CN103204991B - Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone - Google Patents
Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone Download PDFInfo
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- CN103204991B CN103204991B CN201310083688.XA CN201310083688A CN103204991B CN 103204991 B CN103204991 B CN 103204991B CN 201310083688 A CN201310083688 A CN 201310083688A CN 103204991 B CN103204991 B CN 103204991B
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Abstract
The invention relates to fluorenyl polyether sulfone resin with side chains containing benzoxazine and a preparation method of the fluorenyl polyether sulfone resin. The preparation method includes steps of adding 9, 9-bi (4-ammonia phenyl)-2, 7-dyhydroxyl fluorene, anhydrous potassium carbonate and dichlorophenyl sulfone into a container, then adding dimethyl sulfoxide and toluene, feeding nitrogen gas, heating to the temperature of 150-200 DEG C, reacting for 2-4 hours, steaming toluene, continuously reacting for 2-4 hours at the identical temperature, filtering after reacting, adding filtrate into water, precipitating to obtain fluorenyl polyether sulfone with side chains containing amino, adding the fluorenyl polyether sulfone with side chains containing amino, monophenol, paraformaldehyde, chloroform or dimethylbenzene into the container, heating to the temperature 60-160 DEG C, reacting by reflux for 5-24 hours, adding reactant into ethanol, and precipitating to obtain fluorenyl polyether sulfone resin with side chains containing benzoxazine. The fluorenyl polyether sulfone resin with side chains containing benzoxazine can be used independently or used with other resin and has good thermal properties and mechanical properties.
Description
Technical field
What the present invention relates to is a kind of thermoplastic resin and preparation method thereof.
Background technology
Along with the develop rapidly of the technical fields such as aerospace, communications and transportation, information transmission, the requirement of people to macromolecular material is also more and more higher.Excellent mechanical property, thermotolerance, weather resisteant and electrical insulating property etc. all become the target that people pursue.Meanwhile, people are for the research of macromolecular material also constantly towards the future development of lightweight, cost degradation, high performance and multifunction, and the key of realizing this goal needs to have been come by the performance resins of different structure.The exploitation of performance resins can be summed up as three aspects: thermotolerance, humidity resistance and obdurability, is restriction mutually between these three kinds of performances.The cross-linking density increasing cross-linked high polymer effectively can improve thermotolerance, but often causes the decline of toughness, and adds toughner while toughness improves, and thermotolerance reduces greatly.Therefore, resin modified and different structure new type resin are rapidly developed.
Benzoxazine is a kind of by phenols, the six-membered cyclic compound of the nitrogenous oxygen heteroatom that formaldehyde and amine are obtained by polycondensation.Benzoxazine colophony belongs to the one of resol, is found at first by Cope and Holy.The resin that this new development is got up not only has thermal characteristics and the mechanical property of traditional resol, also there is solidification process zero volume change, low water absorbable, high glass-transition temperature, high fixing carbon, solidification process does not need to add strong acid and makees catalyzer, and solidification process, without features such as air releases, is applied in fields such as brake-shoe for train, composite matrix resin, vacuum valve blocks.
But there is the defects such as easily crisp, the crosslinked polymericular weight obtained is less in traditional benzoxazine colophony, and polyethersulfone has good ductility as thermoplastic resin itself, therefore the two is combined, respective characteristic can be retained, can supply a gap mutually again.2011, Yagci etc. are at " Synthesis; characterization and thermally activated curing ofpolysulfones with benzoxazine end groups " [Polymer, 52,1504-1509 (2011)] synthesize bisphenol A polyether sulfone telechelic benzoxazine monomer in article, obtain polyethers sulfuryl Polybenzoxazine resin through thermofixation.Compare with traditional bisphenol A-type benzoxazine, the benzoxazine containing polyethersulfone structure improves a lot in thermal characteristics and mechanical property.
Summary of the invention
The object of this invention is to provide a kind of fluorenyl polyethersulfone resin of side chain containing benzoxazine structure with excellent thermal characteristics.The present invention also aims to the preparation method of the fluorenyl polyethersulfone resin providing a kind of side chain containing benzoxazine structure.
Side chain of the present invention has following general formula containing the fluorenyl polyethersulfone resin of benzoxazinyl group:
In formula, R is H, CH
3or OCH
3in one.
Side chain of the present invention is prepared in such a way containing the fluorenyl polyethersulfone resin of benzoxazinyl group:
The first step: add 9 in container, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes, Anhydrous potassium carbonate and dichloro diphenyl sulfone, 9, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes, the ratio of dichloro diphenyl sulfone amount of substance is 1:1.25 ~ 1.5, dichloro diphenyl sulfone and Anhydrous potassium carbonate amount of substance be 1:1, then dimethyl sulfoxide (DMSO) and toluene is added, pass into nitrogen, be warmed up to 150 ~ 200 DEG C, reaction 2 ~ 4h, steam toluene, continue to react 2 ~ 4h at such a temperature, after reaction terminates, filter, filtrate is added to the water, separate out precipitation, precipitate through washing, ethanol is washed, vacuum-drying, obtain side chain containing amino fluorenyl polyethersulfone,
Second step: the side chain the first step be obtained by reacting joins containing amino fluorenyl polyethersulfone, monohydric phenol, paraformaldehyde, chloroform or dimethylbenzene and is equipped with in container, the ratio of polyethersulfone, monohydric phenol, paraformaldehyde amount of substance is 1:10:20, be warmed up to 60 ~ 160 DEG C, back flow reaction 5 ~ 24h, after reaction terminates, reaction solution is joined in ethanol, separate out precipitation, after filtration, ethanol washes, vacuum-drying, obtains the fluorenyl polyethersulfone resin of side chain containing benzoxazinyl group.
Described monohydric phenol is the one in phenol, meta-cresol, p-cresol, meta-methoxy phenol, p methoxy phenol.
Reaction equation is as follows:
The side chain that the present invention obtains adopts infrared spectrometer (Spotlight100, PE company of the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker) containing the structural characterization of the fluorenyl polyethersulfone resin of benzoxazinyl group.Examination of infrared spectrum adopts pellet technique, Sample Scan 4 times, resolving power 4cm
-1, sweep limit 4000 ~ 500cm
-1, proton nmr spectra is mark in doing with tetramethylsilane (TMS), deuterochloroform (CDCl
3) make solvent.Polymer performance test adopts differential scanning calorimeter (DSC, TA company of the U.S.) and thermogravimetric analyzer (TGA, TA company of the U.S.), and nitrogen atmosphere, temperature rise rate is 20 DEG C/min.
The side chain that the present invention obtains both can be used alone containing the fluorenyl polyethersulfone resin of benzoxazinyl group, also can use with other mixed with resin, the product obtained has good thermal characteristics and mechanical property, can be used for manufacturing high performance structures material, macromolecule member material, electronic package material, corrosion resistant material etc.
The present invention is with 9, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes, dichloro diphenyl sulfone, monohydric phenol and paraformaldehyde are raw material, obtain the fluorenyl polyethersulfone oligomer of side chain containing benzoxazinyl group through polycondensation, Mannich condensation reaction, then obtain the polyethersulfone thermoplastic resin containing Polybenzoxazine structure through thermofixation.Owing to introducing Ke Ju He oxazine cyclic group in molecular structure, make the thermal characteristics of product, mechanical property improves a lot.
Embodiment
Side chain of the present invention containing the basic preparation method of the fluorenyl polyethersulfone resin of benzoxazinyl group is:
The first step: stirring rotator is being housed, water trap, in the there-necked flask of nitrogen inlet and prolong, add 9, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes, Anhydrous potassium carbonate and dichloro diphenyl sulfone, 9, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes, the ratio of dichloro diphenyl sulfone amount of substance is 1:1.25 ~ 1.5, dichloro diphenyl sulfone and Anhydrous potassium carbonate amount of substance be 1:1, then dimethyl sulfoxide (DMSO) (solvent) and toluene (water entrainer) is added, pass into nitrogen, be warmed up to 150 ~ 200 DEG C, reaction 2 ~ 4h, steam toluene, continue to react 2 ~ 4h at such a temperature, after reaction terminates, filter, filtrate is added to the water, separate out precipitation, precipitate through washing, ethanol is washed, vacuum-drying, obtain side chain containing amino fluorenyl polyethersulfone.
Second step: the side chain the first step be obtained by reacting joins in the there-necked flask that stirring rotator, prolong, thermometer are housed containing amino fluorenyl polyethersulfone, monohydric phenol, paraformaldehyde, chloroform or dimethylbenzene, the ratio of polyethersulfone, monohydric phenol, paraformaldehyde amount of substance is 1:10:20, be warmed up to 60 ~ 160 DEG C, back flow reaction 5 ~ 24h, after reaction terminates, reaction solution is joined in ethanol, separate out precipitation, after filtration, ethanol washes, vacuum-drying, obtains the fluorenyl polyethersulfone resin of side chain containing benzoxazinyl group.
In order to understand the present invention better, enumerate specific embodiments of the invention below:
Embodiment 1
Side chain is containing the synthesis of amino fluorenyl polyethersulfone
Stirring rotator is being housed, water trap, 9 are added in the there-necked flask of nitrogen inlet and prolong, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes 3.04g, Anhydrous potassium carbonate 1.48g and dichloro diphenyl sulfone 2.87g, add 50mL dimethyl sulfoxide (DMSO) and 20mL toluene, logical nitrogen, under agitation be warming up to 160 DEG C, react after 3 hours, water trap no longer includes moisture and takes out of, toluene is steamed, continue reaction and after 3 hours, terminate reaction, reaction solution is down to room temperature, filter, filtrate is added to the water, separate out precipitation, wash with water, ethanol is washed, last vacuum-drying 24 hours at 60 DEG C, obtain white side chain containing amino fluorenyl polyethersulfone powder 4.78g, productive rate 87%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR composes, δ=6.39 ~ 7.94ppm is the chemical shift of proton on phenyl ring, and 4.99ppm is amide proton characteristic peak.Examination of infrared spectrum result (KBr, cm
-1): 3433cm
-1and 3375cm
-1for N-H stretching vibration on primary amine, 3030cm
-1for the unsaturated C-H stretching vibration peak of phenyl ring, 2927cm
-1for saturated C-H stretching vibration peak, 1625cm
-1and 1581cm
-1for phenyl ring skeletal vibration, 1294cm
-1for O=S=O asymmetrical stretching vibration, 1236cm
-1and 1072cm
-1for C-O-C is symmetrical and asymmetrical stretching vibration, 874cm
-1for Isosorbide-5-Nitrae-two on phenyl ring replaces charateristic avsorption band, 757cm
-1for C-Cl characteristic peak, the sample synthesized by confirmation is target product.
Embodiment 2
Change 1.65g into except Anhydrous potassium carbonate and dichloro diphenyl sulfone changes 3.44g into, temperature of reaction changes 180 DEG C into, and other conditions, with embodiment 1, finally obtain white side chain containing amino fluorenyl polyethersulfone powder 4.16g, productive rate 75%.
Embodiment 3
Side chain is containing the synthesis of the fluorenyl polyethersulfone of benzoxazinyl group
Side chain 1.5g embodiment 1 synthesized joins in there-necked flask successively containing amino fluorenyl polyethersulfone, 0.94g phenol, 30mL dimethylbenzene and 0.6g paraformaldehyde, temperature rises to 150 DEG C, react 6 hours, be cooled to room temperature, reaction solution poured in ethanol, filter, filter cake washing with alcohol, vacuum-drying again, finally obtain the fluorenyl polyethersulfone powder 1.2g of faint yellow side chain containing benzoxazinyl group, yield is 60%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR composes, δ=6.77 ~ 7.81ppm is the chemical shift of proton on phenyl ring, 5.29ppm Wei oxazine ring on O-CH
2the proton characteristic peak of-N, 4.69ppm is Ar-CH
2the proton characteristic peak of-N.Examination of infrared spectrum result (KBr, cm
-1): 3030cm
-1for the unsaturated C-H stretching vibration of phenyl ring, 2934cm
-1for saturated C-H stretching vibration, 1323cm
-1cH on Wei oxazine ring
2rocking vibration peak, 1296cm
-1for O=S=O asymmetrical stretching vibration, 1229cm
-1and 1074cm
-1for C-O-C is symmetrical and asymmetrical stretching vibration, 1153cm
-1for asymmetrical stretching vibration on C-N-C, 948cm
-1for C-H out-of-plane deformation vibration, be the charateristic avsorption band of Dai You oxazine ring on phenyl ring, 859cm
-1for Isosorbide-5-Nitrae-two on phenyl ring replaces charateristic avsorption band, 756cm
-1for C-Cl charateristic avsorption band.
By the side chain that obtains containing the fluorenyl polyethersulfone of benzoxazinyl group in air dry oven according to 160 DEG C/2h, 180 DEG C/2h, 200 DEG C/2h, 220 DEG C/2h, 240 DEG C/2h, be cured, obtain the polyethersulfone thermoplastic resin (BAPDHF-1.25DCDPS-p-BPES) containing Polybenzoxazine structure, through DSC and TGA test, obtain its second-order transition temperature (being abbreviated as Tg, as follows), weightless heat decomposition temperature corresponding to 5% and 10% (is abbreviated as T
5and T
10, as follows) and 800 DEG C at carbon yield, the results are shown in Table 1.
Embodiment 4
Except raw material phenol changes meta-cresol into, consumption changes into outside 1.08g, and other conditions are with embodiment 3, and finally obtain the fluorenyl polyethersulfone powder 1.11g of faint yellow side chain containing benzoxazinyl group, yield is 59%.
Proton nmr spectra test result (500M, CDCl3, ppm): in 1H NMR composes, δ=6.60 ~ 7.86ppm is the chemical shift of proton on phenyl ring, 5.27ppm and 5.24ppm Wei oxazine ring on O-CH
2the proton characteristic peak of-N, 4.53ppm and 4.45ppm is Ar-CH
2the proton characteristic peak of-N, 2.17ppm ~ 2.52ppm belongs to the proton peak of methyl in meta-cresol structure.Examination of infrared spectrum result (KBr, cm
-1): 2934cm
-1for saturated C-H stretching vibration peak, and strengthening to some extent, is because phenyl ring exists methyl, other characteristic peaks to go out peak position identical with embodiment 3, the sample synthesized by confirmation is target product.
Solidification and test condition, with embodiment 3, obtain the performance of the polyethersulfone thermoplastic resin (BAPDHF-1.25DCDPS-m-mp-BPES) containing Polybenzoxazine structure in table 1.
Embodiment 5
Except raw material side chain contains the polyethersulfone that amino polyethersulfone changes the 2-in-1 one-tenth of embodiment into, dimethylbenzene changes chloroform into, temperature of reaction changes 70 DEG C into, reaction times changes into outside 24 hours, other conditions are with embodiment 3, finally obtain the fluorenyl polyethersulfone powder 1.01g of faint yellow side chain containing benzoxazinyl group, yield is 50%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR composes, δ=6.91 ~ 7.86ppm is the chemical shift of proton on phenyl ring, 5.30ppm and 5.29ppm Wei oxazine ring on O-CH
2the proton characteristic peak of-N, 4.58ppm and 4.57ppm is Ar-CH
2the proton characteristic peak of-N.Examination of infrared spectrum result (KBr, cm
-1): characteristic peak to go out peak position identical with embodiment 3, the sample synthesized by confirmation is target product.
Solidification and test condition, with embodiment 3, obtain the performance of the polyethersulfone thermoplastic resin (BAPDHF-1.5DCDPS-p-BPES) containing Polybenzoxazine structure in table 1.
Embodiment 6
Except raw material phenol changes meta-cresol into, consumption changes into outside 1.08g, and other conditions are with embodiment 5, and finally obtain the fluorenyl polyethersulfone powder 1.06g of faint yellow side chain containing benzoxazinyl group, yield is 51%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR composes, δ=6.60 ~ 7.86ppm is the chemical shift of proton on phenyl ring, 5.27ppm and 5.28ppm Wei oxazine ring on O-CH
2the proton characteristic peak of-N, 4.53ppm is Ar-CH
2the proton characteristic peak of-N.2.37ppm and 2.25ppm belongs to methyl proton peak.Examination of infrared spectrum result (KBr, cm
-1): 2901cm
-1for C-H stretching vibration peak, and strengthen to some extent because there is methyl in phenyl ring, other characteristic peaks to go out peak position identical with embodiment 3, the sample synthesized by confirmation is target product.
Solidification and test condition, with embodiment 3, obtain the performance of the polyethersulfone thermoplastic resin (BAPDHF-1.5DCDPS-m-mp-BPES) containing Polybenzoxazine structure in table 1.
Embodiment 7
Except changing phenol into 3-methoxyphenol, consumption changes into outside 1.24g, and other conditions are with embodiment 5, and finally obtain the fluorenyl polyethersulfone powder 0.95g of faint yellow side chain containing benzoxazinyl group, yield is 44%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR composes, δ=6.34 ~ 7.85ppm is the chemical shift of proton on phenyl ring, 5.27ppm Wei oxazine ring on O-CH
2the proton characteristic peak of-N, 4.51ppm is Ar-CH
2the proton characteristic peak of-N.3.73ppm and 3.71ppm belongs to the proton peak of methoxyl group in meta-methoxy phenol structure.Examination of infrared spectrum result (KBr, cm
-1): 1258cm
-1and 1107cm
-1for C-O-C is symmetrical and asymmetrical stretching vibration, and strengthen to some extent because there is methoxyl group in phenyl ring, other characteristic peaks to go out peak position identical with embodiment 3, the sample synthesized by confirmation is target product.
Solidification and test condition, with embodiment 3, obtain the performance of the polyethersulfone thermoplastic resin (BAPDHF-1.5DCDPS-m-mop-BPES) containing Polybenzoxazine structure in table 1.
Table 1 is containing the polyethersulfone thermoplastic resin Thermal Parameter of Polybenzoxazine structure
Claims (3)
1. side chain is containing a fluorenyl polyethersulfone resin for benzoxazinyl group, it is characterized in that having following general formula:
In formula, R is H, CH
3or OCH
3in one.
2. side chain is containing a preparation method for the fluorenyl polyethersulfone resin of benzoxazinyl group, it is characterized in that:
The first step: add 9 in container, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes, Anhydrous potassium carbonate and dichloro diphenyl sulfone, 9, two (the 4-aminophenyl)-2 of 9-, 7-dihydroxyl fluorenes, the ratio of dichloro diphenyl sulfone amount of substance is 1:1.25 ~ 1.5, dichloro diphenyl sulfone and Anhydrous potassium carbonate amount of substance be 1:1, then dimethyl sulfoxide (DMSO) and toluene is added, pass into nitrogen, be warmed up to 150 ~ 200 DEG C, reaction 2 ~ 4h, steam toluene, continue to react 2 ~ 4h at such a temperature, after reaction terminates, filter, filtrate is added to the water, separate out precipitation, precipitate through washing, ethanol is washed, vacuum-drying, obtain side chain containing amino fluorenyl polyethersulfone,
Second step: the side chain the first step be obtained by reacting joins in the there-necked flask that stirring rotator, prolong, thermometer are housed containing amino fluorenyl polyethersulfone, monohydric phenol, paraformaldehyde, chloroform or dimethylbenzene, side chain is 1:10:20 containing the ratio of amino fluorenyl polyethersulfone, monohydric phenol, paraformaldehyde amount of substance, be warmed up to 60 ~ 160 DEG C, back flow reaction 5 ~ 24h, after reaction terminates, reaction solution is joined in ethanol, separate out precipitation, after filtration, ethanol washes, vacuum-drying, obtains the fluorenyl polyethersulfone resin of side chain containing benzoxazinyl group.
3. side chain according to claim 2 is containing the preparation method of the fluorenyl polyethersulfone resin of benzoxazinyl group, it is characterized in that: described monohydric phenol is the one in phenol, meta-cresol, p-cresol, meta-methoxy phenol, p methoxy phenol.
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| 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 |
| CN110511704B (en) * | 2019-09-02 | 2021-03-23 | 吉林大学 | High-strength recyclable special plastic polymer composite adhesive, preparation method and application thereof |
| CN111187555B (en) * | 2020-03-07 | 2021-10-08 | 山东德源环氧科技有限公司 | High-temperature-resistant epoxy powder coating and preparation method thereof |
| CN116462912B (en) * | 2023-04-28 | 2024-01-05 | 江苏菱盛汽配科技有限公司 | Material for automobile exterior trim and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008051651A1 (en) * | 2006-10-24 | 2008-05-02 | Sabic Innovative Plastics Ip B.V. | Polyethersulfone compositions with high heat and good impact resistance |
| CN101367774A (en) * | 2008-09-27 | 2009-02-18 | 哈尔滨工程大学 | Fluorenyl bi-benzoxazine monomer and method of preparing the same |
| CN102634019A (en) * | 2012-04-25 | 2012-08-15 | 哈尔滨工程大学 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
| CN102660023A (en) * | 2012-04-25 | 2012-09-12 | 哈尔滨工程大学 | Mixed diamine type copolyfluorene benzoxazine prepolymer and preparation method thereof |
| CN102875807A (en) * | 2012-09-14 | 2013-01-16 | 哈尔滨工程大学 | Benzoxazine-terminated fluorenyl polyether ketone ketone thermoplastic resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008051651A1 (en) * | 2006-10-24 | 2008-05-02 | Sabic Innovative Plastics Ip B.V. | Polyethersulfone compositions with high heat and good impact resistance |
| CN101367774A (en) * | 2008-09-27 | 2009-02-18 | 哈尔滨工程大学 | Fluorenyl bi-benzoxazine monomer and method of preparing the same |
| CN102634019A (en) * | 2012-04-25 | 2012-08-15 | 哈尔滨工程大学 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
| CN102660023A (en) * | 2012-04-25 | 2012-09-12 | 哈尔滨工程大学 | Mixed diamine type copolyfluorene benzoxazine prepolymer and preparation method thereof |
| CN102875807A (en) * | 2012-09-14 | 2013-01-16 | 哈尔滨工程大学 | Benzoxazine-terminated fluorenyl polyether ketone ketone thermoplastic resin and preparation method thereof |
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