CN102702523A - Winding moulding fiber-reinforced polyimide resin prepreg tape and preparation method and application thereof - Google Patents
Winding moulding fiber-reinforced polyimide resin prepreg tape and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a winding moulding fiber-reinforced polyimide resin prepreg tape and a preparation method and application thereof. The structure of polyimide resin prepared into the prepreg tape is shown as a formula I; and the polyimide resin is good in solubility and melt fluidity and excellent in heat resistance after being cured at the temperature of 370 DEG C, has a glass transition temperature of more than or equal to 300 DEG C and has good mechanical properties. A polyimide resin solution is used for directly impregnating and reinforcing a fiber, and after a heat drying process in air and removal of a solvent, the prepreg tape with uniform glue quantity and low residual solvent content (lower than or equal to 1%) can be obtained. The prepreg tape is simple in preparation process and convenient to store and transport; and a winding moulding composite material prepared from the prepreg tape has excellent mechanical properties and can be applied to manufacturing of composite material cylinders, pressure containers, storage tanks, pipes, fan blades and other high-temperature-resistant structural components.
Description
Technical field
The present invention relates to a kind of Wrapping formed with fiber reinforced polyimide resin prepreg band and preparation method thereof and application.
Background technology
Wrapping formed is the important moulding technique of making the polymer matrix composites goods.The composite product that adopts winding shaping process to obtain not only has the advantage that matrix materials such as high specific strength, high ratio modulus, antifatigue, damping performance be good have; And, therefore can give full play to the high characteristic of fortifying fibre tensile strength because the direction strength ratio of winding arrangement can be carried out the mechanics design as requested.This moulding process easily is automated continuous production and product does not need mechanical workout, and production efficiency is high.Therefore, Wrapping formed in recent years technology is widely used in the manufacturing of aerospace and structural parts such as civilian industry field matrix material large-size cylinder body, pressurized vessel, basin, pipeline and fan blade.
The matrix resin that is applied to winding shaping process at present mainly contains unsaturated polyester resin, epoxy resin, bimaleimide resin and polyarylether resin etc.Unsaturated polyester and epoxy resin because have that use characteristics is good, resin and characteristics such as fiber strong adhesion, mechanical property excellence, therefore be the most Wrapping formed matrix resin of using of application at present.But the use temperature of unsaturated polyester resin generally is no more than 100 ℃.Though and can reach under the use temperature of epoxy resin about 150 ℃, it solidifies, and back fragility is bigger, shock resistance is undesirable, fibre strength can not effectively be brought into play.With resistance toheat that improves matrix resin and the toughness of improving resin is target; People have successively developed and have been applicable to Wrapping formed modified epoxy and modified bismaleimide resin; Though the toughness of modified epoxy significantly improves, the problem of bringing resistance toheat to descend simultaneously.Though and the resistance toheat of bimaleimide resin is superior to epoxy resin, its maximum operation (service) temperature can be brought up to more than 200 ℃, and curing back matter is crisp, the problem of poor toughness but still exist.Comprise the thermoplastic poly aryl ether resin of polyphenylene sulfide and polyetherketone owing to have good thermotolerance and toughness; In recent years; By broad research, realized commercialization as the Wrapping formed matrix resin of high-performance with continuous fibre enhanced polyarylether resin preimpregnation band.But the second-order transition temperature of this analog thermoplastic polyarylether resin generally is no more than 250 ℃.
Be the more excellent Wrapping formed polymer matrix composites of exploitation resistance toheat, polyimide (PI) resin with outstanding heat-resistant stability and excellent mechanical property receives much concern.But traditional aromaticity polyimide is difficult to dissolving and hot melt owing to have the inflexible chemical structure, therefore can't adopt solution dipping method or resin hot melt process to prepare the preimpregnation band.U.S. TRW Ltd. (US) One Space Park, Redondo Beach CA 90278 U.S.A. adopted norbornene or the end capped thermoset polyimide resin solution impregnation of methyl norbornene spun glass as far back as 1974; And carry out online Wrapping formed preparation composite pressure vessel; This matrix material have an excellent heat resisting, can under 316 ℃ of high temperature, use.But because resin prepolymer molecular weight is lower; Be merely 1050-1300g/mol; Therefore can't adopt the dry method winding shaping process to prepare matrix material (R.W.Vaughan and R.J.Jones; " Filament winding S-glass/polyimide resin composite processing studies ", NASA CR-34590,1974).The U.S. disclosed patent US6222007B1 in NASA Langley research centre discloses a kind of " Salt-like " solution impregnation thomel with thermoplasticity LaRC-IA, LaRC-IAX, LaRC-8515 and PETI-5 polyimide resin, obtains the preparation method that dissolvent residual is the preimpregnation band of 12-15% through the heat baking.This type preimpregnation band is excellent through the composite materials property that Wrapping formed in-situ solidifying prepares, and flexural strength still remains on 1089MPa at room temperature up to 1662MPa under 177 ℃ of high temperature.But the second-order transition temperature of this analog thermoplastic polyimide resin all is no more than 270 ℃, and because the preimpregnation band still contains partial solvent, is unfavorable for obtaining compact structure, matrix material that porosity is low.The domestic related work that only has people such as Jia Lixia to report fiber winding forming polyimide-based composite material performance study, the polyimide resin PI-II that they are developed with Chinese Academy of Sciences's chemistry is matrix and T700 thomel and S
2High-strength glass fibre is compound, adopts winding shaping process to prepare matrix material, finds that matrix material shows excellent heat-resistant stability; Interlaminar shear strength conservation rate under 300 ℃ of high temperature has reached 72% (Jia Lixia, Chen Hui; " fiber winding forming polyimide-based composite material performance study ", fibre composite, 2010; 9 (3), 3-5).But do not see any relevant report about fiber reinforced polyimide resin prepreg band preparation method.
Summary of the invention
The purpose of this invention is to provide a kind of Wrapping formed with fiber reinforced polyimide resin prepreg band and preparation method thereof and application.
The Wrapping formed polyimide resin of using provided by the invention, its general structure is suc as formula shown in the I:
In the said formula I general structure, R
1Be in the following structure any one,
In the said formula I general structure, R
2Be in the following structure any one,
In the said formula I general structure, Ar is any one in the following structure,
X:y=1:0.1 ~ 10, x is 1 ~ 10, y is 10 ~ 1; N is 1 ~ 24 integer.
Polyimide resin shown in the above-mentioned formula I is the resin for getting according to following method preparation provided by the invention also.
The method for preparing polyimide resin shown in the formula I provided by the invention; Comprise the steps: under protection of inert gas; Aromatic diamine, aromatic series tetracarboxylic dianhydride and end-capping reagent be stirred to whole dissolvings and obtain homogeneous phase solution in organic solvent after, heat up and react adding dewatering agent, remove said dewatering agent after reaction finishes; Pour precipitation agent after the cooling into and precipitate, obtain polyimide resin shown in the said formula I;
In the aforesaid method, said aromatic diamine is the mixture of at least a composition in fluorine-containing aromatic diamine and the following aromatic diamines: 4, and 4 '-diaminodiphenyl oxide (4; 4 '-ODA), 3,4 '-diaminodiphenyl oxide (3,4 '-ODA), Ursol D (p-PDA), mphenylenediamine (m-PDA), 4; 4 '-two amido sulfobenzides (4; 4 '-DDS) and 3,3 '-two amido sulfobenzides (3,3 '-DDS);
Said fluorine-containing aromatic diamine is 4; 4 '-diamino--2; 2 '-bis trifluoromethyl biphenyl (TFDB), 1,4-two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) or 4,4 '-two (4-amido-2-4-trifluoromethylphenopendant) biphenyl (6FBAB);
Said aromatic series tetracarboxylic dianhydride is 2,3,3 ', 4 '-BPDA (α-BPDA) or 4,4 '-(the different propylene of hexafluoro) tetracarboxylic dianhydride (6FDA);
Said end-capping reagent is a 4-phenylacetylene base phthalic anhydride (PEPA), and structure is suc as formula shown in the II;
(formula II)
Said organic solvent is selected from N-Methyl pyrrolidone (NMP), N, at least a in N-NMF (DMF), DMAC N,N (DMAc), DMSO 99.8MIN. (DMSO) and the meta-cresol;
Said dewatering agent is toluene or YLENE;
Said precipitation agent is at least a in water, methyl alcohol, the ethanol.
The molar ratio example of said fluorine-containing aromatic diamine and aromatic diamines is 1:0.1 ~ 10, is specially 1:0.2 ~ 5; The solid content of said homogeneous phase solution is 15 ~ 35wt.%, is specially 20 ~ 30wt.%;
The molar ratio example of said aromatic diamine and aromatic series tetracarboxylic dianhydride is 1:1;
In the said reactions step, temperature is 160 ~ 190 ° of C, and the time is 8 ~ 24 hours.
The Wrapping formed preimpregnation band of using by polyimide resin shown in the above-mentioned formula I and continuous fibre are formed also belongs to protection scope of the present invention.
Said Wrapping formed even with fiber reinforced polyimide resin prepreg band kiss-coating, solvent residual amount≤1.0%, resin content are 30 ~ 35wt.%; Said continuous fibre is selected from least a in thomel, aramid fiber, silica fiber and the spun glass.
The method for preparing fiber reinforced polyimide preimpregnation band provided by the invention comprises the steps:
Polyimide resin is dissolved in the organic solvent shown in the formula I that method for preparing is obtained; Obtain the resin solution of polyimide; With the resin solution impregnating continuous fibres of said polyimide, oven dry obtains said fiber reinforced polyimide preimpregnation band after removing and desolvating again.
Among the above-mentioned preimpregnation band preparation method, said organic solvent is selected from N-Methyl pyrrolidone (NMP), DMAC N,N (DMAc) and N, at least a in dinethylformamide (DMF), DMSO 99.8MIN. (DMSO) or the ketopentamethylene;
Said continuous fibre is selected from least a in thomel, aramid fiber, silica fiber and the spun glass;
The solid content of the resin solution of said polyimide is 20 ~ 40wt.%, is specially 25 ~ 35wt.%;
In the said baking step, temperature is 50 ~ 250 ° of C, and the time is 0.5 ~ 8 hour;
The application of fiber reinforced polyimide resin prepreg band in the winding molding compound material product that the invention described above provides also belongs to protection scope of the present invention; Wherein, said winding molding compound material product is selected from least a in the products such as matrix material cylindrical shell, pressurized vessel, basin, pipeline and fan blade.
The present invention adopts aromatic dianhydride or the fluorine-containing aromatic dianhydride with the non-coplanar structure of distortion, and the mixture of fluorine-containing aromatic diamine and other structure aromatic diamines prepares polyimide resin.In resinous molecular structure, introduce the monomer of the non-coplanar structure of distortion and fluoro-containing group with big free volume; Can improve on the one hand the solvability of polyimide resin, prepare in the process infiltration fiber thereby the viscosity that reduces resin solution is beneficial to the preimpregnation band; Can promote the melt fluidity of resin on the other hand, thereby the melt viscosity that reduces resin has the good interface performance to guarantee winding molding compound material.Polyimide resin Good Heat-resistance after 370 ° of C solidify, second-order transition temperature >=300 ° C, and show the good mechanical performance.Fiber reinforced polyimide resin prepreg band preparation technology provided by the invention is simple, stores convenient transportation.This method is with polyimide resin solution direct impregnation fortifying fibre; The heat baking is handled except that obtaining spread after desolvating even in air; The preimpregnation band that solvent residual amount is low; Therefore fundamentally avoided traditional method, caused in the Composite Preparation process and to emit small molecules because of residual solvent and polyamic acid dehydration and bring that technological process is wayward, the surface appears in composite product and the problem of subsurface defect with " Salt-like " solution impregnation fiber production preimpregnation band of polyamic acid resin solution or polyimide resin.Winding molding compound material by its preparation has excellent mechanical property, can be applicable to the manufacturing of high-temperature-resistant structure spares such as matrix material cylindrical shell, pressurized vessel, basin, pipeline and fan blade.
Description of drawings
Fig. 1 is the infrared spectrum of embodiment 1 preparation gained polyimide resin.
Fig. 2 is the infrared spectrum of embodiment 2 preparation gained polyimide resins.
Fig. 3 is the infrared spectrum of embodiment 3 preparation gained polyimide resins.
Fig. 4 is the infrared spectrum of embodiment 4 preparation gained polyimide resins.
Fig. 5 is the infrared spectrum of embodiment 5 preparation gained polyimide resins.
Fig. 6 is the infrared spectrum of embodiment 6 preparation gained polyimide resins.
Fig. 7 is the infrared spectrum of embodiment 7 preparation gained polyimide resins.
Fig. 8 is the infrared spectrum of embodiment 8 preparation gained polyimide resins.
Fig. 9 is the infrared spectrum of embodiment 9 preparation gained polyimide resins.
Figure 10 is the infrared spectrum of embodiment 10 preparation gained polyimide resins.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but the present invention is not limited to following examples.Said method is ordinary method if no special instructions.Said starting material all can get from open commercial sources if no special instructions.
Embodiment 1
In three mouthfuls of round-bottomed flasks of outfit mechanical stirring, water trap, nitrogen gangway and a TM, add 35.90 gram (0.08 moles) 1,4-two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB), 16.78 restrains (0.08 moles) 4; 4 '-diaminodiphenyl oxide (4,4 '-ODA) with 241.17 milliliters of N-Methyl pyrrolidone (NMP), under nitrogen protection, be stirred to fully dissolving after; Add 43.43 gram (0.15 moles) 2; 3,3 ', 4 '-BPDA (α-BPDA) restrain (0.04 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) with 9.93; Be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 30wt.%.18 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ° of C reactions after 10 hours, steamed toluene, stopped heating.Reaction solution is cooled to pour in the ethanol behind 80 ° of C, collects the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 96%.（x：y=1：1，n=7）。The infrared spectrum of gained polyimide resin is as shown in Figure 1.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in the N-Methyl pyrrolidone (NMP), obtains the resin solution that solid content is 30wt.%, again with said resin solution impregnation of carbon fibers band; Under air atmosphere through 80 ° C/1 hour; 100 ° C/1 hour, 120 ° C/1 hour, 150 ° C/1 hour; After the baking of 210 ° of C/1 hour ladder-elevating temperature heat removes and desolvates, obtain thomel and strengthen polyimide resin preimpregnation band.This polyimide resin and thomel thereof strengthen the salient features of preimpregnation band and see table 1.
Employed thomel in the present embodiment is replaced with aramid fiber, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 2
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one, add 130.78 gram (0.31 moles) 1,4-two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB), 30.57 gram (0.15 moles) 3; 4 '-diaminodiphenyl oxide (3,4 '-ODA) with 501 milliliters of N-Methyl pyrrolidone (NMP), under nitrogen protection, be stirred to fully dissolving after; Add 105.33 gram (0.36 moles) 2; 3,3 ', 4 '-BPDA (α-BPDA) restrain (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) with 49.65; Be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 30wt.%.40 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ° of C reactions after 12 hours, steamed toluene, stopped heating.Reaction solution is cooled to pour into after about 60 ℃ in the mixed solution of second alcohol and water (mixed volume is than being 2:1), collects the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 95%.（x:y=2:1，n=4）。The infrared spectrum of gained polyimide resin is as shown in Figure 2.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in N, in the N-methylacetamide (DMAc), obtains the resin solution that solid content is 35wt.%; Again with said resin solution impregnation of carbon fibers band, under air atmosphere through 50 ° C/0.5 hour, 80 ° C/1 hour; 100 ° C/1 hour, 120 ° C/1 hour, 160 ° C/1 hour; After the baking of 180 ° of C/1 hour ladder-elevating temperature heat removes and desolvates, obtain thomel and strengthen polyimide resin preimpregnation band.This polyimide resin and thomel thereof strengthen the salient features of preimpregnation band and see table 1.
Employed thomel in the present embodiment is replaced with aramid fiber, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 3
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one, add 86.41 gram (0.27 moles) 4,4 '-diamino--2; 2 '-bis trifluoromethyl biphenyl (TFDB), 54.03 the gram (0.27 moles) 4,4 '-diaminodiphenyl oxide (4,4 '-ODA) with 740 milliliters of N-Methyl pyrrolidone (NMP); After under nitrogen protection, being stirred to dissolving fully, add 129.36 gram (0.44 moles) 2,3; 3 '; (α-BPDA) restrain (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) with 49.65 is stirred to whole dissolvings to 4 '-BPDA, obtains the homogeneous phase solution that solid content is 30wt.%.70 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ° of C reactions after 12 hours, steamed toluene, stopped heating.Reaction solution is cooled to pour into after 60 ℃ in the mixed solution of first alcohol and water (mixed volume is than being 1:1), collects the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 95%.（x:y=1:1，n=4）。The infrared spectrum of gained polyimide resin is as shown in Figure 3.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in N, in the N-methylacetamide (DMAc), obtains the polyimide solution that solid content is 25wt.%.Again with said resin solution impregnation of carbon fibers band, through 50 ° C/0.5 hour, 80 ° C/0.5 hour; 100 ° C/1 hour, 120 ° C/1 hour, 160 ° C/1 hour; After the baking of 180 ℃/1 hour ladder-elevating temperature heat removes and desolvates, obtain thomel and strengthen polyimide resin preimpregnation band.This polyimide resin and thomel thereof strengthen the salient features of preimpregnation band and see table 1.
Employed thomel in the present embodiment is replaced with aramid fiber, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 4
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one, add 73.97 gram (0.23 moles) 4,4 '-diamino--2; 2 '-bis trifluoromethyl biphenyl (TFDB), 249.79 gram (2.31 moles) mphenylenediamines (m-PDA) and 4772 milliliters of DMAC N,Ns (DMAc), under nitrogen protection, be stirred to dissolve fully after; Add 718.16 gram (2.44 moles) 2; 3,3 ', 4 '-BPDA (α-BPDA) restrain (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) with 49.65; Be stirred to whole dissolvings, obtaining solid content is the 25wt.% homogeneous phase solution.400 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, and reaction system was warming up to 160 ° of C reactions after 16 hours, steamed toluene, stopped heating.Pour in the ethanol after reaction solution is cooled to 60 ℃, collect the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 94%.(x:y=1:10，n=24)。The infrared spectrum of gained polyimide resin is as shown in Figure 4.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in N, in the dinethylformamide (DMF), obtains the polyimide resin solution that solid content is 35wt.%; Again with said resin solution dipping aramid fiber band, under air atmosphere through 50 ° C/1 hour, 100 ° C/1 hour; 120 ° C/1 hour; 150 ° C/1 hour, after the baking of 170 ° of C/1 hour ladder-elevating temperatures heat removes and desolvates, obtain aramid fiber and strengthen polyimide resin preimpregnation band.This polyimide resin and aramid fiber thereof strengthen the salient features of preimpregnation band and see table 1.
Employed aramid fiber in the present embodiment is replaced with thomel, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 5
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one, add 246.11 gram (0.77 moles) 4,4 '-diamino--2; 2 '-bis trifluoromethyl biphenyl (TFDB), 15.39 the gram (0.08 moles) 3,4 '-diamines yl diphenyl ether (3,4 '-ODA) with 2165 milliliters of N; N-methylacetamide (DMAc), under nitrogen protection, be stirred to fully dissolving after, add 219.32 gram (0.75 moles) 2; 3,3 ', 4 '-BPDA (α-BPDA) restrain (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) with 49.65; Be stirred to whole dissolvings, obtaining solid content is the 20wt.% homogeneous phase solution.200 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, and reaction system was warming up to 160 ° of C reactions after 18 hours, steamed toluene, stopped heating.Reaction solution is cooled to 60 ℃ falls back, collect the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 94%.(x:y=10:1，n=7)。The infrared spectrum of gained polyimide resin is as shown in Figure 5.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in the N-Methyl pyrrolidone (NMP), obtains the polyimide resin solution that solid content is 20wt.%, again with said resin solution impregnation of carbon fibers band; Under air atmosphere through 80 ° C/1 hour; 100 ° C/1 hour, 120 ° C/1 hour, 160 ° C/1 hour; After the baking of 220 ° of C/1 hour ladder-elevating temperature heat removes and desolvates, obtain thomel and strengthen polyimide resin preimpregnation band.This polyimide resin and thomel thereof strengthen the salient features of preimpregnation band and see table 1.
Employed thomel in the present embodiment is replaced with aramid fiber, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 6
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one, add 42.00 gram (0.13 mole) 4,4 '-two amidos-2; 2 '-bis trifluoromethyl biphenyl (TFDB), 131.33 gram (0.66 moles) 3; 4 '-diaminodiphenyl oxide (3,4 '-ODA) with 1199 milliliters of N-Methyl pyrrolidone (NMP), under nitrogen protection, be stirred to fully dissolving after; Add 05.33 gram (0.69 mole) 4; 4 '-(the different propylene of hexafluoro) tetracarboxylic dianhydride (6FDA) and 49.65 gram (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) are stirred to whole dissolvings, and obtaining solid content is the 30wt.% homogeneous phase solution.200 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ° of C reactions after 14 hours, steamed toluene, stopped heating.Reaction solution is cooled to 60 ℃ falls back, collect the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 94%.(x:y=1:5，n=7)。The infrared spectrum of gained polyimide resin is as shown in Figure 6.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in the DMSO 99.8MIN. (DMSO), obtains the polyimide resin solution that solid content is 30wt.%, again with said resin solution dipping aramid fiber band; Under air atmosphere through 50 ° C/0.5 hour, 80 ° C/0.5 hour, 120 ° C/1 hour; 160 ° C/1 hour; 180 ° C/1 hour, after the baking of 220 ℃/1 hour ladder-elevating temperature heat removes and desolvates, obtain aramid fiber and strengthen polyimide resin preimpregnation band.This polyimide resin and aramid fiber thereof strengthen the salient features of preimpregnation band and see table 1.
Employed aramid fiber in the present embodiment is replaced with thomel, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 7
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one, add 282.48 gram (0.56 mole) 4,4 '-two (4-amido-2-4-trifluoromethylphenopendant) biphenyl (6FBAB), 15.14 gram (0.14 mole) Ursol D (p-PDA) and 3151 milliliters of N; In the dinethylformamide (DMF); After under nitrogen protection, being stirred to dissolving fully, add 176.53 gram (0.60 moles) 2,3; 3 '; (α-BPDA) restrain (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) with 49.65 is stirred to whole dissolvings to 4 '-BPDA, obtains the homogeneous phase solution that solid content is 15wt.%.300 milliliters of YLENE are joined in the above-mentioned homogeneous phase solution, be warmed up to 170 ° of C reactions after 16 hours, steam toluene, stop heating.Pour in the methyl alcohol after reaction solution is cooled to 40 ℃, collect the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 96%.(x:y=4:1，n=6)。The infrared spectrum of gained polyimide resin is as shown in Figure 7.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Said polyimide resin is dissolved in the ketopentamethylene, obtains the polyimide solution that solid content is 40wt.%.Again with said resin solution impregnation of carbon fibers band, through 50 ° C/1 hour, 80 ° C/1 hour, 120 ° C/1 hour, 150 ° C/1 hour, after the baking of 180 ° of C/2 hour ladder-elevating temperature heat removes and desolvates, obtain thomel and strengthen polyimide resin preimpregnation band.This polyimide resin and thomel thereof strengthen the salient features of preimpregnation band and see table 1.
Employed thomel in the present embodiment is replaced with aramid fiber, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 8
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one, add 65.48 gram (0.20 mole) 4,4 '-two amidos-2; 2 '-bis trifluoromethyl biphenyl (TFDB), 5.64 the gram (0.03 mole) 3,3 '-two amido sulfobenzides (3,3 '-DDS) with 267 milliliters of DMSO 99.8MIN.s (DMSO) in; After under nitrogen protection, being stirred to dissolving fully, add 37.42 gram (0.13 moles) 2,3; 3 '; (α-BPDA) restrain (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA) with 49.65 is stirred to whole dissolvings to 4 '-BPDA, obtains the homogeneous phase solution that solid content is 35wt.%.25 milliliters of YLENE are joined in the above-mentioned homogeneous phase solution, be warmed up to 190 ° of C reactions after 24 hours, steam toluene, stop heating.Pour in the ethanol after reaction solution is cooled to 40 ℃, collect the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 96%.(x:y=9:1，n=1)。The infrared spectrum of gained polyimide resin is as shown in Figure 8.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Said polyimide resin is dissolved in the N-Methyl pyrrolidone (NMP), obtains the polyimide solution that solid content is 25wt.%.Again with said resin solution dipping silica fiber band, through 80 ° C/1 hour, 120 ° C/1 hour, 160 ° C/1 hour, 220 ° C/1 hour, after the baking of 250 ° of C/1 hour ladder-elevating temperature heat removes and desolvates, obtain silica fiber and strengthen polyimide resin preimpregnation band.This polyimide resin and silica fiber thereof strengthen the salient features of preimpregnation band and see table 1.
Employed silica fiber in the present embodiment is replaced with thomel, aramid fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 9
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one; Add 231.30 gram (0.54 moles) 1, two (4 '-amido-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-, 14.90 gram (0.06 mole) 4,4 '-two amido sulfobenzides (4; 4 '-DDS) with 1184 milliliters of meta-cresols; After under nitrogen protection, being stirred to dissolving fully, add 222.12 gram (0.50 mole) 4,4 '-(the different propylene of hexafluoro) tetracarboxylic dianhydrides (6FDA) and 49.65 gram (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA); Be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 25wt.%.110 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, be warmed up to 190 ° of C reactions after 8 hours, steam toluene, stop heating.Pour in the ethanol after reaction solution is cooled to 60 ℃, collect the fiber crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 96%.（x:y=9:1，n=5）。The infrared spectrum of gained polyimide resin is as shown in Figure 9.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in N, in the N-methylacetamide (DMAc), obtains the polyimide solution that solid content is 30wt.%.Again with said resin solution dipping aramid fiber band, through 50 ° C/1 hour, 80 ° C/1 hour; 100 ° C/1 hour, 120 ° C/1 hour, 160 ° C/1 hour; After the baking of 180 ° of C/1 hour ladder-elevating temperature heat removes and desolvates, obtain aramid fiber and strengthen polyimide resin preimpregnation band.This polyimide resin and aramid fiber thereof strengthen the salient features of preimpregnation band and see table 1.
Employed aramid fiber in the present embodiment is replaced with thomel, silica fiber or spun glass, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
Embodiment 10
Be equipped with in mechanical stirring, water trap, nitrogen gangway and three mouthfuls of round-bottomed flasks of TM at one; Add 72.63 gram (0.14 mole) 4,4 '-two (4-amido-2-4-trifluoromethylphenopendant) biphenyl (6FBAB), 201.84 gram (1.00 moles) 3,4 '-diaminodiphenyl oxide (3; 4 '-ODA) with 1803 milliliters of N-Methyl pyrrolidone (NMP) in; After under nitrogen protection, being stirred to dissolving fully, add 467.34 gram (1.04 moles) 4,4 '-(the different propylene of hexafluoro) tetracarboxylic dianhydrides (6FDA) and 49.65 gram (0.20 mole) 4-phenylacetylene base phthalic anhydrides (PEPA); Be stirred to whole dissolvings, obtain the homogeneous phase solution that solid content is 30wt.%.180 milliliters of toluene are joined in the above-mentioned homogeneous phase solution, and reaction system was warming up to 180 ° of C reactions after 14 hours, steamed toluene, stopped heating.Pour in the ethanol after reaction solution is cooled to 60 ℃, collect the fibrous crude product of separating out, with second alcohol and water repetitive scrubbing after-filtration, pulverizing, oven dry, obtain polyimide resin, productive rate is 96%.（x:y=1：7，n=11）。The infrared spectrum of gained polyimide resin is shown in figure 10.Can know that by figure this product structure is correct, be polyimide resin shown in the formula I.
Polyimide resin is dissolved in the N-Methyl pyrrolidone (NMP), obtains the polyimide resin solution that solid content is 30wt.%, again with said resin solution impregnated glass fiber band; Under air atmosphere through 50 ° C/1 hour, 80 ° C/1 hour, 100 ° C/1 hour; 120 ° C/1 hour, 160 ° C/1 hour, 190 ° C/1 hour; 220 ° C/1 hour, the baking of 250 ℃/1 hour ladder-elevating temperature heat obtains glass fiber reinforced polyester imide resin preimpregnation band after removing and desolvating.This polyimide resin and spun glass thereof strengthen the salient features of preimpregnation band and see table 1.
Employed spun glass in the present embodiment is replaced with thomel, aramid fiber or silica fiber, and the preimpregnation band performance that adopts the preparation condition identical with present embodiment to obtain is suitable.
The performance of table 1, polyimide resin, virgin resin molding and preimpregnation band
aRotary viscosity: with the solid content is DMAc resin solution mensuration under 25 ℃ of 35wt.%;
bT
gBe second-order transition temperature, T
dBe initial heat decomposition temperature (nitrogen atmosphere);
cMinimum melt viscosity adopts the intensification rheometry;
dThe mechanical property of virgin resin adopts universal testing machine to measure according to GB/T 1040.3-2006;
ePreimpregnation band solvent residual amount is measured according to JC/T 776-2004, and resin content is measured according to JC/T 780-2004.
Claims (10)
1. polyimide polymer shown in the formula I,
In the said formula I general structure, R
1Be in the following structure any one,
In the said formula I general structure, R
2Be in the following structure any one,
In the said formula I general structure, Ar is any one in the following structure,
X:y=1:0.1 ~ 10, x is 1 ~ 10, and y is 10 ~ 1, and n is 1 ~ 24 integer.
2. method for preparing polyimide resin shown in the said formula I of claim 1; Comprise the steps: under protection of inert gas; Aromatic diamine, aromatic series tetracarboxylic dianhydride and end-capping reagent be stirred to whole dissolvings and obtain homogeneous phase solution in organic solvent after, heat up and react adding dewatering agent, remove said dewatering agent after reaction finishes; Pour precipitation agent after the cooling into and precipitate, obtain polyimide resin shown in the said formula I.
3. method according to claim 2; It is characterized in that: said aromatic diamine is the mixture of at least a composition in fluorine-containing aromatic diamine and the following aromatic diamines: 4; 4 '-diaminodiphenyl oxide, 3; 4 '-diaminodiphenyl oxide, Ursol D, mphenylenediamine, 4,4 '-two amido sulfobenzides and 3,3 '-two amido sulfobenzides;
Said fluorine-containing aromatic diamine is 4,4 '-diamino--2,2 '-bis trifluoromethyl biphenyl, 1,4-two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene or 4,4 '-two (4-amido-2-4-trifluoromethylphenopendant) biphenyl;
Said aromatic series tetracarboxylic dianhydride is 2,3,3 ', 4 '-BPDA or 4,4 '-(the different propylene of hexafluoro) tetracarboxylic dianhydride;
Said end-capping reagent is a 4-phenylacetylene base phthalic anhydride, and structure is suc as formula shown in the II;
Said organic solvent is selected from N-Methyl pyrrolidone, N, at least a in dinethylformamide, DMAC N,N, DMSO 99.8MIN. and the meta-cresol;
Said dewatering agent is toluene or YLENE;
Said precipitation agent is selected from least a in water, methyl alcohol and the ethanol.
4. according to claim 2 or 3 described methods, it is characterized in that: the molar ratio example of said fluorine-containing aromatic diamine and aromatic diamines is specially 1:0.2 ~ 5 for 1:0.1 ~ 10; The solid content of said homogeneous phase solution is 15 ~ 35wt.%, is specially 20 ~ 30wt.%;
The molar ratio example of said aromatic diamine and aromatic series tetracarboxylic dianhydride is 1:1;
In the said reactions step, temperature is 160 ~ 190 ° of C, and the time is 8 ~ 24 hours.
5. the Wrapping formed preimpregnation band of forming by polyimide resin shown in the said formula I of claim 1 and continuous fibre of using.
6. the Wrapping formed preimpregnation band of using according to claim 5 is characterized in that: said Wrapping formed even with fiber reinforced polyimide preimpregnation band kiss-coating, and solvent residual amount≤1.0%, the quality percentage composition of resin is 30 ~ 35%;
Said continuous fibre is selected from least a in thomel, aramid fiber, silica fiber and the spun glass.
7. one kind prepares claim 5 or 6 said Wrapping formed methods with the preimpregnation band; Comprise the steps: polyimide resin shown in the said formula I of claim 1 is dissolved in the organic solvent; Obtain the resin solution of polyimide; With the resin solution impregnating continuous fibres of said polyimide, oven dry obtains the said Wrapping formed preimpregnation band of using after removing and desolvating again.
8. method according to claim 7 is characterized in that: said organic solvent is selected from N-Methyl pyrrolidone, DMAC N,N and N, at least a in dinethylformamide, DMSO 99.8MIN. and the ketopentamethylene;
Said continuous fibre is selected from least a in thomel, aramid fiber, silica fiber and the spun glass;
The solid content of the resin solution of said polyimide is 20 ~ 40wt.%, is specially 25 ~ 35wt.%;
In the said baking step, temperature is 50 ~ 250 ° of C, and the time is 0.5 ~ 8 hour.
9. claim 5 or 6 arbitrary said Wrapping formed with the application of preimpregnation band in the winding molding compound material product;
Contain claim 5 or 6 arbitrary said Wrapping formed winding molding compound material products with the preimpregnation band.
10. application according to claim 9 is characterized in that: said winding molding compound material product is selected from least a in matrix material cylindrical shell, pressurized vessel, basin, pipeline and the fan blade.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417917A (en) * | 2017-09-22 | 2017-12-01 | 长春理工大学 | A kind of solvable fusible type polyimides and preparation method thereof |
| CN108730753A (en) * | 2017-04-14 | 2018-11-02 | 江苏先诺新材料科技有限公司 | A kind of polyimide fiber composites gas cylinder and its preparation method and application |
| CN109265998A (en) * | 2018-09-25 | 2019-01-25 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of fibre reinforced polyimide-based composite material |
| JP2019038920A (en) * | 2017-08-24 | 2019-03-14 | 宇部興産株式会社 | Solvent soluble polyimide and polyimide solution composition |
| CN112708133A (en) * | 2020-12-28 | 2021-04-27 | 长春长光宇航复合材料有限公司 | Low-viscosity thermosetting polyimide resin and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484879A (en) * | 1990-12-17 | 1996-01-16 | Occidental Chemical Corporation | Polyimides containing fluorine |
| CN101190968A (en) * | 2006-11-27 | 2008-06-04 | 中国科学院化学研究所 | Polyimide resin and preparation method thereof |
| CN101985498A (en) * | 2010-10-19 | 2011-03-16 | 中国科学院化学研究所 | High temperature resistant polyimide resin as well as preparation method and application thereof |
-
2012
- 2012-05-29 CN CN2012101714391A patent/CN102702523A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5484879A (en) * | 1990-12-17 | 1996-01-16 | Occidental Chemical Corporation | Polyimides containing fluorine |
| CN101190968A (en) * | 2006-11-27 | 2008-06-04 | 中国科学院化学研究所 | Polyimide resin and preparation method thereof |
| CN101985498A (en) * | 2010-10-19 | 2011-03-16 | 中国科学院化学研究所 | High temperature resistant polyimide resin as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《航空材料学报》 20060601 陈建升等 适用于RTM成型聚酰亚胺树脂的合成与性能研究 第26卷, 第3期 * |
| 陈建升等: "适用于RTM成型聚酰亚胺树脂的合成与性能研究", 《航空材料学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108730753A (en) * | 2017-04-14 | 2018-11-02 | 江苏先诺新材料科技有限公司 | A kind of polyimide fiber composites gas cylinder and its preparation method and application |
| JP2019038920A (en) * | 2017-08-24 | 2019-03-14 | 宇部興産株式会社 | Solvent soluble polyimide and polyimide solution composition |
| CN107417917A (en) * | 2017-09-22 | 2017-12-01 | 长春理工大学 | A kind of solvable fusible type polyimides and preparation method thereof |
| CN109265998A (en) * | 2018-09-25 | 2019-01-25 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of fibre reinforced polyimide-based composite material |
| CN112708133A (en) * | 2020-12-28 | 2021-04-27 | 长春长光宇航复合材料有限公司 | Low-viscosity thermosetting polyimide resin and preparation method and application thereof |
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