CN104497290A - Optical fluorine-containing copolyester, optical film and production method thereof - Google Patents
Optical fluorine-containing copolyester, optical film and production method thereof Download PDFInfo
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Abstract
The invention discloses optical fluorine-containing copolyester, an optical film and a production method thereof. According to the invention, diacid, dihydric alcohol and bisphenol AF with certain proportion are used as monomer to prepare the optical fluorine-containing copolyester, then the optical fluorine-containing copolyester is prepared to the copolyester film through bidirectional stretching, the film has good optical performance, excellent heat-resistance and aging-resistance performance, high tensile strength, and excellent size; and can be widely used for fields of optical film and photovoltaic backboard.
Description
Technical field
The present invention relates to polyester synthesis field, particularly relate to the fluorine-containing copolyesters of a kind of optics, optical thin film and manufacture method thereof.
Background technology
The polyethylene terephthalate (PET) synthesized for polymerization single polymerization monomer with terephthalic acid, ethylene glycol is the synthesizing polyester material that consumption is maximum in the world at present, and PET film is widely used in the fields such as food product pack, finishing material, label, liquid-crystal display.By poly-(terephthalic acid-m-phthalic acid-ethylene glycol) ester introducing the manufacture of three components m-phthalic acid, there is good crystal property, be used in the fields such as blown polyester bottle in a large number.But the ester group in PET macromolecular structure makes it have certain wetting ability, be restricted in its application of the hydrophobic occasion of needs.And due to the impact of PET its own molecular structure, its water vapor barrier property is not ideal enough, cannot be competent at the Application Areas that needs strictly block water, and thermotolerance, scale resistance and optical property etc. also need further raising.
Polyethylene glycol 2，6-naphthalene dicarboxylate (PEN) is by monomer NDA (2,6-NDA) or NDA dimethyl ester (2,6-NDC) and ethylene glycol (EG), through esterification or transesterify aftercondensated.From molecular structure, the difference of PEN and polyethylene terephthalate (PET) is only polyester molecule main chain instead of phenyl ring by the naphthalene nucleus that rigidity is larger, its performance, between PET and polyimide PI, has good barrier properties for gases, thermotolerance and anti-ultraviolet property.But NDA is expensive, the application of PEN is restricted, people urgently find one can keep PEN premium properties, the copolyesters combination that can reduce costs again.
Fluorine element is the maximum element of occurring in nature electronegativity, on fluorine atom, electric charge is more concentrated, C-F bond energy is than the high 72KJ/mol of c h bond energy, therefore fluorine atom has very strong shielding effect to C-C key, fluoropolymer is made to have excellent erosion resistance, weathering resistance and ageing resistance, again because fluorine atom polarizability is low, so the dissipation factor of fluorocarbon and specific inductivity are all less, fluoropolymer is made to have excellent insulativity, unreactiveness and high-temperature stability.Because general polymer is more containing C-H, C-O, N-H key, violent light loss can be caused near interval 1.33 μm and 1.55 μm of light signal communication.Use F atom replacement H atom can reduce by the optical loss of more than 5 times.
Bisphenol AF is mainly used as vulcanizable fluororubber promotor, and little with the viton set resistant of FF34 sulfuration, tensile strength is high; Also can be used as medicine intermediate.But the impurity contained in commercially available bisphenol AF is difficult to purify, and can have a strong impact on the result of use of bisphenol AF in optical articles.Therefore need to carry out purification processes before use.Common method of purification has recrystallization, charcoal absorption, atlapulgite absorption etc.
Document (M.T. Guzman-Gutierrez, F.A. Ruiz-Trevino, M. Zolutukhin, et al. Gas transport properties of high free vol μm of epolyarylates based on isophthalic/terephthalic acid chloride mixtures [J]. Journal of Membrane Science. 2007, 305 (1-2): 347 – 352) report a kind of polyarylester, it is with tetramethyl-dihydroxyphenyl propane (HFBPA) or tetramethyl-hexafluoro bisphenol-a (TMHFBPA) and terephthalic acid, m-phthalic acid Reactive Synthesis, although this polyarylester has good resistance toheat, but due to the impact of tetramethyl-dihydroxyphenyl propane and tetramethyl-hexafluoro bisphenol-a group, its second-order transition temperature is higher than 180 DEG C, molecular chain has very high rigidity, be not suitable for traditional double and manufacture film to stretching method, and fractional free volume is larger in molecule, gas permeation rate is higher.The price of tetramethyl-dihydroxyphenyl propane and tetramethyl-hexafluoro bisphenol-a costly, is not suitable for large-scale production polyarylester simultaneously.
The western Kubo official loyal to his sovereign of Japanese Patent Laid-Open JPA 2002-327051(, Kamei mountain is honest, western river is clear. containing Off ッ element copolymer, そ System making method, お I び optics is with Trees fat [P]. Japan, 2002, Te Open 2002-327051) disclose a kind of fluorine-containing copolyesters, its manufacture method and optical resin, the fluorine-containing copolyesters of one that it is is predominant repeat unit with bisphenol AF diglycidylether, be specially bisphenol AF and in nmp solution, 48 hour generate 2 with cesium carbonate catalysis prior to epoxy bromopropane, 2-bis-(4-hydroxy phenyl) HFC-236fa diglycidyl ether, then within 24 hours, generate copolyesters reacting with di-carboxylic acid such as terephthalic acids.Its shortcoming is a large amount of toxic organic solvents of reaction employing, solvent recuperation and product aftertreatment difficulty, and the polyesterification reaction time is very very long, and monomer is expensive, is not suitable for industrialization scale operation.
Chinese patent CN 100396829C (Cheng Kangsheng, Li Gang, Wei Zheng.Single stage method manufactures the method [P] of multi-stage shrinkage polyester fibre.China, 2008, CN 100396829C) to disclose a kind of be raw material by terephthalic acid, m-phthalic acid, ethylene glycol, Ethoxylated bisphenol A, limiting viscosity 0.67 ~ 0.695, the copolyesters that fusing point is 220 DEG C ~ 235 DEG C, copolyesters, through crystallization, drying, Screw Extrusion, adopts low speed spinning, low temperature high magnification drawing process, manufactures and obtains multistage contraction copolyester fiber.But this copolyesters fusing point is lower, is not suitable for high temperature resistant use occasion.And Ethoxylated bisphenol A compares with bisphenol AF, its to the improvement degree of copolyesters resistance toheat lower than the latter.
Chinese patent CN 102492125 B(once did auspicious, Wang Lujie, Li Zhelong etc.A kind of metal-powder coating copolyesters and manufacture method [P] thereof.China, 2013, CN 102492125 B) disclose a kind of metal-powder coating copolyesters and manufacture method thereof.It mainly comprises the steps: (1) terephthalic acid, m-phthalic acid, hydroxyethylation dihydroxyphenyl propane, C
2~ C
6dibasic alcohol, under tetrabutyl titanate/butyl stannonic acid catalyst action, carries out transesterification reaction; (2) at normal temperatures stablizer triphenyl phosphite is added the product of step (1), at 230 DEG C ~ 250 DEG C, copolycondensation of reducing pressure under 80 ~ 130Pa, obtains copolyesters.But the fusing point of this copolyesters, between 130 DEG C ~ 150 DEG C, cannot meet the application in high-temperature resistant membrane field.
Pu on Chinese patent CN 1029667 C(James river, the red nurse of Na Talajian moorup Ghana, George Louis Broad. based on the semipermeable partition [P] of the tetrabromobisphenol type polyesters of specifying. China, 1995, CN 1029667 C) disclose a kind of thin layer gas separation membrane formed primarily of polyester or copolyesters, said polyester or copolyesters are react obtained by aromatic dicarboxylic acid and derivative thereof with more than the 50 % by mole tetrabromobisphenols with R group substantially, and R group wherein comprises-C (CF
3)
2-structure, namely this tetrabromobisphenol comprises 4,4 '-(2,2,2-tri-fluoro-1-(TRIFLUORO-METHYL) ethylidene) two (2,6-bromophenesic acid).Because the bromine atoms on tetrabromobisphenol phenyl ring adds molecular volume, after making this copolyesters film forming, there is larger gas permeability, and due to the impact of himself structure, be not suitable for two-way stretch method masking, can only short run solution-cast film forming, cannot adapt to the needs of large-scale industrial production, and raw material tetrabromobisphenol is expensive, increases production cost.
Document (Xu Wenhui. the syntheses and properties [D] of fluorine-containing Polycarbonate optical waveguide material. Jilin University, 2013) hexafluoro bisphenol-a (i.e. bisphenol AF), triphosgene is used, low-molecular-weight fluorine-containing polycarbonate has been synthesized by the method for solution polymerization under the catalysis of nucleophilic reagent pyridine, but the main chain rigidity of pure hexafluoro bisphenol-a type polycarbonate is excessively strong, be unfavorable for processing, solvability is also slightly inferior, therefore the flexibility of system segment is changed by introducing bisphenol Z, reduce further the optical loss of material.The method adopts during solution polymerization and employs a large amount of noxious solvent, and aftertreatment is complicated, and polymerization single polymerization monomer triphosgene is highly toxic substance, limits its large-scale application in industrial production.Meanwhile, although grace its change the flexibility of system segment by introducing bisphenol Z, segment integral rigidity is still very large, cannot meet the requirement of stretch processes.
Document (Yu Qiqing, Cao Wei. based on the high-performance fluorine-containing polymkeric substance [J] of Perfluoroacetone. organic fluorine industry, 1999,02:31-39.) describe the application of bisphenol AF in the superpolymer synthesis such as copolyesters, polyarylether, polymeric amide in detail.Point out bisphenol AF and m-phthalic acid, the reaction of terephthalic acid generates polyester 27 and polyester 28 respectively, it has good thermostability and thermo-oxidative stability.Document (Korshak V V, Vinogradova S V, Pankrativ V A. Polyesters. VysokomolSoedin, 1965,7:1689-1691.) describes a kind of linear polyarylester synthesized by bisphenol AF, m-phthalic acid, terephthalic acid.But such polyarylester due in segmented structure containing a large amount of rigid radical, cause it can only casting film, modern industry two-way stretch cannot be adapted to and produce.
But the copolyesters at present also not containing bisphenol AF structure is used for the report in flexible optical film field.
Summary of the invention
The technical problem that the present invention mainly solves is to provide the fluorine-containing copolyesters of a kind of optics, optical thin film and manufacture method thereof, the transmittance of the fluorine-containing copolyesters of optics and optical thin film can be improved, reduce mist degree, good stability of the dimension, heatproof oxidation performance and Good Heat-resistance, manufacture method is simple.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: provide a kind of optics fluorine-containing copolyesters, comprise diprotic acid, dibasic alcohol, bisphenol AF, catalyzer and auxiliary agent composition, described bisphenol AF accounts for total acid massfraction and is less than 50mol%, described dibasic alcohol accounts for total acid massfraction content and is less than 130mol%, and the total amount of described bisphenol AF and dibasic alcohol and the mol ratio of diprotic acid are 1:1.1-1.4.
In a preferred embodiment of the present invention, described diprotic acid is the one or more kinds of combinations in terephthalic acid, m-phthalic acid and NDA.
In a preferred embodiment of the present invention, described dibasic alcohol is the one or more kinds of compositions in ethylene glycol, propylene glycol, BDO and 4-cyclohexane dimethanol.
In a preferred embodiment of the present invention, described catalyzer is the one or more kinds of compositions in antimony glycol, plumbous subacetate and germanium dioxide, and it is 0-0.04% that described catalyzer accounts for total acid massfraction.
In a preferred embodiment of the present invention, described auxiliary agent is one or more in trimethyl phosphite 99, phosphoric acid, triphenylphosphate, and it is 0-0.05% that described auxiliary agent accounts for total acid massfraction.
For solving the problems of the technologies described above, another technical solution used in the present invention is: provide a kind of optics manufacture method of fluorine-containing copolyesters, comprise the following steps:
A. bisphenol AF is dissolved in dimethylbenzene, adds atlapulgite and reflux stirring, then filter and obtain bisphenol AF xylene solution, then after solution is cooled recrystallization, suction filtration obtains the bisphenol AF of purifying;
B. in polyester synthesizer, diprotic acid, dibasic alcohol, purifying bisphenol AF and catalyzer is added, logical nitrogen removing oxygen is vacuumized after stirring, then at 250-350KPa, esterification 1-2.5 hour at 220-270 DEG C, reduces pressure afterwards to normal pressure, then adds auxiliary agent, Pressure Drop is low to moderate-90KPa in 40-60min and carries out precondensation, continue to be less than-103KPa at pressure, temperature is polycondensation 2-4 hour under the condition of 260-280 DEG C, obtains fluorine-containing optics copolyesters.
For solving the problems of the technologies described above, another technical solution used in the present invention is: provide a kind of optical thin film, comprises the fluorine-containing copolyesters of above-mentioned optics.
For solving the problems of the technologies described above, another technical solution used in the present invention is: the manufacture method providing a kind of optical thin film, the optics optics that the manufacture method of fluorine-containing copolyesters is obtained is passed through nitrogen again with fluorine-containing copolyesters, be filtered rear extrusion, cool through deionized water again, pelletizing, dry, finally obtain fluorine-containing optics copolyester section, then at 150 DEG C of vacuum-drying 4-12 hour, make water content lower than 10-50mg/Kg, again by dried fluorine-containing optics copolyester section through slab, two-way stretch, coating function coating, heat setting type, rolling, obtain fluorine-containing copolyesters optical thin film.
The invention has the beneficial effects as follows: the fluorine-containing copolyesters of optics provided by the invention, optical thin film and manufacture method thereof, the transmittance of the fluorine-containing copolyesters of optics and optical thin film can be improved, reduce mist degree, good stability of the dimension, resistance to thermooxidizing voltinism and Good Heat-resistance, manufacture method is simple.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making other embodiments all obtained under creative work prerequisite, belong to the scope of protection of the invention.
The preferred terephthalic acid of diprotic acid of the present invention, m-phthalic acid, NDA and methyl esters compound thereof.Also other diprotic acid such as fumaric acid, sebacic acid, phthalic acid can be selected.
Dibasic alcohol of the present invention is preferably from ethylene glycol, propylene glycol, BDO, 1,4 cyclohexane dimethanol.Also other dibasic alcohol such as neopentyl glycol, spiral shell glycol, Isosorbide, dihydroxyphenyl propane can be selected.
The present invention considers from PET hue, transmittance and mist degree angle, and catalyzer is preferably from antimony glycol, plumbous subacetate, germanium dioxide.Also other antimony-based catalysts such as antimony acetate, antimonous oxide, Virahol antimony can be selected; Other Titanium series catalyst such as tetrabutyl titanate, titanium dioxide; Other aluminum-based catalyst and other custom catalystses such as aluminium sesquioxide, aluminum chloride, aluminum isopropylate.
In order to make fluorine-containing optical polyester film provided by the invention have specific function and strengthening performance, the functional agents such as white dyes, dyestuff, crystallization nucleating agent, ultraviolet preventing agent, softening agent, inorganic nano-particle, oxidation inhibitor can be added in this polyester.
Embodiment 1: add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion (n in polyester synthesizer
terephthalic acid: n
m-phthalic acid=1:0.005), ethylene glycol 95 weight portion, bisphenol AF 5 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.28) and account for the antimony glycol in total acid content 4/10000ths weight portion, logical nitrogen deoxygenation is vacuumized after stirring, then at 250-350KPa, esterification 2 hours under 220-270 DEG C of degree, is reduced pressure afterwards to normal pressure, is added the trimethyl phosphite 99 accounting for total acid content 0.5/10000th by charging opening, then in 40 ~ 60min, Pressure Drop is carried out precondensation to-90KPa, be less than-103Kpa at pressure, temperature is polycondensation 2-4 hour under the condition of 260-280 DEG C, obtains fluorine-containing optics copolyesters.This copolyesters extrudes by logical nitrogen after Stainless Steel Filter (10 μm of contaminant filter efficiency are greater than 99%) filters, through deionized water cooling (filtering through 10 μm of bore filter devices), and pelletizing, dry, obtain fluorine-containing optics copolyester section.
By above-mentioned copolyester section at 150 DEG C, vacuum-drying 4-12 hour under 133Pa, makes water content lower than 10-50mg/Kg.Dried polyester slice is supplied forcing machine through feed hopper, filters through Stainless Steel Filter (10 μm of contaminant filter efficiency are greater than 99%) at melt temperature 280 DEG C, cool rapidly at 20 DEG C of rollers after T connector is extruded, obtain the casting films of 2650 μm.This film is heated to 100 DEG C through infrared heater, longitudinal stretching 3.5 times, (glue spread is 0.5g/m to double spread coating fluid
2) after, through 130 DEG C of Hot-blast Heating dryings, cross directional stretch 4 times, heat setting type 0.6 second at 250 DEG C afterwards, obtains the fluorine-containing copolyesters optical thin film that thickness is 188 μm.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 2: add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion in polyester synthesizer, n
terephthalic acid: n
m-phthalic acid=1:0.005, ethylene glycol 90 weight portion, bisphenol AF 10 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.23) and account for the antimony glycol in total acid content 4/10000ths weight portion, logical nitrogen deoxygenation is vacuumized after stirring, then at 350KPa, esterification 2 hours under 260 DEG C of degree, is reduced pressure afterwards to normal pressure, is added the trimethyl phosphite 99 accounting for total acid content 0.5/10000th by charging opening, then in 40 ~ 60min, Pressure Drop is carried out precondensation to-90KPa, be less than-103Kpa at pressure, temperature is polycondensation 3 hours under the condition of 270 DEG C, obtains fluorine-containing optics copolyesters.This copolyesters extrudes by logical nitrogen after Stainless Steel Filter (10 μm of contaminant filter efficiency are greater than 99%) filters, through deionized water cooling (filtering through 10 μm of bore filter devices), pelletizing, dry, obtains fluorine-containing optics copolyester section.
By above-mentioned copolyester section at 150 DEG C, under 133Pa, vacuum-drying 6 hours, makes water content lower than 10mg/Kg.Dried polyester slice is supplied forcing machine through feed hopper, at melt temperature 280 DEG C, filters (10 μm of contaminant filter efficiency are greater than 99%) through Stainless Steel Filter, cool rapidly at 20 DEG C of rollers after T connector is extruded, obtain the casting films of 2650 μm.This film is heated to 100 DEG C through infrared heater, longitudinal stretching 3.5 times, (glue spread is 0.5g/m to double spread coating fluid
2) after, through 130 DEG C of Hot-blast Heating dryings, cross directional stretch 4 times, heat setting type 0.6 second at 250 DEG C afterwards, obtains the fluorine-containing copolyesters optical thin film that thickness is 188 μm.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 3: change copolyesters monomeric species and ratio, add terephthalic acid 198.474 weight portion, NDA 1.526 weight portion (n
terephthalic acid: n
nDA=1:0.01), ethylene glycol 104 weight portion, bisphenol AF 5 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.40), in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 4: change copolyesters monomeric species and ratio, add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion (n
terephthalic acid: n
m-phthalic acid=1:0.005), ethylene glycol 90 weight portion, propylene glycol 5 weight portion, bisphenol AF 5 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.27), in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 5: change copolyesters monomer ratio, add terephthalic acid 190.476 weight portion, m-phthalic acid 9.524 weight portion (n
terephthalic acid: n
m-phthalic acid=1:0.05), ethylene glycol 95 weight portion, bisphenol AF 5 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.28), in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 6: change copolyesters monomeric species and ratio, add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion (n
terephthalic acid: n
m-phthalic acid=1:0.005), ethylene glycol 90 weight portion, butyleneglycol 1 weight portion, bisphenol AF 9 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.24), in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.
Embodiment 7: change copolyesters monomeric species and ratio, add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion (n
terephthalic acid: n
m-phthalic acid=1:0.005), ethylene glycol 80 weight portion, 1,4 cyclohexane dimethanol 5 weight portion, bisphenol AF 5 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.11), in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.
Embodiment 8: change copolyesters catalyst type and ratio, add the germanium dioxide accounting for total acid content 4/10000ths, in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 9: change copolyesters catalyst type and ratio, add the plumbous subacetate accounting for total acid content 4/10000ths, in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 10: change copolyesters catalyst type and ratio, add the antimony glycol accounting for total acid content 2/10000ths and the eston accounting for total acid content 2/10000ths, in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Comparative example 1: change copolyesters monomeric species and ratio, add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion (n
terephthalic acid: n
m-phthalic acid=1:0.005), ethylene glycol 100 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.34), in addition similarly to Example 1 obtain copolyesters and copolyester film.The test result of gained copolyester film is as shown in table 1.
Comparative example 2: change copolyesters monomeric species and ratio, add terephthalic acid 200 weight portion, ethylene glycol 100 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.34), in addition similarly to Example 1 obtain copolyesters and copolyester film.The test result of gained copolyester film is as shown in table 1.
Comparative example 3: change copolyesters monomeric species and ratio, add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion (n
terephthalic acid: n
m-phthalic acid=1:0.005), bisphenol AF 214.837 weight portion (n
total acid: n
total alcohol=1:1.3), in addition similarly to Example 1 obtain copolyesters.
Comparative example 4: change copolyesters monomeric species and ratio, add terephthalic acid 199.005 weight portion, m-phthalic acid 0.995 weight portion (n
terephthalic acid: n
m-phthalic acid=1:0.005), ethylene glycol 90 weight portion, dihydroxyphenyl propane 10 weight portion (n
dibasic alcohol: n
diprotic acid=1:1.23), in addition similarly to Example 1 obtain copolyesters and copolyester film.The test result of gained copolyesters is as shown in table 1.
Owing to containing a large amount of bisphenol AF in dibasic alcohol, cause the phenomenon occurring rupture of membranes in film stretching process, therefore fail to obtain qualified biaxially oriented film.
Comparative example 5: change copolyesters catalyst type, add the tetrabutyl titanate accounting for total acid content 4/10000ths, in addition similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment of the present invention Raw select producer, specification and treatment process as follows.Under the prerequisite not affecting effect of the present invention, also can select the raw material of other manufacturer production.
Terephthalic acid (CAS:100-21-0): Sinopec Yangzi Petrochemical Co, polymerization-grade.
M-phthalic acid (CAS:121-91-5): Sinopec Beijing Yanshan Mountain branch office, polymerization-grade.
NDA (CAS:1141-38-4): Nanjing remedies medicament research and development company limited, purity 99%.
Bisphenol AF (CAS:1478-61-1): Zigong Tianlong Chemical Co., Ltd., purity 99.5%.Before using in xylene solution by atlapulgite reflow treatment 4 ~ 10 hours, cool recrystallization by after this solution via hole diameter 10 micron filter, more after filtration, dry, obtain recrystallization bisphenol AF.
Ethylene glycol (CAS:107-21-1): Sinopec Beijing Yanshan Mountain branch office, purity 99.8%.
Propylene glycol (CAS:57-55-6): Dow Chemical company, purity >99.8%.
BDO (CAS:110-63-4): BASF Aktiengesellschaft, purity 99%.
1,4 cyclohexane dimethanol (CAS:105-08-8): SK Chemical Co., Ltd of Korea S, purity 99.9%.
Antimony glycol (CAS:29736-75-2): Jinan Hao Hua limited industrial company, antimony content 53%-57%.
Plumbous subacetate (CAS:142-03-0): Shanghai Mai Kun Chemical Co., Ltd., purity >99%.
Germanium dioxide (CAS:1310-53-8): Luoyang nonferrous materials company limited, ge content >=99.999(%).
Trimethyl phosphite 99 (CAS:512-56-1): new Asia, Zhangjiagang Chemical Co., Ltd., purity >99%.
The testing method that the present invention is used and instrument as follows:
Limiting viscosity: by GB/T 14190-2008, adopts capillary viscosity method, with phenol/sym.-tetrachloroethane (mass ratio 60:40) for solvent is tested.
Fusing point (T
m), second-order transition temperature (T
g): by GB/T 14190-2008, by polyester slice vacuum-drying 4 hours at 60 DEG C, then on 200 F3 type DSC of German Nai Chi company, rise to 280 DEG C from room temperature with 10K/min, insulation 3min, be down to 80 DEG C with 10K/min again, be finally warming up to 280 DEG C with 10K/min.
Heat decomposition temperature (T
d): in Germany, sample is heated to 800 DEG C from room temperature to resistance to speeding by company's T G 209 F3 type thermogravimetric analyzer, record decomposition temperature (residual qualities is the time of 95%).
Transmittance, mist degree: the square fluorine-containing optical polyester film after two-way stretch being cut into 50mm*50mm, WGT-2S type light transmittance tester is tested.
Colourity is tested: get the dried polyester slice of 10g on the desk-top spectrophotometer of X. Rite Inc. of U.S. Color i7, carry out 3 measurements, getting average value measured is net result, record L, b value.
Thermal contraction performance: by JIS C2318 respectively at 150 DEG C, test under the condition of 30min and 200 DEG C, 10min.
Tensile strength: undertaken by GBT 1040.3-2006 " test of plastic tensile performance ".Specimen size 10mm*150mm(2 type sample).
Table 1 and table 2 are experimental data:
Table 1
| Polymerization composition (Quality Mgmt Dept) | Catalyzer, additive (accounting for the ratio of total acid content) | IV (dL/g) | Tg (℃） | Tm （℃） | Td （℃） | T（%） | H（%） | L | b | |
| Embodiment 1 | PTA(199.005)/IPA(0.995)/EG(95)/BPAF(5) | Sb(0.0004)/TMP(0.00005) | 0.678 | 77.1 | 260.0 | 425.4 | 92.0 | 0.7 | 82 | 0.9 |
| Embodiment 2 | PTA(199.005)/IPA(0.995)/EG(90)/ BPAF(10) | Sb(0.0004)/TMP(0.00005) | 0.740 | 79.8 | 266.1 | 430.0 | 91.8 | 0.9 | 83 | 0.9 |
| Embodiment 3 | PTA(198.474)/2,6-DNCA(1.526) /EG(104)/BPAF(5) | Sb(0.0004)/TMP(0.00005) | 0.680 | 78.2 | 262.4 | 426.3 | 92.0 | 0.8 | 85 | 0.9 |
| Embodiment 4 | PTA(199.005)/IPA(0.995)/EG(90)/PDO(5)/BPAF(5) | Sb(0.0004)/TMP(0.00005) | 0.655 | 74.0 | 257.2 | 420.7 | 92.0 | 0.9 | 82 | 0.9 |
| Embodiment 5 | PTA(190.476)/IPA(9.524)/EG(95)/BPAF(5) | Sb(0.0004)/TMP(0.00005) | 0.671 | 76.6 | 261.3 | 423.2 | 92.0 | 0.9 | 85 | 0.9 |
| Embodiment 6 | PTA(199.005)/IPA(0.995)/EG(95)/BDO(1)/BPAF(9) | Sb(0.0004)/TMP(0.00005) | 0.670 | 76.0 | 256.5 | 423.4 | 91.6 | 0.9 | 81 | 0.9 |
| Embodiment 7 | PTA(199.005)/IPA(0.995)/EG(80)/ PCT(5)/BPAF(5) | Sb(0.0004)/TMP(0.00005) | 0.689 | 78.0 | 259.7 | 423.7 | 91.8 | 0.9 | 82 | 0.9 |
| Embodiment 8 | PTA(199.005)/IPA(0.995)/EG(95)/BPAF(5) | Ge(0.0004)/TMP(0.00005) | 0.680 | 77.0 | 257.2 | 425.0 | 92.2 | 0.6 | 82 | 0.7 |
| Embodiment 9 | PTA(199.005)/IPA(0.995)/EG(95)/BPAF(5) | Al(0.0004)/TMP(0.00005) | 0.662 | 73.2 | 258.0 | 420.0 | 92.0 | 0.9 | 81 | 1.2 |
| Embodiment 10 | PTA(199.005)/IPA(0.995)/EG(95)/BPAF(5) | Sb(0.0002)/Al(0.0002)/ TMP(0.00005) | 0.674 | 77.0 | 259.5 | 424.9 | 92.0 | 0.9 | 82 | 0.9 |
| Comparative example 1 | PTA(199.005)/IPA(0.995)/EG(100) | Sb(0.0004)/TMP(0.00005) | 0.677 | 75.2 | 255.7 | 419.3 | 90.2 | 1.5 | 80 | 3.0 |
| Comparative example 2 | PTA(200)/EG(100) | Sb(0.0004)/TMP(0.00005) | 0.875 | 74.5 | 255.0 | 415.0 | 89.0 | 2.0 | 80 | 5.0 |
| Comparative example 3 | PTA(199.005)/IPA(0.995)/BPAF(214.837) | Sb(0.0004)/TMP(0.00005) | 0.810 | 133.2 | 272.5 | 431.2 | 87.1 | 10.0 | 79 | 3.3 |
| Comparative example 4 | PTA(199.005)/IPA(0.995)/EG(90)/BPA(10) | Sb(0.0004)/TMP(0.00005) | 0.652 | 75.2 | 255.2 | 421.0 | 89.2 | 8.0 | 79 | 6.0 |
| Comparative example 5 | PTA(199.005)/IPA(0.995)/EG(95)/BPAF(5) | TBT(0.0004)/TMP(0.00005) | 0.670 | 77.0 | 256.5 | 425.0 | 91.8 | 1.1 | 74 | 8.0 |
Table 2
Abbreviation illustrates:
PTA: terephthalic acid
IPA: m-phthalic acid
2,6-DNCA:2,6-naphthalic acid
EG: ethylene glycol
BPAF: bisphenol AF
PDO: propylene glycol
BDO:1,4-butyleneglycol
PCT:1,4-cyclohexanedimethanol
BPA: dihydroxyphenyl propane
Sb: antimony glycol
Al: eston
TBT: tetrabutyl titanate
TMP: trimethyl phosphite 99
The present invention by introducing bisphenol AF (CAS:1478-61-1) group in PET, greatly increase the high-temperature stability of copolyesters, ageing-resistant performance, dimensional stability and optical property, simultaneously due to can intramolecular hydrogen bond be formed between F atom and PET main chain terminal base H atom, make the inner condensed state structure of this fluorine-containing copolyesters more tight, thus make this copolyesters have fabulous water vapor rejection performance.By adding ethylene glycol, propylene glycol, 1,4 butyleneglycols, 1, the flexible chain dibasic alcohol such as 4-cyclohexanedimethanol increase the snappiness of copolyesters optical thin film, make it meet the needs of various film stretching techniques, are adapted at scale operation on existing BOPET stretcher.Fluorine-containing optics copolyesters generated time provided by the invention is short, and cost of material is moderate, can significantly save enterprise's production cost.
Being different from prior art, the fluorine-containing copolyesters of optics of the present invention, optical thin film and manufacture method thereof, adding the thermotolerance of copolyesters, scale resistance, dimensional stability and optical property by introducing bisphenol AF structure; Improving the rigidity of copolyesters molecular structure by adding ethylene glycol, propylene glycol, BDO, 1,4 cyclohexane dimethanol etc., adding the snappiness of fluorine-containing optics copolyesters, make it be met large scale bi-directional stretching and produce; Bisphenol AF used, through recrystallization process, enhances the optical property of fluorine-containing optics copolyesters.
Fluorine-containing optics copolyesters generated time provided by the invention is short, and cost of material is moderate, can significantly save enterprise's production cost.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (8)
1. the fluorine-containing copolyesters of optics, it is characterized in that, comprise diprotic acid, dibasic alcohol, bisphenol AF, catalyzer and auxiliary agent composition, described bisphenol AF accounts for total acid massfraction and is less than 50mol%, described dibasic alcohol accounts for total acid massfraction content and is less than 130mol%, and the total amount of described bisphenol AF and dibasic alcohol and the mol ratio of diprotic acid are 1:1.1-1.4.
2. the fluorine-containing copolyesters of optics according to claim 1, is characterized in that, described diprotic acid is one or more in terephthalic acid, m-phthalic acid, NDA, fumaric acid, sebacic acid and phthalic acid.
3. the fluorine-containing copolyesters of optics according to claim 1, is characterized in that, described dibasic alcohol is one or more in ethylene glycol, propylene glycol, BDO, Isosorbide-5-Nitrae-cyclohexane dimethanol, neopentyl glycol, spiral shell glycol, Isosorbide and dihydroxyphenyl propane.
4. the fluorine-containing copolyesters of optics according to claim 1, it is characterized in that, described catalyzer is one or more in antimony glycol, plumbous subacetate and germanium dioxide, antimony acetate, antimonous oxide, Virahol antimony, tetrabutyl titanate, titanium dioxide, aluminium sesquioxide, aluminum chloride, aluminum isopropylate, and it is 0-0.04% that described catalyzer accounts for total acid massfraction.
5. the fluorine-containing copolyesters of optics according to claim 1, is characterized in that, described auxiliary agent is one or more in trimethyl phosphite 99, phosphoric acid, triphenylphosphate, and it is 0-0.05% that described auxiliary agent accounts for total acid massfraction.
6. an optics as claimed in claim 1 manufacture method for fluorine-containing copolyesters, is characterized in that, comprise the following steps:
A. bisphenol AF is dissolved in dimethylbenzene, adds atlapulgite and reflux stirring, then filter and obtain bisphenol AF xylene solution, then after solution is cooled recrystallization, suction filtration obtains the bisphenol AF of purifying;
B. in polyester synthesizer, diprotic acid, dibasic alcohol, purifying bisphenol AF and catalyzer is added, logical nitrogen deoxygenation is vacuumized after stirring, then at 250-350KPa, esterification 1-2.5 hour at 220-270 DEG C, reduce pressure afterwards to normal pressure, add auxiliary agent again, Pressure Drop is low to moderate-90KPa in 40-60min and carries out precondensation, continue to be less than-103KPa at pressure, temperature is polycondensation 2-4 hour under the condition of 260-280 DEG C, logical nitrogen pressurization extrudes after filtering, then through deionized water cooling, pelletizing, drying, finally obtains fluorine-containing optics copolyesters.
7. an optical thin film, is characterized in that, comprises the fluorine-containing copolyesters of optics according to claim 1.
8. the manufacture method of an optical thin film according to claim 7, it is characterized in that, by optics according to claim 6 with the obtained fluorine-containing copolyesters of optics of the manufacture method of fluorine-containing copolyesters at 150 DEG C of vacuum-drying 4-12 hour, make water content lower than 10-50mg/Kg, again by dried fluorine-containing optics copolyester section through slab, two-way stretch, coating function coating, heat setting type, rolling, obtains fluorine-containing copolyesters optical thin film.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221148A (en) * | 2016-08-23 | 2016-12-14 | 江苏景宏新材料科技有限公司 | A kind of method of aluminum-based catalyst catalyzing and synthetizing modified copolyester section |
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| CN109942853A (en) * | 2019-04-04 | 2019-06-28 | 哈尔滨工业大学 | A kind of preparation method of the polyethylene terephthalate copolyester film of ultraviolet full-shield |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0316960A2 (en) * | 1987-11-20 | 1989-05-24 | The Dow Chemical Company | Gas separation membranes from bisphenol af polycarbonates and polyestercarbonates |
| US6001550A (en) * | 1998-09-21 | 1999-12-14 | Eastman Kodak Company | Photographic element having a annealable transparent magnetic recording layer |
| JP2006184319A (en) * | 2004-12-24 | 2006-07-13 | Nitta Ind Corp | Plastic optical fiber and its manufacturing method |
| CN102532496A (en) * | 2011-12-16 | 2012-07-04 | 东华大学 | Fluorine-containing bisphenol aromatic polyester and preparation method thereof |
| CN102558518A (en) * | 2010-12-07 | 2012-07-11 | 上海杰事杰新材料(集团)股份有限公司 | Aromatic copolyester and preparation method thereof |
| CN103403057A (en) * | 2011-03-02 | 2013-11-20 | 旭硝子株式会社 | Method for producing polyester, and fluorine-containing dicarboxylic acid ester compound |
-
2014
- 2014-11-13 CN CN201410639545.7A patent/CN104497290B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0316960A2 (en) * | 1987-11-20 | 1989-05-24 | The Dow Chemical Company | Gas separation membranes from bisphenol af polycarbonates and polyestercarbonates |
| US6001550A (en) * | 1998-09-21 | 1999-12-14 | Eastman Kodak Company | Photographic element having a annealable transparent magnetic recording layer |
| JP2006184319A (en) * | 2004-12-24 | 2006-07-13 | Nitta Ind Corp | Plastic optical fiber and its manufacturing method |
| CN102558518A (en) * | 2010-12-07 | 2012-07-11 | 上海杰事杰新材料(集团)股份有限公司 | Aromatic copolyester and preparation method thereof |
| CN103403057A (en) * | 2011-03-02 | 2013-11-20 | 旭硝子株式会社 | Method for producing polyester, and fluorine-containing dicarboxylic acid ester compound |
| CN102532496A (en) * | 2011-12-16 | 2012-07-04 | 东华大学 | Fluorine-containing bisphenol aromatic polyester and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221148A (en) * | 2016-08-23 | 2016-12-14 | 江苏景宏新材料科技有限公司 | A kind of method of aluminum-based catalyst catalyzing and synthetizing modified copolyester section |
| CN109097017A (en) * | 2018-08-31 | 2018-12-28 | 中国海洋石油集团有限公司 | A kind of emulsifying and viscosity-reducing agent for condensed oil of heat and salinity tolerance and preparation method thereof |
| CN109097017B (en) * | 2018-08-31 | 2020-08-04 | 中国海洋石油集团有限公司 | Temperature-resistant and salt-resistant thick oil emulsifying viscosity reducer and preparation method thereof |
| CN109942853A (en) * | 2019-04-04 | 2019-06-28 | 哈尔滨工业大学 | A kind of preparation method of the polyethylene terephthalate copolyester film of ultraviolet full-shield |
| CN109942853B (en) * | 2019-04-04 | 2021-07-06 | 哈尔滨工业大学 | Preparation method of ultraviolet full-shielding polyethylene glycol terephthalate copolyester film |
| WO2020218324A1 (en) * | 2019-04-25 | 2020-10-29 | 三菱瓦斯化学株式会社 | Polyester resin composition, polyester injection-molded article, polyester extrusion-molded article, polyester foam, polyester container, polyester bottle, polyester tableware, and polyester feeding bottle |
| CN114479373A (en) * | 2021-12-27 | 2022-05-13 | 江苏双星彩塑新材料股份有限公司 | Polyester film for optical prism film and preparation method thereof |
| CN114479032A (en) * | 2022-01-06 | 2022-05-13 | 中国科学院宁波材料技术与工程研究所 | Polyesters based on 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, methods of making and articles thereof |
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