CN103434236A - Polyimide/polytetrafluoroethylene composite membrane for insulation of electric wire and cable and preparation method thereof - Google Patents
Polyimide/polytetrafluoroethylene composite membrane for insulation of electric wire and cable and preparation method thereof Download PDFInfo
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- CN103434236A CN103434236A CN2013103896134A CN201310389613A CN103434236A CN 103434236 A CN103434236 A CN 103434236A CN 2013103896134 A CN2013103896134 A CN 2013103896134A CN 201310389613 A CN201310389613 A CN 201310389613A CN 103434236 A CN103434236 A CN 103434236A
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Abstract
The invention discloses a polyimide/polytetrafluoroethylene composite membrane for the insulation of electric wires and cables and a preparation method thereof. The preparation method comprises the following steps of firstly preparing a surface modified molecular sieve; then preparing a polyamic acid (PAA)/molecular sieve composite solution, and preparing the polyamic acid/molecular sieve composite solution into a polyimide/molecular sieve composite membrane; then coating the prepared polytetrafluoroethylene/molecular sieve complex liquid on both surfaces of the membrane to obtain the polyimide/polytetrafluoroethylene composite membrane for the insulation of the electric wires and the cables. The polyimide/polytetrafluoroethylene composite membrane disclosed by the invention has good adhesion of polyimide and polytetrafluoroethylene and solves the problem of poor adhesion between a polytetrafluoroethylene coating and other base bodies; the polyimide/polytetrafluoroethylene composite membrane for the insulation of the electric wires and the cables, which is disclosed by the invention, has the advantages of excellent mechanical property and good insulating property, can normally work in a humid environment with electrical property which is not affected under the condition that the polytetrafluoroethylene coating is damaged and has the characteristic of low dielectric constant.
Description
Technical field
The present invention relates to a kind of wire cable insulating material, particularly polyimides/polytetrafluoroethylcomposite composite film and preparation method for a kind of wire cable insulating, belong to the wire cable insulating Material Field.
Background technology
Polyimides (PI) is the aromatic heterocycle polymer compound that contains imide group in repetitive, take extraordinary high polymer high temperature resistant, that radiation hardness is characteristic of property, there are good mechanical property, wearability, dimensional stability, solvent resistance etc., be successfully applied to the sophisticated technology fields such as Aeronautics and Astronautics, also be widely used in the industries such as electronic apparatus, mechanical chemical industry.In order to adapt to high-tech development, the research of PI is also constantly being advanced towards the direction of high performance, multifunction.In the electric wire production process, because the color of PI film is brown color, copper cash is little through PI change color after volume, and on tinuous production, whether copper cash is difficult to make at once accurate judgement by the PI film around volume.During Deng problem discover, substandard product has been produced a lot, bring the tremendous economic loss to enterprise, it is necessary to be coated with one deck color at the PI film surface, make the performance of PI film unaffected even more outstanding simultaneously, and make the workman can find immediately the whether problem around volume by the PI film of copper cash aborning, this is necessary to reducing enterprises' loss.Therefore, in industrial production usually in PI film surface coating tetrafluoroethylene emulsion.
The emulsion polymerisation of polytetrafluoroethylene (PTFE) claims again dispersin polymerization, and product is the aqueous dispersions of PTFE, and solid content 60% left and right can be used for the coating etc. of dipping, form film, metal coating and other base material of fabric and porous metals.But polytetrafluoroethylene (PTFE) structure height symmetry belongs to non-polar high polymer, low surface energy is arranged.Material surface energy is lower, and adhesive force is less, and the contact angle of material surface and liquid is also just larger.But single PTFE material is can not be with coating interface bonding and can not be in normal temperature cure without complicated surface active.There is research to introduce by modified ptfe surface the cementability that other group improves it and other matrix, perhaps modify the PTFE surface and make it there is certain coarse structure and reach ultra-hydrophobicity, but these processes to equipment requirement, higher and process is complicated is difficult to application.Can improve the adhesive property between polytetrafluoroethylene (PTFE) and other matrixes and add micron order or nano level inorganic particulate to prepare polytetrafluoroethylene (PTFE)-inorganic hybridization coating in ptfe emulsion.
Molecular sieve refers to the class crystalline microporous material that a class has uniform pore size, huge internal surface area and pore volume, has again the characteristic such as ion exchangeable simultaneously.Because molecular sieve is porous material, thereby there is the absorption assembling characteristic, specific group of molecules can be contained in its micropore, be released under certain particular case, utilize this characteristic, can give molecular sieve certain function.And micro porous molecular sieve has regular duct to arrange and the skeletal atom order, its pore diameter range is 0.3nm～1.2nm.
Add low cost, high-performance and the multifunction that inorganic particulate can be realized polymer effectively in polymer, this has become a kind of effective way in the new material exploitation.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide the preparation method of a kind of wire cable insulating with polyimides/polytetrafluoroethylcomposite composite film.
Another object of the present invention is to provide the polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating obtained by above-mentioned preparation method.
Purpose of the present invention is achieved through the following technical solutions: the preparation method of polyimides/polytetrafluoroethylcomposite composite film for a kind of wire cable insulating comprises following steps:
(1) processing of molecular sieve
1. molecular sieve being washed till to the pH value is 6～7, dries;
2. coupling agent is dissolved in ethyl acetate, obtains coupling agent ethyl acetate solution; Then the molecular sieve after 1. step being dried adds in coupling agent ethyl acetate solution, and molecular sieve adds in the process of coupling agent ethyl acetate solution and constantly stirs, and the consumption of coupling agent is equivalent to 0.1～2% of molecular sieve quality; Then being warming up to 50～60 ℃ is reacted; Then leach molecular sieve, dry, make the molecular sieve by the coupling agent surface modification;
(2) preparation of polyamic acid PAA/ molecular sieve composite solution
1. the molecular sieve of step (1) being handled well joins in non-polar solven I, is stirred to fully and disperses; Then add diamines, add again dianhydride after diamines dissolves fully, continue to stir in the adition process of dianhydride, then add non-polar solven II, continue stirring and obtain the finely dispersed polyamic acid PAA of molecular sieve composite solution 1; Diamines and dianhydride be (1.01～1.15) in molar ratio: 1 proportioning;
2. re-use and 1. different diamines or dianhydride of step (2), by step (2), 1. make polyamic acid PAA composite solution 2;
3. polyamic acid complex liquid 1 and polyamic acid complex liquid 2 are mixed, obtain polyamic acid PAA/ molecular sieve complex liquid;
(3) preparation of polyimides/Zeolite composite film
The polyamic acid PAA/ molecular sieve complex liquid curtain coating film forming that step (2) is made; Then gradient increased temperature cyclisation rear demoulding, high-temperature heat treatment, obtain polyimides/Zeolite composite film;
(4) preparation of polyimides/polytetrafluoroethylcomposite composite film
1. after molecular sieve step (1) made and ptfe emulsion are uniformly mixed, grind, obtain polytetrafluoroethylene (PTFE)/molecular sieve complex liquid; Prepared by step (3) polytetrafluoroethylene (PTFE) for polyimides/Zeolite composite film/the molecular sieve complex liquid is two-sided films, dry;
2. be soaked in water, then dry, obtain polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating.
Described molecular sieve is preferably micro porous molecular sieve;
Described micro porous molecular sieve comprises 3A, 4A, 5A, 13X molecular sieve, and its particle diameter is 20～50nm, can increase the hydrophobicity of micro porous molecular sieve after coupling agent modified, is easier to it and disperses in matrix resin;
Molecular sieve the be washed till pH value of step (1) described in 1. is 6～7 to be preferably the acetums washing of using 0.1mol/L, and water molecular sieve is washed till to the pH value is 6～7;
The condition of the oven dry of step (1) described in 1. is preferably 180 ℃ and dries 4h;
The coupling agent of step (1) described in 2. is titanate coupling agent, comprises a kind of in isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, three isostearic acid isopropyl titanates and tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanate esters or at least two kinds;
The time of the reaction of step (1) described in 2. is preferably 1h;
The condition of the oven dry of step (1) described in 2. is preferably first dries 1h at 100 ℃, then continues to dry 4h at 150 ℃;
Diamines described in step (2) is preferably p-phenylenediamine (PPD) (PPD), m-phenylene diamine (MPD) (MPD), 4, 4'-diaminodiphenyl ether (ODA), 3, 3'-dimethyl-4, 4'-MDA (DMMDA), 1, 2-DACH (DACH), 4, 4'-bisphenol-A diphenyl ether diamines (BAPP), 4, 4'-bis-(4-amino-phenoxy group) diphenyl ether (BAPE), 4, 4'-diaminobenzophenone (DABP), 4, 4'-diaminourea triphenylamine (DATPA), 4, 4'-diaminodiphenyl-methane (MDA), 4, two (amino-benzene oxygen) benzophenone (BAPB) of 4'-, 1, two (3-amino-benzene oxygen-4'-benzoyl group) benzene (BABB) of 3-, 1, 4-(2', the 4''-diamino phenoxy) benzene (OAPB), 1, 3-bis-(4-amino-benzene oxygen) benzene (TPER) and 1, 4-(2', the 4''-diamino phenoxy) a kind of in benzene (PMAPB) or at least two kinds,
Dianhydride described in step (2) is preferably pyromellitic acid anhydride (PMDA), 3, 3', 4, 4'-bibenzene tetracarboxylic dianhydride (BPDA), 4, the two phthalic anhydrides (ODPA) of 4'-oxygen, triphen diether tetracarboxylic dianhydride (HQDPA), 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride (BTDA), benzophenone tetracarboxylic dianhydride (BDPA), bisphenol-A dianhydride (BPADA), ester ring dianhydride dicyclo [2.2.1] octane-2, 3, 5, 6-tetracarboxylic 2, 3, 5, 6-dianhydride (BHDA), cyclobutane tetracarboxylic acid dianhydride (CBDA), hydrogenated pyromellitic anhydride (HPMDA) and 3, 3', 4, a kind of in 4'-diphenyl sulfide tetracarboxylic dianhydride (TDPA) or at least two kinds,
Non-polar solven I described in step (2) and described non-polar solven II are different non-polar solvens;
Described non-polar solven I is preferably DMF (DMF), DMA (DMAC), 1-METHYLPYRROLIDONE (NMP) or dimethyl sulfoxide (DMSO) (DMSO);
Described non-polar solven II is preferably toluene, dimethylbenzene, carrene, chloroform, acetone or alcohol;
The time that in the adition process of dianhydride continues stir of step (2) described in 1. is preferably 3h;
The add time of non-polar solven II after continuing stir of step (2) described in 1. is preferably 0.5h;
The polyamic acid complex liquid 1 of step (2) described in 3. and polyamic acid complex liquid 2 be 1:(0.5～2 in mass ratio preferably) mix, stir 24h;
The speed that the step of the intensification described in step (3) is preferably with 3～6 ℃/min heats up, and from room temperature, at 90～110 ℃, keeps 1～1.5h, keep 1～1.5h at 140～160 ℃, keep 1～1.5h at 190～210 ℃, at 240～280 ℃, keep 1～1.5h;
Described room temperature is preferably 20～30 ℃;
High-temperature heat treatment described in step (3) refers to from 200 ℃, with the speed of 3～6 ℃/min, is warming up to 290～330 ℃ and keep 0.5～1h;
The quality percentage composition that polyimides/Zeolite composite film described in step (3) is preferably molecular sieve is 0.1～15% of polyimides quality;
The ptfe emulsion preferred D50 value of step (4) described in 1. is 70nm, the ptfe emulsion of solid content 60%;
The quality consumption of the molecular sieve of step (4) described in 1. is equivalent to 0.5～5% of described ptfe emulsion butt quality;
The condition of the grinding of step (4) described in 1. is preferably uses planetary ball mill to grind 30min;
The condition of the oven dry of step (4) described in 1. is preferably in 320～380 ℃ dries 45～75min;
Step (4) being soaked in water to be preferably and using distilled water immersion 2h described in 2.;
The condition of the oven dry of step (4) described in 2. is preferably in 70 ℃ dries 2h;
A kind of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating, prepared by above-mentioned preparation method.
Mechanism of the present invention: utilize the dianhydride of different proportionings, diamines and molecular sieve reaction generate polyamic acid molecular sieve complex liquid, and make the polyimide molecule sieve composite membrane that has different performance after mixing by different proportion., molecular sieve is mixed in ptfe emulsion, dual coating, on polyimide molecule sieve composite membrane, finally makes polyimides/polytetrafluoroethylcomposite composite film simultaneously.
The present invention has following advantage and effect with respect to prior art:
(1) the invention solves the not strong problem of caking property between polytetrafluorethylecoatings coatings and other matrixes, the wire cable insulating provided is good with polyimides in polyimides/polytetrafluoroethylcomposite composite film and polytetrafluoroethylene (PTFE) caking property.
(2) polyimides/polytetrafluoroethylcomposite composite film mechanical property excellence for wire cable insulating provided by the invention, and there are good insulating properties.Even if this wire cable insulating, can work and not affect its electrical property in the situation that the polytetrafluorethylecoatings coatings breakage with polyimides/polytetrafluoroethylcomposite composite film in wet environment, and has the characteristic of low-k.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) the acetum washing of 0.1mol/L for the 13X molecular sieve that the 20g particle diameter is 20nm, and be washed till pH value 6～7 with distilled water, then at 180 ℃ of baking ovens, dry 4h.
(2) 0.02g tri-isostearic acid isopropyl titanate coupling agents are dissolved in 100ml ethyl acetate solvent, and the 13X molecular sieve that step (1) is handled well stirs while adding, be warming up to 50 ℃, reaction 1h, leach molecular sieve.Then, the 13X molecular sieve leached is first dried to 1h at 100 ℃, then continue to dry 4h at 150 ℃, make the 13X molecular sieve by the coupling agent surface modification.
(3) 0.008g is dissolved in 23.5g DMF by the 13X molecular sieve of coupling agent surface modification, then add 3.96g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 4.36g pyromellitic acid anhydride (PMDA), stir 3h, and add solvent toluene 23.5g, and continue to stir 0.5h, make polyamic acid PAA/13X-1.Again 0.01g is dissolved in 28g DMF by the 13X molecular sieve of coupling agent surface modification, then add 3.96g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 6.2g4, the two phthalic anhydrides (ODPA) of 4'-oxygen, stir 3h, and add solvent toluene 28g, continue to stir 0.5h, make polyamic acid PAA/13X-2.Then the polyamic acid PAA/13X-1 and the polyamic acid PAA/13X-2 that make are mixed with the ratio of mass ratio 2:1, stir 24h, make polyamic acid PAA/13X complex liquid.
(4) polyamic acid PAA/13X complex liquid curtain coating film forming step (3) made.Last gradient increased temperature (3 ℃/min of heating rate in baking oven, from room temperature, 90 ℃/1.5h-140 ℃/1.5h-190 ℃/1.5h-240 ℃/1.5h) the cyclisation rear demoulding, pass through again high-temperature heat treatment (3 ℃/min of heating rate, from 200 ℃, 290 ℃/1h) after obtained the tough and tensile polyimides/Zeolite composite film that contains the 0.1%13X molecular sieve.
(5) (the D50 value is 70nm for 13X molecular sieve 0.12g step (2) handled well and 20g ptfe emulsion, solid content 60%) after being uniformly mixed, use planetary ball mill to grind 30min, make the 13X molecular sieve and account for the polytetrafluoroethylene (PTFE) that polytetrafluoroethylene (PTFE) butt quality is 1%/molecular sieve complex liquid.
(6) step for polyimides/Zeolite composite film (5) step (4) made make polytetrafluoroethylene (PTFE)/the molecular sieve complex liquid is two-sided films, and put into baking oven and dry 75min under 320 ℃.Finally, the polyimides/polytetrafluoroethylcomposite composite film made is taken out to 70 ℃ after distilled water immersion 2h and dry 2h, make the composite membrane of ecru.Its key property is in Table 1.
Embodiment 2
(1) the acetum washing of 0.1mol/L for the 4A molecular sieve that the 20g particle diameter is 30nm, and be washed till pH value 6～7 with distilled water, then at 180 ℃ of baking ovens, dry 4h.
(2) 0.2g tri-isostearic acid isopropyl titanate coupling agents are dissolved in 100ml ethyl acetate solvent, and the 4A molecular sieve that step (1) is handled well stirs while adding, be warming up to 54 ℃, reaction 1h, leach molecular sieve.Then, the 4A molecular sieve leached is first dried to 1h at 100 ℃, then continue to dry 4h at 150 ℃, make the 4A molecular sieve by the coupling agent surface modification.
(3) 0.08g is dissolved in 23.5gNMP by the 4A molecular sieve of coupling agent surface modification, then add 3.96g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 4.36g pyromellitic acid anhydride (PMDA), stir 3h, and add etoh solvent 23.5g, and continue to stir 0.5h, make polyamic acid PAA/4A-1.Again 0.1g is dissolved in 28gNMP by the 4A molecular sieve of coupling agent surface modification, then add 3.96g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 6.2g4, the two phthalic anhydrides (ODPA) of 4'-oxygen, stir 3h, and add etoh solvent 28g, continue to stir 0.5h, make polyamic acid PAA/4A-2.Then the polyamic acid PAA/4A-1 and the polyamic acid PAA/4A-2 that make are mixed with the ratio of mass ratio 1:1, stir 24h, make polyamic acid PAA/4A complex liquid.
(4) polyamic acid PAA/4A complex liquid curtain coating film forming step (3) made.Last gradient increased temperature (4 ℃/min of heating rate in baking oven, from room temperature, 100 ℃/1.25h-150 ℃/1.25h-200 ℃/1.25h-250 ℃/1.25h) the cyclisation rear demoulding, pass through again high-temperature heat treatment (5 ℃/min of heating rate, from 200 ℃, 310 ℃/0.75h) after obtained the tough and tensile polyimides/Zeolite composite film that contains the 1%4A molecular sieve.
(5) (the D50 value is 70nm for 4A molecular sieve 0.25g step (2) handled well and 20g ptfe emulsion, solid content 60%) after being uniformly mixed, use planetary ball mill to grind 30min, make the 4A molecular sieve and account for the polytetrafluoroethylene (PTFE) that polytetrafluoroethylene (PTFE) butt quality is 2%/molecular sieve complex liquid.
(6) step for polyimides/Zeolite composite film (5) step (4) made make polytetrafluoroethylene (PTFE)/the molecular sieve complex liquid is two-sided films, and put into baking oven and dry 60min under 340 ℃.Finally, the polyimides/polytetrafluoroethylcomposite composite film made is taken out to 70 ℃ after distilled water immersion 2h and dry 2h, make the composite membrane of ecru.Its key property is in Table 1.
Embodiment 3
(1) the acetum washing of 0.1mol/L for the 5A molecular sieve that the 20g particle diameter is 50nm, and be washed till pH value 6～7 with distilled water, then at 180 ℃ of baking ovens, dry 4h.
(2) 0.4g isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate coupling agent is dissolved in 100ml ethyl acetate solvent, and the 5A molecular sieve that step (1) is handled well stirs while adding, be warming up to 50 ℃, reaction 1h, leach molecular sieve.Then, the 5A molecular sieve leached is first dried to 1h at 100 ℃, then continue to dry 4h at 150 ℃, make the 5A molecular sieve by the coupling agent surface modification.
(3) 0.4g is dissolved in 23.5gNMP by the 5A molecular sieve of coupling agent surface modification, then add 3.64g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 4.36g pyromellitic acid anhydride (PMDA), stir 3h, and add etoh solvent 23.5g, and continue to stir 0.5h, make polyamic acid PAA/5A-1.Again 0.5g is dissolved in 28gNMP by the 5A molecular sieve of coupling agent surface modification, then add 3.64g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 6.2g4, the two phthalic anhydrides (ODPA) of 4'-oxygen, stir 3h, and add etoh solvent 28g, continue to stir 0.5h, make polyamic acid PAA/5A-2.Then the polyamic acid PAA/5A-1 and the polyamic acid PAA/5A-2 that make are mixed with the ratio of mass ratio 1:2, stir 24h, make polyamic acid PAA/5A complex liquid.
(4) polyamic acid PAA/5A complex liquid curtain coating film forming step (3) made.Last gradient increased temperature (6 ℃/min of heating rate in baking oven, from room temperature, 110 ℃/1h-160 ℃/1h-210 ℃/1h-260 ℃/1h) the cyclisation rear demoulding, pass through again high-temperature heat treatment (6 ℃/min of heating rate, from 200 ℃, 330 ℃/0.5h) after obtained the tough and tensile polyimides/Zeolite composite film that contains the 5%5A molecular sieve.
(5) (the D50 value is 70nm for 5A molecular sieve 0.63g step (2) handled well and 20g ptfe emulsion, solid content 60%) after being uniformly mixed, use planetary ball mill to grind 30min, make the 5A molecular sieve and account for the polytetrafluoroethylene (PTFE) that polytetrafluoroethylene (PTFE) butt quality is 5%/molecular sieve complex liquid.
(6) step for polyimides/Zeolite composite film (5) step (4) made make polytetrafluoroethylene (PTFE)/the molecular sieve complex liquid is two-sided films, and put into baking oven and dry 45min under 380 ℃.Finally, the polyimides/polytetrafluoroethylcomposite composite film made is taken out to 70 ℃ after distilled water immersion 2h and dry 2h, make the composite membrane of ecru.Its key property is in Table 1.
Embodiment 4
(1) the acetum washing of 0.1mol/L for the 4A molecular sieve that the 20g particle diameter is 30nm, and be washed till pH value 6～7 with distilled water, then at 180 ℃ of baking ovens, dry 4h.
(2) 0.2g tri-isostearic acid isopropyl titanate coupling agents are dissolved in 100ml ethyl acetate solvent, and the 4A molecular sieve that step (1) is handled well stirs while adding, be warming up to 60 ℃, reaction 1h, leach molecular sieve.Then, the 4A molecular sieve leached is first dried to 1h at 100 ℃, then continue to dry 4h at 150 ℃, make the 4A molecular sieve by the coupling agent surface modification.
(3) 0.94g is dissolved in 20gNMP by the 4A molecular sieve of coupling agent surface modification, then add 1.88g p-phenylenediamine (PPD) (PPD), after dissolving fully, it adds 4.36g pyromellitic acid anhydride (PMDA), stir 3h, and add etoh solvent 20g, continue to stir 0.5h, make polyamic acid PAA/4A-1.Again 1.45g is dissolved in 31gNMP by the 4A molecular sieve of coupling agent surface modification, then add 3.48g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 6.2g4, the two phthalic anhydrides (ODPA) of 4'-oxygen, stir 3h, and add etoh solvent 31g, continue to stir 0.5h, make polyamic acid PAA/4A-2.Then the polyamic acid PAA/4A-1 and the polyamic acid PAA/4A-2 that make are mixed with the ratio of mass ratio 1:2, stir 24h, make polyamic acid PAA/4A complex liquid.
(4) polyamic acid PAA/4A complex liquid curtain coating film forming step (3) made.Last gradient increased temperature (3 ℃/min of heating rate in baking oven, from room temperature, 110 ℃/1h-160 ℃/1h-210 ℃/1h-260 ℃/1h) the cyclisation rear demoulding, pass through again high-temperature heat treatment (4 ℃/min of heating rate, from 200 ℃, 330 ℃/0.5h) after obtained the tough and tensile polyimides/Zeolite composite film that contains the 15%4A molecular sieve.
(5) (the D50 value is 70nm for 4A molecular sieve 0.63g step (2) handled well and 20g ptfe emulsion, solid content 60%) after being uniformly mixed, use planetary ball mill to grind 30min, make the 4A molecular sieve and account for the polytetrafluoroethylene (PTFE) that polytetrafluoroethylene (PTFE) butt quality is 5%/molecular sieve complex liquid.
(6) step for polyimides/Zeolite composite film (5) step (4) made make polytetrafluoroethylene (PTFE)/the molecular sieve complex liquid is two-sided films, and put into baking oven and dry 45min under 380 ℃.Finally, the polyimides/polytetrafluoroethylcomposite composite film made is taken out to 70 ℃ after distilled water immersion 2h and dry 2h, make the composite membrane of ecru.Its key property is in Table 1.
Embodiment 5
(1) the acetum washing of 0.1mol/L for the 13X molecular sieve that the 20g particle diameter is 20nm, and be washed till pH value 6～7 with distilled water, then at 180 ℃ of baking ovens, dry 4h.
(2) 0.2g tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanate coupling agent is dissolved in 100ml ethyl acetate solvent, and the 13X molecular sieve that step (1) is handled well stirs while adding, be warming up to 58 ℃, reaction 1h, leach molecular sieve.Then, the 13X molecular sieve leached is first dried to 1h at 100 ℃, then continue to dry 4h at 150 ℃, make the 13X molecular sieve by the coupling agent surface modification.
(3) 0.65g is dissolved in 20g NMP by the 13X molecular sieve of coupling agent surface modification, then add 2.14g p-phenylenediamine (PPD) (PPD), after dissolving fully, it adds 4.36g pyromellitic acid anhydride (PMDA), stir 3h, and add solvent xylene 20g, continue to stir 0.5h, make polyamic acid PAA/13X-1.Again 1.02g is dissolved in 31g NMP by the 13X molecular sieve of coupling agent surface modification, then add 3.96g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 6.2g4, the two phthalic anhydrides (ODPA) of 4'-oxygen, stir 3h, and add solvent xylene 31g, continue to stir 0.5h, make polyamic acid PAA/13X-2.Then the polyamic acid PAA/13X-1 and the polyamic acid PAA/13X-2 that make are mixed with the ratio of mass ratio 1:1, stir 24h, make polyamic acid PAA/13X complex liquid.
(4) polyamic acid PAA/13X complex liquid curtain coating film forming step (3) made.Last gradient increased temperature (4 ℃/min of heating rate in baking oven, from room temperature, 90 ℃/1.5h-150 ℃/1.25h-200 ℃/1.25h-280 ℃/1h) the cyclisation rear demoulding, pass through again high-temperature heat treatment (5 ℃/min of heating rate, from 200 ℃, 320 ℃/0.75h) after obtained the tough and tensile polyimides/Zeolite composite film that contains the 10%13X molecular sieve.
(5) (the D50 value is 70nm for molecular sieve 0.5g step (2) handled well and 20g ptfe emulsion, solid content 60%) after being uniformly mixed, use planetary ball mill to grind 30min, make the 13X molecular sieve and account for the polytetrafluoroethylene (PTFE) that polytetrafluoroethylene (PTFE) butt quality is 4%/molecular sieve complex liquid.
(6) step for polyimides/Zeolite composite film (5) step (4) made prepare polytetrafluoroethylene (PTFE)/the molecular sieve complex liquid is two-sided films, and put into baking oven and dry 50min under 340 ℃.Finally, the polyimides/polytetrafluoroethylcomposite composite film made is taken out to 70 ℃ after distilled water immersion 2h and dry 2h, make the composite membrane of ecru.Its key property is in Table 1.
Embodiment 6
(1) the acetum washing of 0.1mol/L for the 3A molecular sieve that the 20g particle diameter is 40nm, and be washed till pH value 6～7 with distilled water, then at 180 ℃ of baking ovens, dry 4h.
(2) 0.2g tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanate coupling agent is dissolved in 100ml ethyl acetate solvent, and the 3A molecular sieve that step (1) is handled well stirs while adding, be warming up to 60 ℃, reaction 1h, leach molecular sieve.Then, the 3A molecular sieve leached is first dried to 1h at 100 ℃, then continue to dry 4h at 150 ℃, make the 3A molecular sieve by the coupling agent surface modification.
(3) 0.65g is dissolved in 20g NMP by the 3A molecular sieve of coupling agent surface modification, then add 2.14g p-phenylenediamine (PPD) (PPD), after dissolving fully, it adds 4.36g pyromellitic acid anhydride (PMDA), stir 3h, and add solvent xylene 20g, continue to stir 0.5h, make polyamic acid PAA/3A-1.Again 1.02g is dissolved in 31g NMP by the 3A molecular sieve of coupling agent surface modification, then add 3.96g4,4'-diaminodiphenyl ether (ODA), after dissolving fully, it adds 6.2g4, the two phthalic anhydrides (ODPA) of 4'-oxygen, stir 3h, and add solvent xylene 31g, continue to stir 0.5h, make polyamic acid PAA/3A-2.Then the polyamic acid PAA/3A-1 and the polyamic acid PAA/3A-2 that make are mixed with the ratio of mass ratio 1:1, stir 24h, make polyamic acid PAA/3A complex liquid.
(4) polyamic acid PAA/3A complex liquid curtain coating film forming step (3) made.Last gradient increased temperature (4 ℃/min of heating rate in baking oven, from room temperature, 90 ℃/1.5h-150 ℃/1.25h-200 ℃/1.25h-280 ℃/1h) the cyclisation rear demoulding, pass through again high-temperature heat treatment (5 ℃/min of heating rate, from 200 ℃, 320 ℃/0.75h) after obtained the tough and tensile polyimides/Zeolite composite film that contains the 10%3A molecular sieve.
(5) (the D50 value is 70nm for 3A molecular sieve 0.06g step (2) handled well and 20g ptfe emulsion, solid content 60%) after being uniformly mixed, use planetary ball mill to grind 30min, make the 3A molecular sieve and account for the polytetrafluoroethylene (PTFE) that polytetrafluoroethylene (PTFE) butt quality is 0.5%/molecular sieve complex liquid.
(6) step for polyimides/Zeolite composite film (5) step (4) made make polytetrafluoroethylene (PTFE)/the molecular sieve complex liquid is two-sided films, and put into baking oven and dry 50min under 340 ℃.Finally, the polyimides/polytetrafluoroethylcomposite composite film made is taken out to 70 ℃ after distilled water immersion 2h and dry 2h, make the composite membrane of ecru.Its key property is in Table 1.
Table 1
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for a wire cable insulating comprises following steps:
(1) processing of molecular sieve
1. molecular sieve being washed till to the pH value is 6～7, dries;
2. coupling agent is dissolved in ethyl acetate, obtains coupling agent ethyl acetate solution; Then the molecular sieve after 1. step being dried adds in coupling agent ethyl acetate solution, and molecular sieve adds in the process of coupling agent ethyl acetate solution and constantly stirs, and the consumption of coupling agent is equivalent to 0.1～2% of molecular sieve quality; Then being warming up to 50～60 ℃ is reacted; Then leach molecular sieve, dry, make the molecular sieve by the coupling agent surface modification;
(2) preparation of polyamic acid PAA/ molecular sieve composite solution
1. the molecular sieve of step (1) being handled well joins in non-polar solven I, is stirred to fully and disperses; Then add diamines, add again dianhydride after diamines dissolves fully, continue to stir in the adition process of dianhydride, then add non-polar solven II, continue stirring and obtain the finely dispersed polyamic acid PAA of molecular sieve composite solution 1; Diamines and dianhydride be (1.01～1.15) in molar ratio: 1 proportioning;
2. re-use and 1. different diamines or dianhydride of step (2), by step (2), 1. make polyamic acid PAA composite solution 2;
3. polyamic acid complex liquid 1 and polyamic acid complex liquid 2 are mixed, obtain polyamic acid PAA/ molecular sieve complex liquid;
(3) preparation of polyimides/Zeolite composite film
The polyamic acid PAA/ molecular sieve complex liquid curtain coating film forming that step (2) is made; Then carry out gradient increased temperature cyclisation rear demoulding, high-temperature heat treatment, obtain polyimides/Zeolite composite film;
(4) preparation of polyimides/polytetrafluoroethylcomposite composite film
1. after molecular sieve step (1) made and ptfe emulsion are uniformly mixed, grind, obtain polytetrafluoroethylene (PTFE)/molecular sieve complex liquid; Prepared by step (3) polytetrafluoroethylene (PTFE) for polyimides/Zeolite composite film/the molecular sieve complex liquid is two-sided films, dry;
2. be soaked in water, then dry, obtain polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating.
2. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 1 is characterized in that:
Diamines described in step (2) is p-phenylenediamine (PPD), m-phenylene diamine (MPD), 4, the 4'-diaminodiphenyl ether, 3, 3'-dimethyl-4, the 4'-MDA, 1, the 2-DACH, 4, 4'-bisphenol-A diphenyl ether diamines, 4, 4'-bis-(4-amino-phenoxy group) diphenyl ether, 4, the 4'-diaminobenzophenone, 4, 4'-diaminourea triphenylamine, 4, the 4'-diaminodiphenyl-methane, 4, two (amino-benzene oxygen) benzophenone of 4'-, 1, two (3-amino-benzene oxygen-4'-benzoyl group) benzene of 3-, 1, 4-(2', the 4''-diamino phenoxy) benzene, 1, 3-bis-(4-amino-benzene oxygen) benzene and 1, 4-(2', the 4''-diamino phenoxy) a kind of in benzene or at least two kinds,
Dianhydride described in step (2) is pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 4, the two phthalic anhydrides of 4'-oxygen, triphen diether tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, bisphenol-A dianhydride, ester ring dianhydride dicyclo [2.2.1] octane-2,3,5,6-tetracarboxylic 2,3,5,6-dianhydride, cyclobutane tetracarboxylic acid dianhydride, hydrogenated pyromellitic anhydride and 3,3', a kind of in 4,4'-diphenyl sulfide tetracarboxylic dianhydride or at least two kinds.
3. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 1, it is characterized in that: described molecular sieve is micro porous molecular sieve, comprises 3A, 4A, 5A, 13X molecular sieve, its particle diameter is 20～50nm.
4. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 1 is characterized in that:
The coupling agent of step (1) described in 2. is titanate coupling agent, comprises a kind of in isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, three isostearic acid isopropyl titanates and tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanate esters or at least two kinds.
5. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 1, it is characterized in that: the non-polar solven I described in step (2) and described non-polar solven II are different non-polar solvens.
6. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 5 is characterized in that:
Described non-polar solven I is DMF, DMA, 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO);
Described non-polar solven II is toluene, dimethylbenzene, carrene, chloroform, acetone or alcohol.
7. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 1 is characterized in that:
The polyamic acid complex liquid 1 of step (2) described in 3. and polyamic acid complex liquid 2 be 1:(0.5～2 in mass ratio) mix.
8. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 1 is characterized in that:
The quality percentage composition that polyimides/Zeolite composite film described in step (3) is molecular sieve is 0.1～15% of polyimides quality;
The quality consumption of the molecular sieve of step (4) described in 1. is equivalent to 0.5～5% of described ptfe emulsion butt quality.
9. the preparation method of polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating according to claim 1 is characterized in that:
The condition of the oven dry of step (1) described in 1. is 180 ℃ and dries 4h;
The condition of the oven dry of step (1) described in 2. is first at 100 ℃, to dry 1h, then continues to dry 4h at 150 ℃;
The step of the intensification described in step (3) is the speed intensification with 3～6 ℃/min, from room temperature, at 90～110 ℃, keeps 1～1.5h, at 140～160 ℃, keeps 1～1.5h, at 190～210 ℃, keeps 1～1.5h, at 240～280 ℃, keeps 1～1.5h;
High-temperature heat treatment described in step (3) refers to from 200 ℃, with the speed of 3～6 ℃/min, is warming up to 290～330 ℃ and keep 0.5～1h;
The condition of the oven dry of step (4) described in 1. is to dry 45～75min in 320～380 ℃;
Step (4) being soaked in water as using distilled water immersion 2h described in 2.;
The condition of the oven dry of step (4) described in 2. is to dry 2h in 70 ℃.
10. a polyimides/polytetrafluoroethylcomposite composite film for wire cable insulating, by claim 1～9 any one, described preparation method prepares.
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