Weather-resistant polycarbonate material as well as preparation method and application thereof in plastic particles

Abstract

The invention relates to the technical field of polycarbonate, and discloses a weather-resistant polycarbonate material, a preparation method thereof and application of the weather-resistant polycarbonate material in plastic particles, and the weather-resistant polycarbonate material comprises the following components in parts by weight: 100 parts of polycarbonate resin, 10-25 parts of polycarbonate copolymer and 2-5 parts of fatty acid modified zinc oxide. The side chain of the polycarbonate copolymer contains a flexible and hydrophobic alkyl long chain, so that the toughness and hydrophobicity of the polycarbonate material can be improved, the mechanical properties such as bending strength can be improved, and the water resistance and hydrolysis resistance can be improved. Aliphatic alkyl long chains modified on the surface of the nano-zinc oxide and alkyl long chains of side chains of the polycarbonate copolymer are subjected to a physical chain winding effect, so that the compatibility between the zinc oxide and the polycarbonate material is improved, the mechanical property of the material can be improved, and meanwhile, the ultraviolet aging resistance and weather resistance of the material are improved.

Description

Technical Field

[0001] The invention relates to the technical field of polycarbonate, in particular to a weather-resistant polycarbonate material and a preparation method thereof and application thereof in plastic particles. Background Art

[0002] Polycarbonate has good mechanical properties, excellent flame retardancy and antioxidant properties, and is widely used. Traditional polycarbonate materials have poor hydrolysis stability, poor light aging resistance and weather resistance, which limits the practical application of polycarbonate in outdoor fields. Nano zinc oxide is a cheap and readily available inorganic nano material with excellent mechanical properties and good UV resistance. When added to polymer resins, it can improve the toughness, strength, UV aging resistance and weather resistance of resin materials. Surface modification of nano zinc oxide using fatty acids, polyacrylates, silane coupling agents, etc. can improve its dispersibility and improve its compatibility with polymer resins. Chinese patent CN114292508B discloses a functional nano zinc oxide modified polycarbonate sheet and preparation method, which reacts nano zinc oxide, 2-isocyanatoethyl methacrylate, tris(2-aminoethyl)amine, maleic anhydride grafted polypropylene and other bacterial reactions to obtain maleic anhydride grafted polypropylene modified zinc oxide, which can improve the flexibility, bending strength and impact strength of polycarbonate materials. However, this patent does not solve the problem of poor hydrolysis resistance of polycarbonate. Summary of the invention

[0003] The invention solves the problem that polycarbonate has poor mechanical strength, water resistance and weather resistance.

[0004] The technical solution of the present invention is a weather-resistant polycarbonate material, comprising the following components in parts by weight: 100 parts of polycarbonate resin, 10-25 parts of polycarbonate copolymer, 2-5 parts of fatty acid-modified zinc oxide, and 0.15-0.22 parts of antioxidant.

[0005] Preferably, the preparation method of the weather-resistant polycarbonate material is: add polycarbonate resin, polycarbonate copolymer, fatty acid-modified zinc oxide, and antioxidant into a mixer and mix them evenly, then blend and extrude them in an extruder, with the temperature of sections one to six being 210-260°C and the screw speed being 200-250r / min; and pelletizing to obtain the weather-resistant polycarbonate material.

[0006] Preferably, the preparation method of the carbonate copolymer is:

[0007] (1) The preparation method of N-alkanoylglutamic acid chloride is as follows: a dichloromethane solvent, 140-160 parts by weight of thionyl chloride, 100 parts by weight of N-alkanoylglutamic acid, and 6.2-7.6 parts by weight of catalyst N,N-dimethylformamide are added to a reaction vessel equipped with a condenser reflux tube, reacted at 40-45° C. for 4-6 hours, distilled under reduced pressure, and dried to obtain N-alkanoylglutamic acid chloride; the reaction formula is:

[0008]

[0009] (2) Add N,N-dimethylformamide solvent, polycarbonate diol, N-alkanoyl glutamic acid chloride, and triethylamine to a reaction container, react at 0-5°C for 15-30 minutes, then react at 20-30°C for 18-24 hours, pour the solution into water, filter, wash with water and ethanol, and dry to obtain a polycarbonate copolymer. The reaction formula is:

[0010]

[0011] Preferably, by weight, the amount of polycarbonate diol in (2) is 100 parts, the amount of N-alkanoylglutamic acid chloride is 40-46 parts, and the amount of triethylamine is 22-25 parts.

[0012] Preferably, the preparation method of fatty acid modified zinc oxide is: add ethanol, 100 parts by weight of nano zinc oxide, and 5-15 parts by weight of fatty acid compound into a reaction container equipped with a condenser reflux tube, ultrasonically disperse for 1 hour, heat to 70-80°C, react for 1-2 hours, filter, wash with ethanol, and dry to obtain fatty acid modified zinc oxide.

[0013] Preferably, the fatty acid compound is palmitic acid, myristic acid or stearic acid.

[0014] Preferably, weather-resistant polycarbonate material is used in high-performance plastic pellets.

[0015] The beneficial technical effect of the present invention is as follows: the present invention polymerizes polycarbonate diol and N-alkanoyl glutamic acid to obtain a polycarbonate copolymer containing a long alkyl chain in the side chain, and then melt-co-solidifies with nano zinc oxide modified with fatty acid, polycarbonate resin, etc., and granulates to obtain a weather-resistant polycarbonate material. The polycarbonate copolymer has good compatibility with the polycarbonate material, and the side chain contains a flexible and hydrophobic alkyl long chain, which can improve the toughness and hydrophobicity of the polycarbonate material, is conducive to improving the bending strength and impact strength, and reduces the water absorption performance of the polycarbonate material, thereby reducing the hydrolysis mass loss rate and improving the water resistance and hydrolysis resistance.

[0016] After the nano zinc oxide of the present invention is modified by fatty acids such as stearic acid, its dispersibility becomes better and it is not easy to agglomerate. In addition, during the blending process, the aliphatic alkyl long chain modified on the surface of the zinc oxide and the alkyl long chain of the side chain of the polycarbonate copolymer undergo a physical chain entanglement, thereby modifying the polycarbonate copolymer to the surface of the nano zinc oxide, which is beneficial to improving the compatibility between the zinc oxide and the polycarbonate material. The nano zinc oxide is evenly dispersed in the polycarbonate material, which can improve the mechanical properties of the material such as the bending strength, and at the same time significantly reduce the color difference value after ultraviolet light aging, thereby improving the anti-ultraviolet aging and weather resistance of the material. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] The following polycarbonate resin, model WY-106BR, was purchased from Suzhou Fengjuan Plastic Raw Materials Co., Ltd. Polycarbonate diol, average molecular weight 1000, was purchased from Hubei Xinjiecheng Chemical Technology Co., Ltd. Nano zinc oxide, average particle size 20 nm, was purchased from Ningbo Luofei Nano Technology Co., Ltd.

[0019] N-stearoyl-L-glutamic acid was prepared according to the method of the journal "Journal of Chemistry", Vol. 62, No. 9, 2004, 895-900, the literature "Synthesis and Gelling Properties of N-stearoyl-L-glutamic Acid and Its Ethyl Ester Derivatives", the structural formula is

[0020] N-myristoylglutamic acid was prepared according to the method of Dalian University of Technology's master's thesis "Synthesis and Performance Research of a Series of Amino Acid Surfactants", with the structural formula

[0021] Example 1

[0022] (1) Add 70 mL of dichloromethane solvent, 21 g of thionyl chloride, 15 g of N-stearoyl-L-glutamic acid, and 1.14 g of catalyst N,N-dimethylformamide to a reaction vessel equipped with a condenser reflux tube, react at 40° C. for 6 h, distill under reduced pressure, and dry to obtain N-stearoyl glutamic acid chloride. The structural formula is

[0023]

[0024] (2) Add 500 mL of N,N-dimethylformamide, 50 g of polycarbonate diol, 23 g (51 mmol) of N-stearoyl glutamic acid chloride, and 11.6 g of triethylamine into a reaction container, react at 0° C. for 30 min, then react at 25° C. for 18 h, pour the solution into water, filter, wash with water and ethanol, and dry to obtain a polycarbonate copolymer.

[0025] (3) Add 300 mL of ethanol, 20 g of nano zinc oxide, and 2 g of stearic acid to a reaction vessel equipped with a condenser reflux tube, and after ultrasonic dispersion for 1 h, heat to 70° C., react for 2 h, filter, wash with ethanol, and dry to obtain fatty acid-modified zinc oxide.

[0026] (4) Add 1 kg of polycarbonate resin, 100 g of polycarbonate copolymer, 20 g of fatty acid-modified zinc oxide, and 2.2 g of antioxidant 168 into a mixer and mix well. Then, blend and extrude in an extruder. The temperatures of the first to sixth stages are 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed is 250 r / min. Pelletize to obtain a weather-resistant polycarbonate material.

[0027] Example 2

[0028] (1) Add 80 mL of dichloromethane solvent, 24 g of thionyl chloride, 15 g of N-myristoyl glutamic acid, and 0.93 g of catalyst N,N-dimethylformamide to a reaction vessel equipped with a condenser reflux tube, react at 45° C. for 4 h, distill under reduced pressure, and dry to obtain N-myristoyl glutamic acid chloride. The structural formula is

[0029]

[0030] (2) Add 500 mL of N,N-dimethylformamide, 50 g of polycarbonate diol, 20 g of N-myristoyl glutamic acid chloride, and 12.5 g of triethylamine into a reaction container, react at 5° C. for 15 min, then at 20° C. for 24 h, pour the solution into water, filter, wash with water and ethanol, and dry to obtain a polycarbonate copolymer.

[0031] (3) Add 400 mL of ethanol, 20 g of nano zinc oxide, and 3 g of stearic acid to a reaction vessel equipped with a condenser reflux tube, and after ultrasonic dispersion for 1 hour, heat to 80° C., react for 1 hour, filter, wash with ethanol, and dry to obtain fatty acid-modified zinc oxide.

[0032] (4) Add 1 kg of polycarbonate resin, 170 g of polycarbonate copolymer, 35 g of fatty acid-modified zinc oxide, and 1.5 g of antioxidant 168 into a mixer and mix well. Then, blend and extrude in an extruder. The temperatures of the first to sixth stages are 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed is 200 r / min. Pelletize to obtain a weather-resistant polycarbonate material.

[0033] Example 3

[0034] (1) 600 mL of N,N-dimethylformamide, 50 g of polycarbonate diol, 23 g of N-stearoyl glutamic acid chloride (prepared by Example 1), and 11 g of triethylamine were added to a reaction container, and the mixture was reacted at 0° C. for 30 min and then at 30° C. for 18 h. The solution was poured into water, filtered, washed with water and ethanol, and dried to obtain a polycarbonate copolymer.

[0035] (2) Add 300 mL of ethanol, 20 g of nano zinc oxide, and 1 g of stearic acid into a reaction vessel equipped with a condenser reflux tube, and after ultrasonic dispersion for 1 hour, heat to 80° C., react for 1 hour, filter, wash with ethanol, and dry to obtain fatty acid-modified zinc oxide.

[0036] (3) Add 1 kg of polycarbonate resin, 250 g of polycarbonate copolymer, 50 g of fatty acid-modified zinc oxide, and 2 g of antioxidant 168 into a mixer and mix well. Then, blend and extrude in an extruder. The temperatures of the first to sixth stages are 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed is 200 r / min. Pelletize to obtain a weather-resistant polycarbonate material.

[0037] Comparative Example 1: The difference between this comparative example and Example 1 is that no polycarbonate copolymer and fatty acid-modified zinc oxide are added.

[0038] (1) 1 kg of polycarbonate resin and 2.2 g of antioxidant 168 were added to a mixer and mixed evenly, and then mixed and extruded in an extruder. The temperatures of the first to sixth stages were 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed was 250 r / min. Pelletizing was performed to obtain a weather-resistant polycarbonate material.

[0039] Comparative Example 2: The difference between this comparative example and Example 1 is that no polycarbonate copolymer is added.

[0040] (1) 1 kg of polycarbonate resin, 20 g of fatty acid-modified zinc oxide, and 2.2 g of antioxidant 168 were added to a mixer and mixed evenly, and then blended and extruded in an extruder. The temperatures of the first to sixth stages were 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed was 250 r / min. Pelletizing was performed to obtain a weather-resistant polycarbonate material.

[0041] Comparative Example 3: The difference between this comparative example and Example 1 is that fatty acid-modified zinc oxide is not added.

[0042] (1) 1 kg of polycarbonate resin, 100 g of polycarbonate copolymer, and 2.2 g of antioxidant 168 were added to a mixer and mixed well, and then blended and extruded in an extruder. The temperatures of the first to sixth stages were 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed was 250 r / min. Pelletizing was performed to obtain a weather-resistant polycarbonate material.

[0043] Comparative Example 4: The difference between this comparative example and Example 1 is that when preparing the polycarbonate copolymer, glutaryl chloride is used in an equal molar amount instead of N-stearoyl glutamic acid chloride.

[0044] (1) Add 500 mL of N,N-dimethylformamide, 50 g of polycarbonate diol, 8.5 g (51 mmol) of glutaryl chloride, and 11.6 g of triethylamine into a reaction container, react at 0°C for 30 min, then react at 25°C for 18 h, pour the solution into water, filter, wash with water and ethanol, and dry to obtain a polycarbonate copolymer.

[0045] (2) 1 kg of polycarbonate resin, 100 g of polycarbonate copolymer, 20 g of fatty acid-modified zinc oxide, and 2.2 g of antioxidant 168 were added to a mixer and mixed evenly. The mixture was then blended and extruded in an extruder. The temperatures for the first to sixth stages were 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed was 250 r / min. Pelletizing was performed to obtain a weather-resistant polycarbonate material.

[0046] Comparative Example 5: The difference between this comparative example and Example 1 is that unmodified nano zinc oxide is added.

[0047] (1) 1 kg of polycarbonate resin, 100 g of polycarbonate copolymer, 20 g of nano zinc oxide, and 2.2 g of antioxidant 168 were added to a mixer and mixed evenly, and then blended and extruded in an extruder. The temperatures of the first to sixth stages were 210° C., 225° C., 245° C., 260° C., and 260° C., and the screw speed was 250 r / min. Pelletizing was performed to obtain a weather-resistant polycarbonate material.

[0048] The polycarbonate material is made into a specimen in an injection molding machine, and the temperatures of the first to third sections of the injection molding machine are 220°C, 260°C, and 270°C.

[0049] The bending strength of polycarbonate strips was tested according to the national standard GB / T 9341-2008. The impact strength of polycarbonate strips was tested according to the national standard GB / T1843-2008.

[0050] The polycarbonate strip was made into a 5cm×5cm×2cm sample, placed in a blast dryer, dried at 100℃ for 4h, and weighed (recorded as m 0 ), then soaked in water, heated to 80℃, left for 10 days, changed the water every 12h, took out the specimen, dried at 100℃ for 24h, and weighed (recorded as m 1 ), calculate the hydrolysis mass loss rate W. W=(m 0 -m 1 ) / m 0 × 100%. The smaller W is, the better the water resistance and hydrolysis resistance is.

[0051] The polycarbonate specimens were aged for 720 hours in a UV accelerated aging test chamber (total power of 4.5 kW), and the color difference before and after UV aging was tested according to standard ASTM D2244-16. The smaller the color difference, the better the anti-UV aging and weathering performance.

[0052] Table 1 Polycarbonate performance test

[0053]

[0054] According to the results in Table 1, the polycarbonate in Comparative Example 1 has low bending strength and impact strength, poor toughness, a large hydrolysis mass loss rate, poor water resistance and anti-hydrolysis performance, a large color difference after UV aging, and poor UV resistance and weather resistance.

[0055] Polycarbonate copolymer and fatty acid modified zinc oxide are added to the polycarbonate material of embodiment 1-3, and the polycarbonate copolymer has good compatibility with polycarbonate resin, and the side chain contains flexible and hydrophobic alkyl long chain, which can improve the toughness and hydrophobicity of polycarbonate resin, is conducive to improving bending strength and impact strength, reducing the water absorption performance of polycarbonate material, thereby reducing the hydrolysis mass loss rate, and improving water resistance and hydrolysis resistance. After the nano zinc oxide is modified by fatty acids such as stearic acid, its dispersibility becomes better, it is not easy to agglomerate, and the aliphatic alkyl long chain modified on the surface of zinc oxide and the alkyl long chain of the side chain of the polycarbonate copolymer have a physical chain entanglement during the blending process, thereby modifying the polycarbonate copolymer to the surface of the nano zinc oxide, which is conducive to improving the compatibility between zinc oxide and polycarbonate material, and the nano zinc oxide is evenly dispersed in the polycarbonate material, which can improve the mechanical properties such as bending strength of the material, and the anti-ultraviolet aging and weathering performance are significantly improved, and the color difference value after ultraviolet light aging becomes smaller.

[0056] Compared with Example 1, Comparative Example 2 did not add the polycarbonate copolymer, resulting in poor toughness of the polycarbonate material, low bending strength and impact strength, and poor hydrophobicity, which is not conducive to reducing the water absorption of the polycarbonate material, resulting in a large hydrolysis mass loss rate, poor water resistance and anti-hydrolysis performance.

[0057] Compared with Example 1, Comparative Example 3 did not add fatty acid-modified zinc oxide, resulting in a larger color difference value of the polycarbonate material after ultraviolet aging, and poor anti-ultraviolet aging and weather resistance.

[0058] Comparative Example 4 uses glutaryl chloride as a raw material, and the side chain of the prepared polycarbonate copolymer does not contain a flexible and hydrophobic alkyl long chain, which has a poor toughening effect on the polycarbonate material, and the impact strength and bending strength of the material are low, and the mass loss rate caused by hydrolysis is large, and the water resistance and hydrolysis resistance are poor. The polycarbonate copolymer cannot undergo physical chain entanglement with the aliphatic alkyl long chain modified on the surface of zinc oxide, and the polycarbonate copolymer cannot be modified to the surface of nano zinc oxide, and the compatibility between zinc oxide and polycarbonate resin is not improved, resulting in the impact strength and other mechanical properties of the polycarbonate material being lower than those of Example 1, and the color difference value is greater than that of Example 1.

[0059] In Comparative Example 4, modified nano zinc oxide is added, which has poor dispersibility and cannot undergo physical chain entanglement with the long-chain alkyl group of the polycarbonate copolymer side chain. The polycarbonate copolymer cannot be modified to the surface of the nano zinc oxide, and the compatibility between zinc oxide and the polycarbonate resin is not improved, resulting in the mechanical properties of the polycarbonate material, such as the impact strength, being lower than those in Example 1, and the color difference value being greater than that in Example 1.

[0060] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A weather-resistant polycarbonate material, characterized in that: The weather-resistant polycarbonate material comprises the following components in parts by weight: 100 parts of polycarbonate resin, 10-25 parts of polycarbonate copolymer, 2-5 parts of fatty acid-modified zinc oxide, and 0.15-0.22 parts of antioxidant; The preparation method of the polycarbonate copolymer comprises: adding N,N-dimethylformamide solvent, polycarbonate diol, N-alkanoylglutamic acid chloride and triethylamine into a reaction container, pouring the solution into water after the reaction, filtering, washing with water and ethanol, and drying to obtain the polycarbonate copolymer; The structural formula of the N-alkanoyl glutamic acid chloride is n is any integer value between 13 and 17.

2. The weather-resistant polycarbonate material according to claim 1, characterized in that: The reaction is first carried out at 0-5°C for 15-30 min and then at 20-30°C for 18-24 h.

3. The weather-resistant polycarbonate material according to claim 1, characterized in that: By weight, the usage of the polycarbonate diol is 100 parts, the usage of N-alkanoylglutamic acid chloride is 40-46 parts, and the usage of triethylamine is 22-25 parts.

4. The weather-resistant polycarbonate material according to claim 1, characterized in that: The preparation method of N-alkanoylglutamic acid chloride comprises: adding dichloromethane solvent, thionyl chloride, N-alkanoylglutamic acid, and catalyst N,N-dimethylformamide into a reaction container equipped with a condenser reflux tube, performing reduced pressure distillation after the reaction, and drying to obtain N-alkanoylglutamic acid chloride; The structural formula of the N-alkanoylglutamic acid is n is any integer value between 13 and 17.

5. The weather-resistant polycarbonate material according to claim 4, characterized in that: In terms of weight, the amount of N-alkanoylglutamic acid is 100 parts, the amount of thionyl chloride is 145-160 parts, and the amount of N,N-dimethylformamide is 6.2-7.6 parts.

6. The weather-resistant polycarbonate material according to claim 4, characterized in that: In the preparation method of N-alkanoylglutamic acid chloride, the reaction temperature is 40-45° C. and the reaction time is 4-6 h.

7. The weather-resistant polycarbonate material according to claim 1, characterized in that: The preparation method of the fatty acid modified zinc oxide is as follows: ethanol, 100 parts by weight of nano zinc oxide, and 5-15 parts by weight of fatty acid compounds are added into a reaction container equipped with a condensation reflux tube, ultrasonically dispersed for 1 hour, heated to 70-80° C., reacted for 1-2 hours, filtered, washed with ethanol, and dried to obtain the fatty acid modified zinc oxide.

8. The weather-resistant polycarbonate material according to claim 1, characterized in that: The fatty acid compound is palmitic acid, myristic acid or stearic acid.

9. A method for preparing a weather-resistant polycarbonate material according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: adding polycarbonate resin, polycarbonate copolymer, fatty acid modified zinc oxide and antioxidant into a mixer and mixing them evenly; then blending and extruding them in an extruder, wherein the temperature of the first to sixth stages is 210-260° C. and the screw speed is 200-250 r / min; and pelletizing is performed to obtain a weather-resistant polycarbonate material.

10. Use of the weather-resistant polycarbonate material obtained by the preparation method as claimed in claim 9 in plastic pellets.

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