CN102634019B - Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof - Google Patents
Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof Download PDFInfo
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- CN102634019B CN102634019B CN 201210124347 CN201210124347A CN102634019B CN 102634019 B CN102634019 B CN 102634019B CN 201210124347 CN201210124347 CN 201210124347 CN 201210124347 A CN201210124347 A CN 201210124347A CN 102634019 B CN102634019 B CN 102634019B
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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.A kind of copolymerization fluorenyl benzoxazine performed polymer and preparation method thereof specifically.
Background technology
Benzoxazine is a class novel hot setting resin that grows up on the basis of traditional resol, this resin is except having resol good thermotolerance and flame retardant resistance, fragility and the dimensional instability of resol have also been improved to a certain extent, the most significant advantage is by self ring-opening polymerization formation three-dimensional net structure, discharge without small molecules during curing, the goods porosity is low, and its volume approximate zero is shunk, and high T is arranged
gAnd thermostability, and good mechanical property, electric property, flame retardant properties and high carbon residue rate, thereby use wider at aspects such as advanced composite matrix resin, anti-Ablative resin, electronic product sealing materials.The designability of benzoxazine molecule is very strong, by phenols and the aminated compounds combination of using various structures, and in phenols or amine molecule, introduce the functional groups such as thiazolinyl, alkynyl, itrile group, or carry out blending and modifying with resins such as epoxy, urethane, the functional high molecule material that available can be different.
Bisphenol fluorene is the novel high polymer material monomer that a class has the Cardo ring structure, and its molecular structure is to be linked to each other by a quaternary carbon by four phenyl ring, and huge Cardo side group makes the polymkeric substance chain rigidity that very big raising be 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, the macromolecular materials such as the fluorenyl Resins, epoxy that synthesizes take it as raw material, polyimide, polycarbonate have the characteristics such as good thermostability, humidity resistance, dielectric properties, mechanical property, have widespread use in fields such as matrices of composite material, insulating material, proton exchange membrane.The people such as Wang Jun are at Chinese invention patent " fluorenyl bi-benzoxazine monomer and preparation method thereof " (200810137211.4,2008-09-27) and the people such as Jun Wang at paper " Synthesis, curing behavior and thermal properties of fluorene containing benzoxazines " (" European Polymer Journal ", 46 volume 1024-1031 pages or leaves in 2010) introduced with bisphenol fluorene in, formaldehyde and aromatic series or Armeen are 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) be up to 229 ℃, thermal weight loss 5% and 10% the time corresponding temperature (be 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, because bisphenol fluorene is expensive, and the cured product cross-linking density is low, molecular weight is little, fragility is large.Therefore, need fluorenyl benzoxazine molecular structure is carried out necessary design, to improve polymer performance, enlarge this resinoid further application.
Summary of the invention
The object of the present invention is to provide a kind of mixing bisphenol type copolymerization fluorenyl benzoxazine performed polymer with high molecular of good thermal characteristics.The present invention also aims to provide a kind of is not affecting 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:
Adding diamines in the container, mixing bis-phenol and volume by volume concentration is 37 formaldehyde solution, diamines, mixing bis-phenol, formaldehyde three molar ratio are 1～1.2: 1: 4, add organic solvent dissolution, 50～100 ℃ of lower reactions 4～8 hours, 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 anhydrous sodium sulphate, static 12 hours, filter, filtrate is removed organic solvent through rotary evaporation, and vacuum-drying namely 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 diaminodiphenylmethane.
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 molar ratios are 1～3: 5～1.
Described organic solvent is a kind of in the mixed solvent that forms of trichloromethane, dioxane or dehydrated alcohol and dioxane.
The structural characterization of copolymerization fluorenyl benzoxazine performed polymer of the present invention adopts infrared spectrometer (Spotlight 100, U.S. PE company) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker).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.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 10 ℃/min.
What a kind of in bisphenol fluorene and dihydroxyphenyl propane, bisphenol AF or the Bisphenol F of the present invention formed mixes bis-phenol as the phenol source, take aliphatics, alicyclic or aromatic diamine as the amine source, adopt solvent method to synthesize copoly type fluorenyl benzoxazine performed polymer, by adjusting monomeric species and the ratio of bisphenol fluorene and bisphenol compound or diamines, obtain the different fluorenyl Polybenzoxazine resin of performance, can be used for the 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, the deficiencies such as fluorenyl Polybenzoxazine resin rigidity is large, poor toughness have not only been improved, the cross-linking density of polymkeric substance increases, second-order transition temperature, resistance toheat and wet-hot aging performance improve a lot and improve, but also greatly reduce raw materials cost.
Embodiment
Below by embodiment the present invention is specifically described; 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 limiting the scope of the 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
To agitator is housed, prolong, the formaldehyde solution 3.25g (40mmol) of adding 37% in the there-necked flask of thermometer, bisphenol fluorene 1.75g (5mmol), bisphenol AF 1.68g (5mmol) and hexanediamine 1.15g (10.3mmol), in the trichloromethane of 40mL, dissolve, be heated to 65 ℃, and under this temperature, react 5h, reaction is cooled to room temperature after finishing, with saturated sodium bicarbonate and deionized water wash, separate, organic layer adds the static 12h of anhydrous sodium sulphate, filter, filtrate is removed trichloromethane through rotary evaporation, vacuum-drying, obtain 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), methylene radical rocking vibration on the 1322 (oxazine rings), 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 vibrations), be phenyl ring Lian Jie oxazine characteristic of a ring absorption peak, 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 infrared spectra institute's synthetic sample is target product.
B-BHPF-AF-Hda is put into electric drying oven with forced convection, adopt programmed temperature method that monomer is carried out thermofixation, curing cycle 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 respectively 2.33g and 1.12g (molar ratio is 2: 1), reaction times is outside the 6h, trichloromethane replaces with dioxane, temperature of reaction is outside 90 ℃, 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) sees Table 1.
Embodiment 3
The consumption that removes bisphenol fluorene and bisphenol AF is adjusted into respectively 1.17g and 2.24g (molar ratio is 1: 2), trichloromethane replaces with dioxane and dehydrated alcohol mixed solvent, both volume ratios are 1: 1, temperature of reaction is outside 80 ℃, 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) sees Table 1.
Embodiment 4
Except the consumption of bisphenol fluorene and bisphenol AF is adjusted into respectively 0.70g and the 2.69g (molar ratio is 1: 4), other condition is with embodiment 1, finally obtain yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Hda 1: 4) powder, yield 82.4%.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: 4) sees Table 1.
Embodiment 5
Except the raw material bisphenol AF replaces with dihydroxyphenyl propane, consumption is 1.14g (5mmol), hexanediamine replaces with 4,4 '-diaminodiphenylmethane, 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) sees Table 1.
Embodiment 6
The consumption that removes bisphenol fluorene and dihydroxyphenyl propane is adjusted into respectively 2.8g and 0.91g (molar ratio is 2: 1), 4,4 '-the diaminodiphenylmethane consumption is outside the 2.38g (12mmol), other condition is with embodiment 5, finally obtain yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Mda 2: 1) powder, yield 75.8%.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) sees Table 1.
Embodiment 7
The consumption that removes bisphenol fluorene and dihydroxyphenyl propane is adjusted into respectively 1.40g and 1.82g (molar ratio is 1: 2), 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) sees Table 1.
Embodiment 8
Except the consumption of bisphenol fluorene and dihydroxyphenyl propane is adjusted into respectively 1.05g and the 2.05g (molar ratio is 1: 3), other condition is with embodiment 6, finally obtain yellow copolymerization fluorenyl benzoxazine performed polymer (B-BHPF-AF-Mda 1: 3) powder, yield 84.4%.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) sees Table 1.
Embodiment 9
Except 4,4 '-diaminodiphenylmethane 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) sees Table 1.
Embodiment 10
Except 4,4 '-diaminodiphenylmethane 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) sees Table 1.
Embodiment 11
Except bisphenol AF replaces with Bisphenol F, consumption is 1.00g (5mmol), 4,4 '-diaminodiphenylmethane 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-and-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 target product.
Curing and test condition are with embodiment 1, and the performance of Polybenzoxazine resin (poly (B-BHPF-F-Ipda) 1: 1) sees Table 1.
The Thermal Parameter of table 1 fluorenyl Polybenzoxazine resin
The result as seen from table, be better than single bis-phenol fluorenyl Polybenzoxazine resin system by second-order transition temperature and the thermostability of mixing the synthetic copolymerization fluorenyl Polybenzoxazine of bis-phenol and diamines, and the introducing of wide variety of conventional bis-phenol and diamine monomer, toughness and the processing characteristics of bis-phenol fluorenyl benzoxazine have been improved, reduce raw materials cost, can be used for the fields such as advanced composite material matrix resin, electronic package material, insulating material, fire retardant material, ablation resistant material and laminating material.
Claims (1)
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.
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| 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 |
| 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 |
| CN109081895B (en) * | 2018-07-27 | 2021-06-08 | 贵州理工学院 | Self-toughening benzoxazine thermosetting resin and preparation method thereof |
| 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 |
| 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 |
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| 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 using aqueous solvent |
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| CN102408388A (en) * | 2010-09-23 | 2012-04-11 | 汉高公司 | Method for preparing benzoxazine using aqueous solvent |
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