A method for preparing a high temperature resistant and stable protective film material

Abstract

The invention relates to the technical field of PET materials, and discloses a method for preparing a high-temperature resistant stability protective film material. Polyethylene terephthalate, POSS-based polyester and an antioxidant are added to an extruder, and the mixture is extruded; then the mixture is stretched by a biaxial stretching machine to obtain the high-temperature resistant stability protective film material. POSS-based polyester has good compatibility with PET polyester, and the POSS-based polyester contains a unique nanostructure hybrid system of POSS cage-type polysilsesquioxane, which has high mechanical properties and strong wear resistance, and contains a heat-resistant anthracene-based condensed ring structure. After being blended with PET polyester to make a film, the tensile properties of the film material are significantly improved, the friction and wear amount is reduced, and the mass loss thermal decomposition temperature is increased, so that the film material exhibits excellent mechanical strength, wear resistance, scratch resistance and high temperature resistance.

Description

Technical Field

[0001] The invention relates to the technical field of PET materials, in particular to a method for preparing a high-temperature resistant and stable protective film material. Background Art

[0002] PET polyethylene terephthalate is a common polyester polymer material that can be made into plastics, alloys, films and other materials. It is widely used in packaging, electrical and electronic, insulation materials, car films, etc. Improving the mechanical strength, high temperature resistance, wear resistance and scratch resistance of PET film materials will help expand its practical application in car films, protective films, etc.

[0003] POSS cage-type polysilsesquioxane is a silicon-based nanostructure hybrid functional material with properties such as small size effect of nanoparticles. When added to polymer materials, it can improve the mechanical strength, high temperature resistance, friction resistance and other properties of the material. Patent CN116444799A discloses POSS-based polyphosphazene and PET / POSS-based polyphosphazene composite materials and their preparation methods. 3,4-dihydroxybenzoic acid, amino POSS, and hexachlorocyclotriphosphazene are reacted to obtain a POSS-based polyphosphazene flame retardant, which not only improves the compatibility of the flame retardant with the PET polymer matrix, but also gives the PET material good flame retardant properties, and does not significantly reduce the mechanical properties of the PET polymer. However, the POSS-based polyphosphazene flame retardant of the patent does not improve the wear resistance and high temperature resistance of the PET material. Summary of the invention

[0004] The invention solves the problems of low strength, poor wear resistance and poor high temperature resistance of the PET polyester film.

[0005] The technical solution of the present invention is: a method for preparing a high temperature resistant stability protective film material:

[0006] (1) Add toluene solvent, octaepoxy cage silsesquioxane, and 9-anthracenecarboxylic acid to a flask, stir, and then add triphenylphosphine in a nitrogen atmosphere, heat to 100-110°C, stir and react for 10-18 hours, condense during the reaction and reflux, concentrate under reduced pressure, wash the concentrate with ethanol, and dry at 80°C for 4 hours to obtain hydroxyanthracene POSS. The reaction formula is as follows:

[0007]

[0008] (2) Add N,N-dimethylformamide, hydroxyanthracene POSS, terephthaloyl chloride and pyridine into a flask, stir and react at 25-40°C for 18-24h, pour the solution into ethanol, filter and wash the filter cake with ethanol, and dry at 80°C for 6h to obtain POSS-based polyester.

[0009] (3) Add polyethylene terephthalate, POSS-based polyester and antioxidant into an extruder, set the temperature of the six sections at 240-280°C, and the screw speed at 200-300 r / min for co-extrusion; then stretch through a biaxial stretching machine, with a longitudinal stretching temperature of 110-120°C and a stretching ratio of 3-4 times; and a transverse stretching temperature of 125-135°C and a stretching ratio of 3-4 times; thus obtaining a high temperature resistant and stable protective film material.

[0010] Preferably, in (1), the molar amounts of 9-anthracenecarboxylic acid and triphenylphosphine are 800-880% and 3.2-4% of the molar amount of octaepoxy cage silsesquioxane.

[0011] Preferably, in (2), the molar amounts of hydroxyanthracene POSS and pyridine are 360-440% and 800-960% of the molar amount of terephthaloyl chloride.

[0012] Preferably, in (3), the mass of the POSS-based polyester is 1-10% of the mass of the polyethylene terephthalate.

[0013] Technical effect: The present invention uses triphenylphosphine as a catalyst to carry out a ring-opening reaction on the epoxy group of octaepoxy cage-type silsesquioxane and the carboxyl group of 9-anthracenecarboxylic acid to obtain hydroxyanthracene POSS, and the generated hydroxyl group undergoes an acyl chloride esterification polymerization reaction with terephthaloyl chloride to obtain POSS-based polyester, which is finally blended with polyethylene terephthalate to prepare a film to obtain a high-temperature resistant and stable protective film material.

[0014] The POSS-based polyester of the present invention is a polyester-type polymer, and has good compatibility with PET polyester. At the same time, the POSS-based polyester contains a unique nanostructure hybrid system of POSS cage-type polysilsesquioxane, which has high mechanical properties and strong wear resistance, and contains a heat-resistant anthracene-based condensed ring structure. After being blended with PET polyester to make a film, the tensile properties of the film material are significantly improved, the friction and wear amount is reduced, and the mass loss thermal decomposition temperature is increased, so that the film material exhibits excellent mechanical strength, wear resistance, scratch resistance and high temperature resistance. The PET-based film material of the present invention has good practical applications in aspects such as automobile film, protective film, and high-temperature-resistant electrical insulation film. DETAILED DESCRIPTION

[0015] For ease of understanding of the present invention, preferred embodiments of the present invention are provided below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0016] Example 1

[0017] (1) Add 60 mL of toluene solvent, 2.5 mmol of octaepoxy cage-type silsesquioxane, and 20 mmol of 9-anthracenecarboxylic acid into a flask, stir, and then add 0.1 mmol of triphenylphosphine in a nitrogen atmosphere. Heat to 110°C and stir to react for 12 hours. During the reaction, condense and reflux, concentrate under reduced pressure, wash the concentrate with ethanol, and dry at 80°C for 4 hours to obtain hydroxyanthracene POSS.

[0018] (2) Add 50 mL of N,N-dimethylformamide, 1 mmol of hydroxyanthracene POSS, 4 mmol of terephthaloyl chloride, and 8 mmol of pyridine into a flask, stir and react at 40 °C for 18 h, pour the solution into ethanol, filter and wash the filter cake with ethanol, and dry at 80 °C for 6 h to obtain POSS-based polyester.

[0019] (3) Add 1 kg of polyethylene terephthalate, 10 g of POSS-based polyester and 3 g of antioxidant 1076 into an extruder, and mix and extrude them at six temperature stages of 240°C, 255°C, 265°C, 275°C, 280°C and 280°C, with a screw speed of 300 r / min. Then, stretch them through a biaxial stretching machine, with a longitudinal stretching temperature of 120°C and a stretching ratio of 3.5 times; a transverse stretching temperature of 135°C and a stretching ratio of 3.5 times; and obtain a high-temperature resistant and stable protective film material.

[0020] Example 2

[0021] (1) Add 80 mL of toluene solvent, 2.5 mmol of octaepoxy cage-type silsesquioxane, and 22 mmol of 9-anthracenecarboxylic acid into a flask, stir, and then add 0.08 mmol of triphenylphosphine in a nitrogen atmosphere. Heat to 110°C and stir to react for 10 hours. During the reaction, condense and reflux, concentrate under reduced pressure, wash the concentrate with ethanol, and dry at 80°C for 4 hours to obtain hydroxyanthracene POSS.

[0022] (2) Add 50 mL of N,N-dimethylformamide, 1 mmol of hydroxyanthracene POSS, 4.4 mmol of terephthaloyl chloride, and 9.6 mmol of pyridine into a flask, stir and react at 25 °C for 24 h, pour the solution into ethanol, filter and wash the filter cake with ethanol, and dry at 80 °C for 6 h to obtain POSS-based polyester.

[0023] (3) Add 1 kg of polyethylene terephthalate, 30 g of POSS-based polyester and 3 g of antioxidant 1076 into an extruder, and extrude the mixture at six temperature stages of 240°C, 255°C, 265°C, 275°C, 280°C and 280°C, with a screw speed of 200 r / min. Then, stretch the mixture through a biaxial stretching machine, with a longitudinal stretching temperature of 110°C and a stretching ratio of 4 times; a transverse stretching temperature of 125°C and a stretching ratio of 4 times. A high temperature resistant and stable protective film material is obtained.

[0024] Example 3

[0025] (1) Add 60 mL of toluene solvent, 2.5 mmol of octaepoxy cage-type silsesquioxane, and 20 mmol of 9-anthracenecarboxylic acid into a flask, stir, and then add 0.09 mmol of triphenylphosphine in a nitrogen atmosphere. Heat to 100°C and stir to react for 18 hours. During the reaction, condense and reflux, concentrate under reduced pressure, wash the concentrate with ethanol, and dry at 80°C for 4 hours to obtain hydroxyanthracene POSS.

[0026] (2) Add 40 mL of N,N-dimethylformamide, 1 mmol of hydroxyanthracene POSS, 3.6 mmol of terephthaloyl chloride, and 8 mmol of pyridine into a flask, stir and react at 35 °C for 24 h, pour the solution into ethanol, filter and wash the filter cake with ethanol, and dry at 80 °C for 6 h to obtain POSS-based polyester.

[0027] (3) Add 1 kg of polyethylene terephthalate, 50 g of POSS-based polyester and 3 g of antioxidant 1076 into an extruder, and extrude the mixture at six temperature stages of 240°C, 255°C, 265°C, 275°C, 280°C and 280°C, with a screw speed of 300 r / min. Then, stretch the mixture through a biaxial stretching machine, with a longitudinal stretching temperature of 110°C and a stretching ratio of 3 times; a transverse stretching temperature of 135°C and a stretching ratio of 3 times. A high temperature resistant and stable protective film material is obtained.

[0028] Example 4

[0029] (1) Prepare POSS-based polyester according to the method of Example 1.

[0030] (2) Add 1 kg of polyethylene terephthalate, 75 g of POSS-based polyester and 3 g of antioxidant 1076 into an extruder, and mix and extrude them at six temperature stages of 240°C, 255°C, 265°C, 275°C, 280°C and 280°C, with a screw speed of 300 r / min. Then, stretch them through a biaxial stretching machine, with a longitudinal stretching temperature of 120°C and a stretching ratio of 3.5 times; a transverse stretching temperature of 135°C and a stretching ratio of 3.5 times; and obtain a high-temperature resistant and stable protective film material.

[0031] Example 5

[0032] (1) Prepare POSS-based polyester according to the method of Example 1.

[0033] (2) Add 1 kg of polyethylene terephthalate, 100 g of POSS-based polyester and 3 g of antioxidant 1076 into an extruder, and extrude the mixture at six temperature stages of 240°C, 255°C, 265°C, 275°C, 280°C and 280°C, with a screw speed of 300 r / min. Then, stretch the mixture through a biaxial stretching machine, with a longitudinal stretching temperature of 120°C and a stretching ratio of 3.5 times; and a transverse stretching temperature of 135°C and a stretching ratio of 3.5 times. A high temperature resistant and stable protective film material is obtained.

[0034] Comparative Example 1

[0035] (1) Add 1 kg of polyethylene terephthalate and 3 g of antioxidant 1076 into an extruder, and mix and extrude them at six temperatures of 240°C, 255°C, 265°C, 275°C, 280°C, and 280°C, with a screw speed of 300 r / min; then stretch them through a biaxial stretching machine, with a longitudinal stretching temperature of 120°C and a stretching ratio of 3.5 times; a transverse stretching temperature of 135°C and a stretching ratio of 3.5 times; and obtain a high-temperature resistant and stable protective film material.

[0036] Comparative Example 2

[0037] (1) Add 1 kg of polyethylene terephthalate, 10 g of octaepoxy cage silsesquioxane, and 3 g of antioxidant 1076 into an extruder, and mix and extrude them at six temperature stages of 240°C, 255°C, 265°C, 275°C, 280°C, and 280°C, with a screw speed of 300 r / min; then stretch them through a biaxial stretching machine, with a longitudinal stretching temperature of 120°C and a stretching ratio of 3.5 times; a transverse stretching temperature of 135°C and a stretching ratio of 3.5 times; and obtain a high temperature resistant and stable protective film material.

[0038] Comparative Example 3

[0039] (1) Add 60 mL of toluene solvent, 2.5 mmol of octaepoxy cage-type silsesquioxane, and 20 mmol of benzoic acid into a flask, stir, and then add 0.1 mmol of triphenylphosphine in a nitrogen atmosphere. Heat to 110°C and stir to react for 12 hours. During the reaction, condense and reflux. Concentrate under reduced pressure, wash the concentrate with ethanol, and dry at 80°C for 4 hours to obtain hydroxy POSS.

[0040] (2) Add 50 mL of N,N-dimethylformamide, 1 mmol of hydroxy POSS, 4 mmol of terephthaloyl chloride, and 8 mmol of pyridine into a flask, stir and react at 40 °C for 18 h, pour the solution into ethanol, filter and wash the filter cake with ethanol, and dry at 80 °C for 6 h to obtain POSS-based polyester.

[0041] (3) Add 1 kg of polyethylene terephthalate, 10 g of POSS-based polyester and 3 g of antioxidant 1076 into an extruder, and mix and extrude them at six temperature stages of 240°C, 255°C, 265°C, 275°C, 280°C and 280°C, with a screw speed of 300 r / min. Then, stretch them through a biaxial stretching machine, with a longitudinal stretching temperature of 120°C and a stretching ratio of 3.5 times; a transverse stretching temperature of 135°C and a stretching ratio of 3.5 times; and obtain a high-temperature resistant and stable protective film material.

[0042] The tensile properties of the high temperature stability protective film material are tested according to GB / T 13542.2-2021 standard. The tensile rate is 100 mm / min.

[0043] Table 1 Tensile properties of membrane materials

[0044]

[0045] The friction performance was tested according to ASTM G99-04 standard.

[0046] The thermal properties were tested in a thermogravimetric analyzer under a nitrogen atmosphere with a heating rate of 10°C / min and a maximum test temperature of 700°C.

[0047] Table 2 Wear resistance and heat resistance test of membrane materials

[0048]

[0049] As shown in Table 1 and Table 2, the PET film material of Comparative Example 1 has low transverse and longitudinal tensile strength and elongation at break, large abrasion loss, poor mechanical properties and wear resistance, low mass loss temperature and poor high temperature resistance.

[0050] POSS-based polyester is added to the PET film materials of Examples 1-5. As a polyester-type polymer, POSS-based polyester has good compatibility with PET polyester. At the same time, the POSS-based polyester contains a unique nanostructure hybrid system of POSS cage-type polysilsesquioxane, which has high mechanical properties and strong wear resistance, and contains a heat-resistant anthracene-based condensed ring structure. After being blended with PET polyester to form a film, the tensile properties of the film material are significantly improved, the friction and wear amount is reduced, and the mass loss thermal decomposition temperature is increased, so that the film material exhibits excellent mechanical strength, wear resistance, scratch resistance and high temperature resistance.

[0051] Octaepoxy cage-type silsesquioxane was added to the PET film material of Comparative Example 2, which has poor compatibility with PET polyester, poor dispersibility in the PET film material, poor reinforcement effect on the film material, low tensile strength, elongation at break and thermal decomposition temperature of mass loss, and large abrasion.

[0052] In Comparative Example 3, octaepoxy cage-type silsesquioxane is reacted with benzoic acid, and the obtained hydroxy POSS is then polymerized with terephthaloyl chloride. The obtained POSS-based polyester does not contain the heat-resistant anthracene-based fused ring structure, resulting in a mass loss thermal decomposition temperature of the PET material that is lower than that of the embodiments.

[0053] The above embodiments only express the preferred implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a high temperature resistant and stable protective film material, characterized in that: The preparation method is as follows: (1) Add toluene solvent, octaepoxy cage silsesquioxane, and 9-anthracenecarboxylic acid into a flask, stir, and then add triphenylphosphine in a nitrogen atmosphere, stir to react, concentrate under reduced pressure, wash, and dry to obtain hydroxyanthracene POSS; the reaction formula is as follows: (2) Add N,N-dimethylformamide, hydroxyanthracene POSS, terephthaloyl chloride, and pyridine into a flask, stir to react, pour the solution into ethanol, filter, wash, and dry to obtain POSS-based polyester; (3) Adding polyethylene terephthalate, POSS-based polyester and antioxidant into an extruder, blending and extruding; then stretching through a biaxial stretching machine to obtain a high temperature resistant and stable protective film material; In the above (3), the mass of the POSS-based polyester is 1-10% of the mass of the polyethylene terephthalate.

2. The method for preparing the high temperature resistant stability protective film material according to claim 1, characterized in that: In the above (1), the molar amounts of 9-anthracenecarboxylic acid and triphenylphosphine are 800-880% and 3.2-4% of the molar amount of octaepoxy cage-type silsesquioxane, respectively.

3. The method for preparing the high temperature resistant stability protective film material according to claim 1, characterized in that: In the above (1), the reaction temperature is 100-110°C and the reaction time is 10-18h.

4. The method for preparing the high temperature resistant stability protective film material according to claim 1, characterized in that: In the above (2), the molar amounts of hydroxyanthracene POSS and pyridine are 360-440% and 800-960% of the molar amount of terephthaloyl chloride, respectively.

5. The method for preparing a high temperature resistant stability protective film material according to claim 1, characterized in that: In the above (2), the reaction temperature is 25-40°C and the reaction time is 18-24h.

6. The method for preparing a high temperature resistant stability protective film material according to claim 1, characterized in that: The temperature of the sixth section of the extruder is 240-280° C., and the screw speed is 200-300 r / min.

7. The method for preparing a high temperature resistant stability protective film material according to claim 1, characterized in that: The biaxial stretching machine has a longitudinal stretching temperature of 110-120° C. and a stretching ratio of 3-4 times; a transverse stretching temperature of 125-135° C. and a stretching ratio of 3-4 times.

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