CN115677994A - Preparation and application of polyester and nano-silver conductive film based on biphenyldicarboxylic acid - Google Patents
Preparation and application of polyester and nano-silver conductive film based on biphenyldicarboxylic acid Download PDFInfo
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- CN115677994A CN115677994A CN202110865164.0A CN202110865164A CN115677994A CN 115677994 A CN115677994 A CN 115677994A CN 202110865164 A CN202110865164 A CN 202110865164A CN 115677994 A CN115677994 A CN 115677994A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229920000728 polyester Polymers 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 45
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- QPIAAQDLOJNQMP-UHFFFAOYSA-N 2-ethyl-2-propylpropane-1,3-diol Chemical compound CCCC(CC)(CO)CO QPIAAQDLOJNQMP-UHFFFAOYSA-N 0.000 claims abstract description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 10
- QDSBRPJDULBWBF-UHFFFAOYSA-N 1-piperidin-3-ylpropane-1,2-diol Chemical compound CC(O)C(O)C1CCCNC1 QDSBRPJDULBWBF-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 2-piperidyl Chemical group 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- 238000001914 filtration Methods 0.000 claims description 25
- 229920006267 polyester film Polymers 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 11
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 claims description 10
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 10
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 10
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 10
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 10
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 10
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000011550 stock solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- GXOMJTUKGGNEMI-UHFFFAOYSA-N 1,2-bis(ethenyl)piperidine Chemical group C=CC1CCCCN1C=C GXOMJTUKGGNEMI-UHFFFAOYSA-N 0.000 claims 1
- 229940098691 coco monoethanolamide Drugs 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 20
- 238000002834 transmittance Methods 0.000 abstract description 19
- 230000032050 esterification Effects 0.000 abstract description 11
- 238000005452 bending Methods 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 235000013162 Cocos nucifera Nutrition 0.000 description 7
- 244000060011 Cocos nucifera Species 0.000 description 7
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- KEIMDCSRTSXXBP-UHFFFAOYSA-N 2-[1-(2-hydroxyethyl)piperidin-2-yl]ethanol Chemical compound OCCC1CCCCN1CCO KEIMDCSRTSXXBP-UHFFFAOYSA-N 0.000 description 4
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 4
- 239000002042 Silver nanowire Substances 0.000 description 4
- 238000010101 extrusion blow moulding Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- CTTHAYDUZMEYLD-UHFFFAOYSA-N 1,1'-biphenyl;formic acid Chemical compound OC=O.OC=O.C1=CC=CC=C1C1=CC=CC=C1 CTTHAYDUZMEYLD-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Non-Insulated Conductors (AREA)
Abstract
The invention discloses polyester based on 4,4' -biphenyldicarboxylic acid and application of the polyester to preparation of a nano-silver conductive film. The method comprises the following steps: 4,4' -biphenyl dicarboxylic acid and 3-piperidyl-1, 2-propylene glycol or 2,2- (1, 2-piperidyl) diethylene glycol and menthanediol or 2-ethyl-2-propyl-1, 3-propane diol are used as raw materials, a series of novel polyesters are synthesized through catalytic melt esterification and catalytic melt polycondensation, a film-forming agent, a surfactant and the like are added into a nano silver dispersion liquid to prepare the nano silver wire conductive ink, and the nano silver wire conductive ink is coated on the prepared polyester by utilizing a Meyer rod coating method to prepare the nano silver wire transparent conductive film. The prepared transparent conductive film has the characteristics of bending resistance, high photon transmittance, high conductivity and the like.
Description
Technical Field
The invention relates to a preparation method of a polyester based on 4,4' -biphenyl dicarboxylic acid and a transparent conductive thin polyester film, belonging to the field of polymer composite materials. In particular to a high molecular weight polyester which takes 4,4 '-biphenyl dicarboxylic acid and two alcohols as raw materials and is prepared by catalyzing melt polycondensation reaction based on 4,4' -biphenyl dicarboxylic acid as a monomer; the polyester prepared by the invention is prepared into a film by a blown film method or a cast film method, nano silver paste is prepared by adding a film-forming agent, a surfactant and the like into nano silver dispersion liquid, the nano silver paste is coated on the prepared polyester by a Meyer rod coating method, and nano silver coating liquid is coated on the polyester film to prepare the nano silver wire transparent conductive film.
Background
Research and development capabilities of enterprises related to Chinese communication equipment and electronic equipment are continuously improved, research and development of key technologies are emphasized by enterprises in the flexible display industry chain, and application of flexible display screens is realized by some mobile phone manufacturers in China. The disadvantages of the conventional ITO (indium tin oxide) transparent conductive material are gradually shown: bending resistance, failure to produce a bent screen, poor ITO conductivity and the like. ITO has become unable to meet people's demand, so the development of Flexible Transparent Conductive Film (FTCF) has gained more and more attention. The nano silver wire is a one-dimensional nano material with good light transmission, conductivity and stability [1] 。[1]Murali Shanthi, Xu Teng, Marshall Bennett D, et al. Lyotropic liquid crystalline self-assembly in dispersions of silver nanowires and nanoparticles.[J]. Langmuir, 2010, 26(13):11176-83.
Moreover, the FTCF prepared by taking the nano silver wire as the conductive material has the advantages of lower square resistance, better bending property, higher light transmittance, simple process, easily obtained raw materials and the like [2] . Therefore, the nano silver wire can be used as an ideal alternative material for preparing FTCF.
[2]Hyejin Jang et al. Ultra-mechanically stable and transparent conductive electrodes using transferred grid of Ag nanowires on flexible substrate[J]. Current Applied Physics, 2016, 16(1) : 24-30.
However, the use of nano silver wires for the preparation of transparent conductive films still has many problems, such as: the mechanical properties (including tensile strength, tensile modulus, bending strength, bending modulus and impact strength) of the currently adopted polyester film material are not good enough, so that the adhesion of the silver nanowire is poor, and the conductive path of the silver nanowire is unstable, so that the conductive stability of the whole FTCF is poor; because the selection of the preparation process of the nano silver wire is not suitable, the particle size of the nano silver wire prepared by the prior art is larger than 15 nanometers, the photon transmittance is generally lower than 95 percent after the nano silver wire is compounded on a polymer film material, and when the silver wire with the particle size of 15 nanometers or more prepared by the prior art is attached to a common polymer film material, the square resistance is generally more than 50 omega/sq, therefore, the existing polymer film material compounded by the nano silver still has the defects of large square resistance, low photon transmittance and high haze, and in addition, the problems of poor uniformity of the square resistance of the film and the like are urgently solved.
Disclosure of Invention
In view of the above problems in the prior art, the main object of the present invention is to provide a preparation and application of polyester based on 4,4' -biphenyldicarboxylic acid, specifically: 4,4' -biphenyl dicarboxylic acid and dihydric alcohol are used as raw materials, and a high molecular weight polyester is prepared through two-step reactions of catalytic melt esterification and catalytic melt polycondensation. Compared with the polyester reported in the existing literature, the polyester with high molecular weight has the advantages of high melting point, good thermal stability, high transparency, good light transmittance, good tensile property and film forming property, can be used as a base material of a transparent conductive polyester film material, can be further processed with a nano silver wire coating liquid to prepare a nano silver composite transparent conductive film, can be used as a preparation material of a capacitive touch screen or a touch screen, an intelligent dimming film component and a film component of an intelligent video display screen, and has wide application prospect.
The invention adopts the following technical scheme:
the invention better realizes the technical scheme of the invention, and discloses preparation and application of polyester based on 4,4' -biphenyldicarboxylic acid, which is characterized in that the structure is shown as formula I and formula II:
formula I
Formula II
Wherein: a, c is 100 to 190, b, d is 120 to 230;
the method for preparing the high molecular polyester based on 4,4' -biphenyldicarboxylic acid according to claim 1, comprising the steps of:
1) And (3) synthesis of a polyester crude product: 4,4 '-biphenyldicarboxylic acid is taken as an acid source, 3-piperidyl-1, 2-propanediol or 2,2' - (1, 2-piperidyl-diyl) diethanol is taken as an alcohol source of a first glycol, and menthanediol or 2-ethyl-2-propyl-1, 3-propanediol is taken as an alcohol source of a second glycol respectively; mixing the acid source, the alcohol source of the first glycol and the alcohol source of the second glycol as reaction raw materials according to a certain substance quantity ratio, adding a catalyst, introducing nitrogen for protection, opening a stirring device, and carrying out catalytic melt esterification reaction for 3 to 5 hours under the conditions of normal pressure and 150 to 180 ℃ to obtain an intermediate product; then continuously reacting for 3 to 4h under the conditions of 10 to 20kPa absolute pressure and 190 to 210 ℃ to obtain a series of crude polyester products;
2) And (3) purifying a crude polyester product: adding chloroform into the crude polyester product, dissolving for 2-5 h and filtering; and (3) dropwise adding the clear liquid into enough low-carbon alcohol, precipitating, centrifuging, filtering, washing the obtained solid with ethanol, and filtering again to obtain a solid, and drying the solid in vacuum at 70 to 90 ℃ for 3 to 5 hours to obtain the target polyester P.
Further preferably, the production of biomass polyester based on 4,4' -biphenyldicarboxylic acid according to claim 2, characterized in that: in the step 1), the ratio of the amounts of 4,4' -biphenyldicarboxylic acid to the substances of 3-piperidyl-1, 2-propanediol or 2,2- (1, 2-piperidinediyl) diethylene glycol and menthanediol or 2-ethyl-2-propyl-1, 3-propanediol is: 2.0: (2.0 to 3.0): (2.1 to 3.1).
Further preferably, the preparation of a high molecular weight polyester based on 4,4' -biphenyldicarboxylic acid according to claim 2, characterized in that: the catalyst of claim 1, wherein the catalyst is one of hydroxyethyl iso-bromobutyrate, di (triethanolamine) diisopropyl titanate, n-butyl titanate and isopropyl titanate; the dosage of the catalyst is 0.1-0.5% of the total weight of the reactants.
Further preferably, the production of a high molecular weight polyester based on 4,4' -biphenyldicarboxylic acid according to claim 2, wherein: in the step 2), the lower alcohol is one of methanol, isopropanol, isobutanol and n-butanol.
A preparation method of a transparent conductive thin polyester film based on 4,4' -biphenyl dicarboxylic acid is characterized in that:
1) Preparing a polyester film with the thickness of 10 to 15 mu m by using the polyester prepared in the claim 2 as a raw material through a blown film method or a cast film method;
2) Preparing a nano silver wire: adding 2 parts by mass of PVP and 1 part by mass of AgNO with the concentration of 0.1mol/L 3 Adding the solution, 1 part by mass of trimethylolethane and 10 parts by mass of isopropanol into a reaction vessel, stirring and reacting for 20min under the heating condition of 130-160 ℃, adding 1 part by mass of silver seed crystal into the mixed solution while stirring, and stirring for 160min at constant temperature of 130-160 ℃ to obtain nano silverNaturally cooling the line stock solution, adding 1, 4-dioxane with the same volume to settle the product, and then performing centrifugal settling, filtering and drying to obtain a nano silver line with the length of 15 to 30 mu m and the diameter of 10 to 15nm;
3) Adding 1 part by mass of the nano silver wire, 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoyl monoethanolamide sulfosuccinate monoester into a proper amount of methyl isopropyl ether, stirring for 15min to prepare a nano silver paste coating liquid with the silver concentration of 1% -6%, uniformly coating the coating liquid on a polyester film with the thickness of 10 to 15 mu m by a coating method, and finally drying by a vacuum dust-free oven at 70-80 ℃ to obtain the nano silver wire conductive polyester film material.
Advantageous effects
1. The synthesized 4,4' -biphenyl diformic acid based polyester has outstanding mechanical property and thermal property. By introducing the biphenyldicarboxylic acid with the aromatic ring structure and the fatty alcohol with the ring structure, the mechanical properties such as tensile strength, tensile modulus, impact strength and the like are greatly improved, and the service performance and film-forming performance of the polyester are greatly improved.
2. The square resistance of the nano-silver transparent conductive film prepared by the invention is 30-50 (omega/sq), and the photon light transmittance exceeds 95%, so that the nano-silver transparent conductive film with high conductivity and high transparency is obtained, and can be used as a preparation material of a capacitive touch screen or a touch screen, an intelligent dimming film component and a film component of an intelligent video display screen. The nano-silver compounded polyester film with high conductivity and high transparency is simple to operate, and the comprehensive performance can meet the requirements of curved screens and foldable screens in the existing display field.
Detailed Description
The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples. The raw materials in the invention are all conventional and commercially available.
To determine the structure, molecular weight and thermal properties of the polyesters prepared in this example, the polyesters P1 to P8 prepared in examples 1 to 8 were characterized and tested using a Bruker Avance DMX600 model nuclear magnetic resonance spectrometer from Bruker Spectroscopy, inc. of Germany, a Fourier transform infrared spectrometer from VERTEX70 model from Bruker Spectroscopy, inc. of Germany, a Waters-Breeze gel chromatograph from Waters, inc. of America, and a Netzsch STA 449F 3 Jupite thermogravimetric analyzer from Nay, inc. of Germany.
Transparency test of polyester film in examples: the light transmittance of the polyester film was measured by cutting the polyester film into a sample of 50 mm. Times.50 mm, using a haze meter (WGW, shanghai precision scientific instruments Co., ltd.) in accordance with GB/T2410-1980.
Mechanical testing in the examples: the tensile property test is carried out according to GB/T1040.2-2006 standard; the bending performance is implemented according to the GB/T9341-2008 standard; impact performance is performed according to GB/T1843-2008 standard; the results were averaged over 5 test specimens each.
The preparation method of the nano silver wire comprises the following steps: adding 2 parts by mass of PVP and 1 part by mass of AgNO with the concentration of 0.1mol/L 3 Putting the solution, 1 part by mass of trimethylolethane and 2 parts by mass of deionized water in a reaction container, stirring and reacting for 20min under the heating condition of 160 ℃, adding 1 part by mass of silver seed crystal into the mixed solution while stirring, magnetically stirring at the constant temperature of 130 ℃ for 160min to obtain a nano silver wire stock solution, naturally cooling, adding 1, 4-dioxane with the same volume to settle a product, and performing centrifugal sedimentation, filtration and drying to obtain a nano silver wire with the length of 15 to 30 mu m and the diameter of 10 to 15nm.
Yield =100% x actual amount of target product/theoretical amount of target product produced.
Example 1:
to a dry single-neck flask (50 mL) were added 1.2765g (5.26 mmol) of 4,4' -biphenyldicarboxylic acid, 0.8374g (5.25 mmol) of 3-piperidinyl-1, 2-propanediol, 0.9204g (5.34 mmol) of menthanediol, and 0.0039g (0.018 mmol) of hydroxyethyl isobromobutyrate in that order, and the reaction mixture was reacted at 155 ℃ for 5.0h under nitrogen protection to give the esterified product. And (3) continuously heating the esterification product to 195 ℃, controlling the absolute pressure to be 15kPa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of methanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after filtering again at 70 ℃ for 4 hours in vacuum to obtain the polyester P1, wherein the yield is 91.3%, and the Mw is 62400g/mol.
Carrying out further processing: the polyester P1 prepared by the method of the embodiment 1 is subjected to banburying at 160 ℃, and after the banburying is finished, the polyester film material with the film thickness of 12 mu m is prepared through extrusion blow molding. Taking 1 part by mass of a nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoanut monoethanolamide sulfosuccinate, finally adding a methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 3%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. 4mL of nano silver paste coating liquid is uniformly dripped on a polyester substrate along a Meyer bar, then coating is carried out, the coating speed is 5mm/s, and finally after drying by a vacuum dust-free oven at 80 ℃, the nano silver transparent conductive film material F1 with the photon light transmittance of 96.2% can be obtained and can be used for flexible curved surface display screens.
Example 2:
to a dry, single-neck flask (50 mL) were added 1.2815g (5.3 mmol) of 4,4 '-biphenyldicarboxylic acid, 0.9886g (5.04 mmol) of 2,2' - (1, 2-piperidinediyl) diethanol, 0.7515g (5.6 mmol) of 2-ethyl-2-propyl-1, 3-propanediol, and 0.0035g (0.016 mmol) of hydroxyethyl isobromobutyrate in the order named, and the reaction mixture was reacted at 155 ℃ for 4h under nitrogen protection to give the esterified product. And (3) continuously heating the esterification product to 200 ℃, controlling the absolute pressure to be 12kPa, and reacting for 3.5h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of methanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after secondary filtration at 75 ℃ for 3.5 hours in vacuum to obtain the polyester P2, wherein the yield is 91.23%, and the Mw is 62500 g/mol.
Carrying out further processing: the polyester P2 prepared by the method in the embodiment 2 is subjected to internal mixing at 160 ℃, and after the internal mixing is completed, the polyester film material with the film thickness of 17 mu m is prepared through extrusion blow molding. Taking 1 part by mass of a nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoanut monoethanolamide sulfosuccinate, finally adding a methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 5%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. 4mL of nano silver paste coating liquid is uniformly dripped on a polyester substrate along a Meyer bar, then coating is carried out, the coating speed is 5mm/s, and finally after drying by a vacuum dust-free oven at 80 ℃, a nano silver transparent conductive film material F2 with the photon light transmittance of 97.1% can be obtained and can be used for flexible curved surface display screens.
Example 3:
to a dry, single-neck flask (50 mL) were added 1.453g (6.0 mmol) of 4,4' -biphenyldicarboxylic acid, 0.9713g (6.1 mmol) of 3-piperidinyl-1, 2-propanediol, 1.085g (6.3 mmol) of menthanediol, and 0.0036g (0.008 mmol) of di (triethanolamine) diisopropyl titanate in that order, and the reaction mixture was reacted for 3.5h under nitrogen at 160 ℃ to give the esterified product. And (3) continuously heating the esterification product to 195 ℃, controlling the absolute pressure to be 15kPa, and reacting for 3.5h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of isopropanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after secondary filtration at 85 ℃ for 3.5 hours in vacuum to obtain the polyester P3, wherein the yield is 89.76%, and the Mw is 65400g/mol.
Carrying out further processing: the polyester P3 prepared by the method in the embodiment 3 is subjected to internal mixing at 160 ℃, and after the internal mixing is completed, the polyester film material with the film thickness of 12 mu m is prepared by a casting film method. Taking 1 part by mass of a nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoanut monoethanolamide sulfosuccinate, finally adding a methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 6%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. Uniformly dripping 4mL of nano silver paste coating liquid on a polyester substrate along a Meyer bar, then coating at the coating speed of 5mm/s, and finally drying by a vacuum dust-free oven at 70 ℃ to obtain the nano silver transparent conductive film material F3 with the photon light transmittance of more than 96.4%, wherein the nano silver transparent conductive film material F3 can be used for flexible curved surface display screens.
Example 4:
to a dry, single-neck flask (50 mL) were added 1.396g (5.7 mmol) of 4,4 '-biphenyldicarboxylic acid, 1.136g (5.8 mmol) of 2,2' - (1, 2-piperidinediyl) diethanol, 0.763g (5.7 mmol) of 2-ethyl-2-propyl-1, 3-propanediol, and 0.0033g (0.007 mmol) of diisopropyl di (triethanolamine) titanate, in that order, and the reaction mixture was reacted for 3.5h at 165 ℃ under nitrogen protection to give the esterified product. And continuously heating the esterification product to 200 ℃, controlling the absolute pressure to be 10-20kPa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of isopropanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after secondary filtration in vacuum at 85 ℃ for 3.5 hours to obtain the polyester P4, wherein the yield is 91.27%, and the Mw is 64300g/mol.
Carrying out further processing: the polyester P4 prepared by the method in this embodiment 4 is subjected to internal mixing at 160 ℃, and after the internal mixing is completed, the polyester film material with a film thickness of 12 μm is prepared by a cast film method. Taking 1 part by mass of a nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoanut monoethanolamide sulfosuccinate, finally adding a methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 6%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. And uniformly dripping 4mL of nano silver paste coating liquid on a polyester substrate along a Meyer bar, then coating at the coating speed of 5mm/s, and finally drying by using a vacuum dust-free oven at 70 ℃ to obtain the nano silver transparent conductive film material F4 with the photon light transmittance of 95.2%, wherein the nano silver transparent conductive film material F4 can be used for flexible curved surface display screens.
Example 5:
to a dry, single-neck flask (50 mL) were added 1.447g (6.1 mmol) of 4,4' -biphenyldicarboxylic acid, 0.831g (6.2 mmol) of 3-piperidinyl-1, 2-propanediol, 1.102g (6.4 mmol) of menthanediol and 0.0035g (0.01 mmol) of n-butyl titanate in that order, and the reaction mixture was reacted at 165 ℃ for 4.5h under nitrogen protection to give the esterified product. And continuously heating the esterification product to 195 ℃, controlling the absolute pressure to be 10-20kPa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of isobutanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after secondary filtration at 80 ℃ in vacuum for 4.0 hours to obtain the sulfur-containing copolyester P5, wherein the yield is 90.34%, and the Mw is 78600 g/mol.
Carrying out further processing: the polyester P5 prepared by the method of the embodiment 5 is subjected to banburying at 160 ℃, and after the banburying is finished, the polyester film material with the film thickness of 16 mu m is prepared through extrusion blow molding. Taking 1 part by mass of a nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoanut monoethanolamide sulfosuccinate, finally adding a methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 5%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. 4mL of nano silver paste coating liquid is uniformly dripped on a polyester substrate along a Meyer bar, then coating is carried out, the coating speed is 5mm/s, and finally, after the nano silver paste coating liquid is dried by a vacuum dust-free oven at 75 ℃, the nano silver transparent conductive film material F5 with the photon light transmittance of 96.5% can be obtained and can be used for flexible curved surface display screens.
Example 6:
to a dry, single-neck flask (50 mL) were added 1.453g (6.0 mmol) of 4,4 '-biphenyldicarboxylic acid, 1.234g (6.3 mmol) of 2,2' - (1, 2-piperidinediyl) diethanol, 0.818g (6.1 mmol) of 2-ethyl-2-propyl-1, 3-propanediol, and 0.0030g (0.01 mmol) of n-butyl titanate in that order, and the reaction mixture was reacted at 155 ℃ for 4.0h under nitrogen protection to give the esterified product. And continuously heating the esterification product to 200 ℃, controlling the absolute pressure to be 10-20kPa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of isobutanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after secondary filtration at 80 ℃ for 4.5 hours in vacuum to obtain the sulfur-containing copolyester P6, wherein the yield is 91.06 percent, and the Mw is 66500g/mol.
Carrying out further processing: the polyester P6 prepared by the method of the embodiment 6 was subjected to internal mixing at 160 ℃, and after the internal mixing was completed, a polyester film material with a film thickness of 14 μm was prepared by extrusion blow molding. Taking 1 part by mass of a nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoanut monoethanolamide sulfosuccinate, finally adding a methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 6%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. 4mL of nano silver paste coating liquid is uniformly dripped on a polyester substrate along a Meyer bar, then coating is carried out, the coating speed is 5mm/s, and finally, after the nano silver paste coating liquid is dried by a vacuum dust-free oven at 75 ℃, the nano silver transparent conductive film material F6 with the photon light transmittance of 98.1% can be obtained and can be used for flexible curved surface display screens.
Example 7:
to a dry, single-neck flask (50 mL) were added 1.429g (5.9 mmol) of 4,4' -biphenyldicarboxylic acid, 0.808g (6.2 mmol) of 3-piperidinyl-1, 2-propanediol, 1.083g (6.3 mmol) of menthanediol, and 0.0033g (0.01 mmol) of isopropyl titanate in that order, and the reaction mixture was reacted at 160 ℃ for 3.5h under nitrogen protection to give the esterified product. And continuously heating the esterification product to 195 ℃, controlling the absolute pressure to be 10-20kPa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of n-butanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after secondary filtration at 85 ℃ for 3.5 hours in vacuum to obtain the polyester P7, wherein the yield is 91.38%, and the Mw is 62600 g/mol.
Carrying out further processing: the polyester P7 prepared by the method of the embodiment 7 is subjected to internal mixing at the temperature of 160 ℃, and after the internal mixing is completed, a polyester film material with the film thickness of 13 mu m is prepared by a cast film method. Taking 1 part by mass of nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoyl monoethanolamide sulfosuccinate, finally adding methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 6%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. 4mL of nano silver paste coating liquid is uniformly dripped on a polyester substrate along a Meyer bar, then coating is carried out, the coating speed is 5mm/s, and finally after drying by a vacuum dust-free oven at 80 ℃, a nano silver transparent conductive film material F7 with photon light transmittance of more than 96.9% can be obtained and can be used for flexible curved surface display screens.
Example 8:
to a dry, single-neck flask (50 mL) were added 1.456g (6.0 mmol) of 4,4 '-biphenyldicarboxylic acid, 1.215g (6.2 mmol) of 2,2' - (1, 2-piperidinediyl) diethanol, 0.845g (6.3 mmol) of 2-ethyl-2-propyl-1, 3-propanediol, and 0.0030g (0.35 mmol) of isopropyl titanate in that order, and the reaction mixture was reacted at 165 ℃ for 4h under nitrogen protection to give the esterified product. And continuously heating the esterification product to 200 ℃, controlling the absolute pressure to be 10-20kPa, and reacting for 3.0h to obtain a crude product of the polycondensation product. Dissolving the crude product of the polycondensation product by using sufficient chloroform, taking clear liquid, adding the clear liquid into a certain amount of n-butanol, precipitating, centrifuging and filtering to obtain white solid, washing the obtained solid by using ethanol, and drying the solid after secondary filtration at 85 ℃ for 3.5 hours in vacuum to obtain the polyester P8, wherein the yield is 91.46%, and the Mw is 68900 g/mol.
Carrying out further processing: the polyester P8 prepared by the method of this embodiment 8 is subjected to internal mixing at 160 ℃, and after the internal mixing is completed, the polyester film material with a film thickness of 16 μm is prepared by a cast film method. Taking 1 part by mass of a nano silver wire, adding 2 parts by mass of hydroxypropyl methyl cellulose and 2 parts by mass of disodium cocoanut monoethanolamide sulfosuccinate, finally adding a methyl isopropyl ether solvent, stirring for 15min to obtain a nano silver paste coating liquid with the silver content of 6%, selecting 30cm x 40cm transparent polyester of the embodiment as a substrate, ultrasonically cleaning for 15min by using deionized water, and drying. 4mL of nano silver paste coating liquid is uniformly dripped on a polyester substrate along a Meyer bar, then coating is carried out, the coating speed is 5mm/s, and finally after drying by a vacuum dust-free oven at 80 ℃, a nano silver transparent conductive film material F8 with photon light transmittance of more than 97.1% can be obtained and can be used for flexible curved surface display screens.
The comparison of various mechanical properties of the polyester sample and the comparison of optical and electrical properties of the transparent conductive film sample in the examples are shown in the following two tables:
TABLE 1 comparison of the mechanical Properties of the polyester samples in the examples with those of polyethylene isophthalate PET
| Sample (I) | Tensile strength/MPa | Elongation at break/% | Flexural Strength/MPa | Impact Strength/(kJ. M) -2 ) |
| P1 | 3423 | 356.4 | 60.3 | 25.9 |
| P2 | 3394 | 357.8 | 59.1 | 26.1 |
| P3 | 3386 | 345.1 | 56.2 | 25.7 |
| P4 | 3421 | 342.6 | 58.6 | 25.4 |
| P5 | 3406 | 352.3 | 57.9 | 24.1 |
| P6 | 3386 | 351.6 | 56.8 | 25.2 |
| P7 | 3376 | 348.2 | 57.4 | 23.9 |
| P8 | 3478 | 343.1 | 58.1 | 24.6 |
| PET [3] | 1115 | 291.1 | 21.7 | 9.8 |
[3] Synthesis and characterization of polyethylene glycol random copolyester of polyisophthaloyl benzene dicarboxylic acid-2, 5-furandicarboxylic acid [ J ] polymer science, 2013, 46 (8): 1092-1098.
Table 2 optical properties and electrical properties of transparent conductive polyester films processed from the polyesters P1 to P8 synthesized in the examples
| Sample numbering | F1 | F2 | F3 | F4 | F5 | F6 | F7 | F8 | Reference to the literature |
| Square resistance/omega sq -1 | 32 | 44 | 38 | 33 | 37 | 67 | 42 | 51 | 132 [4] |
| Transmittance/% | 96.2% | 97.1% | 96.4% | 95.2% | 96.5% | 98.1% | 96.9% | 97.1% | 79% [5] |
[4] Qianbaizhu, zhanghua, wangwang, etc. controllable preparation and optical and electric properties of flexible transparent conductive film of silver nanowire [ J ] functional material, 2017,48 (2): 2107-2111,2116. DOI:10.3969/j.issn.1001-9731.2017.02.019
[5] The preparation method comprises the steps of preparing AZO (ZnO: al) transparent conductive film [ J ] by PECVD, wherein the AZO transparent conductive film is prepared by the weight of Chenmega, liuming Hai, liuyuping, and the like, the physical science and science report 2009,58 (6): 4260-4266, and the DOI:10.3321/j.issn:1000-3290.2009.06.102.
As can be seen from the comparison of the data in Table 1, the tensile strength of the ethylene isophthalate PET is 1115MPa, and the tensile strength of the polyesters P1-P8 synthesized by using 4,4' -biphenyldicarboxylic acid and dihydric alcohol as raw materials is 2000-2872 MPa higher than that of the ethylene isophthalate PET; the elongation at break of the ethylene isophthalate PET is 291.1 percent, and the elongation at break of the polyesters P1-P8 synthesized by using 4,4' -biphenyldicarboxylic acid and dihydric alcohol as raw materials is 19.4-107.5 percent higher than that of the ethylene isophthalate PET; the bending strength of the ethylene isophthalate PET is 21.7 Mpa, and the bending strength of polyesters P1-P8 synthesized by using 4,4' -biphenyldicarboxylic acid and dihydric alcohol as raw materials is 29.5-46.4 Mpa higher than that of the ethylene isophthalate PET; the impact strength of the ethylene isophthalate PET is 9.8Mpa, and the impact strength of polyesters P1-P8 synthesized by using 4,4' -biphenyldicarboxylic acid and dihydric alcohol as raw materials is 14.3-19.6 MPa higher than that of the ethylene isophthalate PEO. As can be seen from the comparison of the data in Table 2, the sheet resistance of the nano silver wire transparent conductive film prepared by the invention is lower than that of the transparent conductive film in the reference, and is 65-100 omega.sq -1 (ii) a The light transmittance of the nano silver wire transparent conductive film prepared by the invention is up to 98.The light transmittance of the transparent conductive film is 16.2% -19.1% higher than that of the transparent conductive film in the reference document by 1%.
From the above data, it can be seen that: the invention takes 4,4' -biphenyldicarboxylic acid and 3-piperidyl-1, 2-propylene glycol or 2,2- (1, 2-piperidyl-diyl) diethylene glycol and menthanediol or 2-ethyl-2-propyl-1, 3-propane diol as raw materials, and synthesizes series of polyester, compared with the existing PET, the molecular weight, thermal property, mechanical property and the like of the polyester are obviously improved by catalyzing melt esterification and catalyzing melt polycondensation, the mechanical properties (including tensile strength, tensile modulus, bending strength, bending modulus and impact strength) of the polyester are greatly improved, the thermal property of the polyester is improved, for example, the melting point is far higher than that of commercial polyester PET, and the thermal decomposition temperature is also greatly improved. The surface of the nano silver wire film prepared by the invention has less nano silver particles, the distribution of the nano silver wires is more uniform, the square resistance is smaller, and the transmittance is higher.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. A polyester based on 4,4' -biphenyl dicarboxylic acid is characterized in that the structure is shown as formula I and formula II:
formula I
Formula II
Wherein: a, c is 100 to 190, b, d is 120 to 230.
2. Preparation of a polyester based on 4,4' -biphenyldicarboxylic acid, comprising the following steps:
1) And (3) synthesis of a crude polyester: 4,4 '-biphenyldicarboxylic acid is taken as an acid source, 3-piperidyl-1, 2-propanediol or 2,2' - (1, 2-piperidyl-diyl) diethanol is taken as an alcohol source of a first glycol, and menthanediol or 2-ethyl-2-propyl-1, 3-propanediol is taken as an alcohol source of a second glycol respectively; mixing the acid source, the alcohol source of the first glycol and the alcohol source of the second glycol as reaction raw materials according to a certain substance quantity ratio, adding a catalyst, introducing nitrogen for protection, opening a stirring device, and carrying out catalytic melt esterification reaction for 3 to 5 hours under the conditions of normal pressure and 150 to 180 ℃ to obtain an intermediate product for synthesizing polyester; then, continuously reacting for 3 to 4 hours under the conditions of high vacuum with the absolute pressure of 10 to 20kPa and the temperature of 190 to 210 ℃ to obtain a crude polyester product;
2) Purification of the crude polyester: adding chloroform into the polyester crude product, dissolving for 2-5 h and filtering; and (3) dropwise adding the clear liquid into enough low-carbon alcohol, precipitating, centrifuging, filtering, washing the obtained solid with ethanol, and filtering again to obtain a solid, and drying the solid in vacuum at 70 to 90 ℃ for 3 to 5 hours to obtain the target polyester P.
3. The preparation of a4, 4' -biphenyldicarboxylic acid based polyester according to claim 2, wherein: in the step 1), the ratio of the amounts of 4,4 '-biphenyldicarboxylic acid and 3-piperidyl-1, 2-propanediol or 2,2' - (1, 2-piperidinediyl) diethylene glycol and menthanediol or 2-ethyl-2-propyl-1, 3-propanediol is: 2.0: (2.0 to 2.4): (2.2 to 2.6).
4. The preparation of a4, 4' -biphenyldicarboxylic acid based polyester according to claim 2, wherein: the catalyst of claim 2 is one of hydroxyethyl iso-bromobutyrate, di (triethanolamine) diisopropyl titanate, n-butyl titanate, isopropyl titanate; the dosage of the catalyst is 0.1-0.5% of the total weight of the reactants.
5. The preparation of a4, 4' -biphenyldicarboxylic acid based polyester according to claim 2, wherein: in the step 2), the lower alcohol is one of methanol, isopropanol, isobutanol and n-butanol.
6. A transparent conductive polyester film based on 4,4' -biphenyldicarboxylic acid, which is characterized in that:
1) Preparing a polyester film with the thickness of 10 to 15 mu m by using the polyester prepared in the claim 2 as a raw material through a blown film method or a cast film method;
2) Preparing a nano silver wire: adding 2 parts by mass of PVP and 1 part by mass of AgNO with the concentration of 0.1mol/L 3 Putting the solution, 1 part by mass of trimethylolethane and 10 parts by mass of isopropanol in a reaction vessel, stirring and reacting for 20min under the heating condition of 130-160 ℃, adding 1 part by mass of silver seed crystal into the mixed solution while stirring, stirring for 160min at the constant temperature of 130-160 ℃ to obtain a nano silver wire stock solution, naturally cooling, adding 1, 4-dioxane with the same volume to precipitate a product, centrifuging and precipitating, filtering, and drying to obtain a nano silver wire with the length of 15-30 mu m and the diameter of 10-15nm;
3) Adding 1 part by mass of the nano silver wire, 2 parts by mass of hydroxypropyl methylcellulose and 2 parts by mass of disodium cocomonoethanolamide sulfosuccinate in a proper amount of methyl isopropyl ether, stirring for 15min to obtain a nano silver paste coating liquid with the silver concentration of 1% -6%, uniformly coating the coating liquid on a polyester film with the thickness of 10-15 mu m by a coating method, and finally drying by a vacuum dust-free oven at 70-80 ℃ to obtain the nano silver wire conductive polyester film material.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037424A (en) * | 1996-12-28 | 2000-03-14 | Eastman Chemical Company | Clear blends of polycarbonates and polyesters |
| CN102285184A (en) * | 2011-04-25 | 2011-12-21 | 富维薄膜（山东）有限公司 | Low-temperature high-shrinkage polyester film used for bottle labels and preparation method thereof |
| JP2012012507A (en) * | 2010-07-01 | 2012-01-19 | Japan Carlit Co Ltd:The | Conductive polymer microparticle, conductive polymer microparticle dispersion and production method thereof |
| CN103903817A (en) * | 2014-03-18 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Preparing method and application of transparent conducting thin film |
| CN105209942A (en) * | 2013-05-15 | 2015-12-30 | 柯尼卡美能达株式会社 | Phase difference film, polarization plate, and liquid crystal display device |
| CN107189043A (en) * | 2017-05-22 | 2017-09-22 | 浙江大学 | Weak crystalline polyester of HMW and its preparation method and application |
| CN107359014A (en) * | 2016-05-09 | 2017-11-17 | 深圳前海皓隆科技有限公司 | Transparent conductive film and preparation method thereof |
| CN110791136A (en) * | 2019-09-25 | 2020-02-14 | 深圳市华科创智技术有限公司 | Silver nanowire coating solution and transparent conductive film |
| CN112142962A (en) * | 2019-06-26 | 2020-12-29 | 武汉科技大学 | Preparation method and application of high molecular weight transparent polyester |
| CN112566980A (en) * | 2019-07-26 | 2021-03-26 | 擎天材料科技有限公司 | Polyester resin, preparation method thereof, coating and workpiece |
-
2021
- 2021-07-29 CN CN202110865164.0A patent/CN115677994A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037424A (en) * | 1996-12-28 | 2000-03-14 | Eastman Chemical Company | Clear blends of polycarbonates and polyesters |
| JP2012012507A (en) * | 2010-07-01 | 2012-01-19 | Japan Carlit Co Ltd:The | Conductive polymer microparticle, conductive polymer microparticle dispersion and production method thereof |
| CN102285184A (en) * | 2011-04-25 | 2011-12-21 | 富维薄膜（山东）有限公司 | Low-temperature high-shrinkage polyester film used for bottle labels and preparation method thereof |
| CN105209942A (en) * | 2013-05-15 | 2015-12-30 | 柯尼卡美能达株式会社 | Phase difference film, polarization plate, and liquid crystal display device |
| CN103903817A (en) * | 2014-03-18 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Preparing method and application of transparent conducting thin film |
| CN107359014A (en) * | 2016-05-09 | 2017-11-17 | 深圳前海皓隆科技有限公司 | Transparent conductive film and preparation method thereof |
| CN107189043A (en) * | 2017-05-22 | 2017-09-22 | 浙江大学 | Weak crystalline polyester of HMW and its preparation method and application |
| CN112142962A (en) * | 2019-06-26 | 2020-12-29 | 武汉科技大学 | Preparation method and application of high molecular weight transparent polyester |
| CN112566980A (en) * | 2019-07-26 | 2021-03-26 | 擎天材料科技有限公司 | Polyester resin, preparation method thereof, coating and workpiece |
| CN110791136A (en) * | 2019-09-25 | 2020-02-14 | 深圳市华科创智技术有限公司 | Silver nanowire coating solution and transparent conductive film |
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