CN112646157A - High-hardness polyester film and preparation method and application thereof - Google Patents
High-hardness polyester film and preparation method and application thereof Download PDFInfo
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- CN112646157A CN112646157A CN202011521469.1A CN202011521469A CN112646157A CN 112646157 A CN112646157 A CN 112646157A CN 202011521469 A CN202011521469 A CN 202011521469A CN 112646157 A CN112646157 A CN 112646157A
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- 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
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- 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
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- 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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a high-hardness polyester film and a preparation method and application thereof. The preparation method comprises the following steps: mixing aromatic dicarboxylic acid or derivatives thereof with aliphatic diol, and carrying out esterification reaction to obtain aromatic oligomer; carrying out polycondensation reaction on the aromatic oligomer, sequentially adding an antimony precursor, a silicon precursor and a complex for reaction during the polycondensation reaction, and obtaining a polyester mixture when the viscosity reaches 0.5dl/g-1.0 dl/g; and (3) carrying out melt extrusion, sheet casting, longitudinal drawing, transverse drawing, traction and rolling on the polyester mixture to obtain the polyester film with higher hardness.
Description
Technical Field
The invention relates to a high-hardness polyester film, in particular to a metal particle-based functionalized polyester film and a preparation method thereof, belonging to the field of high polymer materials.
Background
Polyester films, especially polyethylene terephthalate, have excellent performance in mechanical, electrical insulation, chemical and other aspects, excellent optical performance and flexibility, and also have the characteristics of heat resistance, chemical reagent resistance, good mechanical strength, good transparency and the like, and are widely applied in various fields, such as industries of electrical insulation, displays, photovoltaic back panel materials, in-film injection molding, hard protection and the like.
Currently, polyester-based materials are widely used in a variety of highly molecularly oriented elongated articles, such as films and the like. However, because the surface tension and hardness of the polyester film are low, the polyester film is easy to scratch and rub during later processing, which affects the later use of the polyester film. However, this causes a decrease in optical performance, which greatly limits the application of the optical film.
For example, CN201611207114.9 adds rigid groups such as naphthalene ring to the polyester raw material to increase the hardness of the polyester, but this greatly increases the cost of the polyester, and is also not favorable for its wide application.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a polyester film having high hardness and low cost.
Another object of the present invention is to provide a method for preparing a polyester film having high hardness and low cost.
In order to achieve the above technical object, the present invention firstly provides a method for preparing a high hardness polyester film, the method comprising:
mixing aromatic dicarboxylic acid or derivatives thereof with aliphatic diol, and carrying out esterification reaction at 140-230 ℃ to obtain aromatic oligomer; wherein the molar ratio of the aromatic dicarboxylic acid or the derivative thereof to the aliphatic diol is 0.5-2.5: 1.5-3 (preferably 1: 2);
carrying out polycondensation reaction on the obtained aromatic polyester oligomer at 230-250 ℃, and adding an antimony precursor with the content of 100-400ppm, a silicon precursor with the content of 10-3000 ppm and a complex in sequence to carry out reaction when the polycondensation reaction is carried out, so as to obtain a polyester mixture when the viscosity reaches 0.5-1.0 dl/g;
carrying out melt extrusion, sheet casting, longitudinal drawing, transverse drawing, traction and rolling on the polyester mixture to obtain a higher-hardness polyester film;
the complex is obtained by stirring a calcium precursor and a phosphorus precursor in an ethylene glycol solution at the temperature of 80-150 ℃ for 1-6 h.
The high-hardness polyester film obtained by the preparation method of the high-hardness polyester film is a metal particle-based functionalized polyester film, and is prepared by carrying out esterification reaction on aromatic dicarboxylic acid or derivatives thereof and aliphatic diol, and then carrying out polycondensation reaction on the aromatic dicarboxylic acid or derivatives thereof and corresponding aromatic oligomers, wherein complexes formed by antimony compounds, silicon compounds, calcium compounds and phosphorus compounds and ethylene glycol are sequentially added during the polycondensation reaction, so that the surface of the film contains protrusions with the height of 0.01-1.0 um (as shown in figure 1). The metal particle complex is added during the polycondensation reaction to form uniformly dispersed bulges on the surface of the polyester, so that the hardness of the polyester film can be effectively improved, and the polyester film has the advantages of low cost, simple process and good transparency and stability.
In the preparation method of the high-hardness polyester film, the content of calcium element is 10ppm-2000ppm, and when the content is less than 10ppm, surface bulges can not be formed effectively; when the amount is more than 2000ppm, the surface of the film is more protruded due to the higher calcium content, and the surface roughness is increased, which is disadvantageous for the application of the film. The content of the phosphorus element is 50ppm-2000ppm, and when the content of the phosphorus element is less than 50ppm, the phosphorus element cannot effectively form a complex with calcium element, so that the copper-containing compound is agglomerated to form coarse particles to form defects; above 2000ppm, the activity of the polycondensation catalyst is suppressed, the polymerization time is prolonged, and the yellowing of the polyester film affects the use thereof. The content of silicon element is 10ppm-3000ppm, when the content is less than 10ppm, the polyester surface can not form a wear-resistant surface; above 3000ppm, the polyester molecular chains are heavily crosslinked, making the polymer difficult to process. Preparing a complex formed by calcium compounds, phosphorus compounds and glycol, wherein the mass content ratio of calcium element to phosphorus element is more than or equal to 0.01 and less than or equal to 1.0. When the content is less than 0.01, the content of calcium element is less due to the limitation of the content of phosphorus element, and the effect of surface protrusion cannot be achieved; when the content is higher than 1.0, on one hand, the calcium element cannot form a one-to-one ratio with the phosphorus element, and the excessive calcium element may generate self-polymerization reaction to form coarse particles so as to form defects; on the other hand, calcium ions cannot be uniformly dispersed, and uniformly dispersed convex structures are formed on the surface of the polyester film.
In one embodiment of the invention, the mass content ratio of calcium element to phosphorus element in the complex is 0.01-1.0.
In one embodiment of the present invention, the ratio of the addition amount of the antimony precursor to the calcium precursor is 100ppm to 400 ppm: 200ppm to 950 ppm.
In one embodiment of the present invention, the catalyst for the esterification reaction is a cobalt salt hydrate catalyst; the preferred catalyst is cobalt acetate tetrahydrate.
In one embodiment of the present invention, the calcium precursor is selected from one of calcium carbonate, calcium acetate, calcium hydroxide, and calcium chloride.
In one embodiment of the present invention, the phosphorus precursor is selected from one of phosphoric acid, dimethyl phosphate, trimethyl phosphate; phosphoric acid is preferred.
In one embodiment of the invention, the antimony precursor is selected from antimony trioxide or ethylene glycol antimony; ethylene glycol antimony is preferred.
In one embodiment of the present invention, the silicon precursor is selected from one of silica, polysilica, methyl silicone oil; methyl silicone oil is preferred.
In one embodiment of the present invention, the aromatic dicarboxylic acid or derivative thereof used may be specifically one selected from terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid and esterified derivatives thereof; from the viewpoint of mechanical properties, heat resistance and wet heat resistance, one selected from terephthalic acid, naphthalenedicarboxylic acid and esterified derivatives thereof is preferable; terephthalic acid is preferred from the viewpoint of cost.
In one embodiment of the present invention, the aliphatic diol may be an aliphatic diol having six or less carbon atoms, such as ethylene glycol, propylene glycol, or butylene glycol; ethylene glycol is preferred in view of moldability, crystallinity, hydrolysis resistance and the like of the polyester.
The invention also provides a high-hardness polyester film which is prepared by the preparation method of the high-hardness polyester film.
In one embodiment of the invention, the high-hardness polyester film has a thickness of 3-250 um, a hardness of H-4H, 10-2000 ppm of calcium, 10-3000 ppm of silicon, 50-2000 ppm of phosphorus and 100-400ppm of antimony, and the surface of the high-hardness polyester film contains protrusions with a height of 0.01-1.0 um, wherein the protrusions contain calcium and phosphorus.
The invention also provides a product which contains the high-hardness polyester film or a part made of the high-hardness polyester film.
The high-hardness polyester film is a metal particle-based functionalized polyester film, and the metal particle complex is added during the polycondensation reaction to form uniformly dispersed bulges on the surface of the polyester, so that the hardness of the polyester film can be effectively improved, and the high-hardness polyester film has the advantages of low cost, simple process and good transparency and stability.
Drawings
FIG. 1 is a schematic view of the surface protrusion of the polyester of the present invention.
Detailed Description
Example 1
The embodiment provides a metal particle-based functionalized polyester film and a preparation method thereof, and the preparation method specifically comprises the following steps:
(a) adding ethylene glycol and dimethyl terephthalate (molar ratio is 2: 1) into a reaction tank of a rectifying tower, adding cobalt acetate tetrahydrate (as an ester exchange catalyst, the addition amount of which is about 500ppm in an oligomer) and carrying out ester exchange reaction at 140 ℃ to obtain an oligomer (namely, diethylene glycol terephthalate); then raising the temperature in the reaction tank to 250 ℃ to ensure that the generated methanol is continuously rectified out, and obtaining the diethylene glycol terephthalate along with the progress of ester exchange until the ester exchange reaction rate is about 98 percent;
(b) adding 200ppm calcium carbonate calculated by calcium element and 400ppm phosphoric acid calculated by phosphorus element into excessive glycol solution at 100 ℃, and stirring for 5 hours to obtain a calcium-phosphorus complex for later use; terephthalic acid and ethylene glycol were then mixed at a ratio of 1: 1.14 mol ratio is added into a reaction kettle (with a rectifying tower) provided with a bottom material of diethylene glycol terephthalate for esterification reaction until the esterification reaction rate reaches 97 percent (obtained by calculating the production of byproduct water); transferring the prepared diethylene glycol terephthalate oligomer into the reaction kettle, adding ethylene glycol antimony (which is equivalent to 300ppm of the total amount of the polyethylene glycol terephthalate in terms of antimony element) as a catalyst after 5 minutes, adding a calcium-phosphorus complex after 5 minutes, adding 250ppm of methyl silicone oil in terms of silicon element after 5 minutes, starting reducing the pressure to be below 100Pa after 5 minutes of adding, heating to 300 ℃ to continue polycondensation reaction (the whole polycondensation reaction lasts for 2-4 hours), discharging, cooling and pelletizing after the required polymer viscosity reaches 0.69dL/g to obtain polyester raw material particles; then obtaining the polyester film with higher hardness through melt extrusion, sheet casting, longitudinal drawing, transverse drawing, traction and rolling.
Example 2
This example provides a functionalized polyester film based on metal particles and a method for preparing the same, which is substantially the same as in example 1, except that: in the step (b), 350ppm of calcium carbonate calculated by copper element, 800ppm of dimethyl ester silicone oil calculated by silicon element, 1500ppm of phosphoric acid calculated by phosphorus element and 280ppm of antimony trioxide are added.
Example 3
This example provides a functionalized polyester film based on metal particles and a method for preparing the same, which is substantially the same as in example 1, except that: in the step (b), 500ppm of calcium carbonate calculated by calcium element, 1300ppm of methyl silicone oil calculated by silicon element, 1600ppm of phosphoric acid calculated by phosphorus element and 360ppm of antimony trioxide are added.
Example 4
This example provides a functionalized polyester film based on metal particles and a method for preparing the same, which is substantially the same as in example 1, except that: in the step (b), 700ppm of calcium carbonate calculated by calcium element, 1900ppm of methyl silicone oil calculated by silicon element, 1800ppm of phosphoric acid calculated by phosphorus element and 300ppm of antimony trioxide are added.
Example 5
This example provides a functionalized polyester film based on metal particles and a method for preparing the same, which is substantially the same as in example 1, except that: in the step (b), 850ppm of calcium carbonate in terms of calcium element, 2300ppm of methyl silicone oil in terms of silicon element, 1900ppm of phosphoric acid in terms of phosphorus element, and 300ppm of antimony trioxide are added.
Example 6
This example provides a functionalized polyester film based on metal particles and a method for preparing the same, which is substantially the same as in example 1, except that: in the step (b), 920ppm of calcium carbonate calculated by calcium element, 800ppm of methyl silicone oil calculated by silicon element, 2000ppm of phosphoric acid calculated by phosphorus element and 300ppm of antimony trioxide are added.
Comparative example 1
This comparative example provides a polyester and process for its preparation which is essentially the same as in example 1 except that: in step (b), only 200ppm of calcium carbonate, calculated as elemental calcium, was added.
Comparative example 2
This comparative example provides a polyester and process for its preparation which is essentially the same as in example 1 except that: in the step (b), only 600ppm of methyl silicone oil was added based on the silicon element.
Comparative example 3
This comparative example provides a polyester and process for its preparation which is essentially the same as in example 1 except that: in step (b), 1300ppm of phosphoric acid was used based on the phosphorus element.
Comparative example 4
This comparative example provides a polyester and process for its preparation which is essentially the same as in example 1 except that: in the step (b), only 700ppm of methyl silicone oil in terms of silicon element and 500ppm of phosphoric acid in terms of phosphorus element are added.
Comparative example 5
This comparative example provides a polyester and process for its preparation which is essentially the same as in example 1 except that: in the step (b), only 600ppm of calcium carbonate in terms of calcium element and 600ppm of phosphoric acid in terms of phosphorus element were added.
Comparative example 6
This comparative example provides a polyester and process for its preparation which is essentially the same as in example 1 except that: in the step (b), only 400ppm of calcium carbonate in terms of calcium element and 1500ppm of methyl silicone oil in terms of silicon element were added.
TABLE 1 raw material ratios and Performance evaluation tables for products of examples 1 to 6 and comparative examples 1 to 6
In table 1, each english abbreviation is specifically: EG, ethylene glycol; TPA, terephthalic acid; DMT, dimethyl terephthalate.
The evaluation method of each test item in table 1 is as follows:
(1) content of metal element
Taking 5g of polyester raw material, melting the polyester raw material to prepare a test sample, and testing the content of metal elements in the test sample by using a fluorescent X-ray element analyzer;
(2) intrinsic Viscosity (IV) of the polyester starting Material
The sample was dissolved in parachlorophenol and measured at 25 ℃ using an Ostwald viscometer;
(3) film hardness (45 degree pencil hardness test)
Placing a sample on a horizontal table board, holding a pencil by about 45 degrees, pushing the sample on the surface of a film at a speed of about 1cm/s uniformly towards the front of an experimenter by pushing the sample by 1cm at a speed of about 1cm/s, grinding the pencil tip once scraping, and repeating 5 times for pencils with the same label; in the 5-pass scratch test, if two or more passes are considered to scratch the bottom plate of the sample plate, the same test is carried out by using the pencil with the former hardness mark until the pencil with the former hardness mark is found out, and the hardness mark of the latter hardness mark of the pencil hardness mark is recorded (9H 8H 7H 6H 5H 4H 3H 2 HF HB B2B 3B 4B 5B 6B, wherein 9H is the hardest and 6B is the softest in the Chinese-brand advanced drawing pencil group).
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-hardness polyester film comprises the following steps:
mixing aromatic dicarboxylic acid or derivatives thereof with aliphatic diol, and carrying out esterification reaction at 140-230 ℃ to obtain aromatic polyester oligomer; wherein the molar ratio of the aromatic dicarboxylic acid or the derivative thereof to the aliphatic diol is 0.5-2.5: 1.5-3;
carrying out polycondensation reaction on the aromatic polyester oligomer at 230-250 ℃, and adding an antimony precursor with the content of 100-400ppm, a silicon precursor with the content of 10-3000 ppm and a complex in sequence to carry out reaction when the polycondensation reaction is carried out, so as to obtain a polyester mixture when the viscosity reaches 0.5-1.0 dl/g;
carrying out melt extrusion, sheet casting, longitudinal drawing, transverse drawing, traction and rolling on the polyester mixture to obtain a high-hardness polyester film;
the complex is obtained by stirring a calcium precursor and a phosphorus precursor in an ethylene glycol solution at the temperature of 80-150 ℃ for 1-6 h.
2. The preparation method according to claim 1, wherein the mass content ratio of calcium element to phosphorus element in the complex is 0.01. ltoreq. calcium/phosphorus. ltoreq.1.0.
3. The production method according to claim 1, wherein the addition amount ratio of the antimony precursor to the calcium precursor is 100ppm to 400 ppm: 200ppm to 950 ppm.
4. The production method according to claim 1, wherein the catalyst for the esterification reaction is a cobalt salt hydrate catalyst; preferably, the catalyst is cobalt acetate tetrahydrate.
5. The preparation method according to claim 1, wherein the calcium precursor is selected from one of calcium carbonate, calcium acetate, calcium hydroxide, calcium chloride;
preferably, the phosphorus precursor is selected from one of phosphoric acid, dimethyl phosphate and trimethyl phosphate.
6. The production method according to claim 1, wherein the antimony precursor is selected from antimony trioxide or ethylene glycol antimony.
7. The production method according to claim 1, wherein the silicon precursor is one selected from the group consisting of silica, polysilica, and methylsilicone oil.
8. The production method according to claim 1, wherein the aromatic dicarboxylic acid or a derivative thereof is one of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and an esterified derivative thereof;
preferably, the aliphatic diol is ethylene glycol.
9. A high-hardness polyester film produced by the process for producing a high-hardness polyester film according to any one of claims 1 to 8.
10. The high-hardness polyester film as claimed in claim 9, wherein the high-hardness polyester film has a thickness of 3um to 250um, a hardness of H to 4H, and contains 10ppm to 2000ppm of calcium, 10ppm to 3000ppm of silicon, 50ppm to 2000ppm of phosphorus, and 100-400ppm of antimony, and the surface of the high-hardness polyester film contains protrusions having a height of 0.01um to 1.0um, the protrusions containing calcium and phosphorus.
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| CN202011521469.1A CN112646157A (en) | 2020-12-21 | 2020-12-21 | High-hardness polyester film and preparation method and application thereof |
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Application publication date: 20210413 |
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