CN110712412A - Weather-resistant barrier polyester film and manufacturing method thereof - Google Patents
Weather-resistant barrier polyester film and manufacturing method thereof Download PDFInfo
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- CN110712412A CN110712412A CN201910975309.5A CN201910975309A CN110712412A CN 110712412 A CN110712412 A CN 110712412A CN 201910975309 A CN201910975309 A CN 201910975309A CN 110712412 A CN110712412 A CN 110712412A
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- 230000004888 barrier function Effects 0.000 title claims abstract description 90
- 229920006267 polyester film Polymers 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 229920000728 polyester Polymers 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000011265 semifinished product Substances 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- 238000009998 heat setting Methods 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- -1 graphite alkene Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Photovoltaic Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a weather-resistant barrier polyester film and a manufacturing method thereof. Weather-resistant layers are stacked on two sides of the barrier layer of the weather-resistant barrier polyester film, the weather-resistant layers and the barrier layer are made of aromatic polyester, and the content of terminal carboxyl of the aromatic polyester used in the weather-resistant layers is less than 10 mol/t; the barrier layer contains flaky graphene subjected to sulfuric acid oxidation treatment, the average thickness of the flaky graphene is 1.0-5.0 nm, the diameter of each flaky graphene is 1.0-10.0 mu m, and the mass of the flaky graphene accounts for 0.1-10% of the total mass of the barrier layer. The weather-resistant barrier polyester film has excellent weather resistance and barrier property.
Description
Technical Field
The invention relates to the technical field of films, in particular to a weather-resistant barrier polyester film for outdoor protection.
Background
The polyester film has the advantages of excellent optical performance, mechanical performance, insulating performance, chemical resistance and the like, and is widely applied to the outdoor protection industry. Such as back sheets for solar cells, architectural window films, and the like.
The polyester film for outdoor protection is used in an outdoor natural environment for a long time and is required to have good weather resistance. In order to protect the material inside the film from being damaged or deteriorated, it is also required to have a good barrier property to prevent moisture or other corrosive materials from penetrating through the film into the inside. Therefore, such polyester films for outdoor protection are required to have excellent weather resistance and barrier properties.
Although the common polyester film has the advantages of mechanical property, insulating property, chemical resistance and the like, the common polyester film has obvious defects of weather resistance and barrier property. In recent years, with the rapid development of industries such as photovoltaic cells, building window films and the like, the weather resistance technology of polyester films is improved to a certain extent, and the technology is mainly realized by adding chain extenders or end capping agents. However, the substances have great pollution to production equipment and environment, can also cause health hazards to personnel, and can be separated out from the polyester film in the using process to influence the later processing and use of the product.
At present, methods for improving the barrier property of polyester films mainly include chemical coating technology and multilayer film compounding technology. The fatal defect of the chemical coating technology is that the coating has serious insufficient weather resistance and can be rapidly degraded and shed under natural conditions; the multilayer film compounding technology has the disadvantages of complex process, high cost and low production efficiency.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to overcome the defects in the prior art, the weather-resistant barrier polyester film with excellent weather resistance and barrier property is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a weather-resistant barrier polyester film, wherein weather-resistant layers are stacked on two sides of a barrier layer of the weather-resistant barrier polyester film, and the weather-resistant barrier polyester film meets the following conditions:
(1) the barrier layer contains flaky graphene, and the flaky graphene is oxidized graphene which is subjected to sulfuric acid oxidation treatment;
(2) the average thickness of the flaky graphene of the barrier layer is 1.0-5.0 nm;
(3) the sheet diameter of the barrier layer sheet graphene is 1.0-10.0 μm.
The mass of the flaky graphene of the barrier layer accounts for 0.1-10% of the total mass of the barrier layer.
The raw materials of the weather-resistant layer and the barrier layer are aromatic polyester.
The aromatic polyester used in the weather-resistant layer has a terminal carboxyl group content of 10mol/t or less.
A method for manufacturing a weather-resistant barrier polyester film comprises the following steps:
(1) preparing the graphene oxide into a graphene master batch semi-finished product with the content of 10% -30% and the intrinsic viscosity of 0.55-0.65 dl/g by using a polyester synthesis method; preparing flake graphene oxide into ethylene glycol dispersion liquid, adding the ethylene glycol dispersion liquid into a synthesis reaction kettle when the esterification stage of polyester synthesis is completed, enabling the ethylene glycol dispersion liquid to participate in the polycondensation process of polyester synthesis, discharging and granulating when the intrinsic viscosity meets the requirement, and preparing a graphene master batch semi-finished product with the content of 10% -30%;
(2) putting the semi-finished product of the graphene master batch in the step (1) into a tackifying rotary drum, performing vacuum solid-phase tackifying until the intrinsic viscosity meets the requirement, cooling and discharging to obtain the final graphene master batch, performing solid-phase tackifying until the intrinsic viscosity reaches 0.68-0.78 dl/g, and obtaining the final graphene master batch;
(3) respectively blending the weather-resistant layer material and the barrier layer material, then extruding on multilayer co-extrusion film-making equipment, casting, longitudinally stretching, transversely stretching, heat setting, cooling and then rolling to obtain the weather-resistant barrier polyester film;
in the manufacturing method of the weather-resistant barrier polyester film, the melt extrusion temperature is 240-300 ℃, the heat setting temperature is 170-240 ℃, and the stretching ratio of longitudinal stretching and transverse stretching is 2.5-5.0 times.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the flaky graphene oxide is added in the middle layer (namely the barrier layer) of the polyester film, so that the barrier property of the polyester film is greatly improved, and the mechanical property of the polyester film is not influenced; the surface layer (namely the weather-resistant layer) of the polyester film uses aromatic polyester with low terminal carboxyl to reduce active groups in the polyester film, thereby improving the weather resistance of the polyester film.
Drawings
FIG. 1 is a schematic view of the structure of the weather resistant barrier polyester film of the present invention.
In the drawings, the reference numerals denote: 1. a weatherable layer; 2. a barrier layer; 3. flake graphene.
Detailed Description
According to the weather-resistant barrier polyester film, weather-resistant layers are stacked on two sides of the barrier layer. The weather-resistant layer is positioned on the surface layer, so that the whole product is not embrittled and cracked after being aged by the environment, and still keeps excellent mechanical properties. The barrier layer is located the sandwich layer, establishes the barrier of separation steam through adding the graphite alkene of slice, reduces the route that steam passes through, effectively reduces the steam transmissivity.
The barrier layer contains the flake graphene, and the flake graphene can have a larger barrier area in unit mass. The surface of the graphene sheet is treated by concentrated sulfuric acid and potassium permanganate, and the graphene sheet has more active groups, can participate in a polyester synthesis process when synthesizing graphene master batches, is better in compatibility and dispersion phase with polyester, and is not easy to aggregate, migrate and separate out when being prepared into a polyester film, so that the properties of the film, such as barrier property, surface adhesion property and the like, are influenced.
The average thickness of the barrier layer sheet graphene is 1.0-5.0 nm. When the average thickness of the flake graphene is less than 1.0nm, the physical properties of the graphene are easily damaged during processing, so that the barrier property is poor. If the average thickness is more than 5.0nm, the barrier area per unit mass is small, which also results in poor barrier properties, and if the barrier area is increased by increasing the addition ratio, the film forming property and mechanical properties of the barrier layer are affected due to a large addition amount. Considering the aspects of barrier property, dispersibility, film forming property, product cost and the like of the weather-resistant barrier polyester film, the average thickness of the flaky graphene is preferably 1.2-4.5 nm, and more preferably 1.5-3.0 nm.
The sheet diameter of the barrier layer sheet graphene is 1.0-10.0 μm, and more preferably 2.0-7.0 μm. When the diameter is less than 1.0 μm, the water vapor barrier property of the barrier layer is significantly deteriorated. Theoretically, the larger the diameter of the sheet, the better its barrier properties. However, when the diameter is larger than 10.0. mu.m, the probability and proportion of physical loss during processing increase as the diameter of the sheet increases, and problems such as clogging of piping of production equipment are caused.
Similarly, based on the aspects of the barrier property, the dispersibility, the film forming property, the product cost and the like of the comprehensive weather-resistant barrier polyester film, the mass of the flaky graphene of the barrier layer accounts for 0.1-10% of the total mass of the barrier layer. The addition amount of the barrier layer graphene flakes can be appropriately adjusted according to the diameter of the graphene flakes, but the loss of the graphene flakes in the processing process needs to be considered.
The raw materials used by the weather-resistant layer and the barrier layer are aromatic polyester. Among them, the aromatic diacid used for synthesizing the aromatic polyester may be terephthalic acid, terephthalic diacetic acid, terephthalic acid, etc., preferably terephthalic acid and terephthalic acid, more preferably terephthalic acid; the diol for synthesizing the aromatic polyester is mainly an aliphatic diol having 2 to 4 carbon atoms, and may be ethylene glycol, propylene glycol, butylene glycol, or the like, with ethylene glycol and butylene glycol being preferred, and ethylene glycol being more preferred. In addition to the above components, a small amount of a modifying substance such as isophthalic acid, phthalic acid, cyclohexane dimethanol, bisphenol B, or 2, 6-naphthalene dicarboxylic acid may be added during the synthesis of the aromatic polyester. The aromatic polyester suitable for the present invention is polyethylene terephthalate, taking into consideration various properties such as mechanical properties, crystallization properties and processability.
The aromatic polyester is prepared by the steps of feeding ① aromatic diacid and aliphatic diol in a molar ratio of 1: 1.3-1: 1.5 to perform an esterification reaction, feeding ② polycondensation catalyst which is a titanium compound, wherein the addition amount is less than or equal to 35ppm calculated according to titanium element, the intrinsic viscosity is 0.45 dl/g-0.65 dl/g, the polycondensation is finished when the terminal carboxyl is less than or equal to 5mol/t, granulating and discharging, and preparing ③ material, wherein the terminal carboxyl is an active group during the wet heat aging of a polyester film, and the weather resistance is better when the content is lower.
In the barrier layer of the present invention, polyester used for the weather-resistant layer may be used.
The manufacturing method of the weather-resistant barrier polyester film comprises the following steps:
(1) preparing graphene oxide into a graphene master batch semi-finished product with the content of 10% -30% and the intrinsic viscosity of 0.55-0.65 dl/g by using a polyester synthesis method;
(2) solid-phase tackifying the semi-finished product of the graphene master batch in the step (1) to an intrinsic viscosity of 0.68-0.78 dl/g, and preparing a final graphene master batch;
(3) respectively blending the weather-resistant layer material and the barrier layer material, and then extruding, sheet casting, longitudinal stretching, transverse stretching, heat setting, cooling and rolling on multilayer co-extrusion film-making equipment to obtain a weather-resistant barrier polyester film;
in the manufacturing method of the weather-resistant barrier polyester film, the melt extrusion temperature is 240-300 ℃, the heat setting temperature is 170-240 ℃, and the stretching ratio of longitudinal stretching to transverse stretching is 2.5-5.0 times.
In the invention, the requirements of the polyester film on performances such as weather resistance, barrier property, mechanical property, light utilization rate and the like are comprehensively considered, and on the premise of not damaging the effect of the invention, a proper amount of additives such as an anti-thermooxidative degradation agent, an ultraviolet light absorber, a stabilizer, a fluorescent whitening agent and the like can be added according to the needs.
The preparation method comprises the following steps:
step 1: preparation of graphene master batch
Firstly, preparing flake graphene oxide into ethylene glycol dispersion liquid, and adding the ethylene glycol dispersion liquid into a synthesis reaction kettle when the esterification stage of polyester synthesis is completed so as to participate in the polycondensation process of polyester synthesis. And discharging and granulating when the intrinsic viscosity reaches 0.55-0.65 dl/g to prepare a graphene master batch semi-finished product with the content of 10% -30%. And then placing the semi-finished product of the graphene master batch into a tackifying rotary drum, performing vacuum solid-phase tackifying until the intrinsic viscosity is 0.68-0.78 dl/g, cooling and discharging to obtain the final graphene master batch.
Step 2: preparation of weather-resistant barrier polyester film
On multilayer co-extrusion film-making equipment with an extruder (A) and an extruder (B), respectively mixing and drying a weather-resistant layer material and a barrier layer material, then supplying the mixture to the extruder (A) and the extruder (B), melting and extruding the mixture at the temperature of 240-300 ℃, and introducing the mixture into a T-shaped die head.
In the T-shaped die head, two groups of melts are laminated and converged according to an a/b/a three-layer structure with a weather-resistant layer on two sides of a barrier layer, and flow on a rotating cold drum in a sheet shape to form a cast sheet. And (3) preheating the casting sheet, longitudinally (in the length direction) stretching for 2.5-5.0 times, and cooling to obtain a longitudinally-stretched film. And (3) preheating the longitudinally-drawn film again, stretching the longitudinally-drawn film by 2.5-5.0 times along the transverse direction (width direction), performing heat treatment setting at 170-240 ℃, and performing traction rolling to obtain the weather-resistant barrier polyester film. The tensile strength, elongation at break, water vapor permeability, and strength retention and elongation retention after accelerated humid heat aging (abbreviated as PCT) were measured.
The present invention will be described in detail with reference to specific examples, but the embodiments of the present invention are not limited to these examples.
The embodiments of examples 1 to 5 are detailed in table one.
The embodiments of comparative examples 1 to 2 are detailed in table one.
In all examples and comparative examples, the thickness of the weather-resistant barrier polyester film was 250. mu.m.
A comparison of examples 1-5 and comparative examples D1-2 is shown
In the table, the number of the first and second,
1. and ①, intrinsic viscosity of the graphene master batch semi-finished product.
2. And ②, the intrinsic viscosity of the final graphene master batch after solid-phase tackifying.
3. Barrier layer graphene mass ratio/% (graphene master batch) content/% (barrier layer) master batch addition amount/%.
Table two: test results for examples and 1-5 and comparative example D1-2
In the table, the test methods for the respective properties are as follows:
1. tensile strength and elongation at break: tested according to GB/T13542.2-2009 standard.
2. Water vapor transmission rate: tested according to GB/T21529-.
3. Strength retention and elongation retention: the unaged plaques were tested for tensile strength and elongation at break according to GB/T13542.2-2009 and are reported as "initial value (tensile strength)" and "initial value (elongation at break)". After the same batch of sample pieces are put into an accelerated test aging box for accelerated aging (namely PCT aging under the conditions of 121 ℃, 2 kg pressure and 100% saturated vapor pressure) for 60 hours or 72 hours, the tensile strength and the elongation at break of the aged sample pieces are tested according to the GB/T13542.2-2009 standard and are recorded as an aging value (tensile strength) and an aging value (elongation at break). The calculation is as follows:
strength retention ratio (aged value (tensile strength)/initial value (tensile strength) × 100
The elongation retention ratio is an aged value (elongation at break)/initial value (elongation at break) × 100.
Claims (6)
1. The weather-resistant barrier polyester film is characterized in that weather-resistant layers are stacked on two sides of a barrier layer of the weather-resistant barrier polyester film, and the weather-resistant barrier polyester film meets the following conditions:
(1) the barrier layer contains flaky graphene, and the flaky graphene is oxidized graphene which is subjected to sulfuric acid oxidation treatment;
(2) the average thickness of the flaky graphene of the barrier layer is 1.0-5.0 nm;
(3) the sheet diameter of the sheet-shaped graphene of the barrier layer is 1.0-10.0 mu m.
2. The weather-resistant barrier polyester film as claimed in claim 1, wherein the graphene flakes form a barrier layer with a mass of 0.1-10% of the total mass of the barrier layer.
3. The weather-resistant barrier polyester film as claimed in claim 1, wherein the raw material for the weather-resistant layer and the barrier layer is aromatic polyester.
4. The weather-resistant barrier polyester film according to claim 4, wherein the aromatic polyester used in the weather-resistant layer has a terminal carboxyl group content of 10mol/t or less.
5. A method for manufacturing a weather-resistant barrier polyester film for a photovoltaic cell, comprising the steps of:
(1) preparing graphene oxide into a graphene master batch semi-finished product with the content of 10% -30% and the intrinsic viscosity of 0.55-0.65 dl/g by using a polyester synthesis method; preparing flake graphene oxide into ethylene glycol dispersion liquid, adding the ethylene glycol dispersion liquid into a synthesis reaction kettle when the esterification stage of polyester synthesis is completed, enabling the ethylene glycol dispersion liquid to participate in the polycondensation process of polyester synthesis, discharging and granulating when the intrinsic viscosity meets the requirement, and preparing a graphene master batch semi-finished product with the content of 10% -30%;
(2) putting the semi-finished product of the graphene master batch in the step (1) into a tackifying rotary drum, performing vacuum solid-phase tackifying until the intrinsic viscosity meets the requirement, cooling and discharging to obtain the final graphene master batch, performing solid-phase tackifying on the final graphene master batch until the intrinsic viscosity is 0.68-0.78 dl/g, and obtaining the final graphene master batch;
(3) and respectively blending the weather-resistant layer material and the barrier layer material, and then extruding, casting, longitudinally stretching, transversely stretching, heat setting, cooling and then rolling on multilayer co-extrusion film-making equipment to obtain the weather-resistant barrier polyester film.
6. The method for manufacturing a weather-resistant barrier polyester film according to claim 5, wherein the melt extrusion temperature is 240 ℃ to 300 ℃, the heat setting temperature is 170 ℃ to 240 ℃, and the stretching ratio of the longitudinal stretching and the transverse stretching is 2.5 to 5.0 times.
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