CN109677067B - High-stiffness polyester film - Google Patents
High-stiffness polyester film Download PDFInfo
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- CN109677067B CN109677067B CN201811613270.4A CN201811613270A CN109677067B CN 109677067 B CN109677067 B CN 109677067B CN 201811613270 A CN201811613270 A CN 201811613270A CN 109677067 B CN109677067 B CN 109677067B
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- polyester film
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 93
- 229920000728 polyester Polymers 0.000 claims abstract description 151
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000010410 layer Substances 0.000 claims description 141
- 238000005266 casting Methods 0.000 claims description 86
- 238000001125 extrusion Methods 0.000 claims description 45
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002356 single layer Substances 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 130
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 107
- 239000002245 particle Substances 0.000 description 68
- 229910000019 calcium carbonate Inorganic materials 0.000 description 65
- 238000001816 cooling Methods 0.000 description 63
- 238000007493 shaping process Methods 0.000 description 47
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 239000002253 acid Substances 0.000 description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 31
- 239000004594 Masterbatch (MB) Substances 0.000 description 23
- 238000002844 melting Methods 0.000 description 22
- 230000008018 melting Effects 0.000 description 22
- 230000032050 esterification Effects 0.000 description 21
- 238000005886 esterification reaction Methods 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 238000006068 polycondensation reaction Methods 0.000 description 17
- 238000004537 pulping Methods 0.000 description 17
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 16
- 235000013339 cereals Nutrition 0.000 description 16
- 238000005520 cutting process Methods 0.000 description 16
- 238000002156 mixing Methods 0.000 description 16
- 238000005086 pumping Methods 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- 238000010345 tape casting Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000010954 inorganic particle Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- -1 biphenyl sulfone Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229920006302 stretch film Polymers 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B32B27/06—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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention discloses a high-stiffness polyester film, which comprises at least one of an A layer or a B layer, wherein the A layer or/and the B layer comprise a polyester modified by 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone. The polyester film has high stiffness, greatly improves the deformation resistance of the polyester film, effectively simplifies the production process of products, greatly reduces the production cost and improves the product quality. The product can be widely used in the technical fields of liquid crystal display industry, photovoltaic industry, release protection industry and the like.
Description
Technical Field
The invention discloses a laminated product made of synthetic resin, belonging to the technical field of films.
Background
With the progress of technology, the production technology of polyester film is becoming more and more perfect, and the application range is gradually expanding. Polyester films are widely used in the fields of packaging, industry, electronics, electrical, magnetism, light sensing, etc. due to their high mechanical strength, good cold and heat resistance, stable shrinkage, and excellent electrical insulation properties.
With the demand of people for living of materials becoming higher and higher, the screen of liquid crystal electronic display equipment such as mobile phones, televisions and flat panels is continuously pursued to have large size and large visual field feeling, the liquid crystal electronic display equipment is getting larger and the photovoltaic industry size is also getting larger and larger. Because the stiffness of the pure polyester film is insufficient, the requirement of a large-size mainstream market is difficult to meet, so that the high-stiffness polyester film is required to meet the requirement of the large-size mainstream market on the high stiffness of the polyester film. The prior art solutions to the problem at present have: 1. off-line multi-layer lamination is carried out, so that the stiffness of the polyester film is improved; 2. some nano-scale inorganic particles are added, the inorganic particles serve as crystal nuclei in the processes of polyester melt extrusion and stretch film forming, and the stiffness of the polyester film is improved by increasing the crystallinity of the polyester film; 3. by adding some crystalline polyester, the crystallization is accelerated in the processes of polyester melt extrusion and stretch film forming, the crystallinity of the polyester film is increased, and the stiffness of the polyester film is improved.
Although the technicians have conducted a great deal of research on the improvement of stiffness of polyester films, the existing technology for improving stiffness of polyester films still has many problems: 1. when the multilayer compounding is carried out off line, the layers are bonded through glue, so that the working procedures are complicated, the cost is increased, the service life of the polyester film is limited by the aging life of the glue, and the cost performance of the polyester film is greatly reduced; 2. when the nano-scale inorganic particles are used as nucleating agents, the nano-scale inorganic particles are easy to agglomerate to form large-size spherical crystals, and crystal points are formed in the polyester film after the melt extrusion and stretching film forming, so that the quality of the polyester film product is greatly influenced; 3. the crystalline polyester can accelerate crystallization in the processes of polyester melt extrusion and stretching film forming, but the polyester film becomes hard and brittle, the mechanical property of the polyester film in the production process is seriously influenced, the defects of scratch, scratch and the like of the polyester film product are caused, and the product yield is greatly influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-stiffness polyester film. The preparation method can effectively solve the problems of high stiffness requirement of the polyester film in the fields of liquid crystal display industry, photovoltaic industry, release protection industry and the like and the problems of complicated working procedures, high production cost, poor product appearance, low yield and the like of the high stiffness polyester film produced by the prior art, and the prepared film is particularly suitable for the fields of liquid crystal display industry, photovoltaic industry, release protection industry and the like.
The invention aims to solve the problems by the following technical scheme:
a high-stiffness polyester film comprising at least one of an A layer and a B layer, wherein the A layer and/or the B layer comprises a polyester modified with 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid, and 4, 4' -dicarboxybiphenylsulfone.
The high-stiffness polyester film is characterized in that the modified polyester uses terephthalic acid, 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone, wherein the molar ratio of the terephthalic acid to the mixture of the 2, 5-furandicarboxylic acid, the 4,4 '-biphenyldicarboxylic acid and the 4, 4' -dicarboxybiphenylsulfone is 1: 1-5: 1.
The high-stiffness polyester film is characterized in that in a mixture composed of the 2, 5-furandicarboxylic acid, the 4,4 '-biphenyldicarboxylic acid and the 4, 4' -dicarboxybiphenylsulfone, the molar ratio of the 2, 5-furandicarboxylic acid to the 4,4 '-biphenyldicarboxylic acid to the 4, 4' -dicarboxybiphenylsulfone is 1-7: 1-5: 1-6.
The thickness of the high-stiffness polyester film is 9-350 mu m.
The high-stiffness polyester film is a biaxially oriented polyester film formed by single-layer A, double-layer A/B and three-layer A/B/A coextrusion.
According to the high-stiffness polyester film, the high-stiffness polyester film adopts a single-layer structure A, and the thickness of the single-layer structure A is 9-350 μm.
According to the high-stiffness polyester film, the high-stiffness polyester film is of a double-layer structure A/B, and the thickness ratio of the layer A to the layer B is 1: 10-9: 20.
According to the high-stiffness polyester film, the high-stiffness polyester film is of a three-layer structure A/B/A, and the thickness ratio of the layer A to the layer B is 1: 20-7: 25.
The high-stiffness polyester film is prepared by co-extruding through a die head, and performing sheet casting, longitudinal drawing, transverse drawing, sizing, drawing and rolling.
The invention has the beneficial effects that:
1. according to the invention, the layer A or/and the layer B comprise/comprises the polyester modified by 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone, and then the polyester is directly melt extruded and stretched to form a film, and the modified polyester and the polyester are fused into a whole to prepare the high-stiffness polyester film.
2. The invention starts from microstructure, modifies polyester and improves the stiffness of the polyester film. Completely avoids the negative effect brought by the prior art for improving the stiffness of the polyester film.
3. The invention greatly improves the stiffness of the polyester film and the stability of deep processing of the polyester film.
4. When the polyester is modified, the adopted 2, 5-furandicarboxylic acid is derived from plant residues such as straws and rice hulls, belongs to a new energy substance, and meets the sustainable development requirement.
Detailed Description
The high-stiffness polyester film comprises at least one of an A layer or a B layer, wherein the A layer or/and the B layer comprise a polyester modified by 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone. The acid used for modifying the polyester is a mixture consisting of terephthalic acid, 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone. Wherein, the 2, 5-furandicarboxylic acid is an oxygen-containing five-membered ring structure, and the bonding energy, hydrogen bond, van der waals force and the like are extremely large, so that the intramolecular energy and the anti-deformation capability are greatly increased; 4,4 '-Biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone contain a polyphenolic structure such as a biphenyl ring and biphenyl sulfone. The benzene ring is a strong rigid group, and the molecular rigidity is improved. In addition, the oxygen-sulfur double bond in the 4, 4' -dicarboxybiphenyl sulfone improves the molecular polarity, makes the molecular arrangement more compact, and greatly increases the molecular anti-deformation capability. After the 2, 5-furandicarboxylic acid, 4 '-biphenyl dicarboxylic acid and 4, 4' -dicarboxybiphenyl sulfone are added to participate in the modified polyester, the stiffness of the polyester film is greatly enhanced. The preparation method of the modified polyester comprises the following steps:
1. adding the needed dibasic acid, dihydric alcohol, catalyst and stabilizer into a polyester reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3 to 5 hours at the temperature of 225 to 265 ℃ and under the condition of 250 KPa.
2. Judging the esterification end point according to the water yield, starting vacuumizing after the esterification is completed, carrying out polycondensation reaction for 2-4 h at the temperature of 265-280 ℃ and under the pressure of 20-60 Pa, and carrying out yarn making, cooling, grain cutting and drying to obtain the modified polyester.
The high-stiffness polyester film adopts a single-layer A, double-layer A/B and three-layer A/B/A co-extruded two-way stretching polyester film, and the thickness of the film is 9-350 mu m.
The single-layer structure A is adopted, and the thickness of the single-layer structure A is 9-350 mu m.
A double-layer structure A/B is adopted, and the thickness ratio of the layer A to the layer B is 1: 10-9: 20.
A three-layer structure A/B/A is adopted, and the thickness ratio of the layer A to the layer B is 1: 20-7: 25.
Generally, in order to increase the smoothness of the polyester film and improve the winding and slitting performance of the polyester film, micron-sized smooth particles, such as silica, calcium carbonate, kaolin, etc., are often added into the surface layer at a certain concentration.
Then, the composite material is prepared by co-extrusion through a die head, sheet casting, longitudinal drawing, transverse drawing, shaping, traction and rolling. The preparation method comprises the following steps:
1. adding the prepared modified polyester into the layer A or/and the layer B of the polyester film, adding polyester master batch containing micron-sized smooth particles into the layer A, and performing melt extrusion.
2. The melt is co-extruded through a die head and cast on a casting sheet roller to form a single-layer or multi-layer co-extruded casting sheet, and the temperature of the casting sheet roller is 18-30 ℃.
3. And longitudinally stretching the cast sheet, wherein the longitudinal stretching temperature is 65-85 ℃, and the longitudinal stretching ratio is 2.7-4.0.
4. And transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.4-4.7.
5. And (3) shaping and cooling the stretched film, wherein the shaping temperature is 225-240 ℃, and the cooling temperature is 45-60 ℃.
6. And drawing and winding the cooled film.
The present invention is further illustrated by the following examples, but the embodiments of the present invention are not limited to these examples.
Example 1
Preparation of modified polyester:
according to the molar ratio of 1:1.2 of dibasic acid to glycol, wherein the molar ratio of 1:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 1:1:1, and the molar ratio of 1:1 of 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone in the glycol is 3:1 of the glycol; the method comprises the following steps of adding ethylene glycol antimony in an amount of 50ppm, tetrabutyl titanate in an amount of 100ppm, trimethyl phosphate in an amount of 15ppm, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3 hours at the temperature of 225-265 ℃ and under the condition of 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 4 hours at the temperature of 265-280 ℃ and under the condition of 35Pa, and the modified polyester is prepared after the processes of yarn making, cooling, grain cutting and drying.
Adding the modified polyester and calcium carbonate smooth polyester master batch with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 300ppm, adding the calcium carbonate particles into a corresponding extrusion system, melting, extruding through a die head, casting onto a casting sheet roller to form a single-layer A extruded casting sheet, wherein the temperature of the casting sheet roller is 25 ℃; longitudinally stretching the cast sheet at the longitudinal stretching temperature of 65-85 ℃ and the longitudinal stretching ratio of 4.0; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 4.5; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 230 ℃, the cooling temperature is 50 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 9 microns.
Example 2
Preparation of modified polyester:
according to the molar ratio of 1:1.3 of dibasic acid to glycol, wherein the molar ratio of 2:1, 2, 5-furandicarboxylic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 2:1:3 of 2:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone, and the molar ratio of 4:1 of ethylene glycol to propylene glycol in the glycol; adding 100ppm of ethylene glycol antimony, 100ppm of tetrabutyl titanate and 20ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3.5h at the temperature of 265-280 ℃ and under the condition of 30Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 300ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form an AB layer co-extruded casting sheet, wherein the temperature of the casting sheet roller is 22 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.8; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 4.3; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 230 ℃, the cooling temperature is 50 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 50 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 10.
Example 3
Preparation of modified polyester:
according to the molar ratio of 1:1.3 of dibasic acid to glycol, wherein the molar ratio of 2:1, 2, 5-furandicarboxylic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 1:2:3 of 2:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone, and the molar ratio of 3:2 of ethylene glycol to propylene glycol in the glycol; adding ethylene glycol antimony in an amount of 110ppm, tetrabutyl titanate in an amount of 100ppm, trimethyl phosphate in an amount of 22ppm, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3.5h at the temperature of 265-280 ℃ and under the condition of 30Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 300ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form an AB layer co-extruded casting sheet, wherein the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.7; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 4.0; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 45 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 100 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 5.
Example 4
Preparation of modified polyester:
according to the molar ratio of 1:1.35 of dibasic acid to glycol, wherein the molar ratio of 3:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 2:3:2, and the molar ratio of ethylene glycol to propylene glycol in the glycol is 3: 2; the addition amount of ethylene glycol antimony is 110ppm, the addition amount of tetrabutyl titanate is 110ppm, the addition amount of trimethyl phosphate is 22ppm, after uniform mixing, the mixture is added into a polyester synthesis reaction kettle, pulping is carried out for 15 minutes, nitrogen protection is introduced, and esterification is carried out for 3.5 hours under the conditions of 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3.5h at the temperature of 265-280 ℃ and under the condition of 30Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 350ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form an AB layer co-extruded casting sheet, wherein the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.5; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.8; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 45 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 150 mu m, wherein the thickness ratio of the layer A to the layer B is 3: 10.
Example 5
Preparation of modified polyester:
according to the molar ratio of 1:1.4 of dibasic acid to glycol, wherein the molar ratio of 3.5:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 3:1:4, and the molar ratio of ethylene glycol to propylene glycol in the glycol is 3: 2; the addition amount of ethylene glycol antimony is 110ppm, the addition amount of tetrabutyl titanate is 110ppm, the addition amount of trimethyl phosphate is 22ppm, after uniform mixing, the mixture is added into a polyester synthesis reaction kettle, pulping is carried out for 15 minutes, nitrogen protection is introduced, and esterification is carried out for 3.2 hours under the conditions of 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3.5h at the temperature of 265-280 ℃ and under the condition of 30Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the conventional polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 350ppm, and the mixture of the modified polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an AB layer co-extruded casting sheet, wherein the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.5; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.8; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 45 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 150 mu m, wherein the thickness ratio of the layer A to the layer B is 3: 10.
Example 6
Preparation of modified polyester:
according to the molar ratio of 1:1.42 of dibasic acid to glycol, wherein the molar ratio of 3.5:1 of terephthalic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid to 4.5:1 of 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone is 4:3:2, and the molar ratio of 4:1 of ethylene glycol to propylene glycol in the glycol; the addition amount of ethylene glycol antimony is 110ppm, the addition amount of tetrabutyl titanate is 150ppm, the addition amount of trimethyl phosphate is 20ppm, after uniform mixing, the mixture is added into a polyester synthesis reaction kettle, pulping is carried out for 15 minutes, nitrogen protection is introduced, and esterification is carried out for 2.5 hours under the conditions of 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3.2h at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 400ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form an AB layer co-extruded casting sheet, wherein the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.1; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.6; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 50 ℃, and the cooled film is drawn and rolled to obtain a high-stiffness polyester film with the thickness of 188 mu m, wherein the thickness ratio of the layer A to the layer B is 7: 20.
Example 7
Preparation of modified polyester:
according to the molar ratio of 1:1.42 of dibasic acid to glycol, wherein the molar ratio of terephthalic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 4:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone is 5:3:1, and the molar ratio of ethylene glycol to propylene glycol in the glycol is 4: 1; adding 150ppm of ethylene glycol antimony, 150ppm of tetrabutyl titanate and 18ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 2.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3 hours at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared after the processes of yarn making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form an AB layer co-extruded casting sheet, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 450ppm, and adding the mixture of the modified polyester of the layer B, and the temperature of the casting sheet roller is 24 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.0; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.5; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 250 mu m, wherein the thickness ratio of the layer A to the layer B is 9: 20.
Example 8
Preparation of modified polyester:
according to the molar ratio of 1:1.2 of dibasic acid to glycol, wherein the molar ratio of 3:1, 2, 5-furandicarboxylic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 4:3:2 of 4:1 of 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone, and the molar ratio of 4:1 of ethylene glycol to propylene glycol in the glycol; adding 150ppm of ethylene glycol antimony, 200ppm of tetrabutyl titanate and 30ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3 hours at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared after the processes of yarn making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 300ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an ABA layer co-extrusion casting sheet, wherein the temperature of the casting sheet roller is 24 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.8; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 4.3; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 230 ℃, the cooling temperature is 50 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 50 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 20.
Example 9
Preparation of modified polyester:
according to the molar ratio of 1:1.25 of dibasic acid to glycol, wherein the molar ratio of terephthalic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 3.5:1, the molar ratio of 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone is 3:2:1, and the molar ratio of ethylene glycol to propylene glycol in the glycol is 1: 1; adding 150ppm of ethylene glycol antimony, 200ppm of tetrabutyl titanate and 12ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 3 hours at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared after the processes of yarn making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 350ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an ABA layer co-extrusion casting sheet, wherein the temperature of the casting sheet roller is 22 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.7; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 4.0; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 45 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 100 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 10.
Example 10
Preparation of modified polyester:
according to the molar ratio of 1:1.25 of dibasic acid to glycol, wherein the molar ratio of 3.5:1 of terephthalic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid to the molar ratio of 3.5:1 of 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone is 5:2:3, and the molar ratio of 2:1 of ethylene glycol to propylene glycol in the glycol; adding 150ppm of ethylene glycol antimony, 250ppm of tetrabutyl titanate and 12ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 2.8h at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 350ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an ABA layer co-extrusion casting sheet, wherein the temperature of the casting sheet roller is 22 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.5; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.8; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 125 mu m, wherein the thickness ratio of the layer A to the layer B is 3: 20.
Example 11
Preparation of modified polyester:
according to the molar ratio of 1:1.3 of dibasic acid to glycol, wherein the molar ratio of 3:1, 2, 5-furandicarboxylic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 4:3:1, and the molar ratio of ethylene glycol to propylene glycol in the glycol is 2: 1; adding 200ppm of ethylene glycol antimony, 250ppm of tetrabutyl titanate and 15ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 2.5h at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the conventional polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 400ppm, and the mixture of the modified polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an ABA layer co-extrusion casting sheet, wherein the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.1; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.6; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain a high-stiffness polyester film with the thickness of 188 mu m, wherein the thickness ratio of the layer A to the layer B is 9: 50.
Example 12
Preparation of modified polyester:
according to the molar ratio of 1:1.4 of dibasic acid to glycol, wherein the molar ratio of 4:1, 2, 5-furandicarboxylic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 6:5:3 of 4:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone, and the molar ratio of 2.5:1 of ethylene glycol to propylene glycol in the glycol; adding 200ppm of ethylene glycol antimony, 250ppm of tetrabutyl titanate and 15ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 2.5h at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 450ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an ABA layer co-extrusion casting sheet, wherein the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.0; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.5; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 250 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 5.
Example 13
Preparation of modified polyester:
according to the molar ratio of 1:1.4 of dibasic acid to glycol, wherein the molar ratio of 4:1, 2, 5-furandicarboxylic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 6:5:3 of 4:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone, and the molar ratio of 2.5:1 of ethylene glycol to propylene glycol in the glycol; adding 200ppm of ethylene glycol antimony, 250ppm of tetrabutyl titanate and 15ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 3 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 2.5h at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form ABA layer co-extruded casting sheets, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 450ppm, and the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.0; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.5; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 250 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 5.
Example 14
Preparation of modified polyester:
according to the molar ratio of 1:1.42 of dibasic acid to glycol, wherein the molar ratio of terephthalic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 4:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone is 5:5:3, and the molar ratio of ethylene glycol to propylene glycol in the glycol is 3: 1; adding 250ppm of ethylene glycol antimony, 250ppm of tetrabutyl titanate and 15ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 2.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 2 hours at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared through the steps of spinning, cooling, granulating and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 450ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an ABA layer co-extrusion casting sheet, wherein the temperature of the casting sheet roller is 22 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.0; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.5; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the 275 mu m high-stiffness polyester film, wherein the thickness ratio of the layer A to the layer B is 1: 5.
Example 15
Preparation of modified polyester:
according to the molar ratio of 1:1.43 of dibasic acid to glycol, wherein the molar ratio of terephthalic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 4.5:1, the molar ratio of 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone is 6:5:5, and the molar ratio of ethylene glycol to propylene glycol in the glycol is 3: 1; adding 200ppm of ethylene glycol antimony, 200ppm of tetrabutyl titanate and 10ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 2.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 2.5h at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form ABA layer co-extruded casting sheets, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 500ppm, and adding the mixture of the conventional polyester of the layer B into the corresponding extrusion system, and the temperature of the casting sheet roller is 28 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.0; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.45; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 300 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 4.
Example 16
Preparation of modified polyester:
according to the molar ratio of 1:1.43 between dibasic acid and dihydric alcohol, wherein the molar ratio of terephthalic acid to 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone in the dibasic acid is 5:1, 2, 5-furandicarboxylic acid to 4,4 '-biphenyldicarboxylic acid to 4, 4' -dicarboxybiphenylsulfone is 7:5:6, and the molar ratio of ethylene glycol to propylene glycol in the dihydric alcohol is 4: 1; adding 200ppm of ethylene glycol antimony, 200ppm of tetrabutyl titanate and 10ppm of trimethyl phosphate, uniformly mixing, adding into a polyester synthesis reaction kettle, pulping for 15 minutes, introducing nitrogen for protection, and esterifying for 2.5 hours at 225-265 ℃ and 250 KPa; after the esterification is finished, the vacuum pumping is started, the polycondensation reaction is carried out for 2.5h at the temperature of 265-280 ℃ and under the condition of 25Pa, and the modified polyester is prepared by filament making, cooling, grain cutting and drying.
Adding the modified polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 600ppm, and the mixture of the conventional polyester of the layer B into a corresponding extrusion system, carrying out melting and co-extrusion through a die head, and carrying out tape casting on a casting sheet roller to form an ABA layer co-extrusion casting sheet, wherein the temperature of the casting sheet roller is 25 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 2.9; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.41; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 350 mu m, wherein the thickness ratio of the layer A to the layer B is 7: 25.
Comparative example 1
Adding a mixture of conventional and smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m and the conventional polyester with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form an ABA layer co-extruded casting sheet, wherein the temperature of the casting sheet roller is 24 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.8; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 4.3; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 230 ℃, the cooling temperature is 50 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 50 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 20.
Comparative example 2
Adding the conventional polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form ABA layer co-extruded casting sheets, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 350ppm, and the temperature of the casting sheet roller is 22 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.7; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 4.0; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 45 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 100 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 10.
Comparative example 3
Adding the conventional polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form ABA layer co-extruded casting sheets, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 350ppm, and the temperature of the casting sheet roller is 22 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.5; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.8; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 125 mu m, wherein the thickness ratio of the layer A to the layer B is 3: 20.
Comparative example 4
Adding the conventional polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form ABA layer co-extruded casting sheets, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 400ppm, and the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.1; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.6; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 235 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain a high-stiffness polyester film with the thickness of 188 mu m, wherein the thickness ratio of the layer A to the layer B is 9: 50.
Comparative example 5
Adding the conventional polyester of the layer A and the calcium carbonate smooth polyester master batch containing calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form ABA layer co-extruded casting sheets, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 450ppm, and the temperature of the casting sheet roller is 23 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 3.0; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.5; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 250 mu m, wherein the thickness ratio of the layer A to the layer B is 1: 5.
Comparative example 6
Adding the conventional polyester of the layer A and the calcium carbonate smooth polyester master batch containing the calcium carbonate with the average particle size of 2.3 mu m into a corresponding extrusion system, melting, co-extruding through a die head, casting onto a casting sheet roller to form an ABA layer co-extruded casting sheet, wherein the content of calcium carbonate particles with the average particle size of 2.3 mu m in the total polyester is 600ppm, and the temperature of the casting sheet roller is 25 ℃; longitudinally stretching the cast sheet at a longitudinal stretching temperature of 65-85 ℃ and a longitudinal stretching ratio of 2.9; transversely stretching the longitudinally-stretched sheet at the transverse stretching temperature of 110-125 ℃ and the transverse stretching ratio of 3.41; and (3) shaping and cooling the stretched film, wherein the shaping temperature is 240 ℃, the cooling temperature is 55 ℃, and the cooled film is drawn and rolled to obtain the high-stiffness polyester film with the thickness of 350 mu m, wherein the thickness ratio of the layer A to the layer B is 7: 25.
Effects of the invention
As can be seen from the comparison of the examples and the corresponding comparative examples, the stiffness of the polyester film of the invention is far better than that of the common polyester film under the same thickness and film-making process conditions.
The thickness test method comprises the following steps: ASTM D374
The stiffness testing method comprises the following steps: under the condition of ensuring the flatness of the polyester film, a 15mm multiplied by 160mm long strip-shaped polyester film sample sheet is horizontally placed along the MD direction, the clamping length is 20mm, and the horizontal difference between the free end and the clamping end is used as the evaluation standard of the stiffness of the polyester film.
Claims (7)
1. A high-stiffness polyester film comprising at least one of a layer a and a layer B, wherein the layer a and/or the layer B comprises a 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid, 4' -dicarboxybiphenylsulfone-modified polyester;
the modified polyester is prepared from terephthalic acid, 2, 5-furandicarboxylic acid, 4 '-biphenyldicarboxylic acid and 4, 4' -dicarboxybiphenylsulfone, wherein the molar ratio of the terephthalic acid to the mixture of the 2, 5-furandicarboxylic acid, the 4,4 '-biphenyldicarboxylic acid and the 4, 4' -dicarboxybiphenylsulfone is 1: 1-5: 1;
in the mixture composed of the 2, 5-furandicarboxylic acid, the 4,4 '-biphenyldicarboxylic acid and the 4, 4' -dicarboxybiphenylsulfone, the molar ratio of the 2, 5-furandicarboxylic acid to the 4,4 '-biphenyldicarboxylic acid to the 4, 4' -dicarboxybiphenylsulfone is 1-7: 1-5: 1-6.
2. The high stiffness polyester film according to claim 1, wherein the thickness of the high stiffness polyester film is 9 to 350 μm.
3. The high stiffness polyester film according to claim 1, wherein the high stiffness polyester film is a biaxially oriented polyester film coextruded with a single layer a, a double layer a/B, and a triple layer a/B/a.
4. The high stiffness polyester film according to claim 3, wherein the high stiffness polyester film has a single layer structure A having a thickness of 9 to 350 μm.
5. The high-stiffness polyester film according to claim 3, wherein the high-stiffness polyester film is of a double-layer structure A/B, and the thickness ratio of the layer A to the layer B is 1: 10-9: 20.
6. The high-stiffness polyester film according to claim 3, wherein the high-stiffness polyester film is of a three-layer structure A/B/A, and the thickness ratio of the layer A to the layer B is 1: 20-7: 25.
7. The high stiffness polyester film according to claim 3, 4 or 5, wherein the high stiffness polyester film is prepared by die co-extrusion, sheet casting, longitudinal drawing, transverse drawing, sizing, drawing and winding.
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