CN103204991A - 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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- CN103204991A CN103204991A CN201310083688XA CN201310083688A CN103204991A CN 103204991 A CN103204991 A CN 103204991A CN 201310083688X A CN201310083688X A CN 201310083688XA CN 201310083688 A CN201310083688 A CN 201310083688A CN 103204991 A CN103204991 A CN 103204991A
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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 technical fields such as aerospace, communications and transportation, information transmission, people are also more and more higher to the requirement of macromolecular material.Good mechanical property, thermotolerance, weather resisteant and electrical insulating property etc. all become the target that people pursue.Meanwhile, people are also developed in the direction towards lightweight, cost degradation, high performance and multifunction constantly for the research of macromolecular material, and the key of realizing this goal need be finished by the performance resins of different structure.The exploitation of performance resins can be summed up as three aspects: thermotolerance, humidity resistance and obdurability are mutual restriction between these three kinds of performances.The cross-linking density that increases cross-linked high polymer can effectively improve thermotolerance, but tends to cause the decline of toughness, and adds toughner when 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 obtain by polycondensation.Benzoxazine colophony belongs to a kind of of resol, is found by Cope and Holy at first.The resin that this new development is got up not only has thermal characteristics and the mechanical property of traditional resol, also having the solidification process zero volume changes, low water absorbable, high glass-transition temperature, high carbon yield, solidification process need not add strong acid and make catalyzer, and solidification process does not have characteristics such as gas release, is applied in fields such as train brake shoe, composite matrix resin, vacuum valve blocks.
Yet there are easily defectives such as crisp, the crosslinked polymericular weight that obtains is less in traditional benzoxazine colophony, and polyethersulfone has good ductility as thermoplastic resin itself, therefore the two is combined, can keep characteristic separately, can supply a gap mutually again.2011, Yagci etc. are at " Synthesis; characterization and thermally activated curing of polysulfones with benzoxazine end groups " [Polymer, 52,1504-1509 (2011)] synthesized bisphenol A polyether sulfone telechelic benzoxazine monomer in the article, obtained polyethers sulfuryl Polybenzoxazine resin through thermofixation.Compare with traditional bisphenol A-type benzoxazine, the benzoxazine that contains the polyethersulfone structure improves a lot in thermal characteristics and mechanical property.
Summary of the invention
The purpose of this invention is to provide the fluorenyl polyethersulfone resin that a kind of side chain with good thermal characteristics contains benzoxazine structure.The present invention also aims to provide the preparation method of the fluorenyl polyethersulfone resin that a kind of side chain contains benzoxazine structure.
The fluorenyl polyethersulfone resin that side chain of the present invention contains benzoxazinyl group has following general formula:
In the formula, R is H, CH
3Or OCH
3In a kind of.
The fluorenyl polyethersulfone resin that side chain of the present invention contains benzoxazinyl group prepares in such a way:
The first step: in container, add 9, two (the 4-aminophenyls)-2 of 9-, 7-dihydroxyl fluorenes, Anhydrous potassium carbonate and dichloro diphenyl sulfone, 9, two (the 4-aminophenyls)-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, add dimethyl sulfoxide (DMSO) and toluene then, feed nitrogen, be warmed up to 150～200 ℃, reaction 2～4h steams toluene, continuation is reacted 2～4h under this temperature, after reaction finishes, filter, filtrate is added to the water, separate out precipitation, precipitation is through washing, ethanol is washed, and vacuum-drying obtains side chain and contains amino fluorenyl polyethersulfone;
Second step: the side chain that the first step reaction is obtained contains amino fluorenyl polyethersulfone, monohydric phenol, Paraformaldehyde 96, chloroform or dimethylbenzene and joins and be equipped with in the container, the ratio of polyethersulfone, monohydric phenol, Paraformaldehyde 96 amount of substance is 1:10:20, be warmed up to 60～160 ℃, back flow reaction 5～24h, reaction joins reaction solution in the ethanol after finishing, and separates out precipitation, after filtration, ethanol washes, vacuum-drying, obtains the fluorenyl polyethersulfone resin that side chain contains benzoxazinyl group.
Described monohydric phenol is a kind of in phenol, meta-cresol, p-cresol, meta-methoxy phenol, the p methoxy phenol.
Reaction equation is as follows:
The structural characterization that the side chain that the present invention obtains contains the fluorenyl polyethersulfone resin of benzoxazinyl group adopts infrared spectrometer (Spotlight100, U.S. PE company) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker).Examination of infrared spectrum adopts pellet technique, sample scanning 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.Differential scanning calorimeter (DSC, U.S. TA company) and thermogravimetric analyzer (TGA, U.S. TA company) are adopted in the polymer performance test, and nitrogen atmosphere, temperature rise rate are 20 ℃/min.
The fluorenyl polyethersulfone resin that the side chain that the present invention obtains contains benzoxazinyl group both can use separately, also can use with other mixed with resin, the product that obtains has good thermal characteristics and mechanical property, can be used for making high performance structures material, macromolecule member material, electronic package material, corrosion resistant material etc.
The present invention is with 9, two (the 4-aminophenyls)-2 of 9-, 7-dihydroxyl fluorenes, dichloro diphenyl sulfone, monohydric phenol and Paraformaldehyde 96 are raw material, obtain the fluorenyl polyethersulfone oligomer that side chain contains benzoxazinyl group through polycondensation, Mannich condensation reaction, obtain containing the polyethersulfone thermoplastic resin of Polybenzoxazine structure again through thermofixation.Owing to introduce Ke Ju He oxazine cyclic group in the molecular structure, make the thermal characteristics of product, mechanical property improve a lot.
Embodiment
The basic preparation method that side chain of the present invention contains 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-aminophenyls)-2 of 9-, 7-dihydroxyl fluorenes, Anhydrous potassium carbonate and dichloro diphenyl sulfone, two (the 4-aminophenyls)-2 of 9,9-, 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, add dimethyl sulfoxide (DMSO) (solvent) and toluene (band aqua) then, feed nitrogen, be warmed up to 150～200 ℃, reaction 2～4h, steam toluene, continue under this temperature, to react 2～4h, after reaction finishes, filter, filtrate is added to the water, separates out precipitation, precipitation is through washing, ethanol is washed, vacuum-drying obtains side chain and contains amino fluorenyl polyethersulfone.
Second step: the side chain that the first step reaction is obtained contains amino fluorenyl polyethersulfone, monohydric phenol, Paraformaldehyde 96, chloroform or dimethylbenzene and joins in the there-necked flask that stirring rotator, prolong, thermometer are housed, the ratio of polyethersulfone, monohydric phenol, Paraformaldehyde 96 amount of substance is 1:10:20, be warmed up to 60～160 ℃, back flow reaction 5～24h, after reaction finishes, reaction solution is joined in the ethanol, separate out precipitation, after filtration, ethanol washes, vacuum-drying, obtains the fluorenyl polyethersulfone resin that side chain contains benzoxazinyl group.
In order to understand better the present invention, enumerate specific embodiments of the invention below:
Embodiment 1
Side chain contains the synthetic of amino fluorenyl polyethersulfone
Stirring rotator is being housed, water trap, add 9 in the there-necked flask of nitrogen inlet and prolong, two (the 4-aminophenyls)-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 is warming up to 160 ℃, react after 3 hours, water trap no longer includes moisture and takes out of, and toluene is steamed, and continues reaction and finishes reaction after 3 hours, reaction solution is down to room temperature, filter, filtrate is added to the water, separate out precipitation, wash with water, ethanol is washed, 60 ℃ of following vacuum-dryings 24 hours, obtain white side chain and contain amino fluorenyl polyethersulfone powder 4.78g, productive rate 87% at last.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR spectrum, δ=6.39～7.94ppm is proton chemical shifts on the phenyl ring, and 4.99ppm is amino proton characteristic peak.Examination of infrared spectrum result (KBr, cm
-1): 3433cm
-1And 3375cm
-1Be N-H stretching vibration on the primary amine, 3030cm
-1Be the unsaturated C-H stretching vibration peak of phenyl ring, 2927cm
-1Be saturated C-H stretching vibration peak, 1625cm
-1And 1581cm
-1Be phenyl ring skeletal vibration, 1294cm
-1Be O=S=O asymmetrical stretching vibration, 1236cm
-1And 1072cm
-1Be C-O-C symmetry and asymmetrical stretching vibration, 874cm
-1For on the phenyl ring 1,4-two replaces charateristic avsorption bands, 757cm
-1Be the C-Cl characteristic peak, confirm that the sample that is synthesized is target product.
Embodiment 2
Except Anhydrous potassium carbonate changes 1.65g into and dichloro diphenyl sulfone changes 3.44g into, temperature of reaction changes 180 ℃ into, and other conditions obtain white side chain at last and contain amino fluorenyl polyethersulfone powder 4.16g, productive rate 75% with embodiment 1.
Embodiment 3
Side chain contains fluorenyl polyethersulfone synthetic of benzoxazinyl group
1.5g embodiment 1 synthetic side chain is contained amino fluorenyl polyethersulfone, 0.94g phenol, 30mL dimethylbenzene and 0.6g Paraformaldehyde 96 to join in the there-necked flask successively, temperature rises to 150 ℃, reacted 6 hours, be cooled to room temperature, reaction solution is poured in the ethanol, filter, the filter cake washing with alcohol, vacuum-drying again obtains the fluorenyl polyethersulfone powder 1.2g that faint yellow side chain contains benzoxazinyl group at last, and yield is 60%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR spectrum, δ=6.77～7.81ppm is proton chemical shifts on the phenyl ring, O-CH on the 5.29ppm Wei oxazine ring
2The proton characteristic peak of-N, 4.69ppm are Ar-CH
2The proton characteristic peak of-N.Examination of infrared spectrum result (KBr, cm
-1): 3030cm
-1Be the unsaturated C-H stretching vibration of phenyl ring, 2934cm
-1Be saturated C-H stretching vibration, 1323cm
-1CH on the Wei oxazine ring
2The rocking vibration peak, 1296cm
-1Be O=S=O asymmetrical stretching vibration, 1229cm
-1And 1074cm
-1Be C-O-C symmetry and asymmetrical stretching vibration, 1153cm
-1For C-N-C goes up asymmetrical stretching vibration, 948cm
-1Being the C-H out-of-plane deformation vibration, is the charateristic avsorption band of Dai You oxazine ring on the phenyl ring, 859cm
-1For on the phenyl ring 1,4-two replaces charateristic avsorption bands, 756cm
-1Be the C-Cl charateristic avsorption band.
The fluorenyl polyethersulfone that the side chain that obtains is contained benzoxazinyl group in air dry oven according to 160 ℃/2h, 180 ℃/2h, 200 ℃/2h, 220 ℃/2h, 240 ℃/2h, be cured, obtain containing the polyethersulfone thermoplastic resin (BAPDHF-1.25DCDPS-p-BPES) of Polybenzoxazine structure, through DSC and TGA test, obtain its second-order transition temperature (being abbreviated as Tg, as follows), weightless 5% and 10% corresponding heat decomposition temperature (is abbreviated as T
5And T
10, as follows) and 800 ℃ under carbon yield, the results are shown in Table 1.
Embodiment 4
Except raw material phenol changes meta-cresol into, consumption changes into outside the 1.08g, and other conditions obtain the fluorenyl polyethersulfone powder 1.11g that faint yellow side chain contains benzoxazinyl group at last with embodiment 3, and yield is 59%.
The proton nmr spectra test result (ppm): in 1H NMR spectrum, δ=6.60～7.86ppm is proton chemical shifts on the phenyl ring for 500M, CDCl3,5.27ppm and 5.24ppm Wei the oxazine ring on O-CH
2The proton characteristic peak of-N, 4.53ppm and 4.45ppm are Ar-CH
2The proton characteristic peak of-N, 2.17ppm～2.52ppm belongs to the proton peak of methyl in the meta-cresol structure.Examination of infrared spectrum result (KBr, cm
-1): 2934cm
-1Being saturated C-H stretching vibration peak, and strengthening to some extent, is because have methyl on the phenyl ring, other characteristic peaks to go out the peak position identical with embodiment 3, the sample that confirmation is synthesized is target product.
Solidify and test condition with embodiment 3, the performance that obtains containing the polyethersulfone thermoplastic resin (BAPDHF-1.25DCDPS-m-mp-BPES) of Polybenzoxazine structure sees Table 1.
Embodiment 5
Except containing amino polyethersulfone, the raw material side chain changes the polyethersulfone that embodiment 2 synthesizes into, dimethylbenzene changes chloroform into, temperature of reaction changes 70 ℃ into, reaction times changed into outside 24 hours, other conditions are with embodiment 3, obtain the fluorenyl polyethersulfone powder 1.01g that faint yellow side chain contains benzoxazinyl group at last, yield is 50%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR spectrum, δ=6.91～7.86ppm is proton chemical shifts on the phenyl ring, 5.30ppm and 5.29ppm Wei the oxazine ring on O-CH
2The proton characteristic peak of-N, 4.58ppm and 4.57ppm are Ar-CH
2The proton characteristic peak of-N.Examination of infrared spectrum result (KBr, cm
-1): characteristic peak to go out the peak position identical with embodiment 3, confirm that the sample that is synthesized is target product.
Solidify and test condition with embodiment 3, the performance that obtains containing the polyethersulfone thermoplastic resin (BAPDHF-1.5DCDPS-p-BPES) of Polybenzoxazine structure sees Table 1.
Embodiment 6
Except raw material phenol changes meta-cresol into, consumption changes into outside the 1.08g, and other conditions obtain the fluorenyl polyethersulfone powder 1.06g that faint yellow side chain contains benzoxazinyl group at last with embodiment 5, and yield is 51%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR spectrum, δ=6.60～7.86ppm is proton chemical shifts on the phenyl ring, 5.27ppm and 5.28ppm Wei the oxazine ring on O-CH
2The proton characteristic peak of-N, 4.53ppm are Ar-CH
2The proton characteristic peak of-N.2.37ppm and 2.25ppm belongs to the methyl proton peak.Examination of infrared spectrum result (KBr, cm
-1): 2901cm
-1Be the C-H stretching vibration peak, and strengthen to some extent because there is methyl on the phenyl ring, other characteristic peaks to go out the peak position identical with embodiment 3, the sample that confirmation is synthesized is target product.
Solidify and test condition with embodiment 3, the performance that obtains containing the polyethersulfone thermoplastic resin (BAPDHF-1.5DCDPS-m-mp-BPES) of Polybenzoxazine structure sees Table 1.
Embodiment 7
Except changing phenol into the 3-methoxyphenol, consumption changes into outside the 1.24g, and other conditions obtain the fluorenyl polyethersulfone powder 0.95g that faint yellow side chain contains benzoxazinyl group at last with embodiment 5, and yield is 44%.
Proton nmr spectra test result (500M, CDCl
3, ppm): in 1H NMR spectrum, δ=6.34～7.85ppm is proton chemical shifts on the phenyl ring, O-CH on the 5.27ppm Wei oxazine ring
2The proton characteristic peak of-N, 4.51ppm are Ar-CH
2The proton characteristic peak of-N.3.73ppm and 3.71ppm belongs to the proton peak of methoxyl group in the meta-methoxy phenol structure.Examination of infrared spectrum result (KBr, cm
-1): 1258cm
-1And 1107cm
-1Be C-O-C symmetry and asymmetrical stretching vibration, and strengthen to some extent because there is methoxyl group on the phenyl ring, other characteristic peaks to go out the peak position identical with embodiment 3, the sample that confirmation is synthesized is target product.
Solidify and test condition with embodiment 3, the performance that obtains containing the polyethersulfone thermoplastic resin (BAPDHF-1.5DCDPS-m-mop-BPES) of Polybenzoxazine structure sees Table 1.
Table 1 contains the polyethersulfone thermoplastic resin thermal characteristics parameter of Polybenzoxazine structure
Claims (3)
1. a side chain contains the fluorenyl polyethersulfone resin of benzoxazinyl group, it is characterized in that having following general formula:
In the formula, R is H, CH
3Or OCH
3In a kind of.
2. a side chain contains the preparation method of the fluorenyl polyethersulfone resin of benzoxazinyl group, it is characterized in that:
The first step: in container, add 9, two (the 4-aminophenyls)-2 of 9-, 7-dihydroxyl fluorenes, Anhydrous potassium carbonate and dichloro diphenyl sulfone, 9, two (the 4-aminophenyls)-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, add dimethyl sulfoxide (DMSO) and toluene then, feed nitrogen, be warmed up to 150～200 ℃, reaction 2～4h steams toluene, continuation is reacted 2～4h under this temperature, after reaction finishes, filter, filtrate is added to the water, separate out precipitation, precipitation is through washing, ethanol is washed, and vacuum-drying obtains side chain and contains amino fluorenyl polyethersulfone;
Second step: the side chain that the first step reaction is obtained contains amino fluorenyl polyethersulfone, monohydric phenol, Paraformaldehyde 96, chloroform or dimethylbenzene and joins and be equipped with in the container, the ratio of polyethersulfone, monohydric phenol, Paraformaldehyde 96 amount of substance is 1:10:20, be warmed up to 60～160 ℃, back flow reaction 5～24h, reaction joins reaction solution in the ethanol after finishing, and separates out precipitation, after filtration, ethanol washes, vacuum-drying, obtains the fluorenyl polyethersulfone resin that side chain contains benzoxazinyl group.
3. side chain according to claim 2 contains the preparation method of the fluorenyl polyethersulfone resin of benzoxazinyl group, it is characterized in that: described monohydric phenol is a kind of in phenol, meta-cresol, p-cresol, meta-methoxy phenol, the p methoxy phenol.
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| CN111187555A (en) * | 2020-03-07 | 2020-05-22 | 张孟杰 | High-temperature-resistant epoxy powder coating and preparation method thereof |
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