A polycarbonate polyester composition, and a method of making and using the same

Abstract

This invention discloses a polycarbonate polyester composition, its preparation method, and its applications, relating to the technical field of plastics. The polycarbonate polyester composition of this invention comprises the following components in parts by weight: 44-93 parts polycarbonate; 14-46 parts poly(butylene terephthalate); 0.9-12 parts toughening agent; 4-12 parts flame retardant; 0.4-3.2 parts synergistic flame retardant; and 0.09-6 parts anti-dripping agent. The flame retardant is hexaphenoxycyclotriphosphazene, and the synergistic flame retardant includes a silane coupling agent and aluminum diethylphosphonate. The mass ratio of the silane coupling agent to aluminum diethylphosphonate in the synergistic flame retardant is (0.4-2):100. The polycarbonate polyester composition of this invention features halogen-free flame retardancy, high heat resistance, and high toughness.

Description

Technical Field

[0001] This invention relates to the field of plastics, and more particularly to a polycarbonate polyester composition, its preparation method, and its application. Background Technology

[0002] Polycarbonate / poly(terephthalate succinate) (PC / PBT) alloy is a high-performance alloy material with advantages such as good toughness, high surface gloss, and good processing fluidity. At the same time, the addition of PBT can significantly improve the chemical resistance of polycarbonate, further expanding its application fields, such as electronics, kitchen and bathroom appliances, audio-visual equipment, transportation and other fields.

[0003] Currently, commercially available PC / PBT alloy materials primarily use halogenated flame retardants, such as brominated polycarbonate, brominated polystyrene, and brominated epoxy resin. However, halogenated flame retardants have several drawbacks: they produce large amounts of toxic gases during combustion; furthermore, long-term use can lead to their release from the material surface, corroding molds and posing other safety hazards. Moreover, using halogen-free flame retardants requires higher dosages to achieve the UL94 V-0 rating, and their flame retardant performance significantly decreases at high temperatures. Therefore, further research is needed on high-performance PC / PBT alloy modification technologies. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a polycarbonate polyester composition, its preparation method, and its application. The polycarbonate polyester composition of this invention has the characteristics of halogen-free flame retardancy, high heat resistance, and high toughness.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a polycarbonate polyester composition comprising the following components in parts by weight: Polycarbonate 44-93 parts; polysuccinate 14-46 parts; toughening agent 0.9-12 parts; flame retardant 4-12 parts; synergistic flame retardant 0.4-3.2 parts; anti-dripping agent 0.09-6 parts; The flame retardant is hexaphenoxycyclotriphosphazene, and the synergistic flame retardant includes a silane coupling agent and aluminum diethylphosphonate; the mass ratio of the silane coupling agent to aluminum diethylphosphonate is (0.4-2):100.

[0006] Preferably, the mass ratio of silane coupling agent to aluminum diethylphosphonate in the synergistic flame retardant is (1-1.5):100.

[0007] Preferably, the preparation method of the synergistic flame retardant is as follows: Aluminum diethylphosphonate and a silane coupling agent are uniformly dispersed in an ethanol solution and stirred at 55-60°C for 1-2 hours. After standing, filtration, washing, drying, grinding and sieving are performed to obtain the synergistic flame retardant.

[0008] It should be noted that the present invention can use conventional methods in the prior art to prepare synergistic flame retardants. The present invention is not limited to the preparation method. The following is an exemplary preparation method of synergistic flame retardants.

[0009] Method 1: Place aluminum diethylphosphonate and silane coupling agent into a high-speed mixer and stir evenly at 55~65℃ (speed can be 50~400rpm, time can be 0.5~6h) to obtain a synergistic flame retardant.

[0010] Method 2: Disperse the silane coupling agent and aluminum diethylphosphonate in an ethanol solution (concentration of 10~95wt%), stir evenly (heating to 50~70℃ can increase the speed), filter, and dry to obtain the synergistic flame retardant.

[0011] Method 3: Disperse the silane coupling agent in an ethanol solution (concentration of 10~95wt%), spray the mixture evenly on the surface of aluminum diethylphosphinate, and dry to obtain a synergistic flame retardant.

[0012] Preferably, the silane coupling agent comprises at least one selected from γ-aminopropyltriethoxysilane (KH550), γ-glycidoxypropyltrimethoxysilane (KH560), and γ-methacryloyloxypropyltrimethoxysilane (KH570). Preferably, the silane coupling agent comprises γ-glycidoxypropyltrimethoxysilane.

[0013] Preferably, the polycarbonate is bisphenol A type polycarbonate.

[0014] Preferably, the polycarbonate has a melt flow rate of 9-25 g / 10min under a load of 300℃ and 1.2kg, more preferably 11-22 g / 10min, for example, it can be any one or a range between 11g / 10min, 12g / 10min, 13g / 10min, 14g / 10min, 15g / 10min, 16g / 10min, 17g / 10min, 18g / 10min, 19g / 10min, 20g / 10min, and 22g / 10min.

[0015] The melt flow rate of the polycarbonate described in this invention was measured according to ISO 1133-1:2011.

[0016] Preferably, the intrinsic viscosity of the poly(butylene terephthalate) at 25°C is 0.8-1.5 dl / g, more preferably 0.98-1.3 dl / g, for example, it can be any one of 0.98 dl / g, 0.99 dl / g, 1.0 dl / g, 1.1 dl / g, 1.2 dl / g, 1.3 dl / g, or a range between two of them.

[0017] The intrinsic viscosity of the poly(butylene terephthalate) succinate described in this invention was determined by the Ubbelohde viscometer method according to standard GB / T14190, with a test temperature of 25°C and a test solution of phenol / tetrachloroethane mixture.

[0018] Preferably, the polycarbonate accounts for not less than 35% by mass in the polycarbonate polyester composition.

[0019] Preferably, the toughening agent includes at least one of methyl methacrylate-butadiene-styrene copolymer and acrylic-silicone rubber toughening agents.

[0020] Preferably, the anti-dripping agent comprises polytetrafluoroethylene.

[0021] Preferably, the polycarbonate polyester composition comprises the following components in parts by weight: 60-85 parts polycarbonate; 18-30 parts polystyrene terephthalate; 3-8 parts toughening agent; 6-10 parts flame retardant; 1-2 parts synergistic flame retardant; 0.2-1.2 parts anti-dripping agent.

[0022] Preferably, the polycarbonate polyester composition further includes 0-3 parts of additives.

[0023] Preferably, the additives include at least one of antioxidants and lubricants.

[0024] Preferably, the antioxidant is a hindered phenolic antioxidant.

[0025] More preferably, the hindered phenolic antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, vinylbis(oxyvinyl)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] or 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0026] Preferably, the lubricant comprises at least one of pentaerythritol stearate, polyethylene wax, and silicone lubricant.

[0027] Secondly, the present invention also discloses a method for preparing a polycarbonate polyester composition, comprising the following steps: The components are mixed and added to a twin-screw extruder, and after granulation and cooling, a polycarbonate polyester composition is obtained.

[0028] Preferably, the temperature of the twin-screw extruder is 230-250℃ and the screw speed is 300-400 rpm.

[0029] Thirdly, the present invention also discloses the application of a polycarbonate polyester composition in the preparation of kitchen appliances, charging facilities and industrial machinery. In particular, the above-mentioned polycarbonate polyester composition can be used to prepare parts with high flame retardant and heat resistance properties, and is especially suitable for the preparation of automobile charging equipment.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention achieves a significant flame-retardant synergistic effect by simultaneously adding hexaphenoxycyclotriphosphazene, a silane coupling agent, and aluminum diethylphosphonate to the PC / PBT alloy system. This effectively improves the flame-retardant properties of the material even with a lower hexaphenoxycyclotriphosphazene content, enhancing both its flame retardancy and heat distortion temperature. Furthermore, the epoxy-containing functional groups in the synergistic flame retardant react with the terminal carboxyl or hydroxyl groups of PBT, promoting their selective distribution within the PBT phase. This results in more efficient synergistic flame retardancy and effectively avoids the degradation effect of aluminum diethylphosphonate on PC during processing, maintaining the material's high toughness. Detailed Implementation

[0031] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the scope of protection and implementation of the present invention are not limited thereto.

[0032] Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0033] Examples 1-11 Examples of the polycarbonate polyester composition and its preparation method according to the present invention are shown in Table 1.

[0034] The method for preparing the polycarbonate polyester composition includes the following steps: (1) Polycarbonate, polysuccinate, flame retardant, synergistic flame retardant, toughening agent, anti-dripping agent and additives are added to a high-speed mixer and stirred to obtain a premix; (2) The premixed material is fed into the main feed port of the twin-screw extruder, melt-mixed and extruded and granulated in the twin-screw extruder (screw length-to-diameter ratio is 45:1, screw barrel temperature is 230-250 ℃, screw speed is 300 rpm) to obtain the polycarbonate polyester composition.

[0035] Comparative Examples 1-7 The only difference between the comparative examples and the embodiments is the type and ratio of components, as shown in Table 2.

[0036] In the components described in each embodiment and comparative example: The polycarbonate 1 is bisphenol A type, with a melt flow rate of 11 g / 10 min, PC CH9115LT, Cangzhou Dahua; The polycarbonate 2: bisphenol A type, melt flow rate of 22 g / 10 min, PC 1300-22 NP, LG Chem.

[0037] The poly(butylene terephthalate) succinate 1 has a viscosity of 1.0 dl / g, 1100-211M, and is manufactured by Chang Chun Man-made Resin Co., Ltd., Taiwan, China. The poly(butylene terephthalate) succinate 2 has a viscosity of 1.3 dl / g, is GL236, and is manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd. The poly(terephthalic acid succinate) 3 has a viscosity of 0.98 dl / g, is GX121, and is manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd.

[0038] The toughening agent 1 is a methyl methacrylate-butadiene-styrene copolymer: M-521, made by Kanekachi, Japan.

[0039] The toughening agent 2 is an acrylic-silicone rubber toughening agent: S-2130, Mitsubishi, Japan.

[0040] The flame retardant 1 is hexaphenoxycyclotriphosphazene, FP-110T, from Fushimi, Japan; The flame retardant 2 is resorcinol bis(diphenyl phosphate), brand name WSFR-RDP, manufactured by Wansheng Co., Ltd.

[0041] The synergistic flame retardant 1 comprises a silane coupling agent and aluminum diethylphosphinate, with a mass ratio of 1:100. The silane coupling agent is γ-glycidoxypropyltrimethoxysilane, KH560, manufactured by Maclean's Reagent Company.

[0042] The flame retardant synergist 2 comprises a silane coupling agent and aluminum diethylphosphinate, with a mass ratio of 0.4:100. The silane coupling agent is γ-aminopropyltriethoxysilane, KH550, manufactured by Maclean's Reagent Company.

[0043] The flame retardant synergist 3 comprises a silane coupling agent and aluminum diethylphosphinate, with a mass ratio of 1.5:100. The silane coupling agent is γ-methacryloyloxypropyltrimethoxysilane, KH570, manufactured by Maclean's Reagent Company.

[0044] The synergistic flame retardant 4 comprises a silane coupling agent and aluminum diethylphosphinate, with a mass ratio of 2:100. The silane coupling agent is γ-glycidoxypropyltrimethoxysilane, KH560, manufactured by Maclean's Reagent Company.

[0045] The flame retardant synergist 5 comprises a silane coupling agent and aluminum diethylphosphinate, with a mass ratio of 1:100. The silane coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide, Si69, manufactured by Maclean's Reagents.

[0046] The flame retardant synergist 6 comprises a silane coupling agent and aluminum diethylphosphinate, with a mass ratio of 0.2:100. The silane coupling agent is γ-glycidoxypropyltrimethoxysilane, KH560, manufactured by Maclean's Reagent Company.

[0047] The flame retardant synergist 7 comprises a silane coupling agent and aluminum diethylphosphinate, with a mass ratio of 5:100. The silane coupling agent is γ-glycidoxypropyltrimethoxysilane, KH560, manufactured by Maclean's Reagent Company.

[0048] The preparation method of the flame retardant synergists 1-7 is as follows: aluminum diethylphosphonate (EXOLIT OP 1230, Clariant) and silane coupling agent are ultrasonically dispersed in 95% (v / v) ethanol, with the volume ratio of 95% (v / v) ethanol to the mass ratio of aluminum diethylphosphonate being 100 mL: 1 g. The mixture is then continuously stirred at 60 °C for 2 h. After standing, it is filtered and washed twice with anhydrous ethanol, and then dried to obtain the flame retardant synergists.

[0049] The synergistic flame retardant 8 is diethyl aluminum hypophosphite.

[0050] The anti-dripping agent is polytetrafluoroethylene, which is commercially available.

[0051] The antioxidant is antioxidant 1010, which is commercially available.

[0052] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0053] Table 1 Table 2 To verify the performance of the polycarbonate polyester composition described in this invention, the polycarbonate polyester compositions prepared in each example and comparative example were injection molded into specimens for testing the following properties.

[0054] Performance testing methods: (1) Impact strength: The notched impact strength of the cantilever beam was tested according to ASTM D256-2010 standard, and the unit is J / m.

[0055] (2) Heat distortion temperature: The heat distortion temperature was tested in accordance with ISO75-1-2013, and the test load was 1.8MPa.

[0056] (3) Flame retardancy rating: Flame retardancy test shall be conducted in accordance with the UL94-2019 procedure for flammability testing of plastic materials. The sample size used for testing is 125mm*13mm*1.6mm strip.

[0057] The performance parameters obtained from the above tests are shown in Table 3.

[0058] Table 3 As can be seen from Examples 1-11, the impact strength of the polycarbonate polyester composition of the present invention can reach more than 550 J / m, the heat distortion temperature can reach more than 90°C, and the vertical burning rating can reach V-0, indicating that the polycarbonate polyester composition of the present invention has excellent flame retardant properties, heat resistance properties and impact strength.

[0059] Comparing Comparative Examples 1 and 5 with Example 4, it can be seen that in Comparative Example 1, no synergistic flame retardant was added. Although the impact strength of the material increased, the flame retardant performance was significantly reduced. In Comparative Example 5, no silane coupling agent was added, which greatly affected the impact and heat resistance of the material, and the flame retardant performance also decreased. Therefore, the present invention, by simultaneously adding hexaphenoxycyclotriphosphazene, a silane coupling agent, and aluminum diethylphosphonate to the PC / PBT system, can achieve a good synergistic flame retardant effect, effectively improving the flame retardant performance of the material under conditions of lower hexaphenoxycyclotriphosphazene dosage, and also improving the impact strength and heat resistance of the composition.

[0060] A comparison of Comparative Examples 3-4 and Example 4 shows that if the mass ratio of silane coupling agent to aluminum diethylphosphonate is too low, the impact strength, heat distortion temperature, and flame retardant properties all decrease. If the mass ratio is too high, although the impact strength and heat distortion temperature increase somewhat, the flame retardant synergistic effect is not well achieved, resulting in a decrease in flame retardant properties. Therefore, by controlling the mass ratio of silane coupling agent to aluminum diethylphosphonate within the range defined in this invention, the polycarbonate polyester composition can simultaneously possess excellent flame retardant properties, heat resistance, and impact strength.

[0061] Comparing Comparative Examples 6-7 with Example 4, it can be seen that if the content of the synergistic flame retardant is too low or too high, the polycarbonate polyester composition cannot simultaneously possess excellent flame retardant properties, heat resistance properties, and impact strength.

[0062] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polycarbonate polyester composition, characterized in that, The components include the following parts by weight: Polycarbonate 44-93 parts; polysuccinate 14-46 parts; toughening agent 0.9-12 parts; flame retardant 4-12 parts; synergistic flame retardant 0.4-3.2 parts; anti-dripping agent 0.09-6 parts; The flame retardant is hexaphenoxycyclotriphosphazene, and the synergistic flame retardant includes a silane coupling agent and aluminum diethylphosphonate; the mass ratio of the silane coupling agent to aluminum diethylphosphonate in the synergistic flame retardant is (0.4-2):

100.

2. The polycarbonate polyester composition according to claim 1, characterized in that, The mass ratio of silane coupling agent to aluminum diethylphosphonate in the synergistic flame retardant is (1-1.5):

100.

3. The polycarbonate polyester composition according to claim 1, characterized in that, The silane coupling agent includes at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

4. The polycarbonate polyester composition according to claim 1, characterized in that, The polycarbonate has a melt flow rate of 9-25 g / 10 min under conditions of 300℃ / 1.2 kg load.

5. The polycarbonate polyester composition according to claim 1, characterized in that, The intrinsic viscosity of the poly(terephthalic acid succinate) at 25°C is 0.8-1.5 dl / g.

6. The polycarbonate polyester composition according to claim 1, characterized in that, The toughening agent includes at least one of methyl methacrylate-butadiene-styrene copolymer and acrylic-silicone rubber toughening agents.

7. The polycarbonate polyester composition according to claim 1, characterized in that, The polycarbonate polyester composition also includes 0-3 parts of additives.

8. The polycarbonate polyester composition according to claim 7, characterized in that, The additives include at least one of antioxidants and lubricants.

9. A method for preparing a polycarbonate polyester composition according to any one of claims 1-8, characterized in that, Includes the following steps: The components are mixed and added to a twin-screw extruder, and after granulation and cooling, a polycarbonate polyester composition is obtained.

10. The use of a polycarbonate polyester composition as described in any one of claims 1-8 in the manufacture of kitchen appliances, charging facilities, and industrial machinery.

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