CN103434236B - 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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- CN103434236B CN103434236B CN201310389613.4A CN201310389613A CN103434236B CN 103434236 B CN103434236 B CN 103434236B CN 201310389613 A CN201310389613 A CN 201310389613A CN 103434236 B CN103434236 B CN 103434236B
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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 a kind of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film and preparation method, belong to wire cable insulating Material Field.
Background technology
Polyimides (PI) is the aromatic heterocycle polymer compound containing imide group in repetitive, with the extraordinary high polymer that high temperature resistant, radiation hardness are performance characteristics, there are good mechanical property, wearability, dimensional stability, solvent resistance etc., be successfully applied to the sophisticated technology fields such as Aeronautics and Astronautics, be also widely used in the industry such as electronic apparatus, mechanical chemical industry.In order to adapt to high-tech development, the research of PI is also advanced in the continuous direction towards high performance, multifunction.In electric wire production process, the color due to PI film is brown color, and copper cash color change after PI coiling is little, and on tinuous production, whether copper cash is difficult to make accurate judgement at once by PI film coiling.During Deng problem discover, substandard product has produced a lot, tremendous economic is brought to lose to enterprise, it is necessary to be coated with one deck color at PI film surface, make the performance of PI film unaffected even more outstanding simultaneously, and whether copper cash is by the problem of PI film coiling aborning to make workman find immediately, this is necessary to reduction enterprises' loss.Therefore, usual in PI film surface coating tetrafluoroethylene emulsion in industrial production.
The emulsion polymerisation of polytetrafluoroethylene (PTFE) is also known as dispersin polymerization, and product is the aqueous dispersions of PTFE, and solid content about 60% can be used for the coating etc. of the dipping of fabric and porous metals, form film, metal coating and other base material.But polytetrafluoroethylene (PTFE) structure height symmetry belongs to non-polar high polymer, has low surface energy.Material surface energy is lower, and adhesive force is less, and the contact angle of material surface and liquid is also larger.But single PTFE material can not be bonding with coating interface and can not in normal temperature cure without the surface active of complexity.There is research to be introduced other group by modified ptfe surface and improve its cementability with other matrix, or modify PTFE surface makes it have certain coarse structure and reaches ultra-hydrophobicity, but these processes to equipment requirement, higher and process is complicated is difficult to application.And in ptfe emulsion, add micron order or nano level inorganic particulate can improve adhesive property between polytetrafluoroethylene (PTFE) and other matrixes to prepare polytetrafluoroethylene (PTFE)-inorganic hybridization coating.
Molecular sieve refers to that a class has uniform pore size, huge internal surface area and pore volume, has again a class crystalline microporous material of the characteristics such as ion exchangeable simultaneously.Because molecular sieve is porous material, thus there is absorption assembling characteristic, can specific group of molecules is contained in its micropore, be released under certain particular case, utilize this characteristic, can give molecular sieve certain function.And micro porous molecular sieve, have regular duct arrangement and skeletal atom order, its pore diameter range is 0.3nm ~ 1.2nm.
Add inorganic particulate in the polymer and effectively can realize the low cost of polymer, high-performance and multifunction, this has become a kind of effective way in new material exploitation.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film.
Another object of the present invention is to provide the wire cable insulating obtained by above-mentioned preparation method polyimides/polytetrafluoroethylcomposite composite film.
Object of the present invention is achieved through the following technical solutions: a kind of preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film, comprises following steps:
(1) process of molecular sieve
1. molecular sieve being washed till 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 step 1. 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 be warming up to 50 ~ 60 DEG C to react; Then leach molecular sieve, dry, obtain by the molecular sieve of coupling agent surface modification;
(2) preparation of polyamic acid PAA/ molecular sieve composite solution
1. the molecular sieve that step (1) is handled well is joined in non-polar solven I, be stirred to and disperse completely; Then add diamines, after diamines dissolves completely, add dianhydride again, Keep agitation in the adition process of dianhydride, then add non-polar solven II, continue stirring and obtain molecular sieve finely dispersed polyamic acid PAA composite solution 1; Diamines and dianhydride be (1.01 ~ 1.15) in molar ratio: 1 proportioning;
2. the diamines 1. different from step (2) or dianhydride is re-used, by step (2) 1. obtained 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 casting film-forming obtained by step (2); Then gradient increased temperature cyclisation rear demoulding, high-temperature heat treatment, obtains polyimides/Zeolite composite film;
(4) preparation of polyimides/polytetrafluoroethylcomposite composite film
1., after molecular sieve obtained for step (1) and ptfe emulsion being uniformly mixed, grinding, obtains polytetrafluoroethylene (PTFE)/molecular sieve complex liquid; Polyimides step (3) prepared/Zeolite composite film polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid, dries;
2. be soaked in water, then dry, obtain wire cable insulating polyimides/polytetrafluoroethylcomposite composite film.
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;
Step (1) 1. described in pH value that molecular sieve is washed till be 6 ~ 7 be preferably the acetums washing using 0.1mol/L, and with water, molecular sieve to be washed till pH value be 6 ~ 7;
Step (1) 1. described in the condition of oven dry be preferably 180 DEG C and dry 4h;
Step (1) 2. described in coupling agent be titanate coupling agent, comprise the one in isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, three isostearic acid isopropyl titanates and tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters or at least two kinds;
Step (1) 2. described in time of reaction be preferably 1h;
Step (1) 2. described in the condition of oven dry be preferably and first dry 1h at 100 DEG C, then continue to dry 4h at 150 DEG C;
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 diphenyldiamine (BAPP), 4, 4'-bis-(4-Amino-phenoxv) 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', 4''-diamino phenoxy) benzene (OAPB), 1, 3-bis-(4-amino-benzene oxygen) benzene (TPER) and 1, 4-(2', 4''-diamino phenoxy) one 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 anhydride (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), cyclobutanetetracarboxylic dianhydride (CBDA), hydrogenated pyromellitic anhydride (HPMDA) and 3, 3', 4, one 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 is different non-polar solven;
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;
Step (2) 1. described in the time of Keep agitation in the adition process of dianhydride be preferably 3h;
Step (2) 1. described in add non-polar solven II after continue stir time be preferably 0.5h;
Step (2) 3. described in polyamic acid complex liquid 1 and polyamic acid complex liquid 2 preferably 1:(0.5 ~ 2 in mass ratio) mixing, stir 24h;
The step of the intensification described in step (3) is preferably with the ramp of 3 ~ 6 DEG C/min, from room temperature, keeps 1 ~ 1.5h at 90 ~ 110 DEG C, 1 ~ 1.5h is kept at 140 ~ 160 DEG C, keep 1 ~ 1.5h at 190 ~ 210 DEG C, at 240 ~ 280 DEG C, keep 1 ~ 1.5h;
Described room temperature is preferably 20 ~ 30 DEG C;
High-temperature heat treatment described in step (3) refers to from 200 DEG C, keeps 0.5 ~ 1h with ramp to 290 ~ 330 of 3 ~ 6 DEG C/min DEG C;
The mass percentage that polyimides/Zeolite composite film described in step (3) is preferably molecular sieve is 0.1 ~ 15% of polyimides quality;
Step (4) 1. described in the preferred D50 value of ptfe emulsion be the ptfe emulsion of 70nm, solid content 60%;
Step (4) 1. described in the quality consumption of molecular sieve be equivalent to 0.5 ~ 5% of described ptfe emulsion butt quality;
Step (4) 1. described in grinding condition be preferably use planetary ball mill grinding 30min;
Step (4) 1. described in oven dry condition be preferably in 320 ~ 380 DEG C dry 45 ~ 75min;
Step (4) 2. described in be soaked in water and preferably use distilled water immersion 2h;
Step (4) 2. described in oven dry condition be preferably in 70 DEG C dry 2h;
A kind of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film, is prepared by above-mentioned preparation method.
Mechanism of the present invention: the dianhydride utilizing different ratio, diamines and molecular sieve reaction generate polyamic acid molecular sieve complex liquid, and sieve composite membrane by by making the polyimide molecule having different performance after different proportion mixing., mixed by molecular sieve in ptfe emulsion, dual coating, on polyimide molecule sieve composite membrane, finally obtains polyimides/polytetrafluoroethylcomposite composite film meanwhile.
The present invention has following advantage and effect relative to prior art:
(1) the invention solves the problem that between polytetrafluorethylecoatings coatings and other matrixes, caking property is not strong, in the wire cable insulating polyimides/polytetrafluoroethylcomposite composite film provided polyimides and polytetrafluoroethylene (PTFE) caking property good.
(2) wire cable insulating polyimides/polytetrafluoroethylcomposite composite film excellent in mechanical performance provided by the invention, and there are good insulating properties.Even if this wire cable insulating polyimides/polytetrafluoroethylcomposite composite film is when polytetrafluorethylecoatings coatings breakage, can normally works in wet environment and not affect its electrical property, and there is the characteristic of low-k.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) 20g particle diameter is the acetum washing of the 13X molecular sieve 0.1mol/L of 20nm, and is washed till pH value 6 ~ 7 with distilled water, then dries 4h at 180 DEG C of baking ovens.
(2) be dissolved in 100ml ethyl acetate solvent by 0.02g tri-isostearic acid isopropyl titanate coupling agent, and stirred while adding by the 13X molecular sieve that step (1) is handled well, be warming up to 50 DEG C, reaction 1h, leaches molecular sieve.Then, the 13X molecular sieve leached first is dried 1h at 100 DEG C, then continue to dry 4h at 150 DEG C, obtain by the 13X molecular sieve of coupling agent surface modification.
(3) 0.008g is dissolved in 23.5g DMF by the 13X molecular sieve of coupling agent surface modification, then 3.96g4 is added, 4'-diaminodiphenyl ether (ODA), 4.36g pyromellitic acid anhydride (PMDA) is added after it dissolves completely, stir 3h, and add solvent toluene 23.5g, continue to stir 0.5h, obtained polyamic acid PAA/13X-1.Again 0.01g is dissolved in 28g DMF by the 13X molecular sieve of coupling agent surface modification, then 3.96g4 is added, 4'-diaminodiphenyl ether (ODA), 6.2g4 is added after it dissolves completely, the two phthalic anhydride (ODPA) of 4'-oxygen, stirs 3h, and adds solvent toluene 28g, continue to stir 0.5h, obtained polyamic acid PAA/13X-2.Then obtained polyamic acid PAA/13X-1 and polyamic acid PAA/13X-2 is mixed with the ratio of mass ratio 2:1, stir 24h, obtained polyamic acid PAA/13X complex liquid.
(4) by polyamic acid PAA/13X complex liquid casting film-forming obtained for step (3).Last gradient increased temperature (heating rate 3 DEG C/min in an oven, from room temperature, 90 DEG C/1.5h-140 DEG C/1.5h-190 DEG C/1.5h-240 DEG C/1.5h) cyclisation rear demoulding, again through high-temperature heat treatment (heating rate 3 DEG C/min, from 200 DEG C, 290 DEG C/1h) after namely obtain the tough and tensile polyimides/Zeolite composite film containing 0.1%13X molecular sieve.
(5) (D50 value is 70nm for 13X molecular sieve 0.12g step (2) handled well and 20g ptfe emulsion, solid content 60%) be uniformly mixed after, use planetary ball mill grinding 30min, obtained 13X molecular sieve accounts for polytetrafluoroethylene (PTFE)/molecular sieve complex liquid that polytetrafluoroethylene (PTFE) butt quality is 1%.
(6) by polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid that polyimides/Zeolite composite film step (5) obtained for step (4) is obtained, and put into baking oven dry 75min at 320 DEG C.Finally, obtained polyimides/polytetrafluoroethylcomposite composite film is taken out 70 DEG C after distilled water immersion 2h and dries 2h, the composite membrane of obtained ecru.Its key property is in table 1.
Embodiment 2
(1) 20g particle diameter is the acetum washing of the 4A molecular sieve 0.1mol/L of 30nm, and is washed till pH value 6 ~ 7 with distilled water, then dries 4h at 180 DEG C of baking ovens.
(2) be dissolved in 100ml ethyl acetate solvent by 0.2g tri-isostearic acid isopropyl titanate coupling agent, and stirred while adding by the 4A molecular sieve that step (1) is handled well, be warming up to 54 DEG C, reaction 1h, leaches molecular sieve.Then, the 4A molecular sieve leached first is dried 1h at 100 DEG C, then continue to dry 4h at 150 DEG C, obtain by the 4A molecular sieve of coupling agent surface modification.
(3) 0.08g is dissolved in 23.5gNMP by the 4A molecular sieve of coupling agent surface modification, then 3.96g4 is added, 4'-diaminodiphenyl ether (ODA), 4.36g pyromellitic acid anhydride (PMDA) is added after it dissolves completely, stir 3h, and add etoh solvent 23.5g, continue to stir 0.5h, obtained polyamic acid PAA/4A-1.Again 0.1g is dissolved in 28gNMP by the 4A molecular sieve of coupling agent surface modification, then 3.96g4 is added, 4'-diaminodiphenyl ether (ODA), 6.2g4 is added after it dissolves completely, the two phthalic anhydride (ODPA) of 4'-oxygen, stirs 3h, and adds etoh solvent 28g, continue to stir 0.5h, obtained polyamic acid PAA/4A-2.Then obtained polyamic acid PAA/4A-1 and polyamic acid PAA/4A-2 is mixed with the ratio of mass ratio 1:1, stir 24h, obtained polyamic acid PAA/4A complex liquid.
(4) by polyamic acid PAA/4A complex liquid casting film-forming obtained for step (3).Last gradient increased temperature (heating rate 4 DEG C/min in an oven, from room temperature, 100 DEG C/1.25h-150 DEG C/1.25h-200 DEG C/1.25h-250 DEG C/1.25h) cyclisation rear demoulding, again through high-temperature heat treatment (heating rate 5 DEG C/min, from 200 DEG C, 310 DEG C/0.75h) after namely obtain the tough and tensile polyimides/Zeolite composite film containing 1%4A molecular sieve.
(5) (D50 value is 70nm for 4A molecular sieve 0.25g step (2) handled well and 20g ptfe emulsion, solid content 60%) be uniformly mixed after, use planetary ball mill grinding 30min, obtained 4A molecular sieve accounts for polytetrafluoroethylene (PTFE)/molecular sieve complex liquid that polytetrafluoroethylene (PTFE) butt quality is 2%.
(6) by polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid that polyimides/Zeolite composite film step (5) obtained for step (4) is obtained, and put into baking oven dry 60min at 340 DEG C.Finally, obtained polyimides/polytetrafluoroethylcomposite composite film is taken out 70 DEG C after distilled water immersion 2h and dries 2h, the composite membrane of obtained ecru.Its key property is in table 1.
Embodiment 3
(1) 20g particle diameter is the acetum washing of the 5A molecular sieve 0.1mol/L of 50nm, and is washed till pH value 6 ~ 7 with distilled water, then dries 4h at 180 DEG C of baking ovens.
(2) be dissolved in 100ml ethyl acetate solvent by 0.4g isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate coupling agent, and stirred while adding by the 5A molecular sieve that step (1) is handled well, be warming up to 50 DEG C, reaction 1h, leaches molecular sieve.Then, the 5A molecular sieve leached first is dried 1h at 100 DEG C, then continue to dry 4h at 150 DEG C, obtain by the 5A molecular sieve of coupling agent surface modification.
(3) 0.4g is dissolved in 23.5gNMP by the 5A molecular sieve of coupling agent surface modification, then 3.64g4 is added, 4'-diaminodiphenyl ether (ODA), 4.36g pyromellitic acid anhydride (PMDA) is added after it dissolves completely, stir 3h, and add etoh solvent 23.5g, continue to stir 0.5h, obtained polyamic acid PAA/5A-1.Again 0.5g is dissolved in 28gNMP by the 5A molecular sieve of coupling agent surface modification, then 3.64g4 is added, 4'-diaminodiphenyl ether (ODA), 6.2g4 is added after it dissolves completely, the two phthalic anhydride (ODPA) of 4'-oxygen, stirs 3h, and adds etoh solvent 28g, continue to stir 0.5h, obtained polyamic acid PAA/5A-2.Then obtained polyamic acid PAA/5A-1 and polyamic acid PAA/5A-2 is mixed with the ratio of mass ratio 1:2, stir 24h, obtained polyamic acid PAA/5A complex liquid.
(4) by polyamic acid PAA/5A complex liquid casting film-forming obtained for step (3).Last gradient increased temperature (heating rate 6 DEG C/min in an oven, from room temperature, 110 DEG C/1h-160 DEG C/1h-210 DEG C/1h-260 DEG C/1h) cyclisation rear demoulding, again through high-temperature heat treatment (heating rate 6 DEG C/min, from 200 DEG C, 330 DEG C/0.5h) after namely obtain the tough and tensile polyimides/Zeolite composite film containing 5%5A molecular sieve.
(5) (D50 value is 70nm for 5A molecular sieve 0.63g step (2) handled well and 20g ptfe emulsion, solid content 60%) be uniformly mixed after, use planetary ball mill grinding 30min, obtained 5A molecular sieve accounts for polytetrafluoroethylene (PTFE)/molecular sieve complex liquid that polytetrafluoroethylene (PTFE) butt quality is 5%.
(6) by polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid that polyimides/Zeolite composite film step (5) obtained for step (4) is obtained, and put into baking oven dry 45min at 380 DEG C.Finally, obtained polyimides/polytetrafluoroethylcomposite composite film is taken out 70 DEG C after distilled water immersion 2h and dries 2h, the composite membrane of obtained ecru.Its key property is in table 1.
Embodiment 4
(1) 20g particle diameter is the acetum washing of the 4A molecular sieve 0.1mol/L of 30nm, and is washed till pH value 6 ~ 7 with distilled water, then dries 4h at 180 DEG C of baking ovens.
(2) be dissolved in 100ml ethyl acetate solvent by 0.2g tri-isostearic acid isopropyl titanate coupling agent, and stirred while adding by the 4A molecular sieve that step (1) is handled well, be warming up to 60 DEG C, reaction 1h, leaches molecular sieve.Then, the 4A molecular sieve leached first is dried 1h at 100 DEG C, then continue to dry 4h at 150 DEG C, obtain by the 4A molecular sieve of coupling agent surface modification.
(3) 0.94g is dissolved in 20gNMP by the 4A molecular sieve of coupling agent surface modification, then 1.88g p-phenylenediamine (PPD) (PPD) is added, 4.36g pyromellitic acid anhydride (PMDA) is added after it dissolves completely, stir 3h, and add etoh solvent 20g, continue to stir 0.5h, obtained polyamic acid PAA/4A-1.Again 1.45g is dissolved in 31gNMP by the 4A molecular sieve of coupling agent surface modification, then 3.48g4 is added, 4'-diaminodiphenyl ether (ODA), 6.2g4 is added after it dissolves completely, the two phthalic anhydride (ODPA) of 4'-oxygen, stirs 3h, and adds etoh solvent 31g, continue to stir 0.5h, obtained polyamic acid PAA/4A-2.Then obtained polyamic acid PAA/4A-1 and polyamic acid PAA/4A-2 is mixed with the ratio of mass ratio 1:2, stir 24h, obtained polyamic acid PAA/4A complex liquid.
(4) by polyamic acid PAA/4A complex liquid casting film-forming obtained for step (3).Last gradient increased temperature (heating rate 3 DEG C/min in an oven, from room temperature, 110 DEG C/1h-160 DEG C/1h-210 DEG C/1h-260 DEG C/1h) cyclisation rear demoulding, again through high-temperature heat treatment (heating rate 4 DEG C/min, from 200 DEG C, 330 DEG C/0.5h) after namely obtain the tough and tensile polyimides/Zeolite composite film containing 15%4A molecular sieve.
(5) (D50 value is 70nm for 4A molecular sieve 0.63g step (2) handled well and 20g ptfe emulsion, solid content 60%) be uniformly mixed after, use planetary ball mill grinding 30min, obtained 4A molecular sieve accounts for polytetrafluoroethylene (PTFE)/molecular sieve complex liquid that polytetrafluoroethylene (PTFE) butt quality is 5%.
(6) by polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid that polyimides/Zeolite composite film step (5) obtained for step (4) is obtained, and put into baking oven dry 45min at 380 DEG C.Finally, obtained polyimides/polytetrafluoroethylcomposite composite film is taken out 70 DEG C after distilled water immersion 2h and dries 2h, the composite membrane of obtained ecru.Its key property is in table 1.
Embodiment 5
(1) 20g particle diameter is the acetum washing of the 13X molecular sieve 0.1mol/L of 20nm, and is washed till pH value 6 ~ 7 with distilled water, then dries 4h at 180 DEG C of baking ovens.
(2) be dissolved in 100ml ethyl acetate solvent by 0.2g tetra isopropyl two (dioctyl phosphito acyloxy) titanate coupling agent, and stirred while adding by the 13X molecular sieve that step (1) is handled well, be warming up to 58 DEG C, reaction 1h, leaches molecular sieve.Then, the 13X molecular sieve leached first is dried 1h at 100 DEG C, then continue to dry 4h at 150 DEG C, obtain by the 13X molecular sieve of coupling agent surface modification.
(3) 0.65g is dissolved in 20g NMP by the 13X molecular sieve of coupling agent surface modification, then 2.14g p-phenylenediamine (PPD) (PPD) is added, 4.36g pyromellitic acid anhydride (PMDA) is added after it dissolves completely, stir 3h, and add solvent xylene 20g, continue to stir 0.5h, obtained polyamic acid PAA/13X-1.Again 1.02g is dissolved in 31g NMP by the 13X molecular sieve of coupling agent surface modification, then 3.96g4 is added, 4'-diaminodiphenyl ether (ODA), 6.2g4 is added after it dissolves completely, the two phthalic anhydride (ODPA) of 4'-oxygen, stirs 3h, and adds solvent xylene 31g, continue to stir 0.5h, obtained polyamic acid PAA/13X-2.Then obtained polyamic acid PAA/13X-1 and polyamic acid PAA/13X-2 is mixed with the ratio of mass ratio 1:1, stir 24h, obtained polyamic acid PAA/13X complex liquid.
(4) by polyamic acid PAA/13X complex liquid casting film-forming obtained for step (3).Last gradient increased temperature (heating rate 4 DEG C/min in an oven, from room temperature, 90 DEG C/1.5h-150 DEG C/1.25h-200 DEG C/1.25h-280 DEG C/1h) cyclisation rear demoulding, again through high-temperature heat treatment (heating rate 5 DEG C/min, from 200 DEG C, 320 DEG C/0.75h) after namely obtain the tough and tensile polyimides/Zeolite composite film containing 10%13X molecular sieve.
(5) (D50 value is 70nm for molecular sieve 0.5g step (2) handled well and 20g ptfe emulsion, solid content 60%) be uniformly mixed after, use planetary ball mill grinding 30min, obtained 13X molecular sieve accounts for polytetrafluoroethylene (PTFE)/molecular sieve complex liquid that polytetrafluoroethylene (PTFE) butt quality is 4%.
(6) by polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid prepared by polyimides/Zeolite composite film step (5) obtained for step (4), and put into baking oven dry 50min at 340 DEG C.Finally, obtained polyimides/polytetrafluoroethylcomposite composite film is taken out 70 DEG C after distilled water immersion 2h and dries 2h, the composite membrane of obtained ecru.Its key property is in table 1.
Embodiment 6
(1) 20g particle diameter is the acetum washing of the 3A molecular sieve 0.1mol/L of 40nm, and is washed till pH value 6 ~ 7 with distilled water, then dries 4h at 180 DEG C of baking ovens.
(2) be dissolved in 100ml ethyl acetate solvent by 0.2g tetra isopropyl two (dioctyl phosphito acyloxy) titanate coupling agent, and stirred while adding by the 3A molecular sieve that step (1) is handled well, be warming up to 60 DEG C, reaction 1h, leaches molecular sieve.Then, the 3A molecular sieve leached first is dried 1h at 100 DEG C, then continue to dry 4h at 150 DEG C, obtain by the 3A molecular sieve of coupling agent surface modification.
(3) 0.65g is dissolved in 20g NMP by the 3A molecular sieve of coupling agent surface modification, then 2.14g p-phenylenediamine (PPD) (PPD) is added, 4.36g pyromellitic acid anhydride (PMDA) is added after it dissolves completely, stir 3h, and add solvent xylene 20g, continue to stir 0.5h, obtained polyamic acid PAA/3A-1.Again 1.02g is dissolved in 31g NMP by the 3A molecular sieve of coupling agent surface modification, then 3.96g4 is added, 4'-diaminodiphenyl ether (ODA), 6.2g4 is added after it dissolves completely, the two phthalic anhydride (ODPA) of 4'-oxygen, stirs 3h, and adds solvent xylene 31g, continue to stir 0.5h, obtained polyamic acid PAA/3A-2.Then obtained polyamic acid PAA/3A-1 and polyamic acid PAA/3A-2 is mixed with the ratio of mass ratio 1:1, stir 24h, obtained polyamic acid PAA/3A complex liquid.
(4) by polyamic acid PAA/3A complex liquid casting film-forming obtained for step (3).Last gradient increased temperature (heating rate 4 DEG C/min in an oven, from room temperature, 90 DEG C/1.5h-150 DEG C/1.25h-200 DEG C/1.25h-280 DEG C/1h) cyclisation rear demoulding, again through high-temperature heat treatment (heating rate 5 DEG C/min, from 200 DEG C, 320 DEG C/0.75h) after namely obtain the tough and tensile polyimides/Zeolite composite film containing 10%3A molecular sieve.
(5) (D50 value is 70nm for 3A molecular sieve 0.06g step (2) handled well and 20g ptfe emulsion, solid content 60%) be uniformly mixed after, use planetary ball mill grinding 30min, obtained 3A molecular sieve accounts for polytetrafluoroethylene (PTFE)/molecular sieve complex liquid that polytetrafluoroethylene (PTFE) butt quality is 0.5%.
(6) by polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid that polyimides/Zeolite composite film step (5) obtained for step (4) is obtained, and put into baking oven dry 50min at 340 DEG C.Finally, obtained polyimides/polytetrafluoroethylcomposite composite film is taken out 70 DEG C after distilled water immersion 2h and dries 2h, the composite membrane of obtained ecru.Its key property is in table 1.
Table 1
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for wire cable insulating polyimides/polytetrafluoroethylcomposite composite film, comprises following steps:
(1) process of molecular sieve
1. molecular sieve being washed till 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 step 1. 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 be warming up to 50 ~ 60 DEG C to react; Then leach molecular sieve, dry, obtain by the molecular sieve of coupling agent surface modification;
(2) preparation of polyamic acid PAA/ molecular sieve composite solution
1. the molecular sieve that step (1) is handled well is joined in non-polar solven I, be stirred to and disperse completely; Then add diamines, after diamines dissolves completely, add dianhydride again, Keep agitation in the adition process of dianhydride, then add non-polar solven II, continue stirring and obtain molecular sieve finely dispersed polyamic acid PAA composite solution 1; Diamines and dianhydride be (1.01 ~ 1.15) in molar ratio: 1 proportioning;
2. the diamines 1. different from step (2) or dianhydride is re-used, by step (2) 1. obtained 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 casting film-forming obtained by step (2); 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 obtained for step (1) and ptfe emulsion being uniformly mixed, grinding, obtains polytetrafluoroethylene (PTFE)/molecular sieve complex liquid; Polyimides step (3) prepared/Zeolite composite film polytetrafluoroethylene (PTFE)/two-sided film of molecular sieve complex liquid, dries;
2. be soaked in water, then dry, obtain wire cable insulating polyimides/polytetrafluoroethylcomposite composite film.
2. the preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film according to claim 1, is characterized in that:
Diamines described in step (2) is p-phenylenediamine (PPD), m-phenylene diamine (MPD), 4, 4'-diaminodiphenyl ether, 3, 3'-dimethyl-4, 4'-MDA, 1, 2-DACH, 4, 4'-bisphenol-A diphenyldiamine, 4, 4'-bis-(4-Amino-phenoxv) diphenyl ether, 4, 4'-diaminobenzophenone, 4, 4'-diaminourea triphenylamine, 4, 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', 4''-diamino phenoxy) benzene, 1, 3-bis-(4-amino-benzene oxygen) benzene and 1, 4-(2', 4''-diamino phenoxy) one in benzene or at least two kinds,
Dianhydride described in step (2) is pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 4,4'-oxygen two phthalic anhydride, 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, cyclobutanetetracarboxylic dianhydride, hydrogenated pyromellitic anhydride and 3,3', one in 4,4'-diphenyl sulfide tetracarboxylic dianhydride or at least two kinds.
3. the preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film according to claim 1, is characterized in that: described molecular sieve is micro porous molecular sieve, comprises 3A, 4A, 5A, 13X molecular sieve, and its particle diameter is 20 ~ 50nm.
4. the preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film according to claim 1, is characterized in that:
Step (1) 2. described in coupling agent be titanate coupling agent, comprise the one in isopropyl three (dioctylphyrophosphoric acid acyloxy) titanate esters, three isostearic acid isopropyl titanates and tetra isopropyl two (dioctyl phosphito acyloxy) titanate esters or at least two kinds.
5. the preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film according to claim 1, is characterized in that: the non-polar solven I described in step (2) and described non-polar solven II is different non-polar solven.
6. the preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film 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 wire cable insulating polyimides/polytetrafluoroethylcomposite composite film according to claim 1, is characterized in that:
Step (2) 3. described in polyamic acid complex liquid 1 and polyamic acid complex liquid 2 1:(0.5 ~ 2 in mass ratio) mixing.
8. the preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film according to claim 1, is characterized in that:
Polyimides/Zeolite composite film described in step (3) is the mass percentage of molecular sieve is 0.1 ~ 15% of polyimides quality;
Step (4) 1. described in the quality consumption of molecular sieve be equivalent to 0.5 ~ 5% of described ptfe emulsion butt quality.
9. the preparation method of wire cable insulating polyimides/polytetrafluoroethylcomposite composite film according to claim 1, is characterized in that:
Step (1) 1. described in the condition of oven dry be 180 DEG C and dry 4h;
Step (1) 2. described in the condition of oven dry be first dry 1h at 100 DEG C, then continue to dry 4h at 150 DEG C;
The step of the intensification described in step (3) is with the ramp of 3 ~ 6 DEG C/min, from room temperature, keeps 1 ~ 1.5h at 90 ~ 110 DEG C, keeps 1 ~ 1.5h at 140 ~ 160 DEG C, keep 1 ~ 1.5h at 190 ~ 210 DEG C, keep 1 ~ 1.5h at 240 ~ 280 DEG C;
High-temperature heat treatment described in step (3) refers to from 200 DEG C, keeps 0.5 ~ 1h with ramp to 290 ~ 330 of 3 ~ 6 DEG C/min DEG C;
Step (4) 1. described in the condition of oven dry be dry 45 ~ 75min in 320 ~ 380 DEG C;
Step (4) 2. described in be soaked in water as using distilled water immersion 2h;
Step (4) 2. described in the condition of oven dry be dry 2h in 70 DEG C.
10. wire cable insulating polyimides/polytetrafluoroethylcomposite composite film, is prepared by the preparation method described in any one of claim 1 ~ 9.
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| CN104530703A (en) * | 2015-01-20 | 2015-04-22 | 无锡顺铉新材料有限公司 | Low-dielectric constant polyimide and preparation method thereof |
| CN107573842B (en) * | 2016-07-04 | 2020-05-12 | 大亚电线电缆股份有限公司 | Low-dielectric polyimide insulating paint and enameled wire |
| CN107186904A (en) * | 2017-06-14 | 2017-09-22 | 合肥博创机械制造有限公司 | A kind of Novel wire cable insulating barrier preparation method |
| JP2019040790A (en) * | 2017-08-28 | 2019-03-14 | トヨタ自動車株式会社 | Insulation electric wire |
| CN110922618B (en) * | 2019-12-03 | 2020-10-27 | 西安交通大学 | Preparation method of insulating medium for improving energy storage density |
| CN111120871B (en) * | 2020-03-30 | 2020-06-19 | 中国石油大学胜利学院 | Method for preparing functional oil drag reducer by using waste 5A molecular sieve for olefin raw material dehydration |
| CN112382450B (en) * | 2020-10-21 | 2021-06-11 | 扬泰氟（清远）电线电缆有限公司 | Preparation method of polyimide/polytetrafluoroethylene composite film for wire and cable insulation |
| CN113354816A (en) * | 2021-05-28 | 2021-09-07 | 无锡高拓新材料股份有限公司 | Method for synthesizing polyamic acid solution and film prepared by method |
| CN115785509A (en) * | 2022-12-08 | 2023-03-14 | 安徽中科宇顺科技有限公司 | Preparation method of low-dielectric polyimide/polytetrafluoroethylene heat-insulating film |
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