CN112679768A - Higher-hardness polyester film and preparation method and application thereof - Google Patents
Higher-hardness polyester film and preparation method and application thereof Download PDFInfo
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- CN112679768A CN112679768A CN202011523242.0A CN202011523242A CN112679768A CN 112679768 A CN112679768 A CN 112679768A CN 202011523242 A CN202011523242 A CN 202011523242A CN 112679768 A CN112679768 A CN 112679768A
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Abstract
The invention provides a higher-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 higher-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 technical problems, an object of the present invention is to provide a polyester film having high hardness and low cost.
The invention also aims to provide a preparation method of the polyester film with higher hardness and lower cost.
In order to achieve the above technical object, the present invention firstly provides a method for preparing a higher 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 copper precursor and a phosphorus precursor in an ethylene glycol solution at the temperature of between 80 and 150 ℃ for 1 to 6 hours.
The higher-hardness polyester film obtained by the preparation method of the higher-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, copper 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 polyester film with higher hardness, the content of copper element is 10ppm-1000ppm, and when the content is less than 10ppm, surface bulges can not be formed effectively; when the copper content is more than 1000ppm, the surface of the film is more convex due to more copper content, and the surface roughness is increased, which is not favorable 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 the copper 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 a copper compound, a phosphorus compound and ethylene glycol, wherein the content ratio of copper 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 copper element is reduced due to the limitation of the content of phosphorus element, and the effect of surface protrusion cannot be achieved; when the ratio is higher than 1.0, on one hand, the copper element cannot form a one-to-one ratio with the phosphorus element, and the excessive copper element may generate auto-polymerization to form coarse particles and further form defects; on the other hand, copper ions cannot be uniformly dispersed, and a uniformly dispersed convex structure is formed on the surface of the polyester film.
In one embodiment of the invention, the content ratio of copper 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 copper precursor is 100ppm to 400 ppm: 150ppm to 900 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 copper precursor is selected from one of copper sulfate, copper acetate, copper oxide, and copper chloride; copper sulfate is preferred.
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 higher-hardness polyester film, which is prepared by the preparation method of the higher-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, and contains 10-1000 ppm of copper, 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 copper and phosphorus.
The invention also provides a product which contains the higher-hardness polyester film or a part made of the higher-hardness polyester film.
The higher-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 higher-hardness polyester film is lower in cost, simple in process and good in 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 150ppm of copper sulfate calculated by copper element and 350ppm of phosphoric acid calculated by phosphorus element into excessive glycol solution at 100 ℃, and stirring for 5 hours to obtain a copper-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 copper-phosphorus complex after 5 minutes, adding 200ppm 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), 300ppm of copper acetate calculated by copper element, 700ppm of dimethyl silicone oil calculated by silicon element, 1200ppm of phosphoric acid calculated by phosphorus element and 260ppm 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), 450ppm of copper sulfate calculated by copper element, 1200ppm of methyl silicone oil calculated by silicon element, 1500ppm 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), 750ppm of copper sulfate calculated by copper element, 1800ppm of methyl silicone oil calculated by silicon element, 1700ppm 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), 800ppm of copper sulfate calculated by copper element, 2200ppm of methyl silicone oil calculated by silicon element, 1800ppm of phosphoric acid calculated by 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), 900ppm of copper sulfate calculated by copper element, 700ppm 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 300ppm of copper sulfate, calculated as elemental copper, 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 copper sulfate in terms of copper 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 copper sulfate in terms of copper element and 1500ppm of methyl silicone oil in terms of silicon element are 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 2H F 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 higher-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 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 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 copper 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 copper element to phosphorus element in the complex is 0.01. ltoreq. copper/phosphorus. ltoreq.1.0.
3. The production method according to claim 1, wherein the addition amount ratio of the antimony precursor to the copper precursor is 100ppm to 400 ppm: 150ppm to 900 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 method according to claim 1, wherein the copper precursor is one selected from copper sulfate, copper acetate, copper oxide, and copper chloride.
6. The production method according to claim 1, wherein the phosphorus precursor is one selected from phosphoric acid, dimethyl phosphate, and trimethyl phosphate.
7. The production method according to claim 1, wherein the antimony precursor is selected from antimony trioxide or ethylene glycol antimony;
preferably, the silicon precursor is selected from one of silicon dioxide, polysilica and methyl silicone 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 higher-hardness polyester film produced by the process for producing a higher-hardness polyester film according to any one of claims 1 to 8.
10. The higher hardness polyester film according to claim 9, wherein the higher hardness polyester film has a thickness of 3um to 250um, a hardness of H to 4H, and contains 10ppm to 1000ppm of copper, 10ppm to 3000ppm of silicon, 50ppm to 2000ppm of phosphorus, and 100-400ppm of antimony, and the surface of the higher hardness polyester film contains protrusions having a height of 0.01um to 1.0um, and the protrusions contain copper element and phosphorus element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011523242.0A CN112679768A (en) | 2020-12-21 | 2020-12-21 | Higher-hardness polyester film and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011523242.0A CN112679768A (en) | 2020-12-21 | 2020-12-21 | Higher-hardness polyester film and preparation method and application thereof |
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| CN112679768A true CN112679768A (en) | 2021-04-20 |
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| CN202011523242.0A Withdrawn CN112679768A (en) | 2020-12-21 | 2020-12-21 | Higher-hardness polyester film and preparation method and application thereof |
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