CN102863619B - Benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin and preparation method thereof - Google Patents
Benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin and preparation method thereof Download PDFInfo
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- CN102863619B CN102863619B CN201210345143.7A CN201210345143A CN102863619B CN 102863619 B CN102863619 B CN 102863619B CN 201210345143 A CN201210345143 A CN 201210345143A CN 102863619 B CN102863619 B CN 102863619B
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Abstract
The present invention is to provide benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin and preparation method thereof.Add mixing dihydric phenol, dichloro diphenyl sulfone, Anhydrous potassium carbonate, N, N '-dimethyl acetamide and toluene, stirring in a reservoir, pass into nitrogen, be warmed up to 150～180 DEG C, after reaction 3h, steam toluene, continue reaction 3h, drop to room temperature, filter, filtrate is joined in the acetum of 1%, filtering, precipitation, through washing, methanol wash column, vacuum drying, obtains hydroxy-end capped copoly type polyether sulfone；Formaldehyde is dissolved in dioxane, stirring, is slowly added dropwise in mixed solution by primary amine, reacts 20～30min, being warmed up to 110 DEG C, join in reactant liquor by copoly type polyether sulfone, react 5h, reactant liquor joins in ethanol, filtering, precipitation is washed through ethanol, vacuum drying, obtains product.Can be used for manufacturing high performance structures material, electronic package material, resistant material etc..
Description
Technical field
The present invention relates to a kind of thermoplastic resin, particularly relate to a kind of benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin.The preparation method that the present invention also relates to a kind of benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin.
Background technology
Polyether sulfone, polyether-ketone are the engineering plastics with good heat stability, corrosion resistance and mechanical performance developed by ICI Imperial Chemical Industries of Britain (ICI) success in 1972, are widely used in the industries such as aviation, communications electronics.Its molecular structure is by sulfone (ketone) base, ether and phenyl ring composition, and due to the existence of sulfone (ketone) base so that molecule has good thermostability, ether ehter bond makes molecule have good mobility, it is easy to processing and forming.It has excellent heat resistance, physical and mechanical properties, insulating properties etc., particularly have and at high temperature can use continuously and remain in temperature environment jumpy to keep the outstanding advantages such as stable performance, be used widely in many fields such as electronic equipment, medical treatment.The mechanical performance of conventional polyether sulfone is poor, it is impossible to meet people's requirement to material property, thus the mechanical performance how improving polyether sulfone materials is always up the emphasis of people's research.
Benzimidazole dihydrochloride is the six-membered cyclic compound of a kind of nitrogenous oxygen heteroatom obtained by polycondensation reaction by phenols, formaldehyde and amine, belongs to the one of phenolic resin, is found by Cope and Holy at first.The resin that this new development is got up not only has hot property and the mechanical property of traditional phenolic resin, also there is solidification process zero volume change, low water absorbable, high glass-transition temperature, high fixing carbon, solidification process does not need to add strong acid and makees catalyst, and solidification process is without features such as gas releases, thus in recent years obtains the extensive concern of international academic community.But this resin there is also some defects, the molecular resin amount as obtained is less, and product is brittle, thus limiting the application of this material.
Benzimidazole dihydrochloride is incorporated in polyether sulfone structure, respective characteristic can be retained, can supply a gap mutually again, so that the mechanical performance of product obtains arriving very much raising, thus reaching people's requirement to material.2011, Yagci etc. are at " Synthesis; characterizationandthermallyactivatedcuringofpolysulfone swithenzoxazineendgroups " [Polymer, 52,1504-1509 (2011)] article has synthesized polymer with bis phenol A ether sulfone telechelic benzoxazine monomer, solidify and obtain benzoxazine resins.Comparing with tradition bisphenol A-type benzimidazole dihydrochloride, the benzimidazole dihydrochloride containing polyether sulfone structure improves a lot in hot property and mechanical performance.
Fluorenes, due to the cardo structure ring containing a non-co-planar structure, is introduced in PEKK structure, can significantly improve the mechanical performance of material.Compared with PEKK material similar with other, this product has better hot property and mechanical performance, it is possible to meet a lot of field requirement to material of industry.
Summary of the invention
It is an object of the invention to provide a kind of benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin with excellent hot property.The present invention also aims to the preparation method that a kind of benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin is provided.
The object of the present invention is achieved like this:
The benzimidazole dihydrochloride end-blocking copoly type fluorenyl polyether-based thermoplastic resin of the present invention has below formula:
In formula: X is-C (CH3)2-or-C (CF3)2-；A isOrIn one, wherein R is the one in phenyl, o-tolyl, a tolyl, p-methylphenyl, methyl, ethyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl or octyl group.
The preparation method of the benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin of the present invention is:
The first step: add mixing dihydric phenol, dichloro diphenyl sulfone in amount of substance than the ratio being 1.5～2:1 in a reservoir, and to add Anhydrous potassium carbonate be catalyst, N, N '-dimethyl acetamide and toluene are solvent, stir 10min, pass into nitrogen, it is warmed up to 150～180 DEG C, after reaction 3h, steams toluene, continue reaction 3h, reactant liquor is dropped to room temperature, filter, filtrate is joined in the acetum of 1%, filtering, precipitation, through washing, methanol wash column, vacuum drying, obtains hydroxy-end capped copoly type polyether sulfone；
Second step: formalin is dissolved in dioxane, stirring at normal temperature 10min, is slowly added dropwise in mixed solution by primary amine, reacts 20～30min, it is warmed up to 110 DEG C, the copoly type polyether sulfone first step obtained joins in reactant liquor, and copoly type polyether sulfone, primary amine and formaldehyde amount of substance ratio for 1:6:15, reacts 5h, reactant liquor is joined in ethanol, filtering, precipitation is washed through ethanol, vacuum drying, obtains white benzimidazole dihydrochloride end-blocking copoly type fluorenyl polyether sulfone thermoplastic resin.
Described mixing dihydric phenol is the mixture of bisphenol fluorene and bisphenol-A, or the mixture of bisphenol fluorene and bisphenol AF.
The structural characterization of the benzimidazole dihydrochloride end-blocking copoly type fluorenyl polyether sulfone performed polymer of the present invention adopts infrared spectrometer (Spotlight100, PE company of the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker).Examination of infrared spectrum adopts pellet technique, Sample Scan 4 times, resolution 4cm-1, sweep limits 4000～500cm-1, proton nmr spectra is mark in making with tetramethylsilane (TMS), deuterochloroform (CDCl3) make solvent.Polymer performance test adopts differential scanning calorimeter (DSC, TA company of the U.S.) and thermogravimetric analyzer (TGA, TA company of the U.S.), and nitrogen atmosphere, heating rate is 10 DEG C/min.
The present invention is with bisphenol fluorene, bisphenol-A or bisphenol AF, dichloro diphenyl sulfone, monoamine, formaldehyde for raw material, through polyethers condensation, Mannich condensation reaction, obtain benzimidazole dihydrochloride end-blocking copoly type fluorenyl polyether sulfone, the copoly type polyether sulfone thermoplastic resin containing polybenzoxazine structure can be obtained through heat cure；Owing to polymer segment containing fluorenyl, improve rigidity and the dissolubility of molecule, and the introducing of bisphenol-A or bisphenol AF adds the toughness of molecule, the resin obtained has the cost of good hot property, mechanical performance, and product and is substantially reduced, can be used for manufacturing high performance structures material, insulant, fire proofing, conducting polymer composite, electronic package material, resistant material etc., can be widely applied for the fields such as electronics, aviation, machine-building.
The benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin that the present invention obtains can be used alone, it is possible to mixing use with other resin materials, the product obtained has good hot property.Can be used for manufacturing high performance structures material, electronic package material, resistant material etc., it is possible to be widely used in electronics, aviation, machine-building energy field.
Detailed description of the invention
Embodiment 1
It is being connected with water knockout drum, the there-necked flask of nitrogen inlet and condensing tube adds bisphenol fluorene and the 2.736g bisphenol-A of 4.2g, the dichloro diphenyl sulfone of 3.44g, the Anhydrous potassium carbonate of 2.5g, add 60ml dimethyl sulfoxide and 10ml toluene, pass into nitrogen, stirring 10min, is warmed up to 160 DEG C, reacts 2h, steam water entrainer, continue reaction 3h, reactant liquor is dropped to room temperature, filter, filtrate is joined in the acetum of 1%, filter, precipitate through washing, methanol wash column several times, vacuum drying, obtain white polyether sulfone 7.82g, productivity 84%.
The formalin of 3.24g37% is joined in there-necked flask, adds 15ml dioxane, stir 30 minutes.Being dissolved in the dioxane of 15ml by the n-butylamine of 1.46g, 0 DEG C is added drop-wise in reactant liquor and continues to react 20min, join in reactant liquor by the polyether sulfone of 3.2g, be warming up to 110 DEG C, react 6 hours, reactant liquor is down to room temperature.Being joined by reactant liquor in ethanol, precipitation filters, then washes several times with ethanol, and vacuum drying obtains yellow end-product.Product 2.72g, productivity 78%.
Proton nmr spectra test result (500M, CDCl3, ppm): δ=6.71 ~ 7.75ppm is the chemical shift of proton on phenyl ring, and 4.83 is O-CH on piperazine ring2The proton characteristic peak of-N, 3.97 is Ar-CH2The proton characteristic peak of-N, 0.87ppm is the proton peak of methyl in normal-butyl structure, and 1.27 ~ 2.79ppm belongs to the proton peak of normal-butyl structure methylene.Examination of infrared spectrum result (KBr, cm-1): 2996 is that the asymmetric stretch of C-H is shaken, and 1241 is that the asymmetric stretch of C-O-C is shaken, and 1302 is that the asymmetric stretch of O=S=O is shaken;1149 is O=S=O symmetrical stretching vibration, and 1099,1013 is C-O-C symmetrical stretching vibration.
By the benzoxazine monomer that obtains in air dry oven according to 160 DEG C/2h, 180 DEG C/2h, 200 DEG C/2h, 220 DEG C/2h, 240 DEG C/2h solidifies, and obtains benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin.Testing through DSC and TGA, obtaining its glass transition temperature (being abbreviated as Tg, identical below) is 221 DEG C, and the heat decomposition temperature (being abbreviated as T5, identical below) of weightless 5% is 395 DEG C, and the carbon yield (C at 800 DEG C800, identical below) and it is 44.6%.
Example 2
Raw material n-butylamine is changed to methylamine, and reaction condition is identical with embodiment 1.
Proton nmr spectra test result (500M, CDCl3, ppm): 1.24ppm belongs to the proton peak of methyl, and 4.83 and 4.72 is O-CH on piperazine ring2The proton characteristic peak of-N, 3.95 and 3.89 is Ar-CH2The proton characteristic peak of-N, other results are identical with example 1.Examination of infrared spectrum result (KBr, cm-1): 3033 is C-H asymmetrical stretching vibration on methyl, and other results are identical with embodiment 1.Solidifying and test condition is with embodiment 1, the benzimidazole dihydrochloride obtained end-blocking its Tg of copolymer fluorenylpolyethersuthermoplastic thermoplastic resin is 245 DEG C, T5It is 435 DEG C, C800It is 49.0%.
Embodiment 3
N-butylamine is changed to octylame, and other reaction conditions are identical with embodiment 1.Proton nmr spectra test result (500M, CDCl3, ppm): O-CH on δ=4.88 and 4.78ppm respectively piperazine ring2The proton characteristic peak of-N, 3.96 and 3.70 is Ar-CH2The proton characteristic peak of-N, 0.98-2.21 is the proton peak of methyl and methylene on octylame, and other are identical with embodiment 1.Condition of cure is identical with embodiment 1, and the Tg of the benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin obtained is 220 DEG C, T5It is 380, C800It is 42.0%.
Embodiment 4
Bisphenol-A replaces with bisphenol AF, and n-butylamine replaces with para-totuidine.Proton nmr spectra test result (500M, CDCl3, ppm): δ=1.34ppm is Ar-C-H3Proton characteristic peak, δ=4.85ppm is O-CH on piperazine ring2The proton characteristic peak of-N, 3.92 is Ar-CH2The proton characteristic peak of-N.Examination of infrared spectrum result (KBr, cm□1): 3057 is methyl asymmetrical stretching vibration peak, and 821 and 873 is that phenyl ring 1,2,4 three replaces absworption peak, and other test results are identical with embodiment 1.Solidifying and test condition is with embodiment 1, the Tg of the benzimidazole dihydrochloride obtained end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin is 258 DEG C, T5It is 519 DEG C, C800It is 52.1%.
Embodiment 5
Para-totuidine is replaced with aniline, and other conditions are identical with embodiment 4.Examination of infrared spectrum result (KBrcm□1): 755 is that phenyl ring 1,2 two replaces absworption peak, and other test results are identical with embodiment 4.Condition of cure is identical with embodiment 1, and the Tg of the benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin obtained is 249 DEG C, T5It is 525 DEG C, C800It is 55.3%.
Embodiment 6
Para-totuidine is replaced with the ortho-aminotoluene of identical molal weight, other conditions are identical with embodiment 4.Examination of infrared spectrum result (KBr, cm□1): 752,721 is that phenyl ring 1,2,3 three replaces absworption peak, and other test results are identical with embodiment 4.Condition of cure is identical with embodiment 1, and the Tg of the benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin obtained is 245 DEG C, T5It is 501 DEG C, C800It is 49.8%.
Can be seen that from experimental result, compared with tradition benzoxazine resins, polyether sulfone is incorporated in benzimidazole dihydrochloride, the shortcomings such as conventional polyether sulfone bad mechanical strength can be overcome, can overcome the disadvantages that again the problems such as common benzimidazole dihydrochloride is brittle, there is good heat stability, can be used for the fields such as advanced composite material matrix resin, electronic package material, insulant, fire proofing.
Claims (2)
1. a benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin, is characterized in that having below formula:
In formula: X is-C (CH3)2-or-C (CF3)2-；A isOrIn one, wherein R is the one in phenyl, o-tolyl, a tolyl, p-methylphenyl, methyl, ethyl, normal-butyl, isobutyl group, the tert-butyl group, sec-butyl or octyl group.
2. a preparation method for the benzimidazole dihydrochloride end-blocking copolymer fluorenylpolyethersuthermoplastic thermoplastic resin described in claim 1, is characterized in that:
The first step: add mixing dihydric phenol, dichloro diphenyl sulfone in amount of substance than the ratio being 1.5～2:1 in a reservoir, and to add Anhydrous potassium carbonate be catalyst, N, N '-dimethyl acetamide and toluene are solvent, stirring 10min, pass into nitrogen, be warmed up to 150～180 DEG C, after reaction 3h, steam toluene, continue reaction 3h, reactant liquor is dropped to room temperature, filter, filtrate is joined in the acetum of 1%, filtering, precipitation, through washing, methanol wash column, vacuum drying, obtains hydroxy-end capped copoly type polyether sulfone；Described mixing dihydric phenol is the mixture of bisphenol fluorene and bisphenol-A, or the mixture of bisphenol fluorene and bisphenol AF；
Second step: formalin is dissolved in dioxane, stirring at normal temperature 10min, is slowly added dropwise in mixed solution by primary amine, reacts 20～30min, it is warmed up to 110 DEG C, the copoly type polyether sulfone first step obtained joins in reactant liquor, and copoly type polyether sulfone, primary amine and formaldehyde amount of substance ratio for 1:6:15, reacts 5h, reactant liquor is joined in ethanol, filtering, precipitation is washed through ethanol, vacuum drying, obtains white benzimidazole dihydrochloride end-blocking copoly type fluorenyl polyether sulfone thermoplastic resin.
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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 |
| 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 |
| CN102634019A (en) * | 2012-04-25 | 2012-08-15 | 哈尔滨工程大学 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
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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 |
| 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 |
| CN102634019A (en) * | 2012-04-25 | 2012-08-15 | 哈尔滨工程大学 | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof |
Non-Patent Citations (1)
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