A highly weather-resistant and flame-retardant PC alloy material and preparation method thereof

Abstract

The present invention relates to the technical field of polymer materials, with an IPC main classification number of C08L69 / 00, and specifically relates to a highly weather-resistant and flame-retardant PC alloy material and a preparation method thereof. The raw materials for the preparation thereof include 68-78 parts of PC, 6-10 parts of styrene graft copolymers, 0.2-0.4 parts of antioxidants, 0.5-1.0 parts of lubricants, 4-6 parts of toughening agents, 10-12 parts of flame retardants, 0.3-0.5 parts of anti-dripping agents, 1-2 parts of anti-ultraviolet agents, and 0.2-0.4 parts of light stabilizers; the styrene graft copolymers are ABS and / or ASA prepared by a bulk method; the anti-ultraviolet agents are triazine ultraviolet absorbers and / or benzotriazole ultraviolet absorbers; the PC is a medium-low viscosity polycarbonate material, and its melt index under the conditions of 300°C / 1.2kg is not less than 4.5g / 10min. By optimizing and improving the formula system of medium and low viscosity PC components, a PC alloy material with excellent mechanical properties such as tensile strength, flexural strength and impact strength is obtained, while other comprehensive properties such as anti-aging performance, flame retardancy and surface gloss are still good.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, with an IPC main classification number of C08L69 / 00, and specifically relates to a highly weather-resistant and flame-retardant PC alloy material and a preparation method thereof. Background Art

[0002] Polycarbonate (PC) is a non-crystalline thermoplastic polymer material with excellent comprehensive performance. It is widely used in the technical fields of automotive parts, home appliances, communication equipment, medical equipment, lighting equipment, etc. due to its outstanding dimensional stability, mechanical strength and other characteristics. In traditional research, the high viscosity, poor fluidity, poor molding performance and other problems of PC materials are often improved by adding an appropriate amount of polystyrene graft copolymers such as ABS and ASA to PC materials, and the performance complementarity between PC and materials such as ABS / ASA is used to obtain PC alloy materials with excellent comprehensive performance. However, due to the molecular structure characteristics of materials such as ABS and ASA, there are some problems such as compatibility between them and PC materials. At the same time, although the relevant properties of the alloy materials are improved after the above components are blended, it will also cause performance degradation in other aspects, or there are other properties that need to be further improved, such as weather resistance in harsh environments, surface gloss of alloy materials, aging performance, etc. In the traditional improvement scheme, corresponding light stabilizers, anti-UV agents and other additives are added to improve the weather resistance of PC alloys. However, the applicant found in the study of blending and modification of medium and low viscosity PC materials that not all additives such as light stabilizers and UV inhibitors can significantly improve all PC alloy materials. When the main components in the PC alloy change significantly, the use of the same auxiliary components may not significantly improve the comprehensive properties of the PC alloy. To a certain extent, some properties of the PC alloy material (including but not limited to the surface gloss of the alloy material, notched impact strength, etc.) may even be reduced. Summary of the invention

[0003] In view of the above technical problems, the present invention provides a highly weather-resistant and flame-retardant PC alloy material, by optimizing and adjusting the composition, proportion, etc. of the toughening agent, anti-ultraviolet agent and other components in the PC alloy formula system with PC and styrene graft copolymers of specific physical and chemical properties as the main components, so that the tensile strength, bending strength, notched impact strength and other properties of the PC alloy material are comprehensively improved, and the surface gloss, weather resistance, flame retardancy and other properties of the PC alloy material are also comprehensively improved.

[0004] Specifically, the first aspect of the present invention provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0005]

[0006] The styrene graft copolymer is ABS and / or ASA prepared by a bulk method; the anti-ultraviolet agent is a triazine ultraviolet absorber and / or a benzotriazole ultraviolet absorber of a nitrogen-containing heterocyclic compound; the PC is a medium-low viscosity polycarbonate material synthesized by a phosgene method; the melt index of the medium-low viscosity polycarbonate material synthesized by a phosgene method at 300°C / 1.2kg is not less than 4.5g / 10min; preferably, the melt index of the medium-low viscosity polycarbonate material synthesized by a phosgene method at 300°C / 1.2kg is 8-24g / 10min.

[0007] As a preferred technical solution of the present invention, the weight average molecular weight of the medium-low viscosity polycarbonate material synthesized by the phosgene method is 20,000-35,000.

[0008] As a preferred technical solution of the present invention, the toughening agent includes an acrylate toughening agent, and the acrylate toughening agent is an acrylate graft copolymer with a core-shell structure.

[0009] As a preferred technical solution of the present invention, the acrylate graft copolymer with a core-shell structure has a melt index of 16 to 24 g / 10 min at 300° C. / 1.2 kg.

[0010] As a preferred technical solution of the present invention, the toughening agent also includes a siloxane-grafted acrylate graft copolymer; preferably, the mass ratio of the acrylate graft copolymer with a core-shell structure to the siloxane-grafted acrylate graft copolymer is (1.5-3):1.

[0011] As a preferred technical solution of the present invention, the ASA is a mixture of at least two or more ASA materials with different viscosities and / or melt indices.

[0012] As a preferred technical solution of the present invention, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material; the melt index of the high melt index ASA material at 220°C / 10kg is 10-18g / 10min; the melt index of the low melt index ASA material at 220°C / 10kg is 3.4-8g / 10min.

[0013] As a preferred technical solution of the present invention, the ABS is an ABS material prepared by a bulk method; the total residual amount of styrene and acrylonitrile monomers in the ABS material is not higher than 165 ppm.

[0014] As a preferred technical solution of the present invention, the melt index of the ABS material at 220°C / 10kg is 6-24g / 10min.

[0015] A second aspect of the present invention provides a method for preparing the PC alloy material as described above, comprising the following steps:

[0016] The raw materials for preparing the PC alloy material are measured according to the proportion, and each component is added into a high-speed mixer for stirring and mixing, and then added into a twin-screw extruder for melt extrusion, granulation, and drying to obtain the PC alloy material.

[0017] The PC alloy material provided by the present invention has the following beneficial effects compared with the traditional medium and low viscosity PC materials:

[0018] In the present invention, by optimizing and improving the medium and low viscosity PC component formula system, a PC alloy material with excellent mechanical properties such as tensile strength, bending strength, and impact strength is obtained, while other comprehensive properties such as anti-aging performance, flame retardant performance, and surface glossiness are still good. Specifically, by screening the styrene graft copolymer in the formula, optimizing the components and proportions, and matching a series of components such as toughening agents, anti-dripping agents, anti-ultraviolet agents, and light stabilizers with specific component proportions, while ensuring that the mechanical strength of the alloy is comprehensively improved, the anti-aging performance, flame retardant performance, heat deformation temperature, and processing performance of the PC alloy material are effectively improved, so that it can be more widely used. DETAILED DESCRIPTION

[0019] When the content, dosage, or other values ​​or parameters in the present application are expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when the range "2 to 8" is disclosed, the described range should be interpreted as including the range "2 to 8", "2 to 7", "2 to 6", "2 to 5 and 6,7", "2 to 3 and 4 to 8", etc.

[0020] When numerical ranges are described herein, unless otherwise indicated, the ranges are intended to include the endpoints and all integers and fractions within the range. The singular includes the plural unless the context clearly indicates otherwise. "Optional" or "any" means that the item or event described thereafter may or may not occur, and the description includes situations where the event occurs and situations where the event does not occur.

[0021] The raw materials for preparing the highly weather-resistant and flame-retardant PC alloy material provided in the present invention include 68-78 parts of PC, 6-10 parts of styrene graft copolymer, 0.2-0.4 parts of antioxidant, 0.5-1.0 parts of lubricant, 4-6 parts of toughening agent, 10-12 parts of flame retardant, 0.3-0.5 parts of anti-dripping agent, 1-2 parts of anti-ultraviolet agent, and 0.2-0.4 parts of light stabilizer; the PC described in the present invention is polycarbonate, and various types of polycarbonate materials known to those skilled in the art can be used, including but not limited to bisphenol A polycarbonate, bisphenol A polycarbonate, bisphenol B ... Phenol F type polycarbonate, etc. Further, the PC described in the present invention adopts a polycarbonate synthesized by a medium-low viscosity phosgene method. The lower the viscosity of the PC material, the higher the melt index under the same conditions. The melt index of the polycarbonate material synthesized by the medium-low viscosity phosgene method in the present invention is not less than 4.5g / 10min under 300°C / 1.2kg conditions; the term "melt index" in the present invention refers to the number of grams of melt passing through a capillary pore of a specific size within 10 minutes under a specific temperature and load. Unless otherwise specified, the melt index of the present invention is tested and confirmed according to the ASTM D1238 standard.

[0022] Preferably, the melt index of the polycarbonate material synthesized by the phosgene method at 300°C / 1.2kg is 8 to 24 g / 10min; for example, the melt index of the polycarbonate material at 300°C / 1.2kg is 8 g / 10min, 9 g / 10min, 10 g / 10min, 11 g / 10min, 12 g / 10min, 13 g / 10min, 14 g / 10min, 15 g / 10min, 16 g / 10min, 17 g / 10min, 18 g / 10min, 19 g / 10min, 20 g / 10min, 21 g / 10min, 22 g / 10min, 23 g / 10min, 24 g / 10min, etc.

[0023] In some preferred embodiments, the weight average molecular weight of the PC is 20000-35000, and for example, the weight average molecular weight can be 20000, 22000, 24000, 25000, 26000, 28000, 30000, etc. Although the melt index can reflect the size of the polymer molecular chain of the PC material to a certain extent, it has been found through experimental verification that PC materials with the same melt index also exhibit different physical and chemical properties. The present invention mainly optimizes the formulation components and proportions of PC materials with a specific molecular weight in a specific viscosity range to solve the above technical problems.

[0024] The specific source of the PC material that meets the above requirements is not particularly limited in the present invention, and various commercially available PC materials known to those skilled in the art can be used, including but not limited to Wanhua Chemical's CLARNATE series (weight average molecular weight of about 20,000 to 25,000), Japan's Idemitsu FN series, Mitsubishi Chemical E series, LG's LI series and other PC materials.

[0025] In the present invention, based on 68 to 78 parts by weight of the PC raw material, the amount of the styrene graft copolymer is 6 to 10 parts by weight, and the amount can be 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, etc.; the styrene graft copolymer described in the present invention can be ASA prepared by a bulk method, and the ASA is a graft copolymer of an acrylic rubber body and acrylonitrile and styrene.

[0026] Preferably, the ASA is a mixture of at least two or more ASA materials with different viscosities and / or melt indices, that is, the ASA is a mixture of two or more ASAs with different viscosities, or a mixture of two or more ASAs with different melt indices; preferably, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material, wherein the high melt index ASA material has a higher melt index than the low melt index ASA material under the same conditions; further, the high melt index ASA material has a melt index of 10 to 18 g / 10 min at 220°C / 10kg, for example, the high melt index ASA material has a melt index of 10 to 18 g / 10 min at 220°C / 10kg, for example, the high melt index ASA material can have a melt index of 10 g / 10 min, 11 g / 10 min, 12 g / 10 min, 12.5 g / 10 min, 13 g / 10 min, 13.5 g / 10 min, 14 g / 10 min, 15 g / 10 min , 15.5g / 10min, 16g / 10min, 16.5g / 10min, 17g / 10min, 18g / 10min, etc.; the melt index of the low melt index ASA material at 220℃ / 10kg is 3.4-8g / 10min. For example, the melt index of the low melt index ASA material at 220℃ / 10kg can be 3.4g / 10min, 3.5g / 10min, 4g / 10min n, 4.2g / 10min, 4.5g / 10min, 4.8g / 10min, 5g / 10min, 5.2g / 10min, 5.5g / 10min, 5.8g / 10min, 6g / 10min, 6.2g / 10min, 6.5g / 10min, 6.8g / 10min, 7g / 10min, 7.2g / 10min, 7.5g / 10min, 8g / 10min, etc.

[0027] Preferably, the mass ratio of the high melt index ASA material to the low melt index ASA material is (1.5-2.5):1, and the mass ratio can be 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, etc. In the present invention, there is no special limitation on the source of the ASA material meeting the above requirements, and various ASA materials known to those skilled in the art can be used, including but not limited to LG Chemical's LI series ASA, Changsu New Materials' 801, 802, 840BK series ASA, Taiwan Chemical Fiber's SG series ASA, Covestro's W series ASA, Lotte Chemical's WR series ASA, etc.

[0028] The styrene graft copolymer described in the present invention can be an ABS material prepared by a bulk method. The ABS described in the present invention refers to a polymer material obtained by copolymerizing acrylonitrile, butadiene and styrene as monomers; further, the total residual amount of styrene and acrylonitrile monomers in the ABS material described in the present invention is not higher than 165ppm; the monomer residual amount described in the present invention is the residual amount of monomer compounds used to prepare the ABS polymer that do not participate in the reaction, and can be tested and confirmed in a manner familiar to those skilled in the art, including but not limited to nuclear magnetic hydrogen spectrum, carbon spectrum, mass spectrum, HPLC and other means and their combined means; preferably, the ABS material under the conditions of 220℃ / 10kg The melt index is 6 to 24 g / 10min. For example, the melt index of the ABS material at 220°C / 10kg can be 6 g / 10min, 7 g / 10min, 8 g / 10min, 9 g / 10min, 10 g / 10min, 11 g / 10min, 12 g / 10min, 13 g / 10min, 14 g / 10min, 15 g / 10min, 16 g / 10min, 17 g / 10min, 18 g / 10min, 19 g / 10min, 20 g / 10min, 21 g / 10min, 22 g / 10min, 23 g / 10min, 24 g / 10min, etc.

[0029] The styrene graft copolymer of the present invention can use ABS or ASA components alone, or the two can be blended in a certain ratio and used in the preparation of the PC alloy material of the present invention.

[0030] The PC alloy of the present invention contains a certain amount of toughening agent. Based on 68 to 78 parts by weight of the PC raw material, the content of the toughening agent is 4 to 6 parts, and the content thereof can be 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, etc.; further preferably, the toughening agent includes an acrylate toughening agent (ACR), and the acrylate toughening agent is an acrylate graft copolymer with a core-shell structure. In the present invention, there is no special limitation on the preparation monomer, proportion, preparation method, etc. of the acrylate graft copolymer, and there is no special requirement on the specific source of the acrylate graft copolymer. The relevant raw materials well known to those skilled in the art can be used. ; Preferably, the melt index of the core-shell acrylate graft copolymer at 300°C / 1.2kg is 16-24g / 10min. For example, the melt index may be 16g / 10min, 17g / 10min, 18g / 10min, 18.5g / 10min, 19g / 10min, 19.5g / 10min, 20g / 10min, 20.2g / 10min, 20.5g / 10min, 21g / 10min, 22g / 10min, 23g / 10min, 24g / 10min, etc.; In the present invention, KANE ACE FM-40 including but not limited to Hangzhou Zhongju Chemical Industry can be used.

[0031] Further preferably, the toughening agent also includes a siloxane-grafted acrylate graft copolymer; the siloxane-grafted acrylate graft copolymer is a copolymer containing silicone and acrylate compounds in the preparation monomer, and has the characteristics of silicone and acrylate; the specific source of the siloxane-grafted acrylate graft copolymer is not particularly limited in the present invention, and various types of siloxane-grafted acrylate graft copolymers known to those skilled in the art can be used, including but not limited to MR-502 silicone-based acrylate toughening agent developed by Zhonghua.

[0032] Furthermore, the amount of the acrylate graft copolymer with a core-shell structure is higher than that of the siloxane grafted acrylate graft copolymer. Preferably, the amount of the acrylate graft copolymer with a core-shell structure is at least 1.5 times or more of the amount of the siloxane grafted acrylate graft copolymer. Preferably, the mass ratio of the acrylate graft copolymer with a core-shell structure to the siloxane grafted acrylate graft copolymer is (1.5-3):1. For example, the mass ratio is 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3.0:1, etc.

[0033] The PC alloy of the present invention contains a certain amount of antioxidant. Based on 68 to 78 parts by weight of the PC raw material, the content of the antioxidant is 0.2 to 0.4 parts by weight. For example, the amount thereof is 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, etc.; the specific selection of the antioxidant in the present invention is not particularly limited, and can be based on antioxidants well known to those skilled in the art, including but not limited to a combination of one or more of hindered phenol antioxidants, phosphite antioxidants, thioester antioxidants, furan antioxidants, hydroxylamine antioxidants, etc.; preferably, the antioxidant contains an asymmetric hindered phenol antioxidant and a phosphite antioxidant, and preferably, the amount of the asymmetric hindered phenol antioxidant is twice that of the phosphite antioxidant; the asymmetric hindered phenol antioxidant can be used, including but not limited to triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (RIANOX 245), and the phosphite antioxidant may include but is not limited to bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate (RIANOX 636).

[0034] The PC alloy of the present invention contains a certain amount of lubricant. Based on 68 to 78 parts by weight of the PC raw material, the content of the lubricant is 0.5 to 1.0 parts by weight, and the content can be 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1.0 parts by weight, etc.; preferably, the lubricant is a silicone lubricant or a polymer wax lubricant, or the two can be blended and used; further preferably, the silicone lubricant is prepared from ultra-high molecular weight polysiloxane, and various silicone lubricants well known to those skilled in the art can be used, including but not limited to FEIDIAN GM-3200 silicone lubricant.

[0035] The PC alloy of the present invention contains a certain amount of flame retardant. Based on 68 to 78 parts by weight of the PC raw material, the content of the flame retardant is 10 to 12 parts by weight. For example, the content may be 10 parts by weight, 10.5 parts by weight, 11 parts by weight, 11.5 parts by weight, 12 parts by weight, etc. Preferably, the flame retardant is a phosphorus-based flame retardant. Further preferably, the phosphorus-based flame retardant is a bisphenol A-type phosphorus-based flame retardant, and various types of bisphenol A-type phosphorus-based flame retardants well known to those skilled in the art may be used, including but not limited to bisphenol A-bis(diphenyl phosphate) (BDP).

[0036] The PC alloy of the present invention contains a certain amount of anti-dripping agent. Based on 68 to 78 parts by weight of the PC raw material, the content of the anti-dripping agent is 0.3 to 0.5 parts by weight. For example, the content of the anti-dripping agent can be 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, etc. Preferably, the anti-dripping agent is a modified tetrafluoroethylene anti-dripping agent obtained by copolymerization of polytetrafluoroethylene (PTFE) and styrene-acrylonitrile (SAN); further preferably, the polytetrafluoroethylene content of the modified tetrafluoroethylene anti-dripping agent is 47 to 83wt%, and the acrylonitrile content is 8 to 12wt%. In the present invention, no special requirements are made on the specific selection of the modified tetrafluoroethylene anti-dripping agent that meets the above requirements, and the modified tetrafluoroethylene anti-dripping agent (PTFE-SAN) including but not limited to Shangruige Plastic can be used.

[0037] The PC alloy of the present invention contains a certain amount of anti-ultraviolet agent, based on 68 to 78 parts by weight of the PC raw material, the content of the anti-ultraviolet agent is 1 to 2 parts; for example, the content of the anti-ultraviolet agent can be 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, etc.; the anti-ultraviolet agent is a triazine ultraviolet absorber and / or a benzotriazole ultraviolet absorber of a nitrogen-containing heterocyclic compound; it can be used, including but not limited to, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5' -di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octyl)phenylbenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol), 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2-(2'-hydroxy-3'-cumyl-5'-tert-octylphenyl)benzotriazole, 3-benzotriazole-5-tert-butyl-4-hydroxyphenylpropionate reaction product with PEG-300 (UV-1130), 3-benzotriazole-5-tert-butyl-4-hydroxyphenylpropionate reaction product with C7-9 alcohol (UV 384-2), etc.

[0038] The PC alloy of the present invention contains a certain amount of light stabilizer, based on 68 to 78 parts by weight of the PC raw material, the content of the light stabilizer is 0.2 to 0.4 parts by weight; for example, the content is 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, etc.; preferably, the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer, which can be used but not limited to Various types of light stabilizers including UV-119.

[0039] A second aspect of the present invention provides a method for preparing the PC alloy material as described above, comprising the following steps:

[0040] The raw materials for preparing the PC alloy material are measured according to the ratio, and each component is added to a high-speed mixer for stirring and mixing, and then added to a twin-screw extruder for melt extrusion, granulation, and drying to obtain the PC alloy material. Further, the raw materials measured according to the ratio are poured into a mixer for stirring and mixing evenly, and then placed in a twin-screw extruder, the speed of the twin screw is adjusted (for example, 400rpm to 600rpm), and the temperature of each zone of the screw is set to: 260℃ to 270℃, and extrusion granulation is obtained. In the present invention, other process steps and process parameters of the preparation method of the PC alloy material are not specifically limited, and can be adjusted accordingly according to actual needs based on methods familiar to those skilled in the art.

[0041] The present invention is described in detail below by way of examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by professionals and technicians in this field based on the content of the present invention above still belong to the scope of protection of the present invention.

[0042] Example 1

[0043] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0044]

[0045] The PC is a medium viscosity polycarbonate with a melt index of 16 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2150 polycarbonate); the styrene graft copolymer is ABS prepared by a bulk method, wherein the total residual amount of styrene and acrylonitrile monomers is ≤165ppm, and the melt index of the ABS at 220°C / 10kg is 15g / 10min (F332 bulk ABS of Yike Chemical); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a mixture of an acrylate graft copolymer with a core-shell structure and a siloxane grafted acrylate graft copolymer, the mass ratio of which is 2.2:1, and the melt index of the acrylate graft copolymer with a core-shell structure at 300°C / 1.2kg is 20.2g / 10min (KANE ACE FM-40), the siloxane grafted acrylate graft copolymer is (KANE ACE MR-502); the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0046] Example 2

[0047] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0048]

[0049] The PC is a medium viscosity polycarbonate with a melt index of 16 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2150 polycarbonate); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material, the mass ratio is 2:1, the high melt index ASA material has a melt index of 12g / 10min at 220℃ / 10kg (LG Chemical LI970), and the low melt index ASA material has a melt index of 6g / 10min at 220℃ / 10kg (LG Chemical LI951); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a mixture of an acrylate graft copolymer with a core-shell structure and a siloxane grafted acrylate graft copolymer, the mass ratio is 2.2:1, and the acrylate graft copolymer with a core-shell structure has a melt index of 20.2g / 10min at 300℃ / 1.2kg (KANE ACE of Hangzhou Zhongju Chemical FM-40), the siloxane grafted acrylate graft copolymer is (KANE ACE MR-502); the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0050] Example 3

[0051] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0052]

[0053] The PC is a medium viscosity polycarbonate with a melt index of 16 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2150 polycarbonate); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a high melt index ASA material, and the melt index of the high melt index ASA material at 220°C / 10kg is 12g / 10min (LG Chemical LI970); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a mixture of an acrylate graft copolymer with a core-shell structure and a siloxane grafted acrylate graft copolymer, the mass ratio of which is 2.2:1, and the acrylate graft copolymer with a core-shell structure has a melt index of 20.2g / 10min at 300°C / 1.2kg (KANE ACE of Hangzhou Zhongju Chemical FM-40), the siloxane grafted acrylate grafted copolymer is KANE ACE from Hangzhou Zhongju Chemical MR-502; the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0054] Example 4

[0055] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0056]

[0057] The PC is a medium viscosity polycarbonate with a melt index of 16 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2150 polycarbonate); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a low melt index ASA material, and the melt index of the low melt index ASA material at 220°C / 10kg is 6g / 10min (LG Chemical LI951); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a mixture of an acrylate graft copolymer with a core-shell structure and a siloxane grafted acrylate graft copolymer, the mass ratio of which is 2.2:1, and the acrylate graft copolymer with a core-shell structure has a melt index of 20.2g / 10min at 300°C / 1.2kg (KANE ACE of Hangzhou Zhongju Chemical FM-40), the siloxane grafted acrylate grafted copolymer is KANE ACE from Hangzhou Zhongju Chemical MR-502; the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0058] Example 5

[0059] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0060]

[0061] The PC is a medium viscosity polycarbonate with a melt index of 16 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2150 polycarbonate); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material, the mass ratio is 2:1, the high melt index ASA material has a melt index of 12g / 10min at 220℃ / 10kg (LG Chemical LI970), and the low melt index ASA material has a melt index of 6g / 10min at 220℃ / 10kg (LG Chemical LI951); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is an acrylate graft copolymer with a core-shell structure, and the acrylate graft copolymer with a core-shell structure has a melt index of 20.2g / 10min at 300℃ / 1.2kg (KANE ACE of Hangzhou Zhongju Chemical FM-40); the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0062] Example 6

[0063] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0064]

[0065] The PC is a medium viscosity polycarbonate with a melt index of 16 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2150 polycarbonate); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material, the mass ratio is 2:1, the high melt index ASA material has a melt index of 12g / 10min at 220℃ / 10kg (LG Chemical LI970), and the low melt index ASA material has a melt index of 6g / 10min at 220℃ / 10kg (LG Chemical LI951); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a siloxane grafted acrylate grafted copolymer with a core-shell structure, and the siloxane grafted acrylate grafted copolymer is KANE ACE of Hangzhou Zhongju Chemical MR-502; the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0066] Example 7

[0067] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0068]

[0069] The PC is a high-viscosity polycarbonate with a melt index of 2.5 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2030 polycarbonate); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material, the mass ratio is 2:1, the high melt index ASA material has a melt index of 12g / 10min at 220℃ / 10kg (LG Chemical LI970), and the low melt index ASA material has a melt index of 6g / 10min at 220℃ / 10kg (LG Chemical LI951); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a mixture of an acrylate graft copolymer with a core-shell structure and a siloxane grafted acrylate graft copolymer, the mass ratio is 2.2:1, and the acrylate graft copolymer with a core-shell structure has a melt index of 20.2g / 10min at 300℃ / 1.2kg (KANE ACE of Hangzhou Zhongju Chemical FM-40), the siloxane grafted acrylate graft copolymer is (KANE ACE MR-502); the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0070] Example 8

[0071] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0072]

[0073]

[0074] The PC is a mixture of high-viscosity polycarbonate and low-viscosity polycarbonate in a mass ratio of 1:1. The high-viscosity polycarbonate has a melt index of 2.5 g / 10 min at 300° C. / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2030 polycarbonate), the low viscosity polycarbonate has a melt index of 34 g / 10 min at 300°C / 1.2 kg (Japan Mitsubishi HL-3003); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material, the mass ratio is 2:1, the melt index of the high melt index ASA material at 220°C / 10 kg is 12 g / 10 min (LG Chemical LI970), the low melt index AS The melt index of material A at 220°C / 10kg is 6g / 10min (LG Chemical LI951); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a mixture of an acrylate graft copolymer with a core-shell structure and a siloxane grafted acrylate graft copolymer, the mass ratio of which is 2.2:1, and the melt index of the acrylate graft copolymer with a core-shell structure at 300°C / 1.2kg is 20.2g / 10min (KANE ACE of Hangzhou Zhongju Chemical FM-40), the siloxane grafted acrylate graft copolymer is (KANE ACE MR-502); the antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); the anti-drip agent is a modified tetrafluoro anti-drip agent (PTFE-SAN), and its acrylonitrile content is about 10wt%; the light stabilizer is a non-polymeric high molecular weight hindered amine light stabilizer UV-119.

[0075] Example 9

[0076] This embodiment provides a highly weather-resistant and flame-retardant PC alloy material, the raw materials of which include the following components in parts by weight:

[0077]

[0078]

[0079] The PC is a medium viscosity polycarbonate with a melt index of 16 g / 10 min at 300°C / 1.2 kg and a density of 1.2 g / cm 3 (Wanhua Chemical Group 2150 polycarbonate); the styrene graft copolymer is ASA prepared by a bulk method, the ASA is a mixture of a high melt index ASA material and a low melt index ASA material, the mass ratio is 2:1, the high melt index ASA material has a melt index of 12g / 10min at 220℃ / 10kg (LG Chemical LI970), and the low melt index ASA material has a melt index of 6g / 10min at 220℃ / 10kg (LG Chemical LI951); the anti-ultraviolet agent is a benzotriazole ultraviolet absorber UV234; the toughening agent is a mixture of an acrylate graft copolymer with a core-shell structure and a siloxane grafted acrylate graft copolymer, the mass ratio is 2.2:1, and the acrylate graft copolymer with a core-shell structure has a melt index of 20.2g / 10min at 300℃ / 1.2kg (KANE ACE of Hangzhou Zhongju Chemical FM-40), the siloxane grafted acrylate graft copolymer is (KANE ACE The antioxidant is a mixture of asymmetric hindered phenol antioxidant triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, with a mass ratio of 2:1; the lubricant is a silicone lubricant FEIDIAN GM-3200 prepared from ultra-high molecular weight polysiloxane; the flame retardant is bisphenol A-bis(diphenyl phosphate); and the anti-drip agent is a polytetrafluoroethylene anti-drip agent (PTFE).

[0080] The applicant conducted a series of performance tests on the PC alloy material in the above embodiment, and the test methods and test results are as follows:

[0081] Tensile properties: tested according to ISO 527 standard, tensile speed is 50mm / min;

[0082] Bending strength: tested according to ISO 178 standard, bending speed is 2mm / min;

[0083] Notched impact strength: tested according to ISO 180 / 1A standard, sample thickness is 4.0mm;

[0084] Xenon lamp aging performance: tested according to ISO 4892-2:2013 cycle 1 standard, 1000H;

[0085] Flame retardant grade: Flame retardant performance test of 1.5mm and 3.0mm thickness samples was carried out according to UL94-2019 test standard and IEC 60950-1 standard;

[0086] The specific test results are shown in Table 1 and Table 2.

[0087] Table 1 Mechanical properties

[0088]

[0089] It can be seen from the above experimental results that the combination of two ASAs with different melt indexes and toughening agents with different structures can effectively improve the comprehensive strengths of medium and low viscosity PC alloy materials, such as tensile strength, flexural strength and impact strength. Although the above-mentioned specific formula components can significantly improve the tensile strength, flexural strength and other properties of the alloy when applied to the high viscosity (low melt index) PC formula system, its impact strength and other properties are greatly affected. In addition, the application of the above-mentioned specific formula components to the PC system with high viscosity and low viscosity can effectively improve the impact strength of the alloy to a certain extent, but significantly reduce its tensile strength and flexural strength, and also greatly affect the anti-aging properties of the alloy material.

[0090] Table 2

[0091]

[0092] According to the above experimental results, it can be seen that by optimizing and adjusting the toughening agent, styrene graft copolymer and other components and ratios, the anti-aging performance, flame retardancy and other properties can be effectively improved without significantly affecting the mechanical strength of the alloy. Moreover, compared with ABS modification, the anti-aging performance and impact strength of PC alloy modified by using a specific ASA component are more excellent.

[0093] In addition, the applicant also conducted a thermal deformation test on the PC alloy materials in the above embodiments. The thermal deformation temperatures of all materials are basically 85°C and above, and can be widely used in harsh high-temperature outdoor environments. In addition, the applicant observed the production and processing process of the above samples, and the processing performance of the materials was good, which met the normal production and product processing requirements. In addition, when preparing the test samples, the surface gloss of the samples was observed to be good, which significantly improved the appearance of the products.

[0094] The above is only an exemplary embodiment of the present disclosure, and the scope of the present disclosure cannot be limited thereto. That is, any equivalent changes and modifications made according to the teachings of the present disclosure are still within the scope of the present disclosure. After considering the specification and practicing the disclosure here, those skilled in the art will easily think of the implementation scheme of the present disclosure. The present invention is intended to cover any variation, use or adaptive change of the present disclosure, which follows the general principles of the present disclosure and includes common knowledge or customary technical means in the technical field not recorded in the present disclosure. The description and examples are regarded as exemplary only, and the scope and spirit of the present disclosure are defined by the claims.

Claims

1. A highly weather-resistant and flame-retardant PC alloy material, characterized in that: The raw materials include the following components in parts by weight: PC 68~78 copies; 6-10 parts of styrene graft copolymer; Antioxidant 0.2~0.4 parts; Lubricant 0.5~1.0 part; 4~6 parts of toughening agent; Flame retardant 10~12 parts; 0.3~0.5 parts of anti-dripping agent; 1~2 parts of anti-ultraviolet agent; Light stabilizer 0.2~0.4 parts; The styrene graft copolymer is ASA prepared by a bulk method; the anti-ultraviolet agent is a triazine ultraviolet absorber and / or a benzotriazole ultraviolet absorber of a nitrogen-containing heterocyclic compound; the PC is a medium-low viscosity polycarbonate material synthesized by a phosgene method; the melt index of the medium-low viscosity polycarbonate material synthesized by a phosgene method is 8 to 24 g / 10 min under the conditions of 300° C. / 1.2 kg; The toughening agent includes an acrylate toughening agent, and the acrylate toughening agent is an acrylate graft copolymer with a core-shell structure; The toughening agent further comprises a siloxane grafted acrylate grafted copolymer; the mass ratio of the acrylate grafted copolymer with a core-shell structure to the siloxane grafted acrylate grafted copolymer is (1.5-3):1; The core-shell structured acrylate graft copolymer has a melt index of 16 to 24 g / 10 min at 300° C. / 1.2 kg. The ASA is a mixture of a high melt index ASA material and a low melt index ASA material; the high melt index ASA material has a melt index of 10 to 18 g / 10 min at 220° C. / 10 kg; the low melt index ASA material has a melt index of 3.4 to 8 g / 10 min at 220° C. / 10 kg.

2. The PC alloy material according to claim 1, characterized in that: The weight average molecular weight of the medium-low viscosity polycarbonate material synthesized by the phosgene method is 20,000-35,000.

3. The method for preparing the PC alloy material according to claim 1 or 2, characterized in that: It includes the following steps: The raw materials for preparing the PC alloy material are measured according to the proportion, and each component is added into a high-speed mixer for stirring and mixing, and then added into a twin-screw extruder for melt extrusion, granulation, and drying to obtain the PC alloy material.

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