A polycarbonate / polyethylene terephthalate material and a method for its preparation

Abstract

The application provides a polycarbonate / polyethylene terephthalate material and a preparation method thereof. The material comprises the following raw materials: PC, PET, a phosphoric acid triphenyl hypophosphite itaconic anhydride modified chain extender, a filler and the like. By introducing the phosphoric acid triphenyl hypophosphite itaconic anhydride modified chain extender, the material solves the problems of degradation and mechanical property reduction caused by the introduction of the filler into the system, and simultaneously considers the problem of flame retardant performance.

Description

Technical Field

[0001] This invention belongs to the field of modified plastics, specifically relating to a polycarbonate / polyethylene terephthalate material and its preparation method. Background Technology

[0002] PC / PET alloys, prepared by blending polycarbonate (PC) and polyethylene terephthalate (PET), have been widely used in many fields such as automobiles, machinery, and home appliances because they can complement each other's strengths and weaknesses.

[0003] In the automotive industry, various requirements from different manufacturers, such as painting requirements, dimensional tolerances for summer and winter seasons, and high modulus, necessitate the addition of inorganic mineral fillers to PC / PET alloys to enhance dimensional stability and improve modulus. However, polyester materials like PET inherently exhibit low melt strength and melt viscoelasticity during processing, resulting in poor processing performance. Inorganic fillers, such as talc, are inherently alkaline and can cause polymer degradation, significantly increasing processing difficulty. These factors lead to a decline in impact resistance, modulus, and other properties, and the performance defects introduced during processing severely limit the material's application in multiple fields.

[0004] In polyester processing, the introduction of chain extenders is a common method to improve the processability and mechanical properties of materials. While commonly used chain extenders can improve this, they cannot simultaneously address the degradation issues caused by the introduction of fillers. Furthermore, the rise of new energy vehicles has placed new demands on the flame retardant properties of materials.

[0005] In summary, there is an urgent need for a modifier for flame-retardant PC / PET filler materials to solve the problems of degradation and decreased mechanical properties caused by the introduction of fillers into the system, while also taking into account the flame-retardant properties. Summary of the Invention

[0006] To address the aforementioned problems, one objective of this invention is to provide a polycarbonate / polyethylene terephthalate material. This material solves the problems of degradation and decreased mechanical properties caused by the introduction of fillers into the system, as well as the issues of flame retardant performance.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0008] A polycarbonate (PC) / polyethylene terephthalate (PET) material, said material comprising the following parts by weight of raw materials:

[0009] 30-80 parts PC; 10-60 parts PET; 5-30 parts chain extender modified with triphenylphosphine phosphate-based itaconic anhydride; 5-20 parts filler; 0-5 parts processing aid;

[0010] Preferably, the material comprises the following parts by weight of raw materials:

[0011] 50-80 parts PC; 10-40 parts PET; 5-20 parts chain extender modified with triphenylphosphine-based itaconic anhydride; 5-20 parts filler; 0-5 parts processing aid.

[0012] In this invention, triphenylphosphine phosphate is first prepared through a substitution reaction between phosphorus oxychloride and phenylphosphine, and then triphenylphosphine-based itaconic anhydride is prepared through a pH addition reaction with itaconic anhydride. The schematic diagram is as follows:

[0013]

[0014] This invention uses triphenylphosphine-based itaconic anhydride as a modifier mixed with PC / PET materials. Its anhydride structure acts as a chain extender component, binding to multiple binding sites on the molecularly branched structure, thus improving the melt strength and viscoelasticity of the PET material and increasing its molecular weight. This facilitates processing while enhancing the system's impact resistance. Furthermore, the introduction of the phosphine structure also improves the material's flame retardant properties, achieving a highly efficient flame retardant effect without the need for additional flame retardants. The retained phosphine groups neutralize the alkalinity of the filler while also weakening the effect of the catalyst in the system, significantly inhibiting the transesterification reaction. The PC / PET material of this invention exhibits stable molding properties and excellent flame retardant and mechanical properties.

[0015] In one embodiment of the present invention, the melt flow index of the PC at 300°C and 1.2kg is 3-65g / 10min, preferably 5-50g / 10min, and more preferably 7-35g / 10min.

[0016] In one embodiment of the invention, the intrinsic viscosity of the PET is 0.58-0.87 dl / g. The intrinsic viscosity is determined using the capillary method.

[0017] In one embodiment of the present invention, the filler is an inorganic filler, preferably one or more of montmorillonite, talc, and wollastonite. These fillers are commonly used in the art, and those skilled in the art can select and determine the dosage as needed.

[0018] In one embodiment of the present invention, the chain extender is triphenylphosphine-based itaconic anhydride phosphate obtained by reacting phosphorus oxychloride, phenylphosphine acid, and itaconic anhydride; preferably, the reaction temperature is 20-50°C, and the reaction time is 1-4 hours. From the composition of the product triphenylphosphine-based itaconic anhydride phosphate, it can be seen that the theoretical molar ratio of the raw materials phosphorus oxychloride, phenylphosphine acid, and itaconic anhydride is 1:3:3, which can be adjusted as needed by those skilled in the art during actual preparation.

[0019] In this invention, the processing aid is selected from one or more of the following: antioxidants, lubricants, ultraviolet absorbers, flame retardants, toughening agents, compatibilizers, light stabilizers, heat stabilizers, metal passivators, plasticizers, anti-sticking agents, colorants, coupling agents, nucleating agents, foaming agents, antibacterial agents, mildew inhibitors, acid removers, hydrolysis resistant agents, chain extenders, flow modifiers, transesterification inhibitors, matting agents, antistatic agents, reinforcing agents, fillers, antifogging agents, light diffusing agents, infrared absorbers, fluorescent whitening agents, and laser marking agents; preferably, the antioxidant is a hindered phenol or a phosphite. The antioxidants are selected from one or more of the following: thioesters, benzofurans, acryloyl-modified phenols, and hydroxylamines. Preferably, the lubricant is selected from one or more of the following: fatty alcohols, metallic soaps, fatty acids, fatty acid esters, lignite acid and its derivatives, amide waxes, saturated hydrocarbons, polyolefin waxes and their derivatives, organosilicon and silicone powders, and organofluorine compounds. Preferably, the ultraviolet absorber is selected from one or more of the following: benzophenones, benzotriazoles, triazines, benzoic acid esters, cyanoacrylates, and phenylimidazolium compounds. The above-mentioned additives are commonly used in the art, and those skilled in the art can select and determine the dosage as needed.

[0020] Another object of the present invention is to provide a method for preparing polycarbonate (PC) / polyethylene terephthalate (PET) materials.

[0021] A method for preparing a polycarbonate (PC) / polyethylene terephthalate (PET) material, wherein the material is the aforementioned polycarbonate (PC) / polyethylene terephthalate (PET) material, and the preparation method comprises the following steps:

[0022] S1: Add PC, PET, modifier, filler and optional processing aids into a mixer and stir to obtain a premix;

[0023] S2: The mixture is extruded and granulated using a twin-screw extruder to obtain the target material.

[0024] In this invention, the conveying section temperature of the S2 melt extrusion is 230–250°C, the plasticizing section temperature is 250–280°C, the metering section temperature is 260–280°C, and the screw speed is 200–600 rpm. These process parameters are conventional extrusion process parameters in the art, and those skilled in the art can select them as needed.

[0025] Another object of the present invention is to provide a use of a polycarbonate (PC) / polyethylene terephthalate (PET) material.

[0026] Use of a polycarbonate (PC) / polyethylene terephthalate (PET) material, wherein the material is the one described above or the one prepared by the method described above, wherein the material is used as a polycarbonate (PC) / polyethylene terephthalate (PET) material that combines mechanical properties and flame retardant properties, preferably for use in the automotive industry.

[0027] Compared with the prior art, the positive effects of the present invention are as follows:

[0028] The modified material obtained by this invention ensures production stability, effectively inhibits system degradation, and achieves high modulus while maintaining an impact strength of 65 KJ / m. 2 Furthermore, its flame retardant properties can reach V0. Attached Figure Description

[0029] Figure 1 The infrared spectrum of the synthesized product, triphenylphosphine-itaconic anhydride P-PPO-IA-1. Detailed Implementation

[0030] To better explain the present invention, the present invention will be further described in detail below with reference to the embodiments. However, the embodiments described in the present invention are only for illustration and do not limit the scope of the present invention.

[0031] The components of the comparative examples and embodiments are as follows:

[0032] Polycarbonate resin: 2070, melt flow index of 7 g / 10 min (300℃, 1.2 kg), Wanhua Chemical Group Co., Ltd.

[0033] Polycarbonate resin: 2220, melt flow index of 20g / 10min (300℃, 1.2kg), Wanhua Chemical Group Co., Ltd.

[0034] Polyethylene terephthalate resin: CZ-5055, Sanfangxiang Company, with an intrinsic viscosity of 0.68 dl / g;

[0035] Polyethylene terephthalate resin: CZ-328A, Sanfangxiang Company, with an intrinsic viscosity of 0.87 dl / g;

[0036] Phosphorus oxychloride: Adamas Reagents Ltd.

[0037] Phenylephrine (PPO): Adamas Reagents Ltd.

[0038] Itaconic anhydride (IA): Shanghai Maclean Biochemical Technology Co., Ltd.

[0039] Triethylamine (TEA), Jinan Quansheng Chemical Co., Ltd.

[0040] Ethyl acetate: Sinopharm Chemical Reagent Co., Ltd.

[0041] Talc M05SLC: Mengdu Minerals.

[0042] Montmorillonite (MMT): Sodium-based montmorillonite, manufactured by Nanocor Corporation, USA.

[0043] Antioxidant: Irganox 168, manufactured by BASF.

[0044] Diphenyl sulfonate: KSS, Sinopharm Chemical Reagent Co., Ltd.

[0045] Lubricant: PETS, pentaerythritol stearate, Lonza Corporation, USA.

[0046] Performance tests are as follows:

[0047] The melt flow index was tested according to ISO 1133 standard, under the following conditions: 260℃, 5kg.

[0048] Impact strength was tested according to ISO 179 standard. The sample size was 80*10*4mm and the notch depth was 2.0mm.

[0049] Bending strength was tested according to ISO 178, with a sample size of 80*10*4mm and a rate of 2mm / min.

[0050] The Vicat softening temperature (VST) was tested according to ISO 306 standard, with a load of 50 N and a heating rate of 120 °C / h.

[0051] The flammability rating was tested according to UL-94, with a sample size of 130mm*13mm*1.5mm, and tested for vertical burning.

[0052] The linear coefficient of thermal expansion (CLTE) was measured according to ISO 11359, with a sample size of 8mm*10mm*3mm and a test temperature of -45℃ to 100℃.

[0053] Infrared spectroscopy was performed using a Fourier transform infrared spectrometer, model WQF-600N, in total internal reflection mode at wavelengths of 4000–400 cm⁻¹. -1 .

[0054] Preparation of triphenylphosphine-based itaconic anhydride:

[0055] Triphenylphosphine phosphate (P-PPO): 85 parts by mass (0.6 mol) of phenylphosphine and 61 parts by mass (0.6 mol) of triethylamine were added to a three-necked flask equipped with a condenser, thermometer, and dropping funnel. 31 parts by mass (0.2 mol) of phosphorus oxychloride were added dropwise. The mixture was stirred continuously at 23°C to allow the substances to react completely. The reaction was continued for 4 hours. The triethylamine salt was removed by vacuum filtration to obtain P-PPO-1.

[0056] Triphenylphosphine phosphate (P-PPO): 85 parts by mass (0.6 mol) of phenylphosphine and 61 parts by mass (0.6 mol) of triethylamine were added to a three-necked flask equipped with a condenser, thermometer, and dropping funnel. 31 parts by mass (0.2 mol) of phosphorus oxychloride were added dropwise. The mixture was stirred continuously at 45°C to ensure complete reaction. The reaction was continued for 2 hours. The triethylamine salt was removed by vacuum filtration to obtain P-PPO-2.

[0057] Triphenylphosphine-based itaconic anhydride (P-PPO-IA): 95 parts by mass (0.2 mol) of P-PPO-1, 67 parts by mass (0.6 mol) of itaconic anhydride, and an appropriate amount of ethyl acetate were added to a three-necked flask equipped with a condenser and a thermometer. The mixture was stirred continuously at 23°C to allow the substances to react fully. The reaction was continued for 4 hours. The ethyl acetate was removed by rotary evaporation, and the mixture was dried in a vacuum oven at 100°C for 5 hours to obtain P-PPO-IA-1.

[0058] Triphenylphosphine-based itaconic anhydride (P-PPO-IA): 95 parts by mass (0.2 mol) of P-PPO-2, 67 parts by mass (0.6 mol) of itaconic anhydride, and an appropriate amount of ethyl acetate were added to a three-necked flask equipped with a condenser and a thermometer. The mixture was stirred continuously at 45°C to ensure complete reaction. The reaction was continued for 2 hours. The ethyl acetate was removed by rotary evaporation, and the mixture was dried in a vacuum oven at 100°C for 5 hours to obtain P-PPO-IA-2.

[0059] Examples 1-3 and Comparative Examples 1-4:

[0060] The material preparation process is as follows:

[0061] Blending, extrusion, and granulation: Polycarbonate resin, PET, PPO, IA, P-PPO-IA, and M05SLC are mixed in a high-speed mixer according to the raw material types and amounts in Table 1. The mixture is then added to a loss-in-weight feeder above the feed port of the screw extruder. The temperatures of zones 1-10 of the twin-screw extruder are controlled at 200℃, 220℃, 240℃, 250℃, 250℃, 250℃, 250℃, 240℃, and 235℃, respectively, with the die head temperature at 230℃. The screw speed is controlled at 400 rpm. After blending, drawing, water cooling, air drying, pelletizing, and drying processes, the PC / PET composition is obtained.

[0062] Comparative Examples 1-4 were compared with Example 2. Comparative Example 1 differed from Example 2 in that it contained only phenylphosphine, while the rest were the same. Comparative Example 2 differed from Example 3 in that it contained both itaconic anhydride and phenylphosphine, but only through physical blending, while the rest were the same. Comparative Example 4 differed from Example 4 in that it did not contain itaconic anhydride or phenylphosphine, but instead used the common flame retardant KSS, while the rest were the same.

[0063] Table 1. Formulations of Examples 1-3 and Comparative Examples 1-4

[0064] Dosage / parts by weight Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 2150 44.3 24.3 10.3 24.3 24.3 24.3 24.3 2070 35 20 20 20 20 20 20 CZ-328A 2 10 30 10 10 10 10 CZ-5055 8 10 24 10 10 10 10 Antioxidant 168 0.3 0.3 0.3 0.3 0.3 0.3 0.3 PETS 0.4 0.4 0.4 0.4 0.4 0.4 0.4 M05SLC 5 15 / 15 15 15 15 MMT / / 5 / / / / KSS / / / / / / 20 PPO / / / 20 / 10 / IA / / / / 20 10 / P-PPO-IA-1 5 20 / / / / / P-PPO-IA-2 / / 10 / / / /

[0065] Table 2 Performance comparison of Examples 1-3 and Comparative Examples 1-4:

[0066] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Melt index / g / 10min 39 25 45 55 69 50 65 <![CDATA[Impact strength / KJ / m 2 > 30 60 28 15 19 20 15 Flexural modulus / MPa 3200 3700 3200 3300 3100 3300 3300 VST / ℃ 105 114 106 104 100 105 105 CLTE (23~55℃) <![CDATA[55*10 -6 ]]> <![CDATA[45*10 -6 ]]> <![CDATA[55*10 -6 ]]> <![CDATA[55*10 -6 ]]> <![CDATA[60*10 -6 ]]> <![CDATA[55*10 -6 ]]> <![CDATA[60*10 -6 ]]>

[0067] Table 3 Comparison of vertical combustion performance between Examples 1-3 and Comparative Examples 1-4:

[0068] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 flammability rating <![CDATA[V2]]> <![CDATA[V0]]> <![CDATA[V0]]> V2 NG <![CDATA[V2]]> <![CDATA[V1]]>

[0069] Note: Combustion rating V0 > V1 > V2 > NG.

[0070] By comparing the melt flow index and VST of Comparative Examples 1-4 and Examples 1-3, it can be found that compared with pure PC / PET alloys, the addition of fillers causes severe material degradation, a surge in melt flow index, and a decrease in heat resistance. The phosphorous acid in the modifier P-PPO-IA can reduce the antimony-based catalyst in PET, acting as an inhibitor. By comparing the mechanical properties of Comparative Examples 1-4 and Examples 1-3, it can be found that the addition of the modifier P-PPO-IA can improve the impact performance of the material. Due to the presence of three branching sites under the same structure, adding the same or less content of P-PPO-IA significantly improves the impact performance, and the impact performance further improves with increasing addition amount. By comparing the flammability ratings of Comparative Examples 1-4 and Examples 1-3, it can be seen that adding PPO alone can improve the flame retardant effect of the material, but the addition of P-PPO-IA can achieve better flame retardant performance with a smaller amount, and is far superior to the effect of the conventional flame retardant KSS.

[0071] The above results demonstrate that adding the modifier P-PPO-IA to PC / PET filler materials can significantly improve the processability of the materials and enhance their strength, toughness, and flame retardancy.

[0072] Those skilled in the art should understand that this invention is not limited to the above embodiments. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the invention as claimed. The scope of protection of this invention is defined by the appended claims.

Claims

1. A polycarbonate (PC) / polyethylene terephthalate (PET) material, characterized in that, The material comprises the following raw materials in parts by weight: 30-80 PCs; 10-60 PET samples; 5-30 parts of a chain extender modified with triphenylphosphine hypophosphitecanic anhydride; 5-20 parts of filler; 0-5 parts processing aids; The chain extender is triphenylphosphine triphosphate itaconic anhydride obtained by reacting phosphorus oxychloride, phenylphosphine acid and itaconic anhydride; the reaction temperature is 20-50℃ and the reaction time is 1-4h.

2. The material according to claim 1, characterized in that, The material comprises the following raw materials in parts by weight: 50-80 PCs; 10-40 PET samples; 5-20 parts of chain extender modified with triphenylphosphine hypophosphitecanic anhydride; 5-20 parts of filler; 0-5 parts processing aids.

3. The material according to claim 1, characterized in that, The melt flow index of the PC at 300℃ and 1.2kg is 3-65g / 10min; And / or, the intrinsic viscosity of the PET is 0.58-0.87 dl / g; And / or, the packing material is an inorganic packing material.

4. The material according to claim 3, characterized in that, The melt flow index of the PC at 300℃ and 1.2kg is 5-50g / 10min; And / or, the filler is one or more of montmorillonite, talc, and wollastonite.

5. The material according to claim 4, characterized in that, The melt flow index of the PC at 300℃ and 1.2kg is 7-35g / 10min.

6. A method for preparing the polycarbonate (PC) / polyethylene terephthalate (PET) material according to any one of claims 1-5, characterized in that, The preparation method includes the following steps: S1: Add PC, PET, modifier, filler and optional processing aids into a mixer and stir to obtain a premix; S2: The mixture is extruded and granulated using a twin-screw extruder to obtain the material.

7. Use of a polycarbonate (PC) / polyethylene terephthalate (PET) material, wherein the material is the material of any one of claims 1-5, or the material prepared by the preparation method of claim 6, wherein the material is used as a polycarbonate (PC) / polyethylene terephthalate (PET) material that takes into account both mechanical properties and flame retardant properties.

8. The use according to claim 7, characterized in that, The material is used in the automotive industry.

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