CN102634019A - Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof - Google Patents
Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof Download PDFInfo
- Publication number
- CN102634019A CN102634019A CN2012101243478A CN201210124347A CN102634019A CN 102634019 A CN102634019 A CN 102634019A CN 2012101243478 A CN2012101243478 A CN 2012101243478A CN 201210124347 A CN201210124347 A CN 201210124347A CN 102634019 A CN102634019 A CN 102634019A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- fluorenyl
- fluorenyl benzoxazine
- preparation
- mixing
- 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
Abstract
The invention provides a hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and a preparation method thereof. The method comprises the following steps of: adding diamine, hybrid bisphenol and formaldehyde solution with volume ratio concentration being 37 into a container, wherein the amount ratio of the diamine to hybrid bisphenol to formaldehyde is (1-1.2):1:4; adding an organic solvent for dissolution; reacting for 4-8 hours at 50-100 DEG C; cooling to room temperature; adding a saturated aqueous solution of sodium bicarbonate or sodium carbonate for alkaline cleaning; washing by deionized water, and separating; adding anhydrous sodium sulfate into an organic layer; standing for 12 hours, and filtering; performing rotary evaporation on the filtrate to remove the organic solvent; and performing vacuum drying to obtain the hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer. The prepolymer can be applied to the fields of advanced composite matrix resin, electronic packaging material, insulating material, flame-retardant material, anti-ablation material, laminated material and the like.
Description
Technical field
The present invention relates to a kind of organic polymer material, the present invention also relates to a kind of preparation method of organic polymer material.Specifically a kind of copolymerization fluorenyl benzoxazine performed polymer and preparation method thereof.
Background technology
Benzoxazine is the one type of novel hot setting resin that on the basis of traditional resol, grows up; This resin has also improved the fragility and the dimensional instability of resol to a certain extent except that having resol good thermotolerance and flame retardant resistance, the most significant advantage is through self ring-opening polymerization formation three-dimensional net structure; Not having small molecules during curing discharges; The goods porosity is low, and its volume approximate zero is shunk, and high T is arranged
gAnd thermostability, and favorable mechanical performance, electric property, flame retardant properties and high carbon residue rate, thereby use wider at aspects such as advanced composite matrix resin, the resin of anti-ablation the, electronic product sealing materials.The designability of benzoxazine molecule is very strong; Through phenols and the aminated compounds combination of using various structures; And in phenols or amine molecule, introduce functional groups such as thiazolinyl, alkynyl, itrile group; Or carry out blending and modifying with resins such as epoxy, urethane, can obtain the different functional high molecule material of performance.
Bisphenol fluorene is one type of novel high polymer material monomer with Cardo ring structure, and its molecular structure is to be linked to each other through a quaternary carbon by four phenyl ring, and huge Cardo side group makes the polymkeric substance chain rigidity that very big raising arranged.After Cardo ring introducing polymer chain structure, the cross-linking density of cured resin reduces, and the increase of phenyl ring number has improved the molecule chain rigidity, and the second-order transition temperature of resin is improved, and the carbon residue rate of cured resin improves.Therefore; With it is that macromolecular materials such as raw material synthetic fluorenyl epoxy resin, polyimide, polycarbonate have characteristics such as good thermostability, humidity resistance, dielectric properties, mechanical property, has widespread use in fields such as matrices of composite material, insulating material, PEMs.People such as Wang Jun are at Chinese invention patent " fluorenyl bi-benzoxazine monomer and preparation method thereof " (200810137211.4; 2008-09-27) and people such as Jun Wang at paper " Synthesis; Curing behavior and thermal properties of fluorene containing benzoxazines " (" European Polymer Journal "; 2010 46 volume 1024-1031 pages or leaves) having introduced with bisphenol fluorene, formaldehyde and aromatic series or armeen in is raw material; Synthesized a series of fluorenyl benzoxazine monomer and polymkeric substance of containing, the second-order transition temperature of polymkeric substance (is abbreviated as T
g, as follows) and be up to 229 ℃, thermal weight loss 5% and 10% o'clock corresponding temperature (are abbreviated as T
5And T
10, as follows) and be up to 337 and 374 ℃, the carbon residue rate is 52.1% in the time of 800 ℃.Although this resinoid excellent heat resistance, owing to bisphenol fluorene costs an arm and a leg, and the cured product cross-linking density is low, molecular weight is little, fragility is big.Therefore, need fluorenyl benzoxazine molecular structure is carried out necessary design,, enlarge the further application of this resinoid to improve polymer performance.
Summary of the invention
The object of the present invention is to provide a kind of high-molecular weight mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer with good thermal performance.The present invention also aims to provide a kind of is not influencing resin property or is improving under the condition of resin property, can reduce the preparation method of mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer of the production cost of resin.
Mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer of the present invention has following general formula:
In the formula, R be H ,-CH
3Or-CF
3In a kind of, R
1Be C
2～C
8Alkyl,
In a kind of.
Mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer of the present invention prepares in such a way:
In container, adding diamines, mixing bis-phenol and volume by volume concentration is 37 formaldehyde solution, diamines, mix bis-phenol, formaldehyde three amount of substance ratio is 1～1.2: 1: 4, add organic solvent dissolution; Reacted 4～8 hours down at 50～100 ℃, be cooled to room temperature, add saturated sodium bicarbonate or aqueous sodium carbonate and carry out alkali cleaning; Use deionized water wash, separate, organic layer adds SODIUM SULPHATE ANHYDROUS 99PCT; Static 12 hours, to filter, filtrating is removed organic solvent through rotary evaporation; Vacuum-drying promptly obtains mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer.
Described diamines is C
2～C
8Alkyl diamine, isophorone diamine or 4,4 '-a kind of in the MDA.
Described mixing bis-phenol be bisphenol fluorene and dihydroxyphenyl propane, hexafluoro bisphenol-a (bisphenol AF) or 4,4 '-a kind of mixing in the dioxydiphenyl methane (Bisphenol F), both amount of substance ratios are 1～3: 5～1.
Described organic solvent is a kind of in the mixed solvent formed of trichloromethane, dioxane or absolute ethyl alcohol and dioxane.
The structural characterization of copolymerization fluorenyl benzoxazine performed polymer of the present invention adopts IR (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 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 present invention is the phenol source with bisphenol fluorene with a kind of bis-phenol of being formed that mixes in dihydroxyphenyl propane, bisphenol AF or the Bisphenol F; With aliphatics, alicyclic or aromatic diamine is the amine source; Adopt solvent method to synthesize copoly type fluorenyl benzoxazine performed polymer; Through the monomeric species and the ratio of adjustment bisphenol fluorene and bisphenol compound or diamines, the fluorenyl Polybenzoxazine resin that obtained performance is different can be used for fields such as advanced composite material matrix resin, electronic package material, insulating material and laminating material.Owing to contain flexible alkyl or trifluoromethyl in universal bis-phenol and the diamine compounds structure; Be introduced in the fluorenyl Polybenzoxazine main chain; Deficiencies such as fluorenyl Polybenzoxazine resin rigidity is big, poor toughness have not only been improved; The cross-linking density of polymkeric substance increases, and second-order transition temperature, resistance toheat and wet-hot aging performance improve a lot and improve, but also greatly reduces raw materials cost.
Embodiment
Through embodiment the present invention is specifically described below; Be necessary to be pointed out that at this; The embodiment of the invention only is used for the present invention is further specified; But can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field makes some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
Formaldehyde solution 3.25g (40mmol), bisphenol fluorene 1.75g (5mmol), bisphenol AF 1.68g (5mmol) and the hexanediamine 1.15g (10.3mmol) of adding 37% dissolve in the trichloromethane of 40mL in the there-necked flask that whisking appliance, prolong, TM are housed, and are heated to 65 ℃; And under this temperature, react 5h, reaction finishes postcooling to room temperature, with saturated sodium bicarbonate and deionized water wash; Separate, organic layer adds the static 12h of SODIUM SULPHATE ANHYDROUS 99PCT, filters; Filtrating is removed trichloromethane through rotary evaporation; Vacuum-drying obtains faint yellow copolymerization fluorenyl benzoxazine performed polymer (being abbreviated as B-BHPF-AF-Had 1: 1) powder, yield 76.9%.
Proton nmr spectra test result (500M, CDCl
3, ppm): 6.68～7.29 (20H, Ar-H), 4.86 (4H, O-CH on the bis-phenol Wu oxazine ring
2-N), 4.76 (4H, O-CH on the dihydroxyphenyl propane F oxazine ring
2-N), 3.93 (4H, Ar-CH on the bis-phenol Wu oxazine ring
2-N), 3.79 (4H, Ar-CH on the dihydroxyphenyl propane F oxazine ring
2-N), 2.70 (4H, N-CH on the hexanediamine chain
2-), 1.53 and 1.32 (8H, hexanediamine-CH
2-).Examination of infrared spectrum result (KBr, cm
-1): 1614 and 1446 (phenyl ring skeletal vibrations), 1496 and 820 (phenyl ring 1,2,4-three replaces); 1322! methylene radical rocking vibration on the oxazine ring), 1078 and 1237 (C-O-C symmetry and asymmetrical stretching vibrations), 860 and 1167 (C-N-C symmetry and asymmetrical stretching vibrations); 926! oxazine ring C-H out-of-plane deformation vibration), be the charateristic avsorption band of phenyl ring Lian Jie oxazine ring, 820 (C-H out-of-plane deformation vibrations; Phenyl ring contraposition two replaces), 736 (C-H out-of-plane deformation vibrations, phenyl ring ortho position two replaces).Confirm that by proton nmr spectra and ir spectra institute's synthetic sample is a title product.
B-BHPF-AF-Hda is put into electric drying oven with forced convection, adopt programmed temperature method that monomer is carried out thermofixation, the curing system is: 180 ℃/2h; 220 ℃/2h; 220 ℃/2h, 240 ℃/2h, obtain copolymerization fluorenyl Polybenzoxazine resin (being abbreviated as Poly (B-BHPF-AF-Hda) 1: 1); Through DSC and TGA test, the T of Polybenzoxazine resin
g, T
5, T
10Carbon yield test result during with 800 ℃ is listed in table 1.
Embodiment 2
The consumption that removes bisphenol fluorene and bisphenol AF is adjusted into 2.33g and 1.12g (the amount of substance ratio is 2: 1) respectively; Reaction times is outside the 6h; Trichloromethane replaces with dioxane, and temperature of reaction is outside 90 ℃, and other condition is with embodiment 1; Finally obtain faint yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Hda 2: 1) powder, yield 80.8%.Infrared and the proton nmr spectra result is identical with embodiment 1, solidify and test condition with embodiment 1, the performance of Polybenzoxazine resin (poly (B-BHPF-AF-Hda) 2: 1) is seen table 1.
Embodiment 3
The consumption that removes bisphenol fluorene and bisphenol AF is adjusted into 1.17g and 2.24g (the amount of substance ratio is 1: 2) respectively; Trichloromethane replaces with dioxane and absolute ethyl alcohol mixed solvent; Both volume ratios are 1: 1, and temperature of reaction is outside 80 ℃, and other condition is with embodiment 1; Finally obtain faint yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Hda 1: 2) powder, yield 80.4%.Infrared and the proton nmr spectra result is identical with embodiment 1, solidify and test condition with embodiment 1, the performance of Polybenzoxazine resin (poly (B-BHPF-AF-Hda) 1: 2) is seen table 1.
Embodiment 4
Except that the consumption of bisphenol fluorene and bisphenol AF is adjusted into respectively 0.70g and the 2.69g (the amount of substance ratio is 1: 4), other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Hda 1: 4) powder, yield 82.4% with embodiment 1.Infrared and the proton nmr spectra result is identical with embodiment 1, solidify and test condition with embodiment 1, the performance of Polybenzoxazine resin (poly (B-BHPF-AF-Hda) 1: 4) is seen table 1.
Embodiment 5
Remove the raw material bisphenol AF and replace with dihydroxyphenyl propane; Consumption is 1.14g (5mmol), hexanediamine replaces with 4,4 '-MDA; Consumption is outside the 2.18g (11mmol); Other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-A-Mda 1: 1) powder, yield 79.2% with embodiment 1.
Proton nmr spectra test result (ppm): 6.68～7.75 (20H, Ar-H), 5.28 (4H, bisphenol fluorene O-CH
2-N), 4.50 (4H, Ar-CH on the bisphenol fluorene
2-N), 5.23 (4H, O-CH on the dihydroxyphenyl propane
2-N), 4.37 (4H, dihydroxyphenyl propane Ar-CH
2-N), 3.76 (2H, Ar-CH
2-Ar), 1.59 (6H, on the dihydroxyphenyl propane-CH
3).Examination of infrared spectrum result (cm
-1): 1610,1494,1446,1326,1228,1164,1078,938,862,814 and 742.
Curing and test condition are with embodiment 1, and the performance of Polybenzoxazine resin (poly (B-BHPF-A-Mda) 1: 1) is seen table 1.
Embodiment 6
The consumption that removes bisphenol fluorene and dihydroxyphenyl propane is adjusted into 2.8g and 0.91g (the amount of substance ratio is 2: 1) respectively; 4; 4 '-the MDA consumption is outside the 2.38g (12mmol); Other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Mda 2: 1) powder, yield 75.8% with embodiment 5.Infrared and the proton nmr spectra result is identical with embodiment 5, solidify and test condition with embodiment 1, the performance of Polybenzoxazine resin (poly (B-BHPF-A-Mda) 2: 1) is seen table 1.
Embodiment 7
The consumption that removes bisphenol fluorene and dihydroxyphenyl propane is adjusted into 1.40g and 1.82g (the amount of substance ratio is 1: 2) respectively; Reaction times is outside the 7h; Other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Mda 1: 2) powder, yield 80.8% with embodiment 6.Infrared and the proton nmr spectra result is identical with embodiment 5, solidify and test condition with embodiment 1, the performance of Polybenzoxazine resin (poly (B-BHPF-A-Mda) 1: 2) is seen table 1.
Embodiment 8
Except that the consumption of bisphenol fluorene and dihydroxyphenyl propane is adjusted into respectively 1.05g and the 2.05g (the amount of substance ratio is 1: 3), other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Mda 1: 3) powder, yield 84.4% with embodiment 6.Infrared and the proton nmr spectra result is identical with embodiment 5, solidify and test condition with embodiment 1, the performance of Polybenzoxazine resin (poly (B-BHPF-A-Mda) 1: 3) is seen table 1.
Embodiment 9
Remove 4,4 '-MDA replaces with quadrol, and consumption is outside the 0.66g, and other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-A-Eda 1: 1) powder, yield 74.8% with embodiment 5.
Proton nmr spectra test result (ppm): 6.68～7.29 (20H, Ar-H), 4.80 (4H, O-CH on the bisphenol fluorene
2-N), 4.76 (4H, O-CH on the dihydroxyphenyl propane
2-N), 3.84 (4H, Ar-CH on the bisphenol fluorene
2-N), 3.80 (4H, Ar-CH on the dihydroxyphenyl propane
2-N), 2.83 (4H ,-CH
2-), 1.59 (6H, on the dihydroxyphenyl propane-CH
3).Examination of infrared spectrum result (cm
-1): 1611,1495,1443,1320,1230,1188,1072,933,862,818 and 738.
Curing and test condition are with embodiment 1, and the performance of Polybenzoxazine resin (poly (B-BHPF-A-Eda) 1: 1) is seen table 1.
Embodiment 10
Remove 4,4 '-MDA replaces with octamethylenediamine, and consumption is outside the 1.59g, and other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-A-Oda 1: 1) powder, yield 70.2% with embodiment 5.
Proton nmr spectra test result (ppm): 6.66～7.79 (20H, Ar-H), 4.82 (4H, bisphenol fluorene O-CH
2-N), 4.76 (4H, O-CH on the dihydroxyphenyl propane
2-N), 3.84 (4H, bisphenol fluorene Ar-CH
2-N), 3.79 (4H, Ar-CH on the dihydroxyphenyl propane
2-N), 2.72 (4H, N-CH
2-), 1.58 (6H, on the dihydroxyphenyl propane-CH
3), 1.49,1.33 and 1.24 (12H, octamethylenediamine-CH
2-).Examination of infrared spectrum result (cm
-1): 1613,1494,1446,1319,1231,1121,1070,954,864,819 and 739.
Curing and test condition are with embodiment 1, and the performance of Polybenzoxazine resin (poly (B-BHPF-A-Oda) 1: 1) is seen table 1.
Embodiment 11
Remove bisphenol AF and replace with Bisphenol F; Consumption is 1.00g (5mmol), 4,4 '-MDA replaces with isophorone diamine; Consumption is outside the 1.87g (11mmol); Other condition finally obtains yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-F-Ipda 1: 1) powder, yield 81.8% with embodiment 1.
Proton nmr spectra test result (ppm): 6.44～7.72 (14H, Ar-H), 4.88 (4H, bisphenol fluorene O-CH
2-N), 4.75 (4H, O-CH on the Bisphenol F
2-N), 3.88 (4H, Ar-CH on the bisphenol fluorene
2-N), 3.77 (4H, Ar-CH on the Bisphenol F
2-N), 3.72 (2H, on the Bisphenol F-CH
2-), 3.40 (1H, N-CH-), 3.02 (2H, N-CH
2-), 2.26～2.35 (2H ,-CH
2-), 1.26～1.46 (3H ,-CH
2-), 0.81～1.00 (10H ,-CH
2-with-CH
3).Examination of infrared spectrum result (cm
-1): 1610,1496,1443,1325,1236,1170,1068,933,860,819 and 744, confirm that the gained sample is a title product.
Curing and test condition are with embodiment 1, and the performance of Polybenzoxazine resin (poly (B-BHPF-F-Ipda) 1: 1) is seen table 1.
The thermal property parameter of table 1 fluorenyl Polybenzoxazine resin
The result is visible from table; Second-order transition temperature and thermostability by mixing bis-phenol and diamines synthetic copolymerization fluorenyl Polybenzoxazine are superior to single bis-phenol fluorenyl Polybenzoxazine resin system; And the introducing of wide variety of conventional bis-phenol and diamine monomer; Improve the toughness and the processing characteristics of bis-phenol fluorenyl benzoxazine, reduced raw materials cost, 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 (6)
1. one kind is mixed bisphenol type copolymerization fluorenyl benzoxazine performed polymer, it is characterized in that having following general formula:
In the formula, R be H ,-CH
3Or-CF
3In a kind of, R
1Be C
2～C
8Alkyl,
In a kind of.
2. preparation method who mixes bisphenol type copolymerization fluorenyl benzoxazine performed polymer is characterized in that: in container, adding diamines, mixing bis-phenol and volume by volume concentration is 37 formaldehyde solution, diamines, mix bis-phenol, formaldehyde three amount of substance ratio is 1～1.2: 1: 4; Add organic solvent dissolution, reacted 4～8 hours down, be cooled to room temperature at 50～100 ℃; Add saturated sodium bicarbonate or aqueous sodium carbonate and carry out alkali cleaning, use deionized water wash, separate; Organic layer adds SODIUM SULPHATE ANHYDROUS 99PCT, static 12 hours, filters; Filtrating is removed organic solvent through rotary evaporation, and vacuum-drying promptly obtains mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer.
3. the preparation method of mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer according to claim 2, it is characterized in that: described diamines is C
2～C
8Alkyl diamine, isophorone diamine or 4,4 '-a kind of in the MDA.
4. according to the preparation method of claim 2 or 3 described mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymers; It is characterized in that: described mixing bis-phenol is bisphenol fluorene and dihydroxyphenyl propane, hexafluoro bisphenol-a or 4; 4 '-a kind of mixing in the dioxydiphenyl methane, both amount of substance ratios are 1～3: 5～1.
5. according to the preparation method of claim 2 or 3 described mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymers, it is characterized in that: described organic solvent is a kind of in the mixed solvent formed of trichloromethane, dioxane or absolute ethyl alcohol and dioxane.
6. the preparation method of mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer according to claim 4 is characterized in that: described organic solvent is a kind of in the mixed solvent formed of trichloromethane, dioxane or absolute ethyl alcohol and dioxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210124347 CN102634019B (en) | 2012-04-25 | 2012-04-25 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210124347 CN102634019B (en) | 2012-04-25 | 2012-04-25 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102634019A true CN102634019A (en) | 2012-08-15 |
| CN102634019B CN102634019B (en) | 2013-10-30 |
Family
ID=46618603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210124347 Expired - Fee Related CN102634019B (en) | 2012-04-25 | 2012-04-25 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102634019B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103204991A (en) * | 2013-03-15 | 2013-07-17 | 哈尔滨工程大学 | Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone |
| CN105885044A (en) * | 2016-05-09 | 2016-08-24 | 西南石油大学 | Synthesis method of crude phenol-based benzoxazines resin prepolymers |
| CN106750285A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of fluorine-containing nitrogen benzoxazine polymer-type fire retardant and preparation method thereof |
| CN109081895A (en) * | 2018-07-27 | 2018-12-25 | 贵州理工学院 | A kind of self toughening benzoxazine thermosetting resin and preparation method thereof |
| CN110183817A (en) * | 2019-05-27 | 2019-08-30 | 四川东材科技集团股份有限公司 | Low dielectric fluorenyl benzoxazine resin combination of a kind of high heat resistance high tenacity and its preparation method and application |
| CN115260425A (en) * | 2022-07-18 | 2022-11-01 | 镇江利德尔复合材料有限公司 | Main chain type bio-based benzoxazine resin and preparation method thereof |
| CN115285950A (en) * | 2022-06-14 | 2022-11-04 | 安徽理工大学 | Poly-triazine carbon material and preparation method and application thereof |
| TWI800386B (en) * | 2021-12-16 | 2023-04-21 | 元鴻應用材料股份有限公司 | A kind of benzoxazine resin, its composition and copper foil substrate made of it |
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 |
| CN102408388A (en) * | 2010-09-23 | 2012-04-11 | 汉高公司 | Method For Preparing Benzoxazine By Using Water Based Solvent |
-
2012
- 2012-04-25 CN CN 201210124347 patent/CN102634019B/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 |
| CN102408388A (en) * | 2010-09-23 | 2012-04-11 | 汉高公司 | Method For Preparing Benzoxazine By Using Water Based Solvent |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN103204991A (en) * | 2013-03-15 | 2013-07-17 | 哈尔滨工程大学 | Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone |
| CN103204991B (en) * | 2013-03-15 | 2015-03-11 | 哈尔滨工程大学 | Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone |
| CN105885044A (en) * | 2016-05-09 | 2016-08-24 | 西南石油大学 | Synthesis method of crude phenol-based benzoxazines resin prepolymers |
| CN106750285B (en) * | 2016-11-23 | 2019-07-30 | 厦门大学 | A kind of fluorine-containing nitrogen benzoxazine polymer-type fire retardant and preparation method thereof |
| CN106750285A (en) * | 2016-11-23 | 2017-05-31 | 厦门大学 | A kind of fluorine-containing nitrogen benzoxazine polymer-type fire retardant and preparation method thereof |
| CN109081895A (en) * | 2018-07-27 | 2018-12-25 | 贵州理工学院 | A kind of self toughening benzoxazine thermosetting resin and preparation method thereof |
| CN109081895B (en) * | 2018-07-27 | 2021-06-08 | 贵州理工学院 | Self-toughening benzoxazine thermosetting resin and preparation method thereof |
| CN110183817A (en) * | 2019-05-27 | 2019-08-30 | 四川东材科技集团股份有限公司 | Low dielectric fluorenyl benzoxazine resin combination of a kind of high heat resistance high tenacity and its preparation method and application |
| CN110183817B (en) * | 2019-05-27 | 2022-04-05 | 四川东材科技集团股份有限公司 | High-heat-resistance high-toughness low-dielectric fluorenyl benzoxazine resin composition and preparation method and application thereof |
| TWI800386B (en) * | 2021-12-16 | 2023-04-21 | 元鴻應用材料股份有限公司 | A kind of benzoxazine resin, its composition and copper foil substrate made of it |
| CN115285950A (en) * | 2022-06-14 | 2022-11-04 | 安徽理工大学 | Poly-triazine carbon material and preparation method and application thereof |
| CN115260425A (en) * | 2022-07-18 | 2022-11-01 | 镇江利德尔复合材料有限公司 | Main chain type bio-based benzoxazine resin and preparation method thereof |
| CN115260425B (en) * | 2022-07-18 | 2024-01-26 | 镇江利德尔复合材料有限公司 | Main chain type bio-based benzoxazine resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102634019B (en) | 2013-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102634019B (en) | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof | |
| Zhang et al. | Synthesis and copolymerization of benzoxazines with low-dielectric constants and high thermal stability | |
| CN103936686B (en) | N-semiaromatic alkyl diamine-bisphenol type four degree of functionality fluorenyl benzoxazine and preparation methods | |
| CN102702129B (en) | Ester-group-containing diamine type fluorenyl benzoxazine | |
| CN102617382B (en) | 2-amino-fluorene containing ester group and preparation method thereof | |
| CN102702128B (en) | Ether bond-containing diamine flourenyl benzoxazine | |
| CN103936764B (en) | N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof | |
| CN102660023A (en) | Mixed diamine type copolyfluorene benzoxazine prepolymer and preparation method thereof | |
| CN103304558A (en) | Spirofluorene xanthene benzoxazine containing benzoyloxy group and preparation method thereof | |
| CN105153144A (en) | Main-chain diamine type quinoxalinyl benzoxazine and preparation method thereof | |
| CN102659526A (en) | Tetraphenolic hydroxyfluorene compound and preparation method thereof | |
| CN103896867A (en) | N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional 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 | |
| Zhang et al. | Dendritic organic–inorganic hybrid polyphenol and branched benzoxazine monomers with low curing temperature | |
| CN103204991B (en) | Fluorenyl polyether sulfone resin with side chains containing benzoxazine and preparation method of fluorenyl polyether sulfone | |
| CN102702225B (en) | Four-phenolic fluorene based benzoxazine and preparation method of four-phenolic fluorine based benzoxazine | |
| CN105111199B (en) | Single phenol monoamine type quinoxalinyl benzoxazine and preparation method thereof | |
| CN106496558B (en) | One kind can response type poly (arylene ether nitrile) imide resin and preparation method thereof | |
| CN102585186A (en) | Aryl-1,3,5-triazine polyarylester and preparation method thereof | |
| CN103304578A (en) | Spirofluorene xanthenes bisphenol type benzoxazine | |
| CN109810235B (en) | Ethylene glycol modified melamine formaldehyde resin and preparation method thereof | |
| CN102863619B (en) | Benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin and preparation method thereof | |
| KR101806495B1 (en) | Polymer toughened epoxy resin composition | |
| CN103288849A (en) | Mixed amine-based multi-functionality fluorenyl benzoxazine and synthesis method thereof | |
| CN103288680B (en) | Self-catalyzed fluorenyl bisphthalonitrile resin monomer 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: 20131030 Termination date: 20190425 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |