CN104497290B - Optics fluorine-containing copolyesters, optical thin film and manufacture method thereof - Google Patents
Optics fluorine-containing copolyesters, optical thin film and manufacture method thereof Download PDFInfo
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Abstract
The invention discloses a kind of optics fluorine-containing copolyesters, optical thin film and manufacture method thereof, the fluorine-containing optics copolyesters being prepared from for monomer with a certain proportion of binary acid, dihydroxylic alcohols, bisphenol AF, copolyester film is made after biaxial tension, this film has good optical property, heat resistance, ageing-resistant performance are excellent, there is higher hot strength, excellent size stability, can be widely used for the field such as optical thin film, photovoltaic back.
Description
Technical field
The present invention relates to polyester synthesis field, particularly relate to a kind of optics fluorine-containing copolyesters, optical thin film and system thereof
Make method.
Background technology
It is current generation with terephthalic acid (TPA), ethylene glycol for the polyethylene terephthalate (PET) of polymerization monomer synthesis
The synthesizing polyester material that in boundary, consumption is maximum, PET film is widely used in the necks such as packaging for foodstuff, ornament materials, label, liquid crystal display
Territory.Poly-(terephthalic acid (TPA)-M-phthalic acid-ethylene glycol) ester being fabricated by by introducing the 3rd component M-phthalic acid has
Good crystal property, is used in the fields such as blown polyester bottle in a large number.But the ester group in PET macromolecular structure makes it have one
Fixed hydrophily, is 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, it is impossible to the application that competent needs strictly block water, heat resistance, oxidative resistance and optical
Energy etc. also needs to improve further.
Poly-NDA glycol ester (PEN) is by monomer NDA (2,6-NDA) or 2,6-naphthalene diformazan
Dimethyl phthalate (2,6-NDC) and ethylene glycol (EG), through esterification or ester exchange aftercondensated.From the point of view of molecular structure, PEN with
Differing only in of polyethylene terephthalate (PET) be instead of benzene by the naphthalene nucleus that rigidity is bigger on polyester molecule main chain
Ring, its performance, between PET and polyimides PI, has good barrier properties for gases, heat resistance and anti-ultraviolet property.So
And NDA is expensive so that the application of PEN is restricted, people urgently find one and PEN can be kept excellent
Optimum energy, can reduce again the copolyesters combination of cost.
Fluorine element is the element that in nature, electronegativity is maximum, and on fluorine atom, electric charge compares concentration, and C-F bond energy compares c h bond
The high 72KJ/mol of energy, therefore fluorine atom has the strongest shielding action to C-C key so that fluoropolymer has the corrosion-resistant of excellence
Property, weatherability and resistance to ag(e)ing, again because fluorine atom polarizability is low, so the fissipation factor of fluorocarbons and dielectric constant are equal
Less so that fluoropolymer has excellent insulating properties, chemical inertness and high-temperature stability.Owing to general polymer is containing C-
H, C-O, N-H key is more, can cause violent light loss near interval 1.33 μm of light signal communication and 1.55 μm.Use
F atom replaces H atom can reduce by the light loss of more than 5 times.
Bisphenol AF is mainly used as vulcanizable fluororubber accelerator, and the fluorubber set resistant with FF34 sulfuration is little, and anti-tensile is strong
Degree height；It also is used as medicine intermediate.But the impurity contained in commercially available bisphenol AF is difficult to purify, and can have a strong impact on bisphenol AF and exist
Using effect in optical articles.It is thus desirable to carry out purification processes before use.Common method of purification has recrystallization, activity
Charcoal absorption, atlapulgite absorption etc..
Document (M.T. Guzman-Gutierrez, F.A. Ruiz-Trevino, M. Zolutukhin, et al.
Gas transport properties of high free volμmepolyarylates based on
isophthalic/terephthalic acid chloride mixtures[J]. Journal of Membrane
Science. 2007,305 (1-2): 347 352) report a kind of polyarylate, its be with tetramethyl bisphenol-A (HFBPA) or
Tetramethyl hexafluoro bisphenol-a (TMHFBPA) is synthesized with terephthalic acid (TPA), M-phthalic acid, although this polyarylate has
Preferably heat resistance, but due to tetramethyl bisphenol-A and the impact of tetramethyl hexafluoro bisphenol-a group, its vitrification point is higher than
180 DEG C, strand has the highest rigidity, is not suitable for traditional two-way pulling method and manufactures film, and intramolecular free volume
Mark is relatively big, and gas permeation rate is higher.The price of tetramethyl bisphenol-A and tetramethyl hexafluoro bisphenol-a costly, is not suitable for simultaneously
Large-scale production polyarylate.
Japanese Patent Laid-Open JPA 2002-327051(western Kubo official loyal to his sovereign, mountain is honest, and western river is clear. and the ッ element containing Off weighs altogether
Fit, そ makes method, お I び optics fat [P]. Japan, 2002, special 2002-327051) and disclose one and contain
Fluorine copolyesters, its manufacture method and optical resin, it is that the one with bisphenol AF diglycidyl ether as predominant repeat unit contains
Fluorine copolyesters, specially bisphenol AF prior to epoxy bromopropane in nmp solution with cesium carbonate be catalyzed 48 hours generate 2,2-bis-
(4-hydroxy phenyl) HFC-236fa diglycidyl ether, is then reacting life in 24 hours with dicarboxylic acids such as terephthalic acid (TPA)s
Become copolyesters.Its shortcoming uses a large amount of toxic organic solvents, solvent recovery and product post processing difficulty for reaction, and polyesterification is anti-
Between Ying Shi the veryest long, monomer is expensive, be not suitable for industrialization large-scale production.
Chinese patent CN 100396829C (Cheng Kangsheng, Li Gang, Wei Zheng.One-step method manufactures the side of multi-stage shrinkage polyester fibre
Method [P].China, 2008, CN 100396829C) disclose one by terephthalic acid (TPA), M-phthalic acid, ethylene glycol, ethyoxyl
Change bisphenol-A is raw material, inherent viscosity 0.67 ~ 0.695, the copolyesters that fusing point is 220 DEG C ~ 235 DEG C, and copolyesters is crystallized, dry, spiral shell
Bar is extruded, and uses low speed spinning, low temperature high magnification drawing process, manufactures and obtain multistage contraction copolyester fiber.But this copolymerization
Ester fusing point is relatively low, is not suitable for high temperature resistant use occasion.And Ethoxylated bisphenol A is compared with bisphenol AF, it is heat-resisting to copolyesters
The improvement degree of performance is less than the latter.
Chinese patent CN 102492125 B(once made auspicious, Wang Lujie, Li Zhelong etc..A kind of metal dust coating is used altogether
Polyester and manufacture method [P] thereof.China, 2013, CN 102492125 B) disclose a kind of metal dust coating copolyesters
And manufacture method.It mainly comprises the steps: (1) terephthalic acid (TPA), M-phthalic acid, hydroxyethylation bisphenol-A, C2~C6Two
Unit's alcohol, under butyl titanate/butyl stannonic acid catalyst action, carries out ester exchange reaction；(2) at normal temperatures by stabilizer phosphorous
Triphenyl phosphate ester adds the product of step (1), at 230 DEG C ~ 250 DEG C, and copolycondensation of reducing pressure under 80 ~ 130Pa, it is thus achieved that copolyesters.But this
Plant the fusing point of copolyesters between 130 DEG C ~ 150 DEG C, it is impossible to meet the application in high-temperature resistant membrane field.
Pu on Chinese patent CN 1029667 C(James river, Na Talajian moorup Ghana pellet nurse, George
Louis's Broad. semipermeable membrane based on the tetrabromobisphenol type polyesters specified [P]. China, 1995, CN 1029667
C) a kind of thin layer gas separation membrane being mainly made up of, described polyester or copolyesters are disclosed polyester or copolyesters substantially
Reacted with the tetrabromobisphenol of R group with 50 moles of more than % by aromatic dicarboxylic acid and derivative thereof and to prepare, R base therein
Group comprises-C (CF3)2-structure, this tetrabromobisphenol i.e. includes 4,4 '-(2,2,2-tri-fluoro-1-(TRIFLUORO-METHYL) ethylidene) double (2,
6-dibromophenol).Owing to the bromine atoms on tetrabromobisphenol phenyl ring adds molecular volume so that have bigger after this copolyesters film forming
Gas permeability, and due to the impact of himself structure, be not suitable for biaxial tension method masking, can only small lot solution-cast
Film forming, it is impossible to adapt to the needs of large-scale industrial production, and raw material tetrabromobisphenol is expensive, increases production cost.
Document (Xu Wenhui. the synthesis of fluorine-containing Polycarbonate optical waveguide material and sign [D]. Jilin University, 2013) use
Hexafluoro bisphenol-a (i.e. bisphenol AF), triphosgene, synthesized low point by the method for polymerisation in solution under the catalysis of nucleopilic reagent pyridine
The fluorine-containing Merlon of son amount, but the main chain rigidity of pure hexafluoro bisphenol-a type Merlon is too strong, is unfavorable for processing, dissolves
Property also slightly inferior, therefore change the flexibility of system segment by introducing bisphenol Z, reduce further the light loss of material.
The method employs a large amount of toxic solvent when using polymerisation in solution, post processing complexity, and to be polymerized monomer triphosgene be violent in toxicity
Matter, limits its large-scale application in industrial production.Meanwhile, although grace its by introduce bisphenol Z change system segment
Flexibility, but segment integral rigidity is the biggest, it is impossible to meet the requirement of stretch processes.
Document (Yu Qiqing, Cao Wei. high-performance fluorine-containing polymer [J] based on Hexafluoro acetone. Organic fluoride industry, 1999,
02:31-39.) describe bisphenol AF application in the high polymer synthesis such as copolyesters, polyarylether, polyamide in detail.Point out bis-phenol
AF and M-phthalic acid, the reaction of terephthalic acid (TPA) generate polyester 27 and polyester 28 respectively, and it has preferable heat endurance
And thermo oxidative stability.Document (Korshak V V, Vinogradova S V, Pankrativ V A. Polyesters.
VysokomolSoedin, 1965,7:1689-1691.) describe one by bisphenol AF, M-phthalic acid, terephthalic acid (TPA) conjunction
The linear polyarylate become.But such polyarylate due in segmented structure containing a large amount of rigid radicals, cause its can only casting film,
Modern industry biaxial tension cannot be adapted to produce.
But there is presently no the report for flexible optical film field of the copolyesters containing bisphenol AF structure.
Summary of the invention
The technical problem that present invention mainly solves is to provide a kind of optics with fluorine-containing copolyesters, optical thin film and manufacturer thereof
Method, it is possible to increase optics fluorine-containing copolyesters and the light transmittance of optical thin film, reduces mist degree, good stability of the dimension, resistance to thermal oxide
Property and Good Heat-resistance, manufacture method is simple.
For solving above-mentioned technical problem, the technical scheme that the present invention uses is: provide a kind of fluorine-containing copolymerization of optics
Ester, forms including binary acid, dihydroxylic alcohols, bisphenol AF, catalyst and auxiliary agent, and described bisphenol AF accounts for total acid mass fraction and is less than
50mol%, described dihydroxylic alcohols accounts for total acid mass fraction content less than 130mol%, described bisphenol AF and the total amount of dihydroxylic alcohols and binary
The mol ratio of acid is 1:1.1-1.4.
In a preferred embodiment of the present invention, described binary acid is terephthalic acid (TPA), M-phthalic acid and 2,6-naphthalene two
One or more kinds of combinations in formic acid.
In a preferred embodiment of the present invention, described dihydroxylic alcohols is ethylene glycol, propane diols, BDO and 4-ring second
One or more kinds of compositions in alkane dimethanol.
In a preferred embodiment of the present invention, described catalyst is in antimony glycol, basic aluminium acetate and germanium dioxide
One or more kinds of compositions, it is 0-0.04% that described catalyst accounts for total acid mass fraction.
In a preferred embodiment of the present invention, described auxiliary agent is the one in trimethyl phosphate, phosphoric acid, triphenyl phosphate
Or several, it is 0-0.05% that described auxiliary agent accounts for total acid mass fraction.
For solving above-mentioned technical problem, another technical solution used in the present invention is: provide a kind of optics with fluorine-containing common
The manufacture method of polyester, comprises the following steps:
A. bisphenol AF is dissolved in dimethylbenzene, adds atlapulgite and be heated to reflux stirring, being then filtrated to get bis-phenol
AF xylene solution, then suction filtration after solution cooling recrystallization is obtained the bisphenol AF purified；
B. in polyester synthesis device, add binary acid, dihydroxylic alcohols, purifying bisphenol AF and catalyst, take out true after stirring
Empty logical nitrogen removes oxygen, then at 250-350KPa, is esterified 1-2.5 hour at 220-270 DEG C, reduces pressure afterwards to often
Pressure, adds auxiliary agent, and pressure drop as little as-90KPa carries out in 40-60min precondensation, continues at pressure less than-103KPa,
Temperature be 260-280 DEG C under conditions of polycondensation 2-4 hour, obtain fluorine-containing optics copolyesters.
For solving above-mentioned technical problem, another technical solution used in the present invention is: provides a kind of optical thin film, comprises
The fluorine-containing copolyesters of above-mentioned optics.
For solving above-mentioned technical problem, another technical solution used in the present invention is: provide the system of a kind of optical thin film
Make method, the fluorine-containing copolyesters of optics that optics prepares by the manufacture method of fluorine-containing copolyesters is passed through nitrogen, again through filter
Extrude after filtration, then through deionized water cooling, pelletizing, dry, finally obtain fluorine-containing optics copolyester section, then at 150 DEG C
Be vacuum dried 4-12 hour, make water content be less than 10-50mg/Kg, then by dried fluorine-containing optics copolyester section through slab,
Biaxial tension, coating function coating, thermal finalization, rolling, obtain fluorine-containing copolyesters optical thin film.
The invention has the beneficial effects as follows: optics fluorine-containing copolyesters, optical thin film and the manufacture method thereof that the present invention provides,
The fluorine-containing copolyesters of optics and the light transmittance of optical thin film can be improved, reduce mist degree, good stability of the dimension, resistance to thermal oxide
And Good Heat-resistance, manufacture method is simple.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
All other embodiments that technical staff is obtained under not making creative work premise, broadly fall into the model of present invention protection
Enclose.
The preferred terephthalic acid (TPA) of binary acid of the present invention, M-phthalic acid, NDA and methyl esters compound thereof.Can also
Select other binary acid such as fumaric acid, decanedioic acid, phthalic acid.
Dihydroxylic alcohols of the present invention preferably is selected from ethylene glycol, propane diols, BDO, 1,4-CHDM.Also can be selected for
Other dihydroxylic alcohols such as neopentyl glycol, spiral shell glycol, isobide, bisphenol-A.
The present invention considers from PET hue, light transmittance and mist degree angle, and catalyst preferably is selected from antimony glycol, alkali formula acetic acid
Aluminium, germanium dioxide.Also can be selected for other antimony-based catalysts such as antimony acetate, antimony oxide, isopropanol antimony；Butyl titanate, two
Other Titanium series catalyst such as titanium oxide；Other aluminum-based catalysts such as alundum (Al2O3), alchlor, aluminium isopropoxide and other commonly use
Catalyst.
Fluorine-containing optical polyester film in order to make the present invention provide has specific function and strengthening performance, can be to this polyester
The merits such as middle interpolation fluorescent whitening agent, dyestuff, crystallization nucleating agent, ultraviolet preventing agent, plasticizer, inorganic nano-particle, antioxidant
Can auxiliary agent.
Embodiment 1: add terephthalic acid (TPA) 199.005 weight portion, M-phthalic acid 0.995 weight in polyester synthesis device
Amount portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.005), ethylene glycol 95 weight portion, bisphenol AF 5 weight portion (nDihydroxylic alcohols: nBinary acid=1:1.28) and
Account for the antimony glycol in total acid content 4/10000ths weight portion, vacuumize logical nitrogen deoxygenation after stirring, then at 250-
Esterification 2 hours under 350KPa, 220-270 DEG C of degree, reduction pressure is to normal pressure afterwards, is added by charge door and accounts for total acid content very much
0.5 trimethyl phosphate, then in 40 ~ 60min, pressure is down to-90KPa and carries out precondensation, pressure less than-
103Kpa, temperature be 260-280 DEG C under conditions of polycondensation 2-4 hour, obtain fluorine-containing optics copolyesters.Logical nitrogen is by this copolyesters warp
Stainless steel filter (10 μm contaminant filter efficiency are more than 99%) extrudes after filtering, and cools down (through 10 μm bore filter through deionized water
Device filters), pelletizing, it is dried, obtains fluorine-containing optics copolyester section.
By above-mentioned copolyester section at 150 DEG C, it is vacuum dried 4-12 hour under 133Pa, makes water content be less than 10-50mg/
Kg.Dried polyester slice is supplied extruder through feed hopper, through stainless steel filter (10 μ at melt temperature 280 DEG C
M contaminant filter efficiency is more than 99%) filter, cool down rapidly at 20 DEG C of rollers after T connector is extruded, obtain the casting films of 2650 μm.Should
Film is heated to 100 DEG C through infrared heater, longitudinal stretching 3.5 times, and (coating weight is 0.5g/m to double spread coating fluid2After),
Being dried through 130 DEG C of Hot-blast Heatings, cross directional stretch 4 times, afterwards thermal finalization 0.6 second at 250 DEG C, obtaining thickness is containing of 188 μm
Fluorine copolyesters optical thin film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 2: add terephthalic acid (TPA) 199.005 weight portion, M-phthalic acid 0.995 weight in polyester synthesis device
Amount portion, nTerephthalic acid (TPA): nM-phthalic acid=1:0.005, ethylene glycol 90 weight portion, bisphenol AF 10 weight portion (nDihydroxylic alcohols: nBinary acid=1:1.23)
And account for the antimony glycol in total acid content 4/10000ths weight portion, and vacuumize logical nitrogen deoxygenation after stirring, then at 350KPa,
Esterification 2 hours under 260 DEG C of degree, reduction pressure is to normal pressure afterwards, is added the phosphoric acid accounting for total acid content 0.5/10000th by charge door
Trimethyl, is then down to pressure-90KPa in 40 ~ 60min and carries out precondensation, and at pressure less than-103Kpa, temperature is 270
Polycondensation 3 hours under conditions of DEG C, obtain fluorine-containing optics copolyesters.Lead to nitrogen by this copolyesters through stainless steel filter (10 μm impurity
Filter efficiency be more than 99%) filter after extrude, through deionized water cooling (through 10 μm bore filter devices filter), pelletizing, be dried,
Fluorine-containing optics copolyester section.
By above-mentioned copolyester section at 150 DEG C, it is vacuum dried 6 hours under 133Pa, makes water content be less than 10mg/Kg.Will be dry
Polyester slice after dry supplies extruder through feed hopper, and at melt temperature 280 DEG C, through stainless steel filter filtration, (10 μm are miscellaneous
Matter filter efficiency is more than 99%), cool down rapidly at 20 DEG C of rollers after T connector is extruded, obtain the casting films of 2650 μm.By this film through red
Outside line heater is heated to 100 DEG C, longitudinal stretching 3.5 times, and (coating weight is 0.5g/m to double spread coating fluid2After), through 130 DEG C
Hot-blast Heating is dried, cross directional stretch 4 times, afterwards thermal finalization 0.6 second at 250 DEG C, obtains the fluorine-containing copolyesters that thickness is 188 μm
Optical thin film.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 (TPA) 198.474 weight portion, 2,6-naphthalene two
Formic acid 1.526 weight portion (nTerephthalic acid (TPA): nNDA=1:0.01), ethylene glycol 104 weight portion, bisphenol AF 5 weight portion (nDihydroxylic alcohols:
nBinary acid=1:1.40), the most similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.Gained contains
The test result of fluorine copolyesters optical thin film is as shown in table 1.
Embodiment 4: change copolyesters monomeric species and ratio, adds terephthalic acid (TPA) 199.005 weight portion, isophthalic diformazan
Acid 0.995 weight portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.005), ethylene glycol 90 weight portion, propane diols 5 weight portion, bisphenol AF 5 weight
Amount portion (nDihydroxylic alcohols: nBinary acid=1:1.27), the most similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optics
Film.The test result of gained fluorine-containing copolyesters optical thin film is as shown in table 1.
Embodiment 5: change copolyesters monomer ratio, adds terephthalic acid (TPA) 190.476 weight portion, M-phthalic acid
9.524 weight portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.05), ethylene glycol 95 weight portion, bisphenol AF 5 weight portion (nDihydroxylic alcohols: nBinary acid=
1:1.28), the most similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.Gained is fluorine-containing common
The test result of polyester optical thin film is as shown in table 1.
Embodiment 6: change copolyesters monomeric species and ratio, adds terephthalic acid (TPA) 199.005 weight portion, isophthalic diformazan
Acid 0.995 weight portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.005), ethylene glycol 90 weight portion, butanediol 1 weight portion, bisphenol AF 9 weight
Amount portion (nDihydroxylic alcohols: nBinary acid=1:1.24), the most similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optics
Film.
Embodiment 7: change copolyesters monomeric species and ratio, adds terephthalic acid (TPA) 199.005 weight portion, isophthalic diformazan
Acid 0.995 weight portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.005), ethylene glycol 80 weight portion, 1,4-CHDM 5 weight portion,
Bisphenol AF 5 weight portion (nDihydroxylic alcohols: nBinary acid=1:1.11), the most similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing
Copolyesters optical thin film.
Embodiment 8: change copolyesters catalyst type and ratio, adds the germanium dioxide accounting for total acid content 4/10000ths,
The most similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.Gained fluorine-containing copolyesters optics
The test result of film is as shown in table 1.
Embodiment 9: change copolyesters catalyst type and ratio, adds the alkali formula acetic acid accounting for total acid content 4/10000ths
Aluminium, the most similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.Gained fluorine-containing copolyesters light
The test result learning film is as shown in table 1.
Embodiment 10: change copolyesters catalyst type and ratio, adds the antimony glycol accounting for total acid content 2/10000ths
And account for the eston of total acid content 2/10000ths, the most 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, adds terephthalic acid (TPA) 199.005 weight portion, isophthalic diformazan
Acid 0.995 weight portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.005), ethylene glycol 100 weight portion (nDihydroxylic alcohols: nBinary acid=1:1.34), except this it
Outer the most 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, adds terephthalic acid (TPA) 200 weight portion, ethylene glycol 100 weight
Amount portion (nDihydroxylic alcohols: nBinary acid=1:1.34), the most similarly to Example 1 obtain copolyesters and copolyester film.Gained copolymerization
The test result of ester film is as shown in table 1.
Comparative example 3: change copolyesters monomeric species and ratio, adds terephthalic acid (TPA) 199.005 weight portion, isophthalic diformazan
Acid 0.995 weight portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.005), bisphenol AF 214.837 weight portion (nTotal acid:nTotal alcohol=1:1.3), except this
Outside similarly to Example 1 obtain copolyesters.
Comparative example 4: change copolyesters monomeric species and ratio, adds terephthalic acid (TPA) 199.005 weight portion, isophthalic diformazan
Acid 0.995 weight portion (nTerephthalic acid (TPA):nM-phthalic acid=1:0.005), ethylene glycol 90 weight portion, bisphenol-A 10 weight portion (nDihydroxylic alcohols: nBinary acid=
1:1.23), the most similarly to Example 1 obtain copolyesters and copolyester film.The test result of gained copolyesters is such as
Shown in table 1.
Owing to dihydroxylic alcohols containing a large amount of bisphenol AF, cause the phenomenon that rupture of membranes occurs in film drawing process, therefore fail
Obtain qualified biaxially oriented film.
Comparative example 5: change copolyesters catalyst type, adds the butyl titanate accounting for total acid content 4/10000ths, except this
Outside similarly to Example 1 obtain fluorine-containing copolyesters and fluorine-containing copolyesters optical thin film.Gained fluorine-containing copolyesters optical thin film
Test result as shown in table 1.
Producer, specification and processing method that in the embodiment of the present invention, raw material is selected are as follows.Do not affecting effect of the present invention
Under premise, it is possible to select the raw material of other manufacturer production.
Terephthalic acid (TPA) (CAS:100-21-0): Sinopec Yangzi Petrochemical Co, polymer grade.
M-phthalic acid (CAS:121-91-5): Sinopec Beijing Yanshan Mountain branch company, polymer grade.
NDA (CAS:1141-38-4): Nanjing remedies medicament research and development Co., Ltd, purity 99%.
Bisphenol AF (CAS:1478-61-1): Zigong Tianlong Chemical Co., Ltd., purity 99.5%.At dimethylbenzene before using
Solution uses atlapulgite reflow treatment 4 ~ 10 hours, cooling recrystallization after this solution via hole diameter 10 micron filter is filtered,
Again through filtering, being dried, obtain recrystallization bisphenol AF.
Ethylene glycol (CAS:107-21-1): Sinopec Beijing Yanshan Mountain branch company, purity 99.8%.
Propane diols (CAS:57-55-6): Dow Chemical company, purity > 99.8%.
BDO (CAS:110-63-4): BASF Aktiengesellschaft, purity 99%.
1,4-CHDM (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%.
Basic aluminium acetate (CAS:142-03-0): Shanghai Mai Kun Chemical Co., Ltd., purity > 99%.
Germanium dioxide (CAS:1310-53-8): Luoyang nonferrous materials Co., Ltd, Ge content >=99.999(%).
Trimethyl phosphate (CAS:512-56-1): new Asia, Zhangjiagang Chemical Co., Ltd., purity > 99%.
Method of testing and instrument used by the present invention are as follows:
Inherent viscosity: by GB/T 14190-2008, uses capillary viscosity method, with phenol/1,1,2,2-tetrachloroethanes
(mass ratio 60:40) is that solvent is tested.
Fusing point (Tm), vitrification point (Tg): by GB/T 14190-2008, polyester slice is vacuum dried at 60 DEG C 4
Hour, then in 200 F3 types DSC of Nai Chi company of Germany, rise to 280 DEG C from room temperature with 10K/min, insulation 3min, then with
10K/min is down to 80 DEG C, is finally warming up to 280 DEG C with 10K/min.
Heat decomposition temperature (Td): on the resistance to company's T G 209 F3 type thermogravimetric analyzer of speeding of Germany, sample is heated from room temperature
To 800 DEG C, record decomposition temperature (residual qualities is the time of 95%).
Light transmittance, mist degree: the fluorine-containing optical polyester film after biaxial tension is cut into the square of 50mm*50mm,
Test on WGT-2S type light transmittance tester.
Colourity is tested: take the dried polyester slice of 10g at X. Rite Inc. of the U.S. desk-top spectrophotometer of Color i7
On carry out 3 times measure, take measurement mean value be final result, record L, b value.
Thermal contraction performance: by JIS C2318 respectively at 150 DEG C, 30min and 200 DEG C, test under conditions of 10min.
Hot strength: carry out by GBT 1040.3-2006 " test of plastic tensile performance ".Specimen size 10mm*150mm
(2 type sample).
Tables 1 and 2 is experimental data:
Table 1
| Polymerization composition (Quality Mgmt Dept) | Catalyst, additive (accounting for the ratio of total acid content) | IV (dL/g) | Tg (DEG C) | Tm(DEG C) | Td(DEG C) | 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 explanation:
PTA: terephthalic acid (TPA)
IPA: M-phthalic acid
2,6-DNCA:2,6-naphthalenedicarboxylic acid
EG: ethylene glycol
BPAF: bisphenol AF
PDO: propane diols
BDO:1,4-butanediol
PCT:1,4-cyclohexanedimethanol
BPA: bisphenol-A
Sb: antimony glycol
Al: eston
TBT: butyl titanate
TMP: trimethyl phosphate
The present invention, by introducing bisphenol AF (CAS:1478-61-1) group in PET, is greatly increased the high temperature of copolyesters
Stability, ageing-resistant performance, dimensional stability and optical property, simultaneously because between F atom and PET main chain terminal base H atom
Intramolecular hydrogen bond can be formed so that the internal condensed state structure of this fluorine-containing copolyesters is the tightst, so that this copolyesters has pole
Good water vapor rejection performance.By adding the flexible chain binary such as ethylene glycol, propane diols, Isosorbide-5-Nitrae butanediol, 1,4-CHDM
Alcohol increases the pliability of copolyesters optical thin film so that it is meets the needs of various film drawing process, is suitable at existing BOPET
Mass produce on stretcher.The fluorine-containing optics copolyesters generated time that the present invention provides is short, and cost of material is moderate, can be significantly
Save enterprise's production cost.
Being different from prior art, the optics of the present invention fluorine-containing copolyesters, optical thin film and manufacture method thereof, by introducing
Bisphenol AF structure adds the heat resistance of copolyesters, oxidative resistance, dimensional stability and optical property；By add ethylene glycol,
Propane diols, BDO, 1,4-CHDM etc. improve the rigidity of copolyesters molecular structure, add fluorine-containing optics
The pliability of copolyesters so that it is be satisfied large scale bi-directional stretching and produce；Bisphenol AF used processes through recrystallization, enhances
The optical property of fluorine-containing optics copolyesters.
The fluorine-containing optics copolyesters generated time that the present invention provides is short, and cost of material is moderate, can significantly save enterprise and produce
Cost.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every utilize this
Equivalent structure or equivalence flow process that bright description is made convert, or are directly or indirectly used in other relevant technology necks
Territory, is the most in like manner included in the scope of patent protection of the present invention.
Claims (5)
1. the fluorine-containing copolyesters of optics, it is characterised in that include binary acid, dihydroxylic alcohols, bisphenol AF, catalyst and auxiliary agent group
Becoming, described bisphenol AF accounts for total acid molar content and is less than 50mol%, and it is little that described aliphatic diol accounts for total acid molar content
In 130mol%, the total amount of described bisphenol AF and dihydroxylic alcohols and the mol ratio of binary acid are 1:1.1-1.4, and described binary acid is right
In phthalic acid, M-phthalic acid and the combination of one or two kinds of of NDA, described dihydroxylic alcohols be ethylene glycol, third
One or more in glycol, BDO, Isosorbide-5-Nitrae-cyclohexane dimethanol；
Above-mentioned fluorine-containing copolyesters is made by following steps:
A. bisphenol AF is dissolved in dimethylbenzene, adds atlapulgite and be heated to reflux stirring, being then filtrated to get bisphenol AF two
Toluene solution, then suction filtration after solution cooling recrystallization is obtained the bisphenol AF purified；
B. in polyester synthesis device, add binary acid, dihydroxylic alcohols, purifying bisphenol AF and catalyst, vacuumize logical after stirring
Nitrogen deoxygenation, then at 250-350KPa, is esterified at 220-270 DEG C 1-2.5 hour, and reduction pressure is to normal pressure afterwards, adds
Auxiliary agent, carries out precondensation in 40-60min by pressure drop as little as-90KPa, continues at pressure less than-103KPa, and temperature is
Polycondensation 2-4 hour under conditions of 260-280 DEG C, extrudes after logical nitrogen pressure filtration, then through deionized water cooling, pelletizing, dry,
Finally obtain fluorine-containing optics copolyesters.
The fluorine-containing copolyesters of optics the most according to claim 1, it is characterised in that described catalyst is antimony glycol, alkali
Formula aluminium acetate and germanium dioxide, antimony acetate, antimony oxide, isopropanol antimony, butyl titanate, titanium dioxide, alundum (Al2O3),
One or more in alchlor, aluminium isopropoxide, it is 0.04% that described catalyst accounts for total acid mass fraction.
The fluorine-containing copolyesters of optics the most according to claim 1, it is characterised in that described auxiliary agent is trimethyl phosphate, phosphorus
One or more in acid, triphenyl phosphate, it is 0.05% that described auxiliary agent accounts for total acid mass fraction.
4. an optical thin film, it is characterised in that comprise the fluorine-containing copolyesters of the optics described in claim 1.
5. the manufacture method of an optical thin film according to claim 4, it is characterised in that described in claim 1
The fluorine-containing copolyesters of optics that optics prepares by the manufacture method of fluorine-containing copolyesters is vacuum dried 4-12 hour at 150 DEG C, makes to contain
The water yield is less than 10-50mg/Kg, then is coated with through slab, biaxial tension, coating function by dried fluorine-containing optics copolyester section
Layer, thermal finalization, rolling, obtain fluorine-containing copolyesters optical thin film.
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| 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 |
| 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 |
| EP3960807A4 (en) | 2019-04-25 | 2022-06-15 | Mitsubishi Gas Chemical Company, Inc. | 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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| 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 |
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