyl) fluorenes, 9,9-pair-(3-ethyl-4-amine phenyl) fluorenes or 9,9-pair-(3,5-dimethyl-4-amine phenyl) fluorenes.
5, according to the preparation method of claim 2 or 3 described fluorenyl bi-benzoxazine monomers, it is characterized in that: described hydroborate is sodium borohydride or POTASSIUM BOROHYDRIDE.
6, the preparation method of fluorenyl bi-benzoxazine monomer according to claim 4 is characterized in that: described hydroborate is sodium borohydride or POTASSIUM BOROHYDRIDE.
7, according to the preparation method of claim 2 or 3 described fluorenyl bi-benzoxazine monomers, it is characterized in that: described halohydrocarbon is trichloromethane, tetracol phenixin, 1,1-ethylene dichloride or 1,2-ethylene dichloride.
8, the preparation method of fluorenyl bi-benzoxazine monomer according to claim 4 is characterized in that: described halohydrocarbon is trichloromethane, tetracol phenixin, 1,1-ethylene dichloride or 1,2-ethylene dichloride.
9, the preparation method of fluorenyl bi-benzoxazine monomer according to claim 5 is characterized in that: described halohydrocarbon is trichloromethane, tetracol phenixin, 1,1-ethylene dichloride or 1,2-ethylene dichloride.
10, the preparation method of fluorenyl bi-benzoxazine monomer according to claim 6 is characterized in that: described halohydrocarbon is trichloromethane, tetracol phenixin, 1,1-ethylene dichloride or 1,2-ethylene dichloride.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921242A (en) * | 2010-08-23 | 2010-12-22 | 中科院广州化学有限公司 | Fluorenyl benzoxazine and preparation method thereof |
| CN102702129A (en) * | 2012-06-13 | 2012-10-03 | 哈尔滨工程大学 | Ester-group-containing diamine type fluorenyl benzoxazine |
| CN102702128A (en) * | 2012-06-13 | 2012-10-03 | 哈尔滨工程大学 | Ether bond-containing diamine flourenyl benzoxazine |
| CN102863619A (en) * | 2012-09-18 | 2013-01-09 | 哈尔滨工程大学 | Benzoxazine-terminated copolymer fluorenylpolyethersulfone thermoplastic resin and preparation method thereof |
| CN103304558A (en) * | 2013-06-05 | 2013-09-18 | 哈尔滨工程大学 | Spirofluorene xanthene benzoxazine containing benzoyloxy group and preparation method thereof |
| CN103896867A (en) * | 2014-03-21 | 2014-07-02 | 哈尔滨工程大学 | N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof |
| CN103936764A (en) * | 2014-03-21 | 2014-07-23 | 哈尔滨工程大学 | N-semi aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof |
| CN103936765A (en) * | 2014-03-21 | 2014-07-23 | 哈尔滨工程大学 | N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof |
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2008
- 2008-12-08 CN CNA2008102096380A patent/CN101429172A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921242A (en) * | 2010-08-23 | 2010-12-22 | 中科院广州化学有限公司 | Fluorenyl benzoxazine and preparation method thereof |
| CN102702128B (en) * | 2012-06-13 | 2014-06-25 | 哈尔滨工程大学 | Ether bond-containing diamine flourenyl benzoxazine |
| CN102702129A (en) * | 2012-06-13 | 2012-10-03 | 哈尔滨工程大学 | Ester-group-containing diamine type fluorenyl benzoxazine |
| CN102702128A (en) * | 2012-06-13 | 2012-10-03 | 哈尔滨工程大学 | Ether bond-containing diamine flourenyl benzoxazine |
| CN102702129B (en) * | 2012-06-13 | 2014-10-22 | 哈尔滨工程大学 | Ester-group-containing diamine type fluorenyl benzoxazine |
| CN102863619A (en) * | 2012-09-18 | 2013-01-09 | 哈尔滨工程大学 | Benzoxazine-terminated copolymer fluorenylpolyethersulfone thermoplastic resin and preparation method thereof |
| CN102863619B (en) * | 2012-09-18 | 2016-06-29 | 哈尔滨工程大学 | Benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin and preparation method thereof |
| CN103304558A (en) * | 2013-06-05 | 2013-09-18 | 哈尔滨工程大学 | Spirofluorene xanthene benzoxazine containing benzoyloxy group and preparation method thereof |
| CN103304558B (en) * | 2013-06-05 | 2016-01-27 | 哈尔滨工程大学 | Containing benzoyloxy spiral shell fluorenes oxa-anthryl benzoxazine and preparation method |
| CN103896867A (en) * | 2014-03-21 | 2014-07-02 | 哈尔滨工程大学 | N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof |
| CN103936764A (en) * | 2014-03-21 | 2014-07-23 | 哈尔滨工程大学 | N-semi aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof |
| CN103936765A (en) * | 2014-03-21 | 2014-07-23 | 哈尔滨工程大学 | N-full aromatic hydrocarbyl bisphenol-diamine tetrafunctional fluorene-based benzoxazine and preparation method thereof |
| CN103936765B (en) * | 2014-03-21 | 2015-12-09 | 哈尔滨工程大学 | The full aryl radical bis-phenol of N--diamine type four functionality fluorenyl benzoxazine and preparation method thereof |
| CN103896867B (en) * | 2014-03-21 | 2016-01-27 | 哈尔滨工程大学 | N-full aryl radical diamine-bisphenol type four functionality fluorenyl benzoxazine and preparation method thereof |
| CN103936764B (en) * | 2014-03-21 | 2016-05-04 | 哈尔滨工程大学 | N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof |
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Open date: 20090513 |