CN111138824A

CN111138824A - Impact-resistant halogen-free flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) blend alloy and preparation method thereof

Info

Publication number: CN111138824A
Application number: CN202010035179.XA
Authority: CN
Inventors: 徐禄波; 吴剑波; 王旭; 范方虹
Original assignee: Ningbo Dopda Polymer Co Ltd
Current assignee: Ningbo Dopda Polymer Co Ltd
Priority date: 2020-01-14
Filing date: 2020-01-14
Publication date: 2020-05-12
Anticipated expiration: 2040-01-14
Also published as: CN111138824B

Abstract

The impact-resistant halogen-free flame-retardant PC/ABS blending alloy provided by the invention comprises the following components in parts by weight:

Description

Impact-resistant halogen-free flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) blend alloy and preparation method thereof

Technical Field

The invention belongs to the technical field of composite materials, and particularly relates to an impact-resistant halogen-free flame-retardant PC/ABS blending alloy and a preparation method thereof.

Background

Polycarbonate (PC) is a high molecular polymer containing a carbonate group in a molecular chain, and is classified into aliphatic polycarbonate, alicyclic polycarbonate, and aromatic polycarbonate according to the molecular structure. Among them, bisphenol A type aromatic polycarbonates are the most widely used ones with the highest productivity. PC has the advantages of excellent impact toughness, creep resistance, dimensional stability, electrical insulation, weather resistance, transparency, nontoxicity and the like, and is widely applied to the fields of mechanical equipment, constructional engineering, transportation, instruments, electrical appliance illumination and the like. Poly (acrylonitrile-butadiene-styrene) copolymer (ABS) is a typical three-component thermoplastic resin of two-phase structure consisting of a poly (styrene-acrylonitrile) copolymer (SAN) continuous phase and a polybutadiene degrading dispersed phase. The ABS resin components impart their own unique properties, such as AN Acrylonitrile (AN) component imparting chemical resistance, weather resistance, heat resistance, hardness and tensile strength to the resin, a Butadiene (BD) component imparting toughness and low temperature resistance to the resin, and a styrene (St) component imparting excellent electrical properties, processability and surface gloss to the resin. ABS resins have excellent mechanical properties, thermal stability, chemical resistance, and good aesthetic appearance and processability, and are widely used in the fields of electronics, large-sized electrical appliances, small-sized electrical appliances, instrument panels, wheel covers, and the like. However, PC and ABS also have various disadvantages, such as high viscosity, difficulty in processing and molding, easy generation of stress cracking, poor chemical resistance, high price, and the like; ABS is poor in heat resistance and weather resistance, and is not ideal in mechanical properties. The PC and the ABS are mixed to form an alloy, so that the advantages of the PC and the ABS can be integrated. Compared with PC, the PC/ABS alloy reduces the melt viscosity, improves the processing performance and greatly improves the stress cracking resistance of the product; compared with ABS, the heat resistance and the weather resistance are improved. The cost of the PC/ABS alloy is between the two, and the PC/ABS alloy has the advantages of the two, and can be better applied to industries such as automobiles, electronics, electric appliances and the like.

The main chain of PC contains benzene ring, so that aromatic carbon can be synthesized by condensation during combustion, the carbon forming rate is high, the carbon can be self-extinguished, the flame retardant rating is UL94V-2 grade, the oxygen index is about 24%, hot melt can be dropped during combustion, and nearby materials are easy to catch fire. The ABS resin belongs to flammable materials, has an oxygen index of 18-20%, and can release a large amount of toxic gases and black smoke during combustion. When PC and ABS are used as raw materials to prepare PC/ABS alloy, a flame retardant is added into the PC/ABS alloy to improve the flame retardant property of the alloy. The conventional flame retardants are roughly classified into halogen flame retardants, inorganic flame retardants, phosphorus flame retardants, nitrogen flame retardants, and silicon flame retardants according to the element type. Among them, the halogen flame retardant has good flame retardant effect and low cost and is widely applied. However, the halogen flame retardant generates a large amount of toxic and corrosive gases when the material is burnt, and two instructions of ROHS and WEEE issued in 2003 of the european union limit the application of the halogen flame retardant in many fields. The phosphorus flame retardant has the characteristics of high efficiency and low toxicity, has important application value in flame retarding PC and PC/ABS alloy, and is also the most widely applied halogen-free flame retardant at present. The most representative of the phosphorus-based flame retardants are triphenyl phosphate (TPP), resorcinol-bis (diphenyl phosphate) (RDP), and bisphenol a-bis (diphenyl phosphate) (BDP). However, the addition amount of the phosphorus flame retardant is often 10% or more to reach UL94-V0 level, and the phosphorus flame retardant is easy to hydrolyze and difficult to process and recycle. Particularly, in recent years, the green, recycling and environmental protection concepts are more and more keen, and the recyclability of the material is also required to be considered when preparing the PC/ABS alloy. Therefore, there is a need to find more efficient and environmentally friendly flame retardants.

The silicon-containing organic compound is a new-generation environment-friendly flame retardant, and is gradually paid attention to by researchers due to the advantages of high-efficiency flame retardance, low smoke, low toxicity, no pollution, small influence on the processability and physical and mechanical properties of plastics and the like. The silicon-based flame retardant PC has excellent impact strength, especially low-temperature impact strength, because the silicon-oxygen group contained in the main chain of the silicon-based flame retardant polymer can improve the moisture resistance and the flexibility of the chain of the PC/ABS alloy. Most importantly, the silicon-based flame-retardant PC can be recycled. The silicone flame retardant mainly includes silicone oil, silicone resin, silicone rubber, and organosilanolamide. When the high molecular material is burnt, the organic siloxane can migrate to the surface from the inside of the organic matter and is quickly enriched on the surface to form the high molecular gradient material of which the surface is a polysiloxane enrichment layer, and simultaneously, an inorganic oxygen-isolating and heat-insulating protective layer which is peculiar to polysiloxane and contains-Si-O-bond and-Si-C-bond can be formed, so that volatile matters generated by burning can be prevented from escaping outwards, oxygen can be prevented from contacting with a substrate, and the melt is prevented from dropping, thereby achieving the purpose of flame retardance. The Chinese patent CN201480011001.4 adopts organic siloxane oligomer compound sulfonic acid alkali metal salt as a flame retardant, and can reach UL 94V-0 level for PC plates with the thickness of 2 mm. The Chinese patent application CN200910130822.0 adopts the flame-retardant and char-forming effects of phosphorus flame retardant and organosiloxane flame retardant to provide the flame retardancy of PC/PET composite material. However, the compatibility of organosiloxane and PC is poor, and the dispersion effect in PC is not ideal, thereby affecting the use efficiency of the silicon flame retardant.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a flame-retardant PC/ABS blending alloy, which is added with epoxy-terminated modified polysiloxane and an ester exchange catalyst to improve the flame-retardant property of the blending alloy and effectively reduce the dosage of a flame retardant.

The above object of the present invention is achieved by the following technical solutions: an impact-resistant halogen-free flame-retardant PC/ABS blending alloy comprises the following components in parts by weight:

the polysiloxane flame retardant can improve the flame retardant property of the PC/ABS alloy and the impact property of the alloy, and is very suitable for preparing the halogen-free flame retardant PC/ABS alloy. When the high molecular material is burnt, the polysiloxane flame retardant can migrate to the surface from the inside of an organic matter and is quickly enriched on the surface to form a high molecular gradient material with a polysiloxane enrichment layer on the surface, and meanwhile, an inorganic oxygen-insulating and heat-insulating protective layer containing-Si-O-bond and-Si-C-bond peculiar to polysiloxane can be formed, so that volatile matters generated by burning can be prevented from escaping outwards, oxygen can be prevented from contacting with a substrate, and the melt is prevented from dropping, thereby achieving the purpose of flame retardance. However, polysiloxane flame retardants are poorly compatible with PC/ABS alloys and are difficult to disperse during processing, and therefore the flame retardant effect is not ideal.

The invention introduces epoxy-terminated modified polysiloxane, the epoxy active group of which can improve the physical interaction between the polysiloxane flame retardant and the molecular main chains of PC and ABS, and can be grafted on the molecular main chain of PC through chemical reaction to further increase the compatibility with PC/ABS alloy. The chemical reaction compatibilization mechanism is that hydrolysis and thermal degradation reactions can exist in the PC in the thermal processing process, so that PC molecular chains are broken and terminal hydroxyl groups are formed; the epoxy group can react with the terminal hydroxyl group formed after the degradation of the PC molecular chain. The epoxy-terminated modified polysiloxane mainly depends on active end groups participating in side reactions in the processing process of PC to increase the compatibility with PC, but the side reactions in the processing process of PC are not enough to consume a large amount of epoxy-terminated modified polysiloxane, and the flame-retardant efficiency is still limited. According to the invention, the ester exchange catalyst is further added into the PC/ABS alloy, so that the activity of the ester exchange reaction between PC molecules can be improved, and more side reactions such as hydrolysis reaction and the like are initiated, so that more hydroxyl groups are formed at the end group of the PC, a proper amount of end hydroxyl groups generated in the extrusion process of the PC are ensured to carry out chemical reaction with the epoxy-terminated polysiloxane, the efficiency of the epoxy-terminated polysiloxane is improved, the compatibility of the epoxy-terminated modified polysiloxane and a matrix is enhanced, and the flame retardant property is greatly improved.

Preferably, the epoxy-terminated modified polysiloxane of the present invention has the following structure:

wherein R is

In the combustion process of the material, the epoxy-terminated modified polysiloxane needs to be quickly enriched to the surface of the material so as to better exert the flame retardant property. The epoxy-terminated modified polysiloxane molecular chain with the structure is soft, has high free mobility, is grafted on a PC end group, and can rapidly migrate to the surface in the combustion process to block oxygen.

Preferably, the transesterification catalyst of the invention is selected from Li₂CO₃、NaHCO₃、Na₂WO₄、AlCl₃、ZnCl₂，Zn(OAc)₂、Ti(OC₄H₉)₄、n-Bu₂One or more of SnO.

Further preferably, the transesterification catalyst is AlCl₃And Ti (OC)₄H₉)₄The mass ratio of (0.5-5): 1 of the mixture formed. The compound use of the inorganic aluminum chloride and the organic tetrabutyl titanate can greatly improve the combination of the epoxy-terminated modified polysiloxane and the PC-terminated hydroxyl, improve the use efficiency of the epoxy-terminated modified polysiloxane and further reduce the addition amount of the epoxy-terminated modified polysiloxane.

Preferably, the compatilizer can be selected from maleic anhydride grafted compounds, compounds containing epoxy groups or oxazoline groups. Further preferred are graft-modified resins containing glycidyl methacrylate functional groups, such as styrene-acrylonitrile-glycidyl methacrylate (SAG), ethylene-octene elastomer grafted glycidyl methacrylate (POE-g-GMA), ethylene-methyl acrylate-glycidyl methacrylate terpolymer (E-MA-GMA), and the like. Further preferred is an ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

Preferably, the toughening agent is selected from one or more of methyl methacrylate-butadiene-styrene copolymer (MBS), acrylonitrile-butadiene-acrylate copolymer (ABA), methyl methacrylate-silicone rubber copolymer (MMA-SR).

Preferably, the part of the sulfonate flame retardant is 0.03-1 part. One or more selected from 3-benzenesulfonyl potassium benzene sulfonate (KSS), perfluorobutyl potassium sulfonate (PPFBS), and 2,4, 5-trichlorobenzene potassium Sulfonate (STB). The 2,4, 5-trichlorobenzene potassium sulfonate contains halogen, the halogen exceeds the standard when the addition amount is high, and the perfluorobutyl potassium sulfonate is expensive, so the sulfonate flame retardant is preferably 3-benzenesulfonyl potassium sulfonate.

Preferably, the anti-dripping agent is 0.1-2 parts, preferably Polytetrafluoroethylene (PTFE), which can generate anti-dripping performance when plastics are burnt and can be selected from emulsion type PTFE, micro powder type PTFE and coating type PTFE. Since emulsion PTFE is an aqueous dispersion and is not suitable for melt extrusion processes, the anti-dripping agent is preferably a fine powder PTFE or a coated PTFE. The dispersibility of the micro-powder PTFE in PC/ABS alloy is not ideal, and the compatibility of PTFE in PC/ABS can be improved by coating a layer of styrene-acrylonitrile copolymer (SAN) or polymethyl methacrylate (PMMA) on the PTFE micro-powder. The anti-dripping agent of the present invention is therefore preferably a styrene-acrylonitrile copolymer or polymethyl methacrylate-coated polytetrafluoroethylene.

Preferably, the antioxidant is used in an amount of 0.1 to 1 part, and the antioxidant is a hindered phenol-based and/or phosphite-based antioxidant, for example, triethylene glycol bis [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ] pentaerythritol, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-4-methylphenol, β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate octadecyl ester, β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate isooctyl ester, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, thiodiethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] N, N ' -bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propanamide, N ' -bis [3, 5-di-tert-butyl-4-hydroxyphenyl) amide ], bis (3, 5-octylphenyl) tris (3, 5-tert-butyl-4-hydroxyphenyl) amide, 6-octylphenyl) phosphite, N ' -bis [3, N, N ' -bis (3, 5-di-tert-butyl-4-octylphenyl) tris (3,5 ' -bis (3, 5-octylphenyl) amide ], bis (3, 6-bis (3, 5-tert-butyl-4-octylphenyl) tris (2, 6-octylphenyl) amide, 6-bis (2, 5-tert-butyl-tert-butyl-octylphenyl) amide, 6-bis (3, 6-bis (2, 5-butyl-bis.

The antioxidant of the present invention may be selected from one or two of the above-mentioned antioxidants, preferably a hindered phenol antioxidant and a phosphite antioxidant are used in combination, and further preferably tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ] pentaerythritol ester alcohol and tris (2, 4-di-tert-butylphenyl) phosphite.

Preferably, the lubricant is 0.1-1 part. The lubricant can be one or more selected from stearic acid, calcium stearate, paraffin, polyethylene wax, polyethylene oxide wax, pentaerythritol stearate, N '-ethylene bis stearamide and silicone powder, and is preferably a compound of N, N' -ethylene bis stearamide and silicone powder.

The invention is realized by the following technical scheme:

the preparation method of the impact-resistant halogen-free flame-retardant PC/ABS blended alloy comprises the following steps:

weighing the following components in parts by weight: PC: 30-70 parts of ABS: 5-30 parts of epoxy-terminated modified polysiloxane: 1-10 parts of a compatilizer: 1-10 parts of a toughening agent: 1-15 parts of an ester exchange catalyst: 0.01-0.5 parts of sulfonate flame retardant: 0-1 part of an anti-dripping agent: 0-2 parts of antioxidant: 0-1 part of lubricant: 0 to 1 part.

Adding PC, ABS, epoxy-terminated modified polysiloxane, a compatilizer, a flexibilizer, a sulfonate flame retardant, an ester exchange catalyst, an anti-dripping agent, an antioxidant and a lubricant into a high-speed mechanical blending mixer, and uniformly stirring to obtain a premix;

carrying out melt blending on the premix in a double-screw extruder, and dicing to obtain composite granules;

and carrying out injection molding on the composite granules to obtain the composite material.

The invention leads the epoxy-terminated modified polysiloxane to be grafted on the end group of PC by a simple extrusion process.

Preferably, the processing temperature of the double-screw extruder is 180-260 ℃, and the screw rotating speed is 20-100 r/min. The double-screw extruder is divided into 6 zones, wherein the first zone is 180 ℃ minus 190 ℃, the second zone is 210 ℃ minus 230 ℃, the third zone is 230 ℃ minus 250 ℃, the fourth zone is 235 ℃ minus 255 ℃, the fifth zone is 240 ℃ minus 260 ℃ and the sixth zone is 230 ℃ minus 240 ℃.

Compared with the prior art, the invention has the beneficial effects that:

1) the invention adopts the epoxy-terminated modified polysiloxane as the flame retardant, and the epoxy group of the flame retardant can react with the active end group formed after the chain of PC is broken and is grafted to the end group of PC, so that the compatibility of the flame retardant and PC can be increased, the free movement of the molecule of the flame retardant is not influenced, and the flame retardant can rapidly migrate to the surface in the combustion process to block oxygen.

2) The ester exchange catalyst introduced by the invention can improve the activity of the ester exchange reaction among PC molecules and initiate more side reactions such as hydrolysis reaction and the like, so that more hydroxyl groups are formed at the end group of the PC, a proper amount of terminal hydroxyl groups generated in the extrusion process of the PC can be ensured to carry out chemical reaction with the epoxy-terminated polysiloxane, and the efficiency of the epoxy-terminated polysiloxane is improved; and the invention further adopts AlCl₃And Ti (OC)₄H₉)₄The mass ratio of (0.5-5): 1 can reduce the dosage of epoxy-terminated polysiloxane.

3) The siloxane is grafted on the PC main chain by a reactive extrusion process, so that the method is low in cost, simple in process and easy to apply on a large scale.

Detailed Description

Hereinafter, the technical solution of the present invention will be further described and illustrated by specific examples. However, these embodiments are exemplary, and the present disclosure is not limited thereto. Unless otherwise specified, the raw materials used in the following specific examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art.

In the following examples, the sources of the raw materials are as follows:

PC was purchased from LG 1303-15, Korea; ABS is available from PA-757K of Zhenjiangqi beautification industries; glycidyl ether oxypropyl terminated polydiene of epoxy terminated modified polysiloxaneMethylsiloxane EFS-8200. E-MA-GMA is AX8900 from Arkema, France; POE-g-GMA is the easy compatilizer SOG-02 of Jiangsu Limited; MMA-SR is P52 from Wacker, Germany; MBS is TP-801 of Japanese electrochemistry; AlCl₃Purchased from Yundi chemical; ti (OC)₄H₉)₄From Anhui-Thailand chemical, 3-benzenesulfonyl potassium benzenesulfonate from Guangzhou Xijia chemical Co., Ltd, FA500H in which styrene-acrylonitrile copolymer is coated with polytetrafluoroethylene to form Japanese platinum, and tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol and tris (2, 4-di-tert-butylphenyl) phosphite were purchased from taiwan double bond chemical; n, N' -ethylene bis stearamide and polyethylene wax were obtained from New materials science and technology, Inc. of Kipleris, Heizhou; the silicone powder is KJ-B01 from Kyogzhou Qianji plastics science and technology Co.

Example 1

70kg of PC, 30kg of ABS, 1.5kg of epoxy-terminated modified polysiloxane, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of AlCl are weighed₃0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol ester alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylene bis stearamide and 0.2kg of silicone powder were put into a high-speed mechanical blending mixer and uniformly stirred to obtain a premix;

carrying out melt blending on the premix in a double-screw extruder, and dicing to obtain composite granules; and carrying out injection molding on the composite granules to obtain the composite material.

The double-screw extruder is divided into 6 zones, wherein the first zone is 180 ℃, the second zone is 220 ℃, the third zone is 230 ℃, the fourth zone is 245 ℃, the fifth zone is 255 ℃ and the sixth zone is 240 ℃. The screw rotation speed is 60 r/min.

Example 2

70.95kg of PC, 30kg of ABS, 0.5kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of AlCl are weighed₃0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 3

70.45kg of PC, 30kg of ABS, 1.0kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of AlCl are weighed₃0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 4

70kg of PC, 30kg of ABS, 1.45kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of AlCl are weighed₃0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 5

70.95kg of PC, 30kg of ABS, 0.5kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR, and 0.04kg of Ti (OC) were weighed out₄H₉)₄0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 6

70.45kg of PC, 30kg of ABS, 1.0kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of Ti (OC) were weighed out₄H₉)₄0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 7

70kg of PC, 30kg of ABS, 1.45kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of Ti (OC) were weighed out₄H₉)₄0.2kg of FA500H, 0.3kg of Tetrakis[ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 8

70.95kg of PC, 30kg of ABS, 0.5kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.02kg of AlCl are weighed₃、0.02kg Ti(OC₄H₉)₄0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 9

70.45kg of PC, 30kg of ABS, 1.0kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.02kg of AlCl are weighed₃、0.02kg Ti(OC₄H₉)₄0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 10

70kg of PC, 30kg of ABS, 1.45kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.02kg of AlCl are weighed₃、0.02kg Ti(OC₄H₉)₄0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Example 11

68kg of PC, 32kg of ABS, 1.2kg of epoxy-terminated modified polysiloxane, 0.08kg of KSS, 10kg of POE-g-GMA, 11kg of MBS and 0.03kg of AlCl₃、0.02kg Ti(OC₄H₉)₄0.3kg of FA500H, 0.4kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propanoic acid]Pentaerythritol Tetraester alcohol, 0.3kg methylene chlorideAdding tris (2, 4-di-tert-butylphenyl) phosphate, 0.2kg of polyethylene wax and 0.3kg of silicone powder into a high-speed mechanical blending mixer, and uniformly stirring to obtain a premix;

The double-screw extruder is divided into 6 zones, wherein the first zone is 180 ℃, the second zone is 220 ℃, the third zone is 240 ℃, the fourth zone is 250 ℃, the fifth zone is 250 ℃ and the sixth zone is 240 ℃. The screw rotation speed is 45 r/min.

Comparative example 1

71.45kg of PC, 30kg of ABS, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of AlCl are weighed₃0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Comparative example 2

70.95kg of PC, 30kg of ABS, 0.55kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR and 0.04kg of AlCl are weighed₃0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionic acid]Pentaerythritol alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were mixed, and the subsequent steps were the same as in example 1.

Comparative example 3

70.99kg of PC, 30kg of ABS, 0.5kg of epoxy-terminated modified polysiloxane, 0.05kg of KSS, 8kg of E-MA-GMA, 10kg of MMA-SR, 0.2kg of FA500H, 0.3kg of tetrakis [ β - (3, 5-di-tert-butyl, 4-hydroxyphenyl) propionate ] pentaerythritol ester alcohol, 0.3kg of tris (2, 4-di-tert-butylphenyl) phosphite, 0.1kg of N, N' -ethylenebisstearamide and 0.2kg of silicone powder were weighed out and mixed, and the subsequent procedure was followed as in example 1.

The formulations of the composites of examples 1-11 and comparative examples 1-3 are shown in table 1 below.

TABLE 1 summary of composite formulations for examples 1-11 and comparative examples 1-3

The PC/ABS composites obtained in examples 1 to 11 and comparative examples 1 to 3 were subjected to a performance test. The mechanical tensile property of the material is tested according to GB/T1040.2-2006, the bending property of the material is tested according to GB/T9341-. The flame retardant properties of the material were tested according to UL94 and the oxygen index of the material was determined according to GB/T2406.1-2008. The measurement results are shown in Table 2.

TABLE 2 composite Properties of examples 1-11 and comparative examples 1-3

As can be seen from the data of comparative example 1 and example 2 in Table 2, the addition of the epoxy-terminated modified polysiloxane to the matrix can improve the flame retardant rating of the composite to UL 94V-1, and has little effect on the mechanical properties of the composite. The transesterification catalyst of examples 8-10 was AlCl₃And Ti (OC)₄H₉)₄The flame retardant performance of the composite material is obviously higher than that of the composite material prepared by independently adding AlCl in the examples 2-4₃Addition of Ti (OC) alone as transesterification catalyst and examples 5-7₄H₉)₄As transesterification catalysts; and, with AlCl₃And Ti (OC)₄H₉)₄The compound is an ester exchange catalyst, and an excellent flame retardant effect can be achieved when the addition amount of the epoxy-terminated modified polysiloxane is 0.5 part.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims

1. The impact-resistant halogen-free flame-retardant PC/ABS blended alloy is characterized by comprising the following components in parts by weight:

2. the impact-resistant halogen-free flame-retardant PC/ABS blend alloy according to claim 1, wherein the epoxy-terminated modified polysiloxane has the following structure:

wherein R is

3. The impact-resistant halogen-free flame-retardant PC/ABS blend alloy according to claim 1, wherein the transesterification catalyst is selected from Li₂CO₃、NaHCO₃、Na₂WO₄、AlCl₃、ZnCl₂，Zn(OAc)₂、Ti(OC₄H₉)₄、n-Bu₂One or more of SnO.

4. The impact-resistant halogen-free flame-retardant PC/ABS blend alloy as claimed in claim 1, wherein the transesterification catalyst is AlCl₃And Ti (OC)₄H₉)₄The mass ratio of (0.5-5): 1 of the mixture formed.

5. The impact-resistant halogen-free flame retardant PC/ABS blend alloy according to claim 1, wherein the toughening agent is selected from one or more of methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-acrylate copolymer and methyl methacrylate-silicone rubber copolymer.

6. The impact-resistant halogen-free flame-retardant PC/ABS blend alloy as claimed in claim 1, wherein the sulfonate flame retardant is one or more selected from potassium 3-benzenesulfonyl benzenesulfonate, potassium perfluorobutylsulfonate, and potassium 2,4, 5-trichlorobenzenesulfonate.

7. The impact-resistant halogen-free flame-retardant PC/ABS blend alloy according to claim 1, wherein the anti-dripping agent is polytetrafluoroethylene.

8. The impact-resistant halogen-free flame-retardant PC/ABS blend alloy according to claim 7, wherein the anti-dripping agent is styrene-acrylonitrile copolymer or poly (methyl methacrylate) -coated polytetrafluoroethylene.

9. The preparation method of the impact-resistant halogen-free flame-retardant PC/ABS blend alloy as claimed in claim 1, wherein the preparation method comprises the following steps:

weighing the components according to the weight part of claim 1, adding PC, ABS, epoxy-terminated modified polysiloxane, compatilizer, flexibilizer, sulfonate flame retardant, ester exchange catalyst, anti-dripping agent, antioxidant and lubricant into a high-speed mechanical blending mixer, and uniformly stirring to obtain a premix;

10. The preparation method of claim 9, wherein the processing temperature of the twin-screw extruder is 180-260 ℃ and the screw rotation speed is 20-100 r/min.