CN103435802A - Para-oriented diketoanhydride type polyimide TDPA-PI resin and production method thereof - Google Patents
Para-oriented diketoanhydride type polyimide TDPA-PI resin and production method thereof Download PDFInfo
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Abstract
The invention provides high temperature resistant, high-strength and high-modulus 4,4'-terephthaloyl diphthalicanhydride type polyimide resins, which have the following structure shown in specification, wherein Tg of a TDPA-PI-4,4'-MDA thin film is 278.4 DEG C, Td (5%) of the TDPA-PI-4,4'-MDA thin film is 540 DEG C, the tensile strength of the TDPA-PI-4,4'-MDAthin film is 158.0 MPa, the elongation at break of the TDPA-PI-4,4'-MDA thin film is 15.7% and the elasticity modulus of the TDPA-PI-4,4'-MDA thin film is 2.26 GPa; Tg of a TDPA-PI-4,4'-ODA thin film is 262.4 DEG C, Td (5%) of the TDPA-PI-4,4'-ODA thin film is 581.7 DEG C, the tensile strength of the TDPA-PI-4,4'-ODA thin film is 261.7 MPa, the elongation at break of the TDPA-PI-4,4'-ODA thin film is 12.6% and the elasticity modulus of the TDPA-PI-4,4'-ODA thin film is 3.75 MPa. The invention also discloses a production method of the high temperature resistant, high-strength and high-modulus 4,4'-terephthaloyl diphthalicanhydride type polyimide resins.
Description
Technical field:
The present invention relates to the high-performance polyimide technology of preparing, particularly a class is high temperature resistant, high-strength and high-modulus 4,4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin and preparation method thereof.
Background technology:
High-performance polyimide (PI) has the performances such as outstanding thermo-oxidative stability, electrical insulating property, cohesiveness, excellent mechanical mechanics property and workability, in high-technology field widespread uses such as aerospace industry, military equipment, microelectronics and electromechanical equipments.
The PI preparation method who has reported has more than ten to plant, the two-step synthesis that aromatic series tetracarboxylic acid dicarboxylic anhydride and aryl diamine be monomer of take is method the most frequently used in the PI suitability for industrialized production, its technique is relatively ripe, the monomer dianhydride of preparation PI and the kind of diamines are more, and the combination of different monomers can obtain the different PI kind of performance.By fragrant dianhydride difference used, principal item has equal benzene type, ether acid anhydride type, ketone acid anhydride type, biphenyl dianhydride type, fluorine acid anhydride type etc.Main goods comprise moulding compound component, wire enamel, film, fiber, prepreg/matrix material, coating, sizing agent and foam etc.
By 3,3 ', 4, the single ketones acid anhydride type polyimide that 4 '-benzophenone tetracarboxylic acid dianhydride and aromatic diamine polycondensation make, its preparation technology is simple, the excellent property of goods, and the life-time service temperature is 260 ℃～300 ℃, at first About Monsanto Chemicals realized suitability for industrialized production in 1967, and had formed sky bond700,720, the series product trades mark such as 6234.It is LARC-TPI that langley company of NASA (NASA, Langley Co) discloses the serial trade mark, LARC-2, patent (US.pat.4,065,345,1977 of 3,4 polyimide such as type such as acid anhydride such as single ketones such as grade; US.pat.4,094,862,1978; US.pat.4,543,295,1985).
Single ketones acid anhydride type PI, for making layer pressing plate, flexible printed circuit board, matrix material, film, binding agent, coating and porous plastics etc., can prepare the high-temperature-resistant structure parts, as the part in supersonic plane, rocket, jet engine etc.
United States Patent (USP) (US.pat.4,937,317,1990) disclose by 4,4 '-isophthaloyl diphthalic anhydrides (IDPA) and mphenylenediamine (m-PDA) prepare end-blocking and the method for the high temperature resistant PI resin of end-blocking diketone acid anhydride type not, trade mark called after LARC-I-TPI.
LARC-I-TPI can regard the isomer of LARC-TPI as, and they have similar mechanical mechanics property and thermal characteristics, but avoids having used mutagenic high toxicity diamine monomer 3,3 '-diaminobenzophenone (3,3 '-DABP).End-blocking and not the LARC-I-TPI of end-blocking there is good molding performance, adhesiveproperties, thermo-oxidative stability and melt fluidity, be particularly useful for making matrix resin, thermal structure tackiness agent and the laminating material etc. of large complicated shape carbon fibre reinforced composite.
Summary of the invention:
4,4 '-paraphenylene terephthalamide diphthalic anhydrides (TDPA) can be regarded as 4, the isomer of 4 '-isophthaloyl diphthalic anhydrides (IDPA), and they have similar structure.The invention discloses by TDPA and 4,4 '-diaminodiphenylmethane (4,4 '-MDA) or TDPA and 4,4 '-diaminodiphenyl oxide (4,4 '-ODA) make polyamic acid solution through solution polycondensation, after desolventizing, adopt the high temperature hot imidization to prepare the method for two kinds of novel polyimide based on TDPA.
Technical scheme of the present invention is as follows:
4 of a kind of high molecular, 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, they have following structure:
The N,N-DIMETHYLACETAMIDE that their concentration is 0.5g/dL (DMAc) solution, under 1 ℃ of 30 ℃ of scholar with the logarithmic specific concentration viscosity (η inh) of determination of ubbelohde viscometer >=1.0dL/g.
One class is high temperature resistant, high-strength and high-modulus 4, and 4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin, they have following structure:
They are by 4 of above-mentioned high molecular, 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid hot imidization make 4,4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin, the tensile strength >=158MPa of their films, elongation at break >=12.6%.
A kind of prepare above-mentioned 4, the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, it comprises the steps:
Step 1. is with homemade polymerization-grade TDPA and commercially available 4,4 '-MDA or 4,4 '-ODA is monomer, with N, N-N,N-DIMETHYLACETAMIDE (DMAc) or N-Methyl pyrrolidone are solvent, adopt-5 ℃～60 ℃ of solution polycondensations to make the TDPA-PAA-4 of high molecular, 4 '-MDA or TDPA-PAA-4,4 '-ODA polyamic acid solution;
The polyamic acid that step 2a. obtains step 1 with solvent is Precipitation from DMAc solution, after filtration, filtrate is reclaimed, precipitation solvent and DMAc recycle, the polyamic acid solid separated by methanol wash for several times, make TDPA-PAA-4 after drying, 4 '-MDA or TDPA-PAA-4,4 '-ODA moulding compound.
Above-mentioned preparation 4, the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, described step 2a can substitute with following step 2b:
The DMAc solution of the polyamic acid that step 2b. makes step 1 directly salivates into film on clean sheet glass, and the thickness of controlling film is 0.2-0.4mm, then, at air dry oven desolventizing DMAc, obtains Polyamic Acid Film.
Above-mentioned preparation 4, the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, the described fragrant dianhydride TDPA of step 1 and aryl diamine 4,4 '-MDA or 4, mole proportioning of 4 '-ODA is 0.98～1.05:1.00, the optimum molar proportioning is 1.02:1.00.
Above-mentioned preparation 4, the method of 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, the solvent of the described polycondensation of step 1 is DMAc preferably, water-content in solvent should be lower than 150ppm, monomer molar concentration is 0.20～0.50, the optimum molar concentration of monomer is 0.30～0.40, and controlling solid content is 18.0～20.0%.
Above-mentioned preparation 4, the method of 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, the temperature of the described polycondensation of step 1 preferably initial reaction temperature is controlled at-5 ℃～5 ℃, after reacting one hour, slowly heat up, temperature of reaction is controlled at 10 ℃～25 ℃.
Above-mentioned preparation 4, the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, the time of the described polycondensation of step 1 is controlled in 5h～16h scope, and the preferred reaction times is 7h～8h.
Above-mentioned preparation 4, the method of 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, the precipitation agent of the described polyamic acid of step 2a can be methyl alcohol, ethanol, acetone, butanone, 1, organic solvent or their mixtures such as 2-ethylene dichloride or methylene dichloride, 1.0～3.0 times (V/V) that the consumption of precipitation agent is DMAc; Best selection is methyl alcohol, is characterized in differing greatly with the boiling point of DMAc, easily recovery and cheap.
A kind of prepare above-mentioned 4, the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin, it comprises the steps:
Step 3a. is by above-mentioned preparation 4, the TDPA-PAA-4 that the step 2a of the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid makes, 4 '-MDA and TDPA-PAA-4,4 '-ODA moulding compound is hot-forming, hot-forming temperature: 180 ℃ of 1h, 220 ℃ of 1h, 250 ℃ of 1h, 280 ℃ of 1h, 300 ℃ of 1h, 320 ℃ of 30min, obtain 4,4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin.
A kind of prepare above-mentioned 4, the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin, it comprises the steps:
Step 3b. is by above-mentioned preparation 4, and the film after the step 2b desolventizing of the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid is placed on fixture and applies the power drawing-off, puts into the retort furnace heating, temperature programming hot imidization: 180 ℃ of 1h, 220 ℃ of 1h, 250 ℃ of 1h, 280 ℃ of 1h, 300 ℃ of 1h, 320 ℃ of 30min, be cooled to normal temperature, makes golden yellow tough and tensile TDPA-PI-4,4 '-MDA or TDPA-PI-4,4 '-ODA resin film.
Described TDPA-PAA-4,4 '-MDA and TDPA-PAA-4, the hot imidization system of 4 '-ODA polyamic acid is determined (seeing Fig. 1, Fig. 2) by dsc (DSC).From Fig. 1 and Fig. 2, TDPA-PAA-4,4 '-MDA or TDPA-PAA-4,2 endotherm(ic)peaks appear in the intensification line of 4 '-ODA, first endotherm(ic)peak is that solvent evaporates or residue (acid anhydrides and amino) further generation condensation reaction in temperature-rise period are caused.The 2nd peak is to lose H in the imidization process
2the endotherm(ic)peak of O, the 2nd line is the DSC curve after the polyamic acid hot imidization, can observe second-order transition temperature (T
g).The results are shown in table 1.
The dsc analysis of table 1.TDPA-PAA and TDPA-PI
* T
i: the imidization starting temperature; T
t: the imidization summit temperature; T
f: imidization peak finishing temperature; T
g: second-order transition temperature.
The imidization degree characterizes (Fig. 3, Fig. 4, Fig. 5, Fig. 6) with FT-IR, and the ownership of the principal character absorption peak after polyamic acid and imidization is listed in table 2 and table 3.
The ownership of the principal character absorption peak of table 2.TDPA-PAA
The ownership of the principal character absorption peak of table 3.TDPA-PI
8) the superpolyamide acid 1) refers to the logarithmic specific concentration viscosity (η of solution of the DMAc of 0.5% polyamic acid
inh)>=1.0.
The accompanying drawing explanation
Fig. 1 is the dsc analysis curve, and a is TDPA-PAA-4, and 4 '-MDA and b are TDPA-PI-4,4 '-MDA;
Fig. 2 is the dsc analysis curve, and a is TDPA-PAA-4, and 4 '-ODA and b are TDPA-PI-4,4 '-ODA;
Fig. 3 is TDPA-PAA-4, the infared spectrum of 4 '-MDA;
Fig. 4 is TDPA-PI-4, the infrared spectrum of 4 '-MDA;
Fig. 5 is TDPA-PAA-4, the infared spectrum of 4 '-ODA;
Fig. 6 is TDPA-PI-4, the infared spectrum of 4 '-ODA.
Embodiment:
Following examples are to further illustrate of the present invention, rather than limit the scope of the invention.
The condition determination of the logarithmic specific concentration viscosity of TDPA-PAA diketone acid anhydride type polyamic acid: the DMAc solution of the TDPA-PAA that polycondensation is made is diluted to 0.5g/dL with DMAc, with Ubbelohde viscometer, in 30 ℃ of Water Tanks with Temp.-controlled, measures, and presses η
inh=C
-1lnt
1/ t
0calculate the concentration that in formula, C is polyamic acid (g/dL), t
0, t
1be respectively the time that the DMAc solution of solvent DMAc and polyamic acid is flowed through in the Ubbelohde viscometer kapillary, unit is second; 4,4 '-diaminodiphenyl oxide (4,4 '-ODA), 4,4 '-diaminodiphenylmethane (4,4 '-MDA) is chemically pure reagent; DMAc, commercially available industrial goods, add a small amount of CaH
2rear heavy steaming; Differential scanning calorimeter (DSC): NetzchDSC200F3 type differential scanning calorimeter, Germany, nitrogen atmosphere, gas flow rate is 20mL/min, temperature rate is 10 ℃/min; Mechanics Performance Testing is carried out on the SANS microcomputer controlled electronic universal tester, model: CMT8102, Shenzhen Sans Material Detection Co., Ltd; Infrared spectroscopy: Perkin-Elmer SP one FT-IR spectrograph, U.S. PE company, KBr compressing tablet.
The preparation of polymerization-grade TDPA:
(1) preparation of Isosorbide-5-Nitrae-bis-(3 ', 4 '-dimethylbenzoyl) benzene (I)
In tri-mouthfuls of vials of the 1000ml of the dried and clean that prolong and electric mixer are housed, add successively 66.8g(0.50mol) aluminum trichloride (anhydrous), o-Xylol 46.64g(0.44mol), the 150ml orthodichlorobenzene, 1mlDMF, bathe cooling reaction mixture with-20 ℃～-10 ℃ cryosels, stirs, by 40.60g(0.20mol) p-phthaloyl chloride (TPC) adds in reaction flask every minutes 3～4 batches, about 30min, and the HCl gas that reaction is emitted enters anhydrous CaCl through surge flask
2after drying tower, with dilute NaOH solution, absorb.Bathe cooling lower reaction 1h at cryosel after adding last batch of TPC, remove cryosel and bathe, (20 ℃～30 ℃) lower stirring reaction 4～5h that continues under normal temperature.Bathe in cooling downhill reaction bottle and drop into 200ml left and right frozen water 1 time at cryosel, decompression steams the azeotrope of o-Xylol, orthodichlorobenzene and water, static layering, and the orthodichlorobenzene separated is cycled to repeat use after dehydration is heavily steamed.After having steamed orthodichlorobenzene, separate out faint yellow powdery solid in reaction flask, after filtration, soak with rare HCl, diluted alkaline successively, filter, solid is neutrality with deionized water wash 3～5 times to pH value in filtrate.Solid 1:1(v/v) 95% ethanol and ethylene dichloride recrystallization obtain white crystalline solid 65.2g, yield: 95.4%(calculates with the TPC consumption), mp:180 ℃～181.5 ℃.
FT-IR(KBr):
1605.28cm-1,1570.01cm-1,1493.93cm-1,1443.13cm-1 all belongs to phenyl ring skeletal vibration absorption peak; 2973.13cm-1,2942.35cm-1,2917.34cm-1 belongs to the C-H vibration absorption peak; 1384.27cm-1 be-CH
3charateristic avsorption band; 735.64cm-1 be that adjacent dimethyl replaces on phenyl ring; 826.12cm-1 Isosorbide-5-Nitrae-carbonyl substituted on phenyl ring; 1644.32cm-1 the stretching vibration charateristic avsorption band of carbonyl.
1H-NMR(CDCl
3,δppm):7.878(4H,d);7.669(2H,s);7.600-7.581(2H,d);7.290-7.271(2H,d);2.384(6H,s);2.362(6H,s)
(2) preparation of Isosorbide-5-Nitrae-bis-(3 ', 4 '-diformazan carboxylbenzoyl) benzene (II)
Electric mixer is being housed; in the 500ml there-necked flask of reflux condensing tube, add 17.1g(0.05mol) Isosorbide-5-Nitrae-bis-(3 '; 4 '-dimethylbenzoyl) benzene (I); deionized water 100ml, stir and add the 1mL bromine, is heated to 50 ℃～75 ℃; slowly drip the aqueous solution 20ml of 0.05g dibenzoyl peroxide; bromine water brown adds the 150ml pyridine after taking off fully, is warming up to 90 ℃～100 ℃ minutes 3～4 times and adds 63.2g(0.4mol) KMnO
4solid, stirring reaction is to KMnO
4aqueous solution purple takes off fully.Filter, hot wash 2～3 times for filter residue MnO2, merging filtrate, the azeotrope of Distillation recovery pyridine and water is cycled to repeat use.Filtrate is adjusted pH value to 1～2 with concentrated hydrochloric acid, separates out white solid, filter, and with deionized water wash 3～4 times, predrying 4～6h under 80 ℃～100 ℃, 120 ℃ of lower vacuum-drying 6h left and right, obtain white powder solid II 21.8g, yield 94.3%.
FT-IR(KBr): 3202cm
-1carboxyl-OH association absorption peak; 1724.4cm
-1-COOH charateristic avsorption band; 1498.8cm
-1, 1567.5cm
-1, 1603.4cm
-1for phenyl ring skeletal vibration peak; 1655.3cm
-1the carbonyl charateristic avsorption band; 729cm
-1the adjacent dicarboxyl of phenyl ring replaces; 830.4cm
-1phenyl ring Isosorbide-5-Nitrae two replaces.
1H-NMR(CF
3COOD,CDCl
3,δppm):8.252-8.275(2H,s);8.205-8.223(2H,d);8.070-8.125(4H,d);7.774-7,810(2H,d).
(3) 4, the preparation of 4 '-paraphenylene terephthalamide diphthalic anhydrides (TDPA)
Reflux condensing tube is being housed, N
2in the 500ml there-necked flask of gas delivery line and electric mixer, add 18.48g(0.04mol) II, 23ml(38g, 0.32mol) thionyl chloride, the anhydrous ZnCl of 0.5g
2, the 60ml ethylene dichloride, stir, and is heated to react 6～7h under reflux temperature, and excessive thionyl chloride and solvent ethylene dichloride are reclaimed in air distillation.Add the ethylene dichloride that 60ml is cold, the solid in the agitator treating reaction flask, filter, and repeats 2～3 times, after filtrate merges, reclaims ethylene dichloride, and the white powder solid obtained, at 120 ℃ of vacuum drying oven inner drying 4～6h, obtain 16.1g TDPA, yield 93.5%.
Embodiment 1:
Electric mixer, N are being housed
2derive in the 250mL there-necked flask of dried and clean of pipe, add 2.97g(0.015mol) 4,4 '-MDA, 25mLDMAc, pass into dry N
2stirring is dissolved diamines fully, add 6.52g(0.0153mol under-5 ℃～5 ℃ cryosels baths are cooling) TDPA and 25mLDMAc, stirring reaction 30min recession deicing salt bath, continue stirring reaction 7h under 15 ℃～25 ℃, obtain faint yellow TDPA-PAA-4, the thick solution of 4 '-MDA polyamic acid.Solid content 18.96%, η
inh=1.18dL/g.
By TDPA-PAA-4,4 '-MDA polyamic acid solution sand core filter suction filtration, discontinuous degassing, resin liquid is filmed on clean glass plate, control the thickness 0.30mm left and right of film, after 90 ℃ ± 10 ℃ desolventizing film forming, film is fixed on to drawing-off on homemade stainless steel shelf, heat up and carry out hot imidization at the retort furnace Program: 180 ℃ of 1h, 220 ℃ of 1h, 250 ℃ of 1h, 280 ℃ of 1h, 300 ℃ of 1h, 320 ℃ of 30min.Be cooled to normal temperature, make TDPA-PI-4,4 '-MDA film.The Tg:278.4 ℃ of film, (5%) 540 ℃ of Td, tensile strength 158.0MPa, elongation at break 15.7%, Young's modulus 2.26GPa.
Embodiment 2:
Change TDPA and 4,4 '--the reinforced order of MDA, adopt reverse reinforced method, first add after TDPA dissolves and add again 4,4 '-MDA, experimentation is as embodiment 1, the polyamic acid TDPA-PAA-4 made, the η of 4 '-MDA
inh=0.73dL/g.
Embodiment 3:
According to the method for embodiment 1, the volumetric molar concentration of monomer is 0.30, and the polycondensation temperature is-5 ℃～20 ℃, and reaction times 7～8h changes TDPA and 4, mole proportioning of 4 '-MDA, and experimental result is listed in table 4.
Table 4.TDPA and 4, mole proportioning of 4 '-MDA is to TDPA-PAA-4, the η of 4 '-MDA
inhimpact
Embodiment 4:
According to the method for embodiment 1,4, mole proportioning of 4 '-MDA, TDPA is 1.00:1.02, and the polycondensation temperature is-5 ℃～20 ℃, and reaction times 7～8h changes monomer 4, the volumetric molar concentration of 4 '-MDA, TDPA, experimental result is listed in table 5.
Table 5.TDPA and 4, the volumetric molar concentration of 4 '-MDA is to TDPA-PAA-4, the η of 4 '-MDA
inhimpact
Embodiment 5:
Electric mixer, N are being housed
2derive in the 250mL there-necked flask of dried and clean of pipe, add 3.00g(0.015mol) 4,4 '-ODA, 25mLDMAc, pass into N
2stirring makes 4,4 '-ODA dissolves fully, add 6.518g(0.0153mol under-5 ℃～5 ℃ cryosels baths are cooling) TDPA and 25mLDMAc, stirring reaction 30min, remove cryosel and bathe, and continues stirring reaction 7h under 15 ℃～25 ℃, make faint yellow TDPA-PAA-4,4 '-ODA polyamic acid solution.Solid content 19.04%, η
inh=1.28dL/g.
By TDPA-PAA-4,4 '-ODA polyamic acid solution sand core filter suction filtration, discontinuous degassing, resin liquid is filmed on clean sheet glass, control the thickness 0.30mm left and right of film, in 90 ℃ ± 10 ℃ air dry ovens, after the desolventizing film forming, film is fixed on to drawing-off on homemade stainless steel shelf, heat up and carry out hot imidization at the retort furnace Program: 180 ℃ of 1h, 220 ℃ of 1h, 250 ℃ of 1h, 280 ℃ of 1h, 300 ℃ of 1h, 320 ℃ of 30min.Be cooled to normal temperature, make TDPA-PI-4,4 '-ODA film.The Tg:262.4 ℃ of film, (5%) 581.7 ℃ of Td, tensile strength 261.7MPa, elongation at break 12.6%, Young's modulus 3.75GPa.
Embodiment 6:
According to the described method of embodiment 5, TDPA and 4,4 '--mole proportioning of bis-kinds of monomers of ODA is set as 1.02:1.00, polycondensation reaction time 8h, the TDPA-PAA-4 made under condition of different temperatures, the η of 4 '-ODA polyamic acid
inhchange and list in table 6.
Table 6. polycondensation temperature is to TDPA-PAA-4,4 '-ODA η
inhimpact
Embodiment 7:
According to the described method of embodiment 5, TDPA and 4, mole proportioning of 4 '-ODA is set as 1.02:1.00, and the polycondensation temperature is-5 ℃～20 ℃, and the reaction times is 7～8h, changes the volumetric molar concentration of monomer, the results are shown in table 7.
Table 7. monomer molar concentration is to TDPA-PAA-4,4 '-ODA η
inhimpact
Embodiment 8
According to the described method of embodiment 5, TDPA and 4, mole proportioning of 4 '-ODA is set as 1.02:1.00, and monomer molar concentration is 0.30mol/L, and the polycondensation temperature is-5 ℃～20 ℃, and polycondensation reaction time is to TDPA-PAA-4,4 '-ODA η
inhimpact, experimental result is listed in table 8.
Table 8. polycondensation reaction time is to TDPA-PAA-4,4 '-ODA η
inhimpact
Claims (9)
1. 4 of a high molecular, 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid is characterized in that they have following structure:
The N,N-DIMETHYLACETAMIDE that their concentration is 0.5g/dL (DMAc) solution, the logarithmic specific concentration viscosity (η of use determination of ubbelohde viscometer under 30 ℃ ± 1 ℃
inh)>=1.0dL/g.
2. a class is high temperature resistant, high-strength and high-modulus 4, and 4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin is characterized in that they have following structure:
They are by 4 of high molecular claimed in claim 1,4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid through hot imidization, make 4,4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin, tensile strength >=the 158MPa of their films, elongation at break >=12.6%.
3. one kind prepares claimed in claim 1ly 4, and the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, is characterized in that it comprises the steps:
Step 1. is with homemade polymerization-grade TDPA and commercially available 4,4 '-MDA or 4,4 '-ODA is monomer, with N, N-N,N-DIMETHYLACETAMIDE (DMAc) or N-Methyl pyrrolidone are solvent, adopt-5 ℃～60 ℃ of solution polycondensation 5-16 hour to make the TDPA-PAA-4 of high molecular, 4 '-MDA or TDPA-PAA-4,4 '-ODA polyamic acid solution;
The polyamic acid that step 2a. obtains step 1 with solvent is Precipitation from DMAc solution, after filtration, filtrate is reclaimed, precipitation solvent and DMAc recycle, the polyamic acid solid separated by methanol wash for several times, make TDPA-PAA-4 after drying, 4 '-MDA or TDPA-PAA-4,4 '-ODA moulding compound.
4. preparation 4 according to claim 3, the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid is characterized in that described step 2a substitutes with following step 2b:
The DMAc solution of the polyamic acid that step 2b. makes step 1 directly salivates into film on clean sheet glass, and the thickness of controlling film is 0.2-0.4mm, then, at air dry oven desolventizing DMAc, obtains Polyamic Acid Film.
5. according to the described preparation 4 of claim 3 or 4, the method of 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, it is characterized in that: the described fragrant dianhydride TDPA of step 1 and aryl diamine 4,4 '-MDA or 4, mole proportioning of 4 '-ODA is 0.98～1.05:1.00, and the optimum molar proportioning is 1.02:1.00.
6. according to the described preparation 4 of claim 3 or 4, the method of 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, it is characterized in that: the solvent of the described polycondensation of step 1 is DMAc, and the water-content in solvent should be lower than 150ppm, and monomer molar concentration is 0.20～0.50.
7. the above-mentioned preparation 4 according to claim, the method of 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid, the precipitation agent of the described polyamic acid of step 2a can be methyl alcohol, ethanol, acetone, butanone, 1, organic solvent or their mixtures such as 2-ethylene dichloride or methylene dichloride, 1.0～3.0 times (V/V) that the consumption of precipitation agent is DMAc.
8. one kind prepares claimed in claim 2ly 4, and the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin, is characterized in that it comprises the steps:
Step 3a. is by the described preparation 4 of claim 3, the TDPA-PAA-4 that the step 2a of the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid makes, 4 '-MDA and TDPA-PAA-4,4 '-ODA moulding compound is hot-forming, hot-forming temperature: 180 ℃ of 1h, 220 ℃ of 1h, 250 ℃ of 1h, 280 ℃ of 1h, 300 ℃ of 1h, 320 ℃ of 30min, obtain 4,4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin.
9. one kind prepares claimed in claim 2ly 4, and the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides polyimide type resin, is characterized in that it comprises the steps:
Step 3b. is by the described preparation 4 of claim 4, and the film after the step 2b desolventizing of the method for 4 '-paraphenylene terephthalamide diphthalic anhydrides type polyamic acid is placed on fixture and applies the power drawing-off, puts into the retort furnace heating, temperature programming hot imidization: 180 ℃ of 1h, 220 ℃ of 1h, 250 ℃ of 1h, 280 ℃ of 1h, 300 ℃ of 1h, 320 ℃ of 30min, be cooled to normal temperature, makes golden yellow tough and tensile TDPA-PI-4,4 '-MDA or TDPA-PI-4,4 '-ODA resin film.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623544A (en) * | 2018-07-10 | 2018-10-09 | 江西师范大学 | A kind of preparation method of 4,4 '-two (3,4- dicarboxylic acid anhydrides benzoyl) biphenyl |
| CN114210180A (en) * | 2021-12-17 | 2022-03-22 | 宁波威霖住宅设施有限公司 | Dehumidifying device |
-
2013
- 2013-08-29 CN CN2013103841644A patent/CN103435802A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108623544A (en) * | 2018-07-10 | 2018-10-09 | 江西师范大学 | A kind of preparation method of 4,4 '-two (3,4- dicarboxylic acid anhydrides benzoyl) biphenyl |
| CN114210180A (en) * | 2021-12-17 | 2022-03-22 | 宁波威霖住宅设施有限公司 | Dehumidifying device |
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Application publication date: 20131211 |