CN109354676B - Preparation method of low-surface-tension PET copolyester material and non-coating low-surface-tension PET film prepared from material - Google Patents
Preparation method of low-surface-tension PET copolyester material and non-coating low-surface-tension PET film prepared from material Download PDFInfo
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Abstract
The invention discloses a preparation method of a low-surface-tension PET copolyester material and a non-coating low-surface-tension PET film prepared by adopting the material. Firstly, carboxyl-terminated hyperbranched polysiloxane is prepared as a modifier, the carboxyl-terminated hyperbranched polysiloxane is copolycondensed with terephthalic acid and ethylene glycol to prepare homogeneous PET copolyester, and then the homogeneous PET copolyester is stretched to prepare the PET film with lower surface tension. The carboxyl-terminated hyperbranched polysiloxane is uniformly dispersed in a PET matrix in a chemical bonding mode, the problem of micro-phase separation does not exist, the stability is good after long-term use, the siloxane molecular chain segment and the polyester molecular chain segment naturally overturn to the surface of a material due to different polarities, a low surface energy chain segment is formed on the surface of a PET film, and the low surface tension film can be prepared without carrying out secondary modification on PET.
Description
Technical Field
The invention relates to the field of preparation of PET (polyethylene terephthalate) polyester materials and PET films, in particular to a preparation method of a low-surface-tension PET copolyester material and a non-coating low-surface-tension PET film prepared by adopting the material.
Background
Polyethylene terephthalate (PET) is a polymer having excellent properties, and is widely used in the fields of fibers, polyester bottles, engineering plastics, films, and the like, because it has high strength, high rigidity, good heat resistance, chemical resistance, and electrical insulation properties. The PET film has great market application in the fields of outdoor monitoring, outdoor display screens, curtain walls and the like. The low surface tension PET is a typical functional film, and the low surface tension PET is modified on the basis of a common PET film by a physical or chemical method to reduce the surface energy of the film, so that the processing requirement of a downstream market is met. The low surface tension PET film is widely applied to various adhesive tape products, various release film products and protective film products at present. The method is limited by the production technology, no general method is available at present for directly reducing the surface tension during the production of the PET film, only the PET film can be subjected to secondary processing, and at present, the PET surface is modified and coated with a low-surface-tension coating mainly in an off-line coating processing mode, so that the low-surface-tension PET film is obtained.
The invention patent CN105538853B discloses a low surface energy PET film prepared by co-extrusion of a PET polyester homopolymer, a silicon dioxide additive and a polysiloxane additive, wherein the PET film prepared by the method has low surface energy, but the process is complex, the silicon dioxide and the polysiloxane additive are difficult to be uniformly distributed in PET copolyester, and the stability in long-term use has a problem. Patent CN103088629B discloses a method for chemically treating PET surface with hydrophobic alkylsilane compound to prepare low surface tension PET film; patent CN106280995B discloses a low surface tension PET film prepared by coating polyethylene wax particles, vinyl MQ silicone resin, epoxy modified silicone resin, fluorine-containing polysiloxane and other fillers on the surface of PET. The main problems associated with the PET films produced by these methods are: the process is complex, the coating cost is high, a series of quality problems such as uneven coating and the like are easy to generate, and the coating process has the problem of environmental pollution caused by solvent. Therefore, a new non-coating method for preparing a PET film material having a low surface tension by itself is sought.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects in the prior art, and provides a preparation method of a low-surface-tension PET copolyester material and a non-coating low-surface-tension PET film prepared by the material. Firstly, carboxyl-terminated hyperbranched polysiloxane is prepared as a modifier, the carboxyl-terminated hyperbranched polysiloxane, a terephthalic acid monomer and ethylene glycol are copolycondensed to prepare homogeneous PET copolyester, and then the homogeneous PET copolyester is stretched to prepare the PET film with low surface tension. The carboxyl-terminated hyperbranched polysiloxane is uniformly dispersed in a PET matrix in a chemical bonding mode, the problem of micro-phase separation does not exist, the stability is good after long-term use, the siloxane molecular chain segment and the polyester molecular chain segment naturally overturn to the surface of a material due to different polarities, a low surface energy chain segment is formed on the surface of a PET film, and the low surface tension film can be prepared without carrying out secondary modification on PET.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a low surface tension PET copolyester material specifically comprises the following steps:
(1) the preparation of the carboxyl-terminated hyperbranched polysiloxane modified body specifically comprises the following steps:
(a) preparing the following raw materials in parts by weight:
(b) adding vinyl trichlorosilane, dimethylchlorosilane, a catalyst II, diethyl ether and water into a reaction kettle, and stirring for 4-6 hours at the temperature of 30-50 ℃; heating to 100-150 ℃, removing water and solvent ether by vacuum pumping under reduced pressure, and reducing the pressure to-0.096 to-0.092 Mpa for 2-4 hours to obtain a polymer monomer;
(c) adding acrylic acid into the polymer monomer prepared in the step (b), and reacting for 4-6 hours under the protection of nitrogen to prepare a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) the preparation method of the PET copolyester melt through polycondensation comprises the following steps:
(a) preparing the following raw materials in parts by weight:
(b) mixing a terephthalic acid monomer, ethylene glycol, a catalyst I and the modified carboxyl-terminated hyperbranched polysiloxane prepared in the step (1) in phase, adding the mixture into a reaction kettle in the order of solid and liquid, and pulping for 10-30 minutes at normal temperature;
(c) heating to 230-270 ℃, carrying out esterification reaction, and forming an esterified prepolymer after the esterification reaction reaches more than 95%;
(d) adding a stabilizer and an opening agent into the esterified prepolymer, and carrying out mixed vacuum polycondensation reaction at the temperature of 250-280 ℃ for 2-4 hours to obtain a PET copolyester melt;
(3) and (3) discharging, cooling and granulating the PET copolyester melt prepared in the step (2) to prepare the low surface tension PET copolyester material.
Further, the following steps: and (3) when the intrinsic viscosity of the polyester of the PET copolyester melt reaches 0.72-0.78, discharging, cooling and granulating the PET copolyester melt to obtain the low surface tension PET copolyester material.
Further, the catalyst I is one of antimony-based, titanium-based or germanium-based catalysts.
Further, the stabilizer is one of phosphate esters or phosphite esters.
Further, the opening agent is one or more of barium sulfate, calcium carbonate or silicon dioxide.
Further, the catalyst II comprises but is not limited to one of hydrogen silicon addition catalysts such as chloroplatinic acid, phosphine coordination rhodium complex and the like.
The non-coating low-surface-tension PET film is a polyester film prepared by casting, biaxial stretching, drawing and rolling the low-surface-tension PET copolyester material.
Further, the draw ratio in the biaxial stretching is: 2-3 times in the longitudinal direction and 3-3.5 times in the transverse direction.
The invention has the beneficial effects that: the invention has reasonable design and simple and convenient operation, and adopts the copolycondensation of the carboxyl-terminated hyperbranched polysiloxane, the terephthalic acid and the ethylene glycol to prepare the homogeneous PET copolyester, wherein the molecular chain segment of the carboxyl-terminated hyperbranched polysiloxane with low surface energy is not coated on the surface of a PET material in an external coating way, but is uniformly dispersed in a PET matrix in a chemical bonding way, and the product is homogeneous and has good stability in long-term use; the siloxane chain segment and the polyester chain segment naturally turn over to the surface of the PET due to different polarities, so that the surface tension of the PET film is reduced.
Detailed Description
The invention will now be further described with reference to preferred examples and comparative examples.
Example 1
A low surface tension PET copolyester material, this example 1 contains a modified carboxyl-terminated hyperbranched polysiloxane, and is synthesized from the following raw materials in mass: 800g of terephthalic acid monomer, 200g of ethylene glycol, 10g of ethylene glycol antimony catalyst, 10g of trimethyl phosphate stabilizer, 50g of silicon dioxide opening agent with the particle size of 5 mu m and 10g of carboxyl-terminated hyperbranched polysiloxane modified body;
wherein the modified carboxyl-terminated hyperbranched polysiloxane comprises the following raw materials by mass: 0.35g of vinyl trichlorosilane, 5.48g of dimethylchlorosilane, 4.17g of acrylic acid, 0.1g of chloroplatinic acid catalyst, 30g of diethyl ether and 1.5g of water.
The preparation method of the low surface tension PET copolyester material comprises the following steps:
(1) adding 0.35g of vinyl trichlorosilane, 5.48g of dimethylchlorosilane, 0.1g of chloroplatinic acid catalyst, 30g of diethyl ether and 1.5g of water into a reaction kettle, stirring for 6 hours at 50 ℃, heating to 150 ℃, removing water and diethyl ether by vacuum pumping under reduced pressure of-0.096 MPa for 2 hours to obtain a polymer monomer; adding 4.17g of acrylic acid, and reacting for 6 hours under the protection of nitrogen to obtain a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) 10g of modified carboxyl-terminated hyperbranched polysiloxane, 800g of terephthalic acid monomer, 200g of ethylene glycol and 10g of ethylene glycol antimony catalyst are mixed in the same phase, added into a reaction kettle in the order of solid and liquid, and pulped for 30 minutes at normal temperature; closing stirring, starting a vacuum system to slowly pump out oxygen in the kettle, introducing nitrogen to normal pressure, repeatedly vacuumizing and introducing nitrogen for 3 times, pressurizing and heating to perform esterification reaction, keeping the reaction temperature at 230 ℃, performing esterification reaction, keeping the pressure in the kettle at about 400kPa, and forming an esterified prepolymer when the esterification reaches more than 95 percent, wherein the pressure in the kettle is below 20kPa, and the temperature at the top of the tower is below 100 ℃; adding 10g of trimethyl phosphate stabilizer and 50g of silicon dioxide opening agent with the particle size of 5 mu m into the esterified prepolymer, and carrying out mixed vacuum polycondensation reaction at the temperature of 250 ℃ for 2 hours to obtain a PET copolyester melt;
(3) and discharging, cooling and dicing the PET copolyester melt to obtain the PET copolyester material.
A non-coating low surface tension PET film is prepared by casting PET copolyester material, longitudinally stretching by 3 times, transversely stretching by 3 times, and drawing and rolling.
Example 2
A low surface tension PET copolyester material, this example 2 contains a modified carboxyl-terminated hyperbranched polysiloxane, and is synthesized from the following raw materials in mass: 700g of terephthalic acid monomer, 300g of ethylene glycol, 1g of ethylene glycol antimony catalyst, 2g of trimethyl phosphate stabilizer, 5g of silicon dioxide opening agent with the particle size of 5 mu m, and 30g of carboxyl-terminated hyperbranched polysiloxane modified body;
wherein the modified carboxyl-terminated hyperbranched polysiloxane comprises the following raw materials by mass: 1.2g of vinyl trichlorosilane, 16.59g of dimethylchlorosilane, 12.21g of acrylic acid, 0.03g of chloroplatinic acid catalyst, 45g of diethyl ether and 3g of water.
The preparation method of the low surface tension PET copolyester material comprises the following steps:
(1) adding 1.2g of vinyl trichlorosilane, 16.59g of dimethylchlorosilane, 0.03g of chloroplatinic acid catalyst, 45g of diethyl ether and 3g of water into a reaction kettle, stirring for 4 hours at the temperature of 30 ℃, heating to 100 ℃, removing water and diethyl ether by vacuum pumping under reduced pressure at the pressure of-0.092 Mpa for 4 hours to obtain a polymer monomer; adding 12.21g of acrylic acid, and reacting for 4 hours under the protection of nitrogen to obtain a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) 30g of carboxyl-terminated hyperbranched polysiloxane modified body, 700g of terephthalic acid monomer, 300g of ethylene glycol and 1g of ethylene glycol antimony catalyst are mixed in the same phase, added into a reaction kettle in the order of solid and liquid, and pulped for 30 minutes at normal temperature; closing stirring, starting a vacuum system to slowly pump out oxygen in the kettle, introducing nitrogen to normal pressure, repeatedly vacuumizing and introducing nitrogen for 3 times, pressurizing and heating to perform esterification reaction, keeping the reaction temperature at 230 ℃, performing esterification reaction, keeping the pressure in the kettle at about 400kPa, and forming an esterified prepolymer when the esterification reaches more than 95 percent, wherein the pressure in the kettle is below 20kPa, and the temperature at the top of the tower is below 100 ℃; 2g of trimethyl phosphate stabilizer and 5g of silicon dioxide opening agent with the particle size of 5 mu m are added into the esterified prepolymer to carry out mixing vacuum polycondensation reaction at the temperature of 250 ℃ for 2 hours to prepare PET copolyester melt;
(3) and discharging, cooling and dicing the PET copolyester melt to obtain the PET copolyester material.
A non-coating low surface tension PET film is prepared by casting PET copolyester material, longitudinally stretching by 2.5 times, transversely stretching by 2.5 times, and drawing and rolling.
Example 3
A low surface tension PET copolyester material, this example 3 contains a modified carboxyl-terminated hyperbranched polysiloxane, and is synthesized from the following raw materials in mass: 700g of terephthalic acid monomer, 300g of ethylene glycol, 2g of tetrabutyl titanate catalyst, 3g of trimethyl phosphite stabilizer, 9g of calcium carbonate opening agent and 50g of carboxyl-terminated hyperbranched polysiloxane modified body;
wherein the modified carboxyl-terminated hyperbranched polysiloxane comprises the following raw materials by mass: 1.8g of vinyl trichlorosilane, 28g of dimethylchlorosilane, 20.2g of acrylic acid, 0.05g of phosphine coordination rhodium complex catalyst, 100g of diethyl ether and 6g of water.
The preparation method of the low surface tension PET copolyester material comprises the following steps:
(1) adding 1.8g of vinyl trichlorosilane, 28g of dimethylchlorosilane, 100g of diethyl ether, 6g of water and 0.05g of phosphine coordination rhodium complex catalyst into a reaction kettle, stirring for 5 hours at 40 ℃, heating to 120 ℃, removing water and diethyl ether by vacuum pumping under reduced pressure, and obtaining a polymer monomer under the pressure of-0.094 Mpa for 3 hours; adding 20.2g of acrylic acid, and reacting for 5 hours under the protection of nitrogen to obtain a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) 50g of carboxyl-terminated hyperbranched polysiloxane modified body, 700g of terephthalic acid monomer, 300g of ethylene glycol and 2g of tetrabutyl titanate catalyst are mixed in the same phase, added into a reaction kettle in the order of solid and liquid, and pulped for 10 minutes at normal temperature; closing stirring, starting a vacuum system to slowly pump out oxygen in the kettle, introducing nitrogen to normal pressure, repeatedly vacuumizing and introducing nitrogen for 3 times, pressurizing and heating to perform esterification reaction, keeping the reaction temperature at 250 ℃, performing esterification reaction, keeping the pressure in the kettle at about 400kPa, and forming an esterified prepolymer when the esterification reaches more than 95 percent, wherein the pressure in the kettle is below 20kPa, and the temperature at the top of the tower is below 100 ℃; adding 3g of trimethyl phosphite stabilizer and 9g of calcium carbonate opening agent into the esterified prepolymer, and carrying out mixed vacuum polycondensation reaction at the temperature of 260 ℃ for 2 hours to obtain a PET copolyester melt;
(3) and discharging, cooling and dicing the PET copolyester melt to obtain the PET copolyester material.
A non-coating low surface tension PET film is prepared by casting PET copolyester material, longitudinally stretching by 2 times, transversely stretching by 2.5 times, and drawing and rolling.
Example 4
A low surface tension PET copolyester material, this example 4 contains a modified carboxyl-terminated hyperbranched polysiloxane, and is synthesized from the following raw materials in mass: 720g of terephthalic acid monomer, 280g of ethylene glycol, 3g of three-well MP type titanium catalyst SA135, 3g of trimethyl phosphite stabilizer, 10g of calcium carbonate opening agent and 60g of carboxyl-terminated hyperbranched polysiloxane modified body;
wherein the modified carboxyl-terminated hyperbranched polysiloxane comprises the following raw materials by mass: 2.2g of vinyl trichlorosilane, 33g of dimethylchlorosilane, 24.8g of acrylic acid, 0.06g of phosphine coordination rhodium complex catalyst, 120g of diethyl ether and 6g of water.
The preparation method of the low surface tension PET copolyester material comprises the following steps:
(1) adding 2.2g of vinyl trichlorosilane, 33g of dimethylchlorosilane, 120g of diethyl ether, 6g of water and 0.06g of phosphine coordination rhodium complex catalyst into a reaction kettle, stirring for 5 hours at 40 ℃, heating to 100 ℃, removing water and diethyl ether by vacuum pumping under reduced pressure, and obtaining a polymer monomer under the pressure of-0.094 Mpa for 3 hours; adding 24.8g of acrylic acid, and reacting for 5 hours under the protection of nitrogen to obtain a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) 60g of carboxyl-terminated hyperbranched polysiloxane modified body, 720g of terephthalic acid monomer, 280g of ethylene glycol and 3g of three-well MP type titanium catalyst SA135 are mixed in phase, added into a reaction kettle in the order of solid and liquid, and pulped for 20 minutes at normal temperature; closing stirring, starting a vacuum system to slowly pump out oxygen in the kettle, introducing nitrogen to normal pressure, repeatedly vacuumizing and introducing nitrogen for 3 times, pressurizing and heating to perform esterification reaction, keeping the reaction temperature at 270 ℃, performing esterification reaction, keeping the pressure in the kettle at about 400kPa, and forming an esterified prepolymer when the esterification reaches more than 95 percent, wherein the pressure in the kettle is below 20kPa, and the temperature at the top of the tower is below 100 ℃; adding 3g of trimethyl phosphite stabilizer and 10g of calcium carbonate opening agent into the esterified prepolymer, and carrying out mixed vacuum polycondensation reaction at the temperature of 280 ℃ for 4 hours to obtain a PET copolyester melt;
(3) and discharging, cooling and dicing the PET copolyester melt to obtain the PET copolyester material.
A non-coating low surface tension PET film is prepared by casting PET copolyester material, longitudinally stretching by 3 times, transversely stretching by 3.5 times, and drawing and rolling.
Example 5
A low surface tension PET copolyester material, this example 5 contains a modified carboxyl-terminated hyperbranched polysiloxane, and is synthesized from the following raw materials in mass: 700g of terephthalic acid, 300g of ethylene glycol, 5g of germanium catalyst TG17 from Meldfrom germanium, England, 6g of trimethyl phosphite stabilizer, 12g of barium sulfate opening agent and 80g of modified carboxyl-terminated hyperbranched polysiloxane;
wherein the modified carboxyl-terminated hyperbranched polysiloxane comprises the following raw materials by mass: 3g of vinyl trichlorosilane, 44g of dimethylchlorosilane, 33g of acrylic acid, 0.1g of phosphine coordination rhodium complex catalyst, 200g of diethyl ether and 12g of water.
The preparation method of the low surface tension PET copolyester material comprises the following steps:
(1) adding 3g of vinyl trichlorosilane, 44g of dimethylchlorosilane, 200g of diethyl ether, 12g of water and 0.1g of phosphine coordination rhodium complex catalyst into a reaction kettle, stirring for 5 hours at the temperature of 45 ℃, heating to 120 ℃, removing water and diethyl ether by vacuum pumping under reduced pressure at the pressure of-0.092 MPa for 4 hours to obtain a polymer monomer; adding 33g of acrylic acid, and reacting for 5 hours under the protection of nitrogen to obtain a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) 80g of carboxyl-terminated hyperbranched polysiloxane modified body, 700g of terephthalic acid monomer, 300g of ethylene glycol and 5g of germanium catalyst TG17 of Meldfrom germanium company in UK are mixed in phase, added into a reaction kettle in the order of solid and liquid, and pulped for 20 minutes at normal temperature; closing stirring, starting a vacuum system to slowly pump out oxygen in the kettle, introducing nitrogen to normal pressure, repeatedly vacuumizing and introducing nitrogen for 3 times, pressurizing and heating to perform esterification reaction, keeping the reaction temperature at 270 ℃, performing esterification reaction, keeping the pressure in the kettle at about 400kPa, and forming an esterified prepolymer when the esterification reaches more than 95 percent, wherein the pressure in the kettle is below 20kPa, and the temperature at the top of the tower is below 100 ℃; 6g of trimethyl phosphite stabilizer and 12g of barium sulfate opening agent are added into the esterified prepolymer to carry out mixing vacuum polycondensation reaction at the temperature of 280 ℃ for 4 hours to prepare PET copolyester melt;
(3) and discharging, cooling and dicing the PET copolyester melt to obtain the PET copolyester material.
A non-coating low surface tension PET film is prepared by casting PET copolyester material, longitudinally stretching by 2.5 times, transversely stretching by 3.5 times, and drawing and rolling.
Example 6
A low surface tension PET copolyester material, in this example 6, a modified carboxyl-terminated hyperbranched polysiloxane is synthesized from the following raw materials in parts by mass: 680g of terephthalic acid monomer, 320g of ethylene glycol, 0.1g of ethylene glycol antimony catalyst, 0.2g of trimethyl phosphate stabilizer, 0.2g of silicon dioxide opening agent with the particle size of 5 mu m and 100g of modified carboxyl-terminated hyperbranched polysiloxane;
wherein the modified carboxyl-terminated hyperbranched polysiloxane comprises the following raw materials: 3.5g of vinyl trichlorosilane, 54.8g of dimethylchlorosilane, 41.7g of acrylic acid, 1g of chloroplatinic acid catalyst, 300g of diethyl ether and 15g of water.
The preparation method of the low surface tension PET copolyester material comprises the following steps:
(1) adding 3.5g of vinyl trichlorosilane, 54.8g of dimethylchlorosilane, 1g of chloroplatinic acid catalyst, 300g of diethyl ether and 15g of water into a reaction kettle, stirring for 6 hours at 50 ℃, heating to 150 ℃, removing water and diethyl ether by vacuum pumping under reduced pressure at-0.096 MPa for 2 hours to obtain a polymer monomer; adding 41.7g of acrylic acid, and reacting for 6 hours under the protection of nitrogen to obtain a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) 100g of carboxyl-terminated hyperbranched polysiloxane modified body, 680g of terephthalic acid monomer, 320g of ethylene glycol and 0.1g of ethylene glycol antimony catalyst are mixed in phase, added into a reaction kettle in the order of solid first and liquid second, and pulped for 30 minutes at normal temperature; closing stirring, starting a vacuum system to slowly pump out oxygen in the kettle, introducing nitrogen to normal pressure, repeatedly vacuumizing and introducing nitrogen for 3 times, pressurizing and heating to perform esterification reaction, keeping the reaction temperature at 230 ℃, performing esterification reaction, keeping the pressure in the kettle at about 400kPa, and forming an esterified prepolymer when the esterification reaches more than 95 percent, wherein the pressure in the kettle is below 20kPa, and the temperature at the top of the tower is below 100 ℃; adding 0.2g of trimethyl phosphate stabilizer and 0.2g of silicon dioxide opening agent with the particle size of 5 mu m into the esterified prepolymer, and carrying out mixing vacuum polycondensation reaction at the temperature of 250 ℃ for 2 hours to obtain a PET copolyester melt;
(3) and discharging, cooling and dicing the PET copolyester melt to obtain the PET copolyester material.
A non-coating low surface tension PET film is prepared by casting PET copolyester material, longitudinally stretching by 3 times, transversely stretching by 3 times, and drawing and rolling.
Comparative example 1
A preparation method of PET copolyester material, which does not add carboxyl-terminated hyperbranched polysiloxane modifier, comprises the following steps: 800g of terephthalic acid monomer, 200g of ethylene glycol, 10g of ethylene glycol antimony catalyst, 10g of trimethyl phosphate stabilizer and 50g of silica opening agent with the particle size of 5 mu m.
The preparation method of the PET copolyester material comprises the following steps: 800g of terephthalic acid monomer, 200g of ethylene glycol and 10g of ethylene glycol antimony catalyst are mixed in the same phase, added into a reaction kettle in the order of solid and liquid, and pulped for 30 minutes at normal temperature. Closing stirring, starting a vacuum system to slowly pump out oxygen in the kettle, introducing nitrogen to normal pressure, repeatedly vacuumizing and introducing nitrogen for 3 times, pressurizing and heating to perform esterification reaction, keeping the reaction temperature at 230 ℃, performing esterification reaction, keeping the pressure in the kettle at about 400kPa, forming an esterified prepolymer when the esterification reaches more than 95%, wherein the pressure in the kettle is below 20kPa, and the temperature at the top of the tower is below 100 ℃. 10g of trimethyl phosphate stabilizer and 50g of silicon dioxide opening agent with the particle size of 5 mu m are added into the esterified prepolymer to carry out mixing vacuum polycondensation reaction at the temperature of 250 ℃ for 2 hours. Discharging, cooling and dicing to obtain the PET copolyester material.
A PET film is prepared from PET copolyester through casting, longitudinal stretching by 2 times, transverse stretching by 3 times, drawing and rolling.
In order to determine the performance of the PET films prepared in examples 1 to 6 and comparative example 1, a water contact angle test was performed on the performance of the PET film. Table 1 shows the results of the water contact angle mechanical property tests of the PET films prepared in examples 1-6 and comparative example 1.
TABLE 1 Water contact Angle mechanical Properties of PET films prepared in different examples
As can be seen from the data analysis in Table 1, the contact angle of the PET film is obviously improved as the content of the modified carboxyl-terminated hyperbranched polysiloxane participating in copolymerization in the system is increased.
The above-mentioned embodiments are merely illustrative of the technical idea 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 scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.
Claims (8)
1. A preparation method of a low surface tension PET copolyester material is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) the preparation of the carboxyl-terminated hyperbranched polysiloxane modified body specifically comprises the following steps:
(a) preparing the following raw materials in parts by weight:
(b) adding vinyl trichlorosilane, dimethylchlorosilane, a catalyst II, diethyl ether and water into a reaction kettle, and stirring for 4-6 hours at the temperature of 30-50 ℃; heating to 100-150 ℃, removing water and solvent ether by vacuum pumping under reduced pressure, and reducing the pressure to-0.096 to-0.092 Mpa for 2-4 hours to obtain a polymer monomer;
(c) adding acrylic acid into the polymer monomer prepared in the step (b), and reacting for 4-6 hours under the protection of nitrogen to prepare a carboxyl-terminated hyperbranched polysiloxane modified body;
(2) the preparation method of the PET copolyester melt through polycondensation comprises the following steps:
(a) preparing the following raw materials in parts by weight:
(b) mixing a terephthalic acid monomer, ethylene glycol, a catalyst I and the modified carboxyl-terminated hyperbranched polysiloxane prepared in the step (1) in phase, adding the mixture into a reaction kettle in the order of solid and liquid, and pulping for 10-30 minutes at normal temperature;
(c) heating to 230-270 ℃, carrying out esterification reaction, and forming an esterified prepolymer after the esterification reaction reaches more than 95%;
(d) adding a stabilizer and an opening agent into the esterified prepolymer, and carrying out mixed vacuum polycondensation reaction at the temperature of 250-280 ℃ for 2-4 hours to obtain a PET copolyester melt;
(3) and (3) discharging, cooling and dicing the PET copolyester melt prepared in the step (2) to prepare the low surface tension PET copolyester material.
2. The preparation method of low surface tension PET copolyester material according to claim 1, characterized by comprising the following steps: and (3) when the intrinsic viscosity of the polyester of the PET copolyester melt reaches 0.72-0.78, discharging, cooling and granulating the PET copolyester melt to obtain the low-surface-tension PET copolyester material.
3. The preparation method of low surface tension PET copolyester material according to claim 1, characterized by comprising the following steps: the catalyst I is one of antimony-based, titanium-based or germanium-based catalysts.
4. The preparation method of low surface tension PET copolyester material according to claim 1, characterized by comprising the following steps: the stabilizer is one of phosphate esters or phosphite esters.
5. The preparation method of low surface tension PET copolyester material according to claim 1, characterized by comprising the following steps: the opening agent is one or more of barium sulfate, calcium carbonate or silicon dioxide.
6. The preparation method of low surface tension PET copolyester material according to claim 1, characterized by comprising the following steps: the catalyst II is one of hydrosilylation catalysts.
7. A non-coated low surface tension PET film prepared using the low surface tension PET copolyester material prepared according to the preparation method of any one of claims 1 to 6 as a raw material, characterized in that: the non-coating low surface tension PET film is a polyester film prepared by casting, biaxial stretching, drawing and rolling a low surface tension PET copolyester material.
8. The non-coated low surface tension PET film of claim 7, characterized in that: the stretching multiplying power in the bidirectional stretching is as follows: 2-3 times in the longitudinal direction and 3-3.5 times in the transverse direction.
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| CN110016141A (en) * | 2019-04-26 | 2019-07-16 | 无锡时生高分子科技有限公司 | A kind of anti-scratch is from release inkjet printing UV resin and preparation method thereof |
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| CN110183669A (en) * | 2019-06-04 | 2019-08-30 | 无锡博强高分子材料科技有限公司 | A kind of amphiphilic hyper-branched structure UV matt antifouling resin preparation method and the resin |
| CN110511368B (en) * | 2019-08-09 | 2021-07-27 | 浙江恒澜科技有限公司 | Vinyl nano-silicon sphere compounded high-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparation method thereof |
| CN113501948A (en) * | 2021-07-26 | 2021-10-15 | 智谱纳米科技(上海)有限公司 | Polyester hydrophobic master batch and preparation method and application thereof |
| CN115785419B (en) * | 2023-01-31 | 2023-05-02 | 富海(东营)新材料科技有限公司 | Modified PETG copolyester, preparation method thereof and preparation method of foamed particles thereof |
| CN117700799A (en) * | 2023-11-29 | 2024-03-15 | 广东诚和信新材料有限公司 | Production and preparation method of antistatic PET release film |
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