CN102702128A - Ether bond-containing diamine flourenyl benzoxazine - Google Patents
Ether bond-containing diamine flourenyl benzoxazine Download PDFInfo
- Publication number
- CN102702128A CN102702128A CN2012101928831A CN201210192883A CN102702128A CN 102702128 A CN102702128 A CN 102702128A CN 2012101928831 A CN2012101928831 A CN 2012101928831A CN 201210192883 A CN201210192883 A CN 201210192883A CN 102702128 A CN102702128 A CN 102702128A
- Authority
- CN
- China
- Prior art keywords
- benzoxazine
- ether bond
- flourenyl
- fluorenes
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses an ether bond-containing diamine flourenyl benzoxazine, which is shown as a formula in the specifications, wherein A is fluorenyl containing a substituted or unsubstituted aromatic ring; and R1 is one of hydrogen, methyl, methoxyl, trifluoromethyl or cyan. Due to the introducing of an ether bond into the ether bond-containing diamine flourenyl benzoxazine disclosed by the invention, the toughness and processing performance of a benzoxazine resin can be improved, the quantity of benzene rings is increased, and the glass transition temperature, heat resistance and humidity resistance of the polymer are not reduced greatly due to the introduction of flexible radicals. The ether bond-containing diamine flourenyl benzoxazine can be applied in the fields of compound material substrate resins, electronic encapsulating materials, insulating materials and the like.
Description
Technical field
What the present invention relates to is a kind of organic polymer material, specifically a kind of ether-containing key diamine type fluorenyl benzoxazine monomer.
Background technology
The seventies in 20th century, Schreiber reports in patent and use the benzoxazine oligopolymer that epoxy resin is carried out modification (German Patent 2217099, " Phenolic resin as electric insulator ").The eighties in 20th century; Higginbottom has at first found the crosslinking reaction (USP 4501864, " Polymerizable compositions comprising polyamines and poly (dihydrobenzoxazines) ") of polyfunctionality benzoxazine in the research of doing coating material.1994; Ishida and Ning accomplish performance study (the Ning X of p-poly-phenyl Bing oxazine at first; Ishida H.Phenolic materials via ring-opening polymerization-synthesis and characterization of bisphenol-A based benzoxazines and their polymers.J Polym Sci A Polym Chem; 1994,32:1121-1129P).Through a large amount of discovering, benzoxazine colophony is the new type resin material with phenolic aldehyde, epoxy and the same excellent performance of maleimide.Benzoxazine colophony can adapt to the mechanical property of different use range, the needs of mechanical property through molecular designing property flexibly.Benzoxazine colophony also has excellent thermal property, chemical resistance and electrical property.In addition, for the application of some particular requirements, it also has volume zero shrinks, high carbon residue, and second-order transition temperature is higher than solidification value, characteristics such as low-k and low water absorption.The benzoxazine material cost is cheap, and the building-up process no coupling product generates, and through self ring-opening polymerization, need not to add catalyzer such as strong acid or highly basic in the solidification process.And benzoxazine has powerful molecular designing property, and this characteristic has greatly been expanded the Application Areas of benzoxazine colophony.Simultaneously can also join traditional resol, polyester, epoxy resin, as material modified, quicken the commercial applications of Polybenzoxazine in bimaleimide resin, urethane, the polyimide.
Fluorenes has rigid plane biphenyl structural, wide energy gap, high-luminous-efficiency, good thermostability, light stability, chemicalstability and is easy to performances such as processing.Introduce two phenylor and aminophenyl through 9, can be made into a series of polyimide resins with excellent heat stability, humidity resistance, dielectric properties, mechanical property, chemicals-resistant, high transparent, high refractive index, polycarbonate, epoxy resin etc.Through Yin Ru oxazine ring in the fluorenes molecule, reach the effect that improves thermotolerance and flame retardant resistance too.People such as Wang Jun have reported synthetic, the polymerization behavior and the Thermal Properties of fluorenyl benzoxazine colophony the earliest; Promptly with bisphenol fluorene [9; Two (4-phenylor) fluorenes of 9-] (one Chinese patent application number 200810137211.4, fluorenyl bi-benzoxazine monomer and preparation method thereof) and diamine fluorenes [9,9-pair of (4-aminophenyl) fluorenes] be raw material (one Chinese patent application numbers 200810209638.0; Fluorenyl bi-benzoxazine monomer and preparation method thereof), obtain a series of fluorenyl benzoxazine monomers.Existing fluorenyl benzoxazine colophony makes the fragility of Polybenzoxazine resin bigger owing to contain the fluorenyl that dangles in the molecule, has limited the further application of this resinoid.
Summary of the invention
The object of the present invention is to provide a kind of ether-containing key diamine type fluorenyl benzoxazine that can improve the toughness and the processing characteristics of benzoxazine colophony.
The objective of the invention is to realize like this:
Ether-containing key diamine type fluorenyl benzoxazine of the present invention has following structure:
In the formula: A contains the fluorenyl that replaces or do not replace aromatic ring, R
1A kind of in hydrogen, methyl, methoxyl group, trifluoromethyl or the cyanic acid.
The said structural formula that replaces or do not replace the fluorenyl of aromatic ring that contains is expressed as:
In the formula: X is a kind of in hydrogen, methyl, methoxyl group, trifluoromethyl or the cyanic acid.
Ether-containing key diamine type fluorenyl benzoxazine of the present invention prepares in such a way:
Ether-containing key fluorenediamine monomer, phenolic cpd and Paraformaldehyde 96 are joined in the container that whisking appliance, prolong, TM are housed, and ether-containing key fluorenediamine monomer, phenolic cpd and Paraformaldehyde 96 amount of substance ratio are 1: 2: 4, add YLENE simultaneously as solvent; Under 150 ℃ of temperature, react 4～15h, reaction finishes postcooling to room temperature, adds ethanol; Throw out dissolves crude product after washing, filtration, vacuum-drying with methylene dichloride, add the 1mol/L sodium hydroxide solution and carry out alkali cleaning; Deionized water wash separates, and organic layer adds SODIUM SULPHATE ANHYDROUS 99PCT; Leave standstill 24h, filter, filtrating is removed organic solvent through rotary evaporation; Vacuum-drying promptly obtains white or faint yellow ether-containing key diamine type fluorenyl benzoxazine monomer.
Described ether-containing key fluorenediamine monomer is 9; Two (4-(4-amino-benzene oxygen) phenyl) fluorenes, 9 of 9-; 9 pairs of (3-methyl 4-(4-amino-benzene oxygen) phenyl) fluorenes, 9; Two (3-methoxyl group-4-(4-amino-benzene oxygen) phenyl) fluorenes or 9 of 9-, a kind of in two (3-trifluoromethyl-4-(4-amino-benzene oxygen) phenyl) fluorenes of 9-.
Described phenolic cpd is phenol, ortho-cresol, meta-cresol, p-cresol, 4-methoxyphenol, 3-methoxyphenol, 4-trifloro methyl phenol, 3-trifloro methyl phenol or a kind of in the itrile group phenol.
The present invention introduces flexible ehter bond, with toughness and the processing characteristics of improving benzoxazine colophony from fluorenediamine monomer molecule structure design in the diamine molecule.
Ether-containing key diamine type fluorenyl benzoxazine monomer structural characterization of the present invention utilizes ir spectra, and (Spotlight 100; 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 to 4000～500cm
-1, proton nmr spectra is a mark in doing with TMS (TMS), deuterochloroform (CDCl
3) make solvent.DSC (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 10 ℃/min.
The ether-containing key diamine type fluorenyl benzoxazine of the present invention's preparation can be used for fields such as advanced composite material matrix resin, electronic package material, insulating material.
Ether-containing key diamine type fluorenyl benzoxazine of the present invention and preparation method thereof is with ether-containing key fluorenediamine monomer, with phenolic cpd, Paraformaldehyde 96 be raw material, adopt the synthetic diamin type benzoxazine monomer of single stage method.Compare traditional three-step approach, not only reactions step, reaction times shorten greatly, and have avoided reaction raw materials from salicylic aldehyde, and the restriction benzoxazine is the shortcoming of molecular designing property flexibly.In addition; Because the introducing of ehter bond in its structure; Can improve the toughness and the processing characteristics of benzoxazine colophony, add increasing of phenyl ring quantity, the second-order transition temperature of polymkeric substance, resistance toheat and wet-hot aging performance can not decline to a great extent because of the introducing of flexible group.
Embodiment
For example the present invention is done more detailed description below:
Embodiment 1
In the 100mL there-necked flask that has magnetic stirring apparatus, tap funnel and TM, add 5.32g (0.01mol) 9,9-pair-(4-(4-amino-benzene oxygen) phenyl) fluorenes, 1.88g (0.02mol) phenol, 1.2g (0.04mol) Paraformaldehyde 96 and 50mL YLENE.Be heated to 150 ℃ of back flow reaction 6h, reaction finishes postcooling to room temperature, adds ethanol, throw out washing, filtration, and crude product is dry 24h in 60 ℃ of vacuum drying ovens.Crude product is dissolved with methylene dichloride, add the 1mol/L sodium hydroxide solution and carry out alkali cleaning, use deionized water wash; Separate, organic layer adds SODIUM SULPHATE ANHYDROUS 99PCT, leaves standstill 24h; Filter, filtrating is removed organic solvent, vacuum-drying through rotary evaporation; Promptly obtain white powder 9,9-pair-(4-(4-amino-benzene oxygen) phenyl) fluorenes-phenylol benzoxazine monomer (BEF-p), yield 81.2%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.75～7.74 (m, 32H, ArH), 5.30 (d, 4H, O-CH
2-N), 4.58 (d, 4H, Ar-CH
2-N); Examination of infrared spectrum result (KBr, cm
-1): 1608,1584,1489 and 750 (ortho position two of phenyl ring replaces characteristic peak), 1373! CH on the oxazine ring
2The rocking vibration peak), 1239 and 1067 (the asymmetric and symmetrical stretching vibrations of C-O-C), 1138 (the last asymmetrical stretching vibrations of C-N-C), 951 (c h bond out-of-plane bending characteristics) are the charateristic avsorption bands of Dai You oxazine ring on the phenyl ring.Confirm that in conjunction with proton nmr spectra and ir spectra products therefrom is the target monomer.
BEF-p puts into electric drying oven with forced convection with benzoxazine monomer, adopts programmed temperature method that monomer is carried out thermofixation, and the curing system is: 180 ℃/2h; 200 ℃/2h; 220 ℃/2h, 240 ℃/2h, obtain Polybenzoxazine resin (being abbreviated as poly-(BEF-p)); Through DSC and TGA test, the second-order transition temperature that obtains the Polybenzoxazine resin (is abbreviated as T
g, as follows), weightless 5% pairing heat decomposition temperature (is abbreviated as T
5, as follows) and 800 ℃ under carbon yield.
Embodiment 2
Remove raw material phenol and use Ortho Cresol instead, outside the quality 2.16g, other conditions are with embodiment 1, obtain faint yellowly 9 at last, and 9-is two-(4-(4-amino-benzene oxygen) phenyl) fluorenes-Ortho Cresol base benzoxazine monomer (BEF-o-mp), yield 71.3%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.75～7.74 (m, 30H, Ar-H), 5.30 (d, 4H, O-CH
2-N), 4.55 (d, 4H, Ar-CH
2-N), 2.16 (d, 6H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 1383,1224,1078,1159 and 951.
Curing and test condition are with embodiment 1, and Polybenzoxazine resin (poly (BEF-o-mp)) performance is seen table 1.
Embodiment 3
Except that raw material phenol is used m-cresol instead, quality 2.16g, outside the reaction times 4h, other conditions are with embodiment 1, obtain faint yellowly 9 at last, and 9-is two-(4-(4-amino-benzene oxygen) phenyl) fluorenes-m-cresol base benzoxazine monomer (BEF-m-mp), yield 62.5%.
The proton nmr spectra test result (500M, CDCl3, ppm): 6.61～7.74 (m, 30H, Ar-H), 5.27 (d, 4H, O-CH
2-N), 4.45 (d, 4H, Ar-CH
2-N), 2.26 (d, 6H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 1385,1259,1076,1162 and 956.
Curing and test condition are with embodiment 1, and Polybenzoxazine resin (poly (BEF-m-mp)) performance is seen table 1.
Embodiment 4
Remove raw material phenol and use p-cresol instead, quality 2.16g, outside the return time 15h, other conditions are with embodiment 6, obtain faint yellowly 9 at last, and 9-is two-(4-(4-amino-benzene oxygen) phenyl) fluorenes-p-cresol base benzoxazine monomer (BEF-p-mp), yield 74.8%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.68～7.74 (m, 30H, Ar-H), 5.26 (d, 4H, O-CH
2-N), 4.52 (d, 4H, Ar-CH
2-N), 2.24 (d, 6H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 1383,1227,1075,1162 and 952.
Curing and test condition are with embodiment 1, and Polybenzoxazine resin (poly (BEF-p-mp)) performance is seen table 1.
Embodiment 5
Remove raw material phenol and use the 4-methoxyphenol instead, quality 2.48g is outside the return time 12h; Other conditions are with embodiment 1; Obtain faint yellowly 9 at last, 9-is two-(4-(4-amino-benzene oxygen) phenyl) fluorenes-p methoxy phenol base benzoxazine monomer (BEF-mop), yield 71.8%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.67～7.82 (m, 30H, ArH), 5.31 (d, 4H, O-CH
2-N), 4.55 (d, 4H, Ar-CH
2-N), 3.75 (d, 6H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 1384,1226,1075,1177 and 948.
Solidify and test condition with embodiment 1, Polybenzoxazine resin (poly-(BEFmop)), performance is seen table 1.
Embodiment 6
Remove raw material phenol and use the 4-trifloro methyl phenol instead, quality is outside the 3.24g, and other conditions are with embodiment 1, obtains faint yellowly 9 at last, 9-is two-and (4-(4-amino-benzene oxygen) phenyl) fluorenes-p-trifluoromethyl-phenol base benzoxazine monomer (BEF-fp), yield 73.6%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.65～7.87 (m, 30H, Ar-H), 5.31 (d, 4H, O-CH
2-N), 4.57 (d, 4H, Ar-CH
2-N); Examination of infrared spectrum result (KBr, cm
-1): 1383,1228,1200,1078,1175 and 951.
Solidify and test condition with embodiment 1, Polybenzoxazine resin (poly-(BEF-fp)), performance is seen table 1.
Embodiment 7
Remove raw material phenol and use 4-hydroxybenzonitrile instead, quality is outside the 2.38g, and other conditions are with embodiment 1, obtains faint yellowly 9 at last, 9-is two-and (4-(4-amino-benzene oxygen) phenyl) fluorenes-4-hydroxybenzonitrile base benzoxazine monomer (BEF-cp), yield 64.8%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.66～7.82 (m, 30H, Ar-H), 5.28 (d, 4H, O-CH
2-N), 4.56 (d, 4H, Ar-CH
2-N); Examination of infrared spectrum result (KBr, cm
-1): 2220cm
-1(stretching vibration of C ≡ N key on the phenyl ring), 1383,1240,1078,1175 and 952.
The thermofixation system of BEF-cp is: 180 ℃/2h, 200 ℃/2h, 220 ℃/2h, 240 ℃/2h, 260 ℃/2h, test condition obtains Polybenzoxazine resin (poly-(BEF-cp)) at last with embodiment 1, and performance is seen table 1.
Embodiment 8
Remove raw material 9; 9-pair-(4-(4-amino-benzene oxygen) phenyl) fluorenes uses 9 instead, and 9-pair-(3-methyl-4-(4-amino-benzene oxygen) phenyl) fluorenes, quality is outside the 5.61g; Other conditions are with embodiment 1; Obtain faint yellowly 9 at last, 9-is two-(3-methyl-4-(4-amino-benzene oxygen) phenyl) fluorenes-phenylol benzoxazine monomer (BMEF-p), yield 65.5%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.68～7.77 (m, 30H, Ar-H), 5.29 (d, 4H, O-CH
2-N), 4.53 (d, 4H, Ar-CH
2-N), 2.07 (d, 6H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 1384,1226,1078,1164 and 950.
Curing and test condition are with embodiment 1, and Polybenzoxazine resin (poly (BMEF-p)) performance is seen table 1.
Embodiment 9
Remove raw material 9; 9-pair-(4-(4-amino-benzene oxygen) phenyl) fluorenes uses 9 instead, and 9-pair-(3-methoxyl group-4-(4-amino-benzene oxygen) phenyl) fluorenes, quality is outside the 5.93g; Other conditions are with embodiment 1; Obtain faint yellow 9,9 pairs-(3-methoxyl group 4-(4-amino-benzene oxygen) phenyl) fluorenes-phenylol benzoxazine monomer (BMOEFp) at last, yield 57.2%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.68～7.84 (m, 30H, ArH), 5.32 (d, 4H, O-CH
2-N), 4.61 (d, 4H, Ar-CH
2-N), 3.81 (d, 6H ,-CH
3); Examination of infrared spectrum result (KBr, cm
-1): 1381,1228,1081,1167 and 952.
Curing and test condition are with embodiment 1, and Polybenzoxazine resin (poly (BMOEF-p)) performance is seen table 1.
Embodiment 10
Remove raw material 9; 9-pair-(4-(4-amino-benzene oxygen) phenyl) fluorenes uses 9 instead, and 9-pair-(3-three fluoro-4-(4-amino-benzene oxygen) phenyl) fluorenes, quality is outside the 6.68g; Other conditions are with embodiment 1; Obtain faint yellowly 9 at last, 9-is two-(3-three fluoro-4-(4-amino-benzene oxygen) phenyl) fluorenes-phenylol benzoxazine monomer (BFEF-p), yield 62.3%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.72～7.87 (m, 30H, Ar-H), 5.28 (d, 4H, O-CH
2-N), 4.57 (d, 4H, Ar-CH
2-N); Examination of infrared spectrum result (KBr, cm
-1): 1377,1228,1203,1077,1166 and 946.
Curing and test condition are with embodiment 1, and Polybenzoxazine resin (poly (BFEF-p)) performance is seen table 1.
The thermal property parameter of table 1 benzoxazine colophony
The result is visible from table; The introducing of ehter bond in the structure; Can improve the toughness and the processing characteristics of benzoxazine colophony; Add increasing of phenyl ring quantity, the second-order transition temperature of polymkeric substance, resistance toheat and wet-hot aging performance can not decline to a great extent because of the introducing of flexible group, can be used for fields such as advanced composite material matrix resin, electronic package material, insulating material, fire retardant material, ablation resistant material and laminating material.
Claims (2)
1. ether-containing key diamine type fluorenyl benzoxazine is characterized in that having following structure:
In the formula: A contains the fluorenyl that replaces or do not replace aromatic ring, R
1A kind of in hydrogen, methyl, methoxyl group, trifluoromethyl or the cyanic acid.
2. ether-containing key diamine type fluorenyl benzoxazine according to claim 1 is characterized in that the said structural formula that replaces or do not replace the fluorenyl of aromatic ring that contains is expressed as:
In the formula: X is a kind of in hydrogen, methyl, methoxyl group, trifluoromethyl or the cyanic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210192883.1A CN102702128B (en) | 2012-06-13 | 2012-06-13 | Ether bond-containing diamine flourenyl benzoxazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210192883.1A CN102702128B (en) | 2012-06-13 | 2012-06-13 | Ether bond-containing diamine flourenyl benzoxazine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102702128A true CN102702128A (en) | 2012-10-03 |
| CN102702128B CN102702128B (en) | 2014-06-25 |
Family
ID=46895236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210192883.1A Expired - Fee Related CN102702128B (en) | 2012-06-13 | 2012-06-13 | Ether bond-containing diamine flourenyl benzoxazine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102702128B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103319501A (en) * | 2013-05-31 | 2013-09-25 | 哈尔滨工程大学 | Four-functional spiro(fluorene-xanthene)benzoxazine |
| 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 |
| CN105061466A (en) * | 2015-09-01 | 2015-11-18 | 哈尔滨工程大学 | Main chain bisphenol type quinoxaline benzoxazine and preparation method thereof |
| CN105061464A (en) * | 2015-07-30 | 2015-11-18 | 哈尔滨工程大学 | Monophenol-diamine type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof |
| CN105824192A (en) * | 2016-04-05 | 2016-08-03 | 浙江康尔达新材料股份有限公司 | Infrared sensitive composition and printing plate precursors prepared by composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101429172A (en) * | 2008-12-08 | 2009-05-13 | 哈尔滨工程大学 | Fluorenyl di-benzoxazine monomer and method of preparing the same |
-
2012
- 2012-06-13 CN CN201210192883.1A patent/CN102702128B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101429172A (en) * | 2008-12-08 | 2009-05-13 | 哈尔滨工程大学 | Fluorenyl di-benzoxazine monomer and method of preparing the same |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319501A (en) * | 2013-05-31 | 2013-09-25 | 哈尔滨工程大学 | Four-functional spiro(fluorene-xanthene)benzoxazine |
| CN103319501B (en) * | 2013-05-31 | 2016-04-20 | 哈尔滨工程大学 | Four functionality spiral shell fluorenes oxa-anthryl benzoxazines |
| 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 |
| 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 |
| 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 |
| CN105061464A (en) * | 2015-07-30 | 2015-11-18 | 哈尔滨工程大学 | Monophenol-diamine type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof |
| CN105061466A (en) * | 2015-09-01 | 2015-11-18 | 哈尔滨工程大学 | Main chain bisphenol type quinoxaline benzoxazine and preparation method thereof |
| CN105061466B (en) * | 2015-09-01 | 2017-06-20 | 哈尔滨工程大学 | Main chain bisphenol type quinoxalinyl benzoxazine and preparation method thereof |
| CN105824192A (en) * | 2016-04-05 | 2016-08-03 | 浙江康尔达新材料股份有限公司 | Infrared sensitive composition and printing plate precursors prepared by composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102702128B (en) | 2014-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102702128B (en) | Ether bond-containing diamine flourenyl benzoxazine | |
| CN102702129B (en) | Ester-group-containing diamine type fluorenyl benzoxazine | |
| Zhang et al. | Synthesis of high thermal stability polybenzoxazoles via ortho‐imide‐functional benzoxazine monomers | |
| Agag | Preparation and properties of some thermosets derived from allyl‐functional naphthoxazines | |
| CN102634019B (en) | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof | |
| CN106589348B (en) | The polyarylether and preparation method thereof of main chain containing double benzene base fluorenes and triaryl s-triazine structure | |
| CN103936686B (en) | N-semiaromatic alkyl diamine-bisphenol type four degree of functionality fluorenyl benzoxazine and preparation methods | |
| JP7335722B2 (en) | Phenylene ether oligomers, curable compositions containing phenylene ether oligomers, and thermoset compositions obtained therefrom | |
| CN103304558B (en) | Containing benzoyloxy spiral shell fluorenes oxa-anthryl benzoxazine and preparation method | |
| CN102659526B (en) | Tetraphenolic hydroxyfluorene compound and preparation method thereof | |
| CN102617382B (en) | 2-amino-fluorene containing ester group and preparation method thereof | |
| CN105153144A (en) | Main-chain diamine type quinoxalinyl benzoxazine and preparation method thereof | |
| CN105348527B (en) | Thermosetting resin, the compositions of thermosetting resin containing it, solidfied material, prepreg, laminate and printed circuit board | |
| CN103936764B (en) | N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof | |
| CN103204991B (en) | Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone | |
| CN103896867B (en) | N-full aryl radical diamine-bisphenol type four functionality fluorenyl benzoxazine and preparation method thereof | |
| CN103936765B (en) | The full aryl radical bis-phenol of N--diamine type four functionality fluorenyl benzoxazine and preparation method thereof | |
| CN103304578B (en) | Spiral shell fluorenes xanthene bisphenol type benzoxazine | |
| CN102702225A (en) | Four-phenolic fluorene based benzoxazine and preparation method of four-phenolic fluorine based benzoxazine | |
| CN102660023A (en) | Mixed diamine type copolyfluorene benzoxazine prepolymer and preparation method thereof | |
| KR102383690B1 (en) | Benzoxazine mixture and the usage thereof | |
| JP2009149729A (en) | Method for manufacturing thermosetting resin having dihydrobenzoxazine ring structure | |
| CN103288680B (en) | Self-catalyzed fluorenyl bisphthalonitrile resin monomer and preparation method thereof | |
| CN103288849A (en) | Mixed amine-based multi-functionality fluorenyl benzoxazine and synthesis method thereof | |
| CN105061466B (en) | Main chain bisphenol type quinoxalinyl benzoxazine and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140625 Termination date: 20200613 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |