WO2024082522A1 - Flame-retardant polycarbonate composite material, preparation method therefor, and application thereof - Google Patents

Flame-retardant polycarbonate composite material, preparation method therefor, and application thereof Download PDF

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WO2024082522A1
WO2024082522A1 PCT/CN2023/080275 CN2023080275W WO2024082522A1 WO 2024082522 A1 WO2024082522 A1 WO 2024082522A1 CN 2023080275 W CN2023080275 W CN 2023080275W WO 2024082522 A1 WO2024082522 A1 WO 2024082522A1
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resin
composite material
polycarbonate
burning
slow
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PCT/CN2023/080275
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French (fr)
Chinese (zh)
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艾军伟
陈平绪
叶南飚
岑茵
王培涛
董相茂
张志铭
蒋刚军
丁超
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金发科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to the field of engineering plastics, and more specifically, to a slow-burning polycarbonate composite material and a preparation method and application thereof.
  • Polycarbonate is a transparent material with excellent mechanical properties, flame retardancy and high temperature resistance. As one of the five major engineering plastics, polycarbonate is used in many fields such as construction panels, automotive parts, medical equipment, aerospace, electronics, optical lenses, optical disc base materials, LED lighting, etc.
  • the primary purpose of the present invention is to overcome the problem of the high combustion rate of the polycarbonate of the non-flame retardant system in the prior art, and to provide a slow-burning polycarbonate composite material.
  • the slow-burning polycarbonate composite material is added with a specific modified high carbon resin, so that the obtained slow-burning polycarbonate composite material not only has a low combustion rate, but also maintains excellent impact strength (including low-temperature impact strength) and good appearance.
  • a further object of the present invention is to provide a method for preparing the above-mentioned slow-burning polycarbonate composite material.
  • a further object of the present invention is to provide the use of the above-mentioned slow-burning polycarbonate composite material in the preparation of communication network equipment products or electronic and electrical appliance products.
  • a slow-burning polycarbonate composite material comprises the following components in parts by weight:
  • the modified high carbon content resin is obtained by modifying the high carbon content resin with citric acid, and the high carbon content resin has a residual carbon content of ⁇ 18% under the conditions of an inert atmosphere, a heating rate of 20°C/min, and a calculated temperature fixed at 750°C;
  • the residual carbon content of the present invention refers to the ratio of the mass of residual carbon after thermal cracking of high carbon resin under the conditions of inert atmosphere, heating rate of 20°C/min and calculated temperature fixed at 750°C to the mass of high carbon resin.
  • the styrene resin is at least one of styrene-acrylonitrile copolymer and styrene-butadiene-styrene copolymer.
  • the inventors of the present invention have found through multiple studies that a high carbon content resin with a specific carbon residue is modified with citric acid to obtain a modified high carbon content resin, and the modified high carbon content resin is added to a polycarbonate resin-styrene resin system to obtain a slow-burning polycarbonate composite material, the combustion rate of which is ⁇ 56 mm/min, achieving a good slow-burning effect.
  • the reason is that the presence of citric acid will increase the compatibility of the high carbon content resin with the polycarbonate resin and the styrene resin, thereby increasing the carbonization rate and carbon skeleton strength of the slow-burning polycarbonate composite material, and achieving a slow-burning effect.
  • the residual carbon content of the high carbon content resin is too low, it will be unfavorable for improving the carbon content and the strength of the carbon skeleton, and the combustion rate cannot be slowed down; if citric acid is not used for modification, but other polar modifiers are used to modify the high carbon content resin, such as phosphoric acid or toluenesulfonic acid, because these modifiers are sensitive to water, their introduction will cause severe degradation of the polycarbonate resin matrix during processing, and the presence of their degradation products will hinder the rearrangement reaction of the polycarbonate resin during high-temperature combustion, reduce the integrity of the alloy skeleton, and result in poor combustion rate reduction effect of the polycarbonate composite material, and also cause degradation of the resin matrix, thereby producing more flammable small molecules, resulting in a decrease in the impact strength (including low-temperature impact strength) of the material and deterioration of the appearance.
  • citric acid is not used for modification, but other polar modifiers are used to modify the high carbon content resin, such as phosphoric acid
  • the invention adds a specific modified high carbon resin, so that the obtained slow-burning polycarbonate composite material not only has a lower burning rate, but also maintains excellent impact strength (including low-temperature impact strength) and good appearance.
  • the high carbon resin is at least one of polyphenylene ether resin, polyphenylene sulfide resin, new material polycarbonate resin or polyparaphenylene terephthalamide resin.
  • the high carbon content resin is polyphenylene ether resin.
  • the slow-burning polycarbonate composite material obtained by selecting polyphenylene ether resin has a low burning rate while maintaining better impact strength and low-temperature impact strength.
  • the preparation process of the modified high carbon content resin is as follows: 100 parts by weight of high carbon content resin is mixed with 0.01 to 1 parts by weight of citric acid, and the mixture is extruded into master batches to obtain the modified high carbon content resin.
  • the styrene resin is a styrene-acrylonitrile copolymer.
  • the content of acrylonitrile in the styrene-acrylonitrile copolymer is 28-40 wt %.
  • the residual carbon content of the high carbon content resin is 28-52%.
  • the polycarbonate resins commonly used in the art can be used in the present invention.
  • the polycarbonate resin is virgin polycarbonate resin and/or recycled polycarbonate resin.
  • new polycarbonate resin refers to polycarbonate resin that is directly used after polymerization without injection molding or use.
  • Recycled polycarbonate resin refers to recycled material obtained by classifying and collecting discarded polycarbonate resin according to conventional physical recycling treatment methods in the art.
  • the number average molecular weight of the recycled polycarbonate is 20,000 to 25,000
  • the terminal hydroxyl content is 72 to 372 ppm
  • the BPA content is 18 to 133 ppm.
  • terminal hydroxyl content of recycled polycarbonate is measured according to HG/T 2709-1995 standard; the BPA content is measured according to GB/T 32889-2016 standard.
  • Tougheners and stabilizers commonly used in the art can be used in the present invention.
  • the toughening agent is a core-shell structure toughening agent
  • the core of the core-shell structure toughening agent includes but is not limited to silicone rubber, polybutadiene, etc.
  • the shell includes but is not limited to acrylate, etc.
  • the stabilizer is a hindered phenol antioxidant, including but not limited to hindered phenol antioxidants 1024, 3114, 1010, 1076, etc.
  • the polycarbonate alloy material may further include 0.01 to 5 parts of other additives.
  • the other auxiliary agent is at least one of a lubricant or a filler.
  • the lubricant is at least one of stearic acid, stearate or silicone.
  • the filler is at least one of talc, mica or wollastonite.
  • the method for preparing the polycarbonate alloy material is characterized by comprising the following steps: mixing the components
  • the slow-burning polycarbonate composite material is obtained by combining, melt-extruding and granulating.
  • the preparation method comprises the following steps: stirring and mixing the components in a high-speed mixer, and then melt-extruding and granulating the components in a twin-screw extruder to obtain a polycarbonate alloy composition.
  • the stirring and mixing speed is 20 to 100 rpm; the aspect ratio of the twin-screw extruder is 32 to 60:1, the barrel temperature is 220 to 260° C., and the screw speed is 200 to 900 rpm.
  • the polycarbonate alloy material is used in the preparation of communication network equipment products or electronic and electrical appliance products.
  • the communication network equipment product is a mobile phone component, a portable writing tablet component, an Internet access device housing or an Internet access device housing antenna.
  • the electronic and electrical product is a small household appliance housing, an electrical component bracket or a charging device housing.
  • the present invention has the following beneficial effects:
  • the invention adds a specific modified high carbon resin, so that the obtained slow-burning polycarbonate composite material not only has a lower burning rate ( ⁇ 56mm/min), but also maintains excellent impact strength (above 40KJ/ m2 ) and low-temperature impact strength (above 24KJ/ m2 ) as well as good appearance (above Grade B).
  • Styrene resin 1# styrene-acrylonitrile copolymer, SAN 310, Kumho, South Korea, acrylonitrile content 18wt%;
  • Styrene resin 2# styrene-acrylonitrile copolymer, SAN2200, Taiwan Chemical Fiber, acrylonitrile content 28wt%;
  • Styrene resin 3# styrene-acrylonitrile copolymer, SAN 3400, Taiwan Chemical Fiber, acrylonitrile The content of 32wt%;
  • Styrene resin 4# styrene-acrylonitrile copolymer, SAN CN40, Benzol Chemical, acrylonitrile content 40wt%;
  • Styrene resin 5# styrene-butadiene-styrene copolymer, PA 757, acrylonitrile content 28wt%;
  • Toughener 1# core-shell toughener, MBS, M-521 Japan Zhongyuan;
  • Toughener 2# non-core-shell toughener, EBA, Elvaloy PTW DuPont, USA;
  • Stabilizer hindered phenol antioxidant, antioxidant 1076, commercially available
  • additives fillers, talc, commercially available;
  • High carbon resin 1# residual carbon content is 28%, PPE, LXN035, Shanxi Bluestar;
  • High carbon resin 2# residual carbon content is 33%, PPE, LXN050, Shanxi Bluestar;
  • High carbon resin 3# residual carbon content is 43%, PPS, 3418, South Korea SK;
  • High carbon resin 4# residual carbon content is 52%, PPS, 3450, South Korea SK;
  • High carbon resin 5# residual carbon content is 18%, PC, FG1760, Japan Idemitsu;
  • High carbon resin 6# residual carbon content is 5%, PBT, 1200-211, Changchun, Taiwan;
  • Modifier 1# citric acid, CAS 77-92-9, commercially available;
  • Modifier 2# phosphoric acid, CAS 7664-38-2, commercially available;
  • Modifier 3# Toluenesulfonic acid, CAS104-15-4, commercially available
  • the preparation process of the modified high carbon content resin is as follows: 100 parts by weight of the high carbon content resin is mixed with 0.05 parts by weight of the modifier, and the mixture is extruded into a master batch to serve as the modified high carbon content resin.
  • Modified high carbon resin 1# the matrix is high carbon resin 1#, and the modifier is citric acid;
  • Modified high carbon resin 2# the matrix is high carbon resin 2#, and the modifier is citric acid;
  • Modified high carbon resin 3# the matrix is high carbon resin 3#, and the modifier is citric acid;
  • Modified high carbon resin 4# the matrix is high carbon resin 4#, and the modifier is citric acid;
  • Modified high carbon resin 5# the matrix is high carbon resin 5#, and the modifier is citric acid;
  • Modified high carbon resin 6# the matrix is high carbon resin 6#, and the modifier is citric acid;
  • Modified high carbon resin 7# the base is high carbon resin 1#, and the modifier is phosphoric acid;
  • Modified high carbon resin 8# the matrix is high carbon resin 1#, and the modifier is toluenesulfonic acid.
  • the components (such as stabilizers, other auxiliary agents) selected in the parallel examples and comparative examples are all the same commercially available products.
  • Burning rate The flammability test is carried out according to the procedure of "Flammability Test of Plastic Materials, UL94-2018".
  • the flame retardant grade is derived based on the burning rate, extinguishing time, ability to resist falling, and whether the falling is burning. Samples used for testing: 125mm length and 13mm width.
  • the thickness of the present invention is selected as 0.8mm during the test.
  • the flame retardant grade of the material can be classified as (UL94-HB): The burning rate (mm/min) at this thickness can be obtained by calculation, where the larger the burning rate value, the faster the burning propagation speed, and vice versa, the slower the burning propagation speed.
  • Impact strength 3.0mm IZOD impact strength was tested according to ASTM D256-2010 standard. The specimen was placed in an environment with room temperature of 25°C and humidity of 50% for more than 48 hours, and then tested and the results were recorded as room temperature impact strength.
  • Low-temperature impact strength According to the ASTM D256-2010 standard, the 3.0mm IZOD impact strength is tested in an environmental conditioning box with a preset temperature of -30°C for more than 8 hours, and then tested and the results are recorded as low-temperature impact strength. The higher the test result value, the better the toughness.
  • the injection molding temperature is fixed at 280°C, the injection molding speed is 85%, and the injection molding pressure is 85% to form a square plate with a thickness of 1.0mm and a side length of 100mm.
  • the appearance is graded by visually inspecting the surface of 10 samples continuously. If all 10 samples have no defects, they are rated as Grade A. If 1 to 3 samples have slight defects such as water splashes or silver threads, they are rated as Grade B. If more than 3 samples have slight defects such as water splashes or silver threads, they are rated as Grade C. If at least 1 sample has serious water splashes or silver threads, it is rated as Grade D.
  • the preparation process of the slow-burning polycarbonate composite material of each embodiment of the present invention and the comparative polycarbonate composite material provided in each comparative example is as follows: weigh each component according to the ratio, add it into a high mixer, stir and blend it, obtain a premix, and then extrude it in a twin-screw extruder, and obtain the slow-burning polycarbonate composite material/comparative polycarbonate composite material after the melt granulation process.
  • the stirring speed is 65 rpm
  • the aspect ratio of the twin-screw extruder is 40:1
  • the barrel temperature is 220-260°C
  • the screw speed is 250-650 rpm.
  • Examples 1 to 17 provide a series of slow-burning polycarbonate composite materials, the formulations of which are shown in Tables 1 and 2.
  • This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that modified high carbon content resin 1# is replaced by modified high carbon content resin 6#.
  • This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that modified high carbon content resin 1# is replaced by modified high carbon content resin 7#.
  • This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that: modified high carbon resin 8# is not added.
  • This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that: modified high carbon resin 1# is not added.
  • the slow-burning polycarbonate composite materials of Examples 1 to 17 not only have a lower burning rate (burning rate ⁇ 56 mm/min), but also maintain excellent impact strength (including low-temperature impact strength) and good appearance. From the comparison of Examples 1 to 5, it can be seen that the amount of each component has a certain influence on the burning rate, impact strength, low-temperature impact strength and appearance.
  • the impact strength and low-temperature impact strength are also affected by the amount of other components. Under the comprehensive regulation of each component, the impact strength and low-temperature impact strength of Example 1 are the best, and the low-temperature impact strength of Examples 4 and 5 are better than the low-temperature impact strength of Examples 2 and 3, respectively.
  • modified high carbon resin 6# was added, and the obtained comparative polycarbonate composite material had a higher combustion rate.
  • modified high carbon resin 7# was added, and the combustion rate was higher, and the impact strength (including low-temperature impact strength) was lower, and the appearance grade was poor;
  • modified high carbon resin 8# was added, and the effect of slowing down the combustion rate was poor, and the impact strength (including low-temperature impact strength) was lower, and the appearance grade was poor; in Comparative Example 4, no modified high carbon resin was added, and the combustion rate was higher.

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  • Health & Medical Sciences (AREA)
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Abstract

The present invention relates to a flame-retardant polycarbonate composite material, a preparation method therefor and an application thereof. The flame-retardant polycarbonate composite material is characterized in comprising the following components in parts by weight: 10-99.9 parts polycarbonate resin, 5-50 parts styrene resin, 0.05-5 parts modified high-carbon resin, 1-30 parts toughening agent, and 0.01-2 parts stabilizer. Adding a specific modified high-carbon resin to the flame-retardant polycarbonate composite material results in a flame-retardant polycarbonate composite material which not only has a relatively low combustion rate, but also maintains excellent impact strength (including low-temperature impact strength) and good appearance.

Description

一种缓燃聚碳酸酯复合材料及其制备方法和应用A slow-burning polycarbonate composite material and its preparation method and application 技术领域Technical Field
本发明涉及工程塑料领域，更具体地，涉及一种缓燃聚碳酸酯复合材料及其制备方法和应用。The present invention relates to the field of engineering plastics, and more specifically, to a slow-burning polycarbonate composite material and a preparation method and application thereof.
背景技术Background technique
聚碳酸酯是一种透明材料，有很好的力学性能、阻燃性能和耐高温性。作为五大工程塑料之一，聚碳酸酯被应用于建筑业板材、汽车零部件、医疗器械、航空航天、电子电器、光学透镜、光盘基础材料、LED照明等许多领域。Polycarbonate is a transparent material with excellent mechanical properties, flame retardancy and high temperature resistance. As one of the five major engineering plastics, polycarbonate is used in many fields such as construction panels, automotive parts, medical equipment, aerospace, electronics, optical lenses, optical disc base materials, LED lighting, etc.
现有研究中，一般是阻燃体系的聚碳酸酯的研究较多，比如公开号为CN112759913A的中国专利通过加入磷腈类阻燃剂来实现聚碳酸酯的阻燃。但实际应用中，非阻燃体系的聚碳酸酯材料仍占多数，减缓非阻燃体系的聚碳酸酯的燃烧速率，可以提高其安全性。目前对非阻燃体系的聚碳酸酯材料的研究仍然较少，故需研究开发一种具有低燃烧速率的聚碳酸酯材料。In existing research, there are generally more studies on flame retardant polycarbonate systems. For example, the Chinese patent with publication number CN112759913A achieves flame retardancy of polycarbonate by adding phosphazene flame retardants. However, in actual applications, non-flame retardant polycarbonate materials still account for the majority. Slowing down the burning rate of non-flame retardant polycarbonate can improve its safety. At present, there are still few studies on non-flame retardant polycarbonate materials, so it is necessary to study and develop a polycarbonate material with a low burning rate.
发明内容Summary of the invention
本发明的首要目的是克服现有技术中非阻燃体系的聚碳酸酯的燃烧速率较快的问题，提供一种缓燃聚碳酸酯复合材料。该缓燃聚碳酸酯复合材料加入特定的改性高成碳树脂，使得得到的缓燃聚碳酸酯复合材料不仅具有较低的燃烧速率，而且保持了优异的冲击强度(包括低温冲击强度)和良好的外观。The primary purpose of the present invention is to overcome the problem of the high combustion rate of the polycarbonate of the non-flame retardant system in the prior art, and to provide a slow-burning polycarbonate composite material. The slow-burning polycarbonate composite material is added with a specific modified high carbon resin, so that the obtained slow-burning polycarbonate composite material not only has a low combustion rate, but also maintains excellent impact strength (including low-temperature impact strength) and good appearance.
本发明的进一步目的是提供上述缓燃聚碳酸酯复合材料的制备方法。A further object of the present invention is to provide a method for preparing the above-mentioned slow-burning polycarbonate composite material.
本发明的进一步目的是提供上述缓燃聚碳酸酯复合材料在制备通信网络设备产品或电子电器制件产品中的应用。A further object of the present invention is to provide the use of the above-mentioned slow-burning polycarbonate composite material in the preparation of communication network equipment products or electronic and electrical appliance products.
本发明的上述目的通过以下技术方案实现：The above-mentioned object of the present invention is achieved by the following technical solutions:
一种缓燃聚碳酸酯复合材料，包括如下重量份数的组分：
A slow-burning polycarbonate composite material comprises the following components in parts by weight:
所述改性高成碳树脂通过柠檬酸对高成碳树脂改性得到，所述高成碳树脂在惰性氛围、升温速率为20℃/min和计算温度固定为750℃的条件下的残碳量≥18％；The modified high carbon content resin is obtained by modifying the high carbon content resin with citric acid, and the high carbon content resin has a residual carbon content of ≥18% under the conditions of an inert atmosphere, a heating rate of 20°C/min, and a calculated temperature fixed at 750°C;
应当理解的是，本发明的残碳量是指高成碳树脂在惰性氛围、升温速率为20℃/min和计算温度固定为750℃的条件下热裂解后残碳的质量占高成碳树脂的质量的比值。It should be understood that the residual carbon content of the present invention refers to the ratio of the mass of residual carbon after thermal cracking of high carbon resin under the conditions of inert atmosphere, heating rate of 20°C/min and calculated temperature fixed at 750°C to the mass of high carbon resin.
所述苯乙烯类树脂为苯乙烯-丙烯腈共聚物或苯乙烯-丁二烯-苯乙烯共聚物中的至少一种。The styrene resin is at least one of styrene-acrylonitrile copolymer and styrene-butadiene-styrene copolymer.
本发明的发明人通过多次研究发现，采用柠檬酸对特定碳残量的高成碳树脂进行改性，得到改性高成碳树脂，将该改性高成碳树脂加入到聚碳酸酯树脂-苯乙烯类树脂体系中，得到缓燃聚碳酸酯复合材料，该缓燃聚碳酸酯复合材料的燃烧速率为≤56mm/min，达到良好的缓燃效果。其原因是：柠檬酸的存在会提高高成碳树脂与聚碳酸酯树脂和苯乙烯类树脂的相容性，从而提高缓燃聚碳酸酯复合材料的成碳率和碳骨架强度，实现燃烧速率的减缓。The inventors of the present invention have found through multiple studies that a high carbon content resin with a specific carbon residue is modified with citric acid to obtain a modified high carbon content resin, and the modified high carbon content resin is added to a polycarbonate resin-styrene resin system to obtain a slow-burning polycarbonate composite material, the combustion rate of which is ≤56 mm/min, achieving a good slow-burning effect. The reason is that the presence of citric acid will increase the compatibility of the high carbon content resin with the polycarbonate resin and the styrene resin, thereby increasing the carbonization rate and carbon skeleton strength of the slow-burning polycarbonate composite material, and achieving a slow-burning effect.
如高成碳树脂的残碳量太低，则不利于成碳率和碳骨架强度的提高，无法实现燃烧速率的减缓；如不采用柠檬酸进行改性，而是采用其他极性改性剂对高成碳树脂进行改性，比如磷酸或甲苯磺酸，由于这些改性剂其对水敏感，其引入会加工过程中会引发聚碳酸酯树脂基体的剧烈降解，其降解产物的存在会阻碍了聚碳酸酯树脂的在高温燃烧过程中的重排反应，降低合金骨架的完整性，导致聚碳酸酯复合材料的燃烧速率减缓效果不佳，而且还会由于引起树脂基体的降解，从而产生更多的可燃性小分子导致材料的冲击强度(包括低温冲击强度)的下降以及外观的劣化。If the residual carbon content of the high carbon content resin is too low, it will be unfavorable for improving the carbon content and the strength of the carbon skeleton, and the combustion rate cannot be slowed down; if citric acid is not used for modification, but other polar modifiers are used to modify the high carbon content resin, such as phosphoric acid or toluenesulfonic acid, because these modifiers are sensitive to water, their introduction will cause severe degradation of the polycarbonate resin matrix during processing, and the presence of their degradation products will hinder the rearrangement reaction of the polycarbonate resin during high-temperature combustion, reduce the integrity of the alloy skeleton, and result in poor combustion rate reduction effect of the polycarbonate composite material, and also cause degradation of the resin matrix, thereby producing more flammable small molecules, resulting in a decrease in the impact strength (including low-temperature impact strength) of the material and deterioration of the appearance.
即本发明加入特定的改性高成碳树脂，使得得到的缓燃聚碳酸酯复合材料不仅具有较低的燃烧速率，而且保持了优异的冲击强度(包括低温冲击强度)和良好的外观。That is, the invention adds a specific modified high carbon resin, so that the obtained slow-burning polycarbonate composite material not only has a lower burning rate, but also maintains excellent impact strength (including low-temperature impact strength) and good appearance.
优选地，包括如下重量份数的组分：

Preferably, the following components are included in parts by weight:

优选地，所述高成碳树脂为聚苯醚树脂、聚亚苯基硫醚树脂、新料聚碳酸酯树脂或聚对亚苯基对苯二甲酰胺树脂中的至少一种。Preferably, the high carbon resin is at least one of polyphenylene ether resin, polyphenylene sulfide resin, new material polycarbonate resin or polyparaphenylene terephthalamide resin.
更为优选地，所述所述高成碳树脂为聚苯醚树脂。More preferably, the high carbon content resin is polyphenylene ether resin.
选用聚苯醚树脂，得到的缓燃聚碳酸酯复合材料具有低燃烧速率的同时，可保持更好的冲击强度和低温冲击强度。The slow-burning polycarbonate composite material obtained by selecting polyphenylene ether resin has a low burning rate while maintaining better impact strength and low-temperature impact strength.
优选地，所述改性高成碳树脂的制备过程如下：将100重量份高成碳树脂与0.01～1重量份柠檬酸混合，挤出成母粒，即得所述改性高成碳树脂。Preferably, the preparation process of the modified high carbon content resin is as follows: 100 parts by weight of high carbon content resin is mixed with 0.01 to 1 parts by weight of citric acid, and the mixture is extruded into master batches to obtain the modified high carbon content resin.
优选地，所述苯乙烯类树脂为苯乙烯-丙烯腈共聚物。Preferably, the styrene resin is a styrene-acrylonitrile copolymer.
优选地，所述苯乙烯-丙烯腈共聚物中丙烯腈的含量为28～40wt％。Preferably, the content of acrylonitrile in the styrene-acrylonitrile copolymer is 28-40 wt %.
优选地，所述高成碳树脂的残碳量为28～52％。Preferably, the residual carbon content of the high carbon content resin is 28-52%.
本领域常用的聚碳酸酯树脂都可用于本发明中。The polycarbonate resins commonly used in the art can be used in the present invention.
优选地，所述聚碳酸酯树脂为新料聚碳酸酯树脂和/或回收聚碳酸酯树脂。Preferably, the polycarbonate resin is virgin polycarbonate resin and/or recycled polycarbonate resin.
应当理解的是，新料聚碳酸酯树脂是指经过聚合后直接使用未经注塑或者使用的聚碳酸酯树脂。回收聚碳酸酯树脂是指按照本领域常规的物理回收处理方式对废弃的聚碳酸酯树脂进行分类收集得到的回收料。It should be understood that new polycarbonate resin refers to polycarbonate resin that is directly used after polymerization without injection molding or use. Recycled polycarbonate resin refers to recycled material obtained by classifying and collecting discarded polycarbonate resin according to conventional physical recycling treatment methods in the art.
更为优选地，所述回收聚碳酸酯的数均分子量为20000～25000，端羟基含量为72～372ppm，BPA含量为18～133ppm。More preferably, the number average molecular weight of the recycled polycarbonate is 20,000 to 25,000, the terminal hydroxyl content is 72 to 372 ppm, and the BPA content is 18 to 133 ppm.
需要说明的是，回收聚碳酸酯的端羟基含量按照HG/T 2709-1995标准测得；BPA含量按照GB/T 32889-2016标准测得。It should be noted that the terminal hydroxyl content of recycled polycarbonate is measured according to HG/T 2709-1995 standard; the BPA content is measured according to GB/T 32889-2016 standard.
本领域常用的增韧剂、稳定剂都可用于本发明。Tougheners and stabilizers commonly used in the art can be used in the present invention.
优选地，所述增韧剂为核壳结构增韧剂，核壳结构增韧剂的核包括但不限于硅橡胶、聚丁二烯等，壳包括但不限于丙烯酸酯等。Preferably, the toughening agent is a core-shell structure toughening agent, the core of the core-shell structure toughening agent includes but is not limited to silicone rubber, polybutadiene, etc., and the shell includes but is not limited to acrylate, etc.
优选地，所述稳定剂为受阻酚类抗氧剂，包括但不限于受阻酚类抗氧剂1024、3114、1010、1076等。Preferably, the stabilizer is a hindered phenol antioxidant, including but not limited to hindered phenol antioxidants 1024, 3114, 1010, 1076, etc.
优选地，所述聚碳酸酯合金材料还可包括其他助剂0.01～5份。Preferably, the polycarbonate alloy material may further include 0.01 to 5 parts of other additives.
更为优选地，所述其他助剂为润滑剂或填料中的至少一种。More preferably, the other auxiliary agent is at least one of a lubricant or a filler.
可选地，所述润滑剂为硬脂酸、硬脂酸酯或硅酮中的至少一种。Optionally, the lubricant is at least one of stearic acid, stearate or silicone.
可选地，所述填料为滑石粉、云母或硅灰石中的至少一种。Optionally, the filler is at least one of talc, mica or wollastonite.
上述聚碳酸酯合金材料的制备方法，其特征在于，包如下步骤：将各组分混 合，熔融挤出，造粒，即得所述缓燃聚碳酸酯复合材料。The method for preparing the polycarbonate alloy material is characterized by comprising the following steps: mixing the components The slow-burning polycarbonate composite material is obtained by combining, melt-extruding and granulating.
优选地，所述制备方法包括如下步骤：将各组分在高混机中搅拌混合，然后在双螺杆挤出机中熔融挤出，造粒，即得聚碳酸酯合金组合物。Preferably, the preparation method comprises the following steps: stirring and mixing the components in a high-speed mixer, and then melt-extruding and granulating the components in a twin-screw extruder to obtain a polycarbonate alloy composition.
更为优选地，所述搅拌混合的转速为20～100转/min；所述双螺杆挤出机的长径比为32～60:1，螺筒温度为220～260℃，螺杆转速为200～900转/mim。More preferably, the stirring and mixing speed is 20 to 100 rpm; the aspect ratio of the twin-screw extruder is 32 to 60:1, the barrel temperature is 220 to 260° C., and the screw speed is 200 to 900 rpm.
上述聚碳酸酯合金材料在制备通信网络设备产品或电子电器制件产品中的应用。The polycarbonate alloy material is used in the preparation of communication network equipment products or electronic and electrical appliance products.
优选地，所述通信网络设备产品为手机部件、便捷式书写板部件、上网设备外壳或上网设备外壳天线。Preferably, the communication network equipment product is a mobile phone component, a portable writing tablet component, an Internet access device housing or an Internet access device housing antenna.
优选地，所述电子电器制件产品为小家电外壳、电器元件支架或充电设备外壳。Preferably, the electronic and electrical product is a small household appliance housing, an electrical component bracket or a charging device housing.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
本发明加入特定的改性高成碳树脂，使得得到的缓燃聚碳酸酯复合材料不仅具有较低的燃烧速率(≤56mm/min)，而且保持了优异的冲击强度(40KJ/m2以上)和低温冲击强度(24KJ/m2以上)以及良好的外观(B级以上)。The invention adds a specific modified high carbon resin, so that the obtained slow-burning polycarbonate composite material not only has a lower burning rate (≤56mm/min), but also maintains excellent impact strength (above 40KJ/ m2 ) and low-temperature impact strength (above 24KJ/ m2 ) as well as good appearance (above Grade B).
具体实施方式Detailed ways
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。In order to more clearly and completely describe the technical solution of the present invention, the present invention is further described in detail through specific embodiments below. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not used to limit the present invention. Various changes can be made within the scope of the rights of the present invention.
本发明各实施例及对比例选用的部分试剂说明如下：Some of the reagents selected in the embodiments and comparative examples of the present invention are described as follows:
聚碳酸酯树脂(新料)：S-2000F，日本三菱，数均分子量为25500；Polycarbonate resin (new material): S-2000F, Mitsubishi, Japan, number average molecular weight is 25500;
聚碳酸酯树脂(回收)1#：ASL-06，奥赛尔，水桶PCR来源，数均分子量为25000，端羟基含量为72ppm，BPA含量为18ppm；Polycarbonate resin (recycled) 1#: ASL-06, Osel, bucket PCR source, number average molecular weight of 25000, terminal hydroxyl content of 72ppm, BPA content of 18ppm;
聚碳酸酯树脂(回收)2#：PC TJ-20A，天炬，板材PCR来源，数均分子量20000，端羟基含量为372ppm，BPA含量为133ppm；Polycarbonate resin (recycled) 2#: PC TJ-20A, Tianju, plate PCR source, number average molecular weight 20000, terminal hydroxyl content 372ppm, BPA content 133ppm;
苯乙烯类树脂1#：苯乙烯-丙烯腈共聚物，SAN 310，韩国锦湖，丙烯腈的含量18wt％；Styrene resin 1#: styrene-acrylonitrile copolymer, SAN 310, Kumho, South Korea, acrylonitrile content 18wt%;
苯乙烯类树脂2#：苯乙烯-丙烯腈共聚物，SAN2200，台湾化纤，丙烯腈的含量28wt％；Styrene resin 2#: styrene-acrylonitrile copolymer, SAN2200, Taiwan Chemical Fiber, acrylonitrile content 28wt%;
苯乙烯类树脂3#：苯乙烯-丙烯腈共聚物，SAN 3400，台湾化纤维，丙烯腈 的含量32wt％；Styrene resin 3#: styrene-acrylonitrile copolymer, SAN 3400, Taiwan Chemical Fiber, acrylonitrile The content of 32wt%;
苯乙烯类树脂4#：苯乙烯-丙烯腈共聚物，SAN CN40，苯领化学，丙烯腈的含量40wt％；Styrene resin 4#: styrene-acrylonitrile copolymer, SAN CN40, Benzol Chemical, acrylonitrile content 40wt%;
苯乙烯类树脂5#：苯乙烯-丁二烯-苯乙烯共聚物，PA 757，丙烯腈的含量28wt％；Styrene resin 5#: styrene-butadiene-styrene copolymer, PA 757, acrylonitrile content 28wt%;
增韧剂1#：核壳增韧剂，MBS，M-521日本钟渊；Toughener 1#: core-shell toughener, MBS, M-521 Japan Zhongyuan;
增韧剂2#：非核壳增韧剂，EBA，Elvaloy PTW美国杜邦；Toughener 2#: non-core-shell toughener, EBA, Elvaloy PTW DuPont, USA;
稳定剂：受阻酚抗氧剂，抗氧剂1076，市售；Stabilizer: hindered phenol antioxidant, antioxidant 1076, commercially available;
其他助剂：填料，滑石粉，市售；Other additives: fillers, talc, commercially available;
高成碳树脂1#：残碳量为28％，PPE，LXN035，山西蓝星；High carbon resin 1#: residual carbon content is 28%, PPE, LXN035, Shanxi Bluestar;
高成碳树脂2#：残碳量为33％，PPE，LXN050，山西蓝星；High carbon resin 2#: residual carbon content is 33%, PPE, LXN050, Shanxi Bluestar;
高成碳树脂3#：残碳量为43％，PPS，3418，韩国SK；High carbon resin 3#: residual carbon content is 43%, PPS, 3418, South Korea SK;
高成碳树脂4#：残碳量为52％，PPS，3450，韩国SK；High carbon resin 4#: residual carbon content is 52%, PPS, 3450, South Korea SK;
高成碳树脂5#：残碳量为18％，PC,FG1760，日本出光；High carbon resin 5#: residual carbon content is 18%, PC, FG1760, Japan Idemitsu;
高成碳树脂6#：残碳量为5％，PBT，1200-211，台湾长春；High carbon resin 6#: residual carbon content is 5%, PBT, 1200-211, Changchun, Taiwan;
改性剂1#：柠檬酸，CAS 77-92-9，市售；Modifier 1#: citric acid, CAS 77-92-9, commercially available;
改性剂2#：磷酸，CAS 7664-38-2，市售；Modifier 2#: phosphoric acid, CAS 7664-38-2, commercially available;
改性剂3#：甲苯磺酸，CAS104-15-4，市售Modifier 3#: Toluenesulfonic acid, CAS104-15-4, commercially available
改性高成碳树脂的制备过程如下：将100重量份高成碳树脂与0.05重量份改性剂的混合，挤出成母粒，作为改性高成碳树脂。The preparation process of the modified high carbon content resin is as follows: 100 parts by weight of the high carbon content resin is mixed with 0.05 parts by weight of the modifier, and the mixture is extruded into a master batch to serve as the modified high carbon content resin.
改性高成碳树脂1#：基体为高成碳树脂1#，改性剂为柠檬酸；Modified high carbon resin 1#: the matrix is high carbon resin 1#, and the modifier is citric acid;
改性高成碳树脂2#：基体为高成碳树脂2#，改性剂为柠檬酸；Modified high carbon resin 2#: the matrix is high carbon resin 2#, and the modifier is citric acid;
改性高成碳树脂3#：基体为高成碳树脂3#，改性剂为柠檬酸；Modified high carbon resin 3#: the matrix is high carbon resin 3#, and the modifier is citric acid;
改性高成碳树脂4#：基体为高成碳树脂4#，改性剂为柠檬酸；Modified high carbon resin 4#: the matrix is high carbon resin 4#, and the modifier is citric acid;
改性高成碳树脂5#：基体为高成碳树脂5#，改性剂为柠檬酸；Modified high carbon resin 5#: the matrix is high carbon resin 5#, and the modifier is citric acid;
改性高成碳树脂6#：基体为高成碳树脂6#，改性剂为柠檬酸；Modified high carbon resin 6#: the matrix is high carbon resin 6#, and the modifier is citric acid;
改性高成碳树脂7#：基体为高成碳树脂1#，改性剂为磷酸；Modified high carbon resin 7#: the base is high carbon resin 1#, and the modifier is phosphoric acid;
改性高成碳树脂8#：基体为高成碳树脂1#，改性剂为甲苯磺酸。Modified high carbon resin 8#: the matrix is high carbon resin 1#, and the modifier is toluenesulfonic acid.
如未特别说明，各平行实施例和对比例中选用的各组分(例如稳定剂、其他助剂)均为相同的市售产品。 Unless otherwise specified, the components (such as stabilizers, other auxiliary agents) selected in the parallel examples and comparative examples are all the same commercially available products.
本发明各实施例的缓燃聚碳酸酯复合材料和各对比例提供的对比聚碳酸酯复合材料按如下测试方法进行性能测定：The slow-burning polycarbonate composite materials of each embodiment of the present invention and the comparative polycarbonate composite materials provided in each comparative example were tested for performance according to the following test methods:
燃烧速率：按照“塑料材料的可燃性测试，UL94-2018”的规程进行可燃性测试。基于燃烧速率、熄灭时间、抵抗低落的能力、以及低落是否正燃烧，来得出阻燃等级。用于测试的样品：125mm长度13mm宽度，本发明在进行测试时厚度选为0.8mm，根据UL94规程，可以将材料阻燃等级分类为(UL94-HB)：通过计算可以得到该厚度下的燃烧速率(mm/min)，其中燃烧速率数值越大，燃烧传播速度越快，反之，燃烧传播速度越慢。Burning rate: The flammability test is carried out according to the procedure of "Flammability Test of Plastic Materials, UL94-2018". The flame retardant grade is derived based on the burning rate, extinguishing time, ability to resist falling, and whether the falling is burning. Samples used for testing: 125mm length and 13mm width. The thickness of the present invention is selected as 0.8mm during the test. According to the UL94 procedure, the flame retardant grade of the material can be classified as (UL94-HB): The burning rate (mm/min) at this thickness can be obtained by calculation, where the larger the burning rate value, the faster the burning propagation speed, and vice versa, the slower the burning propagation speed.
冲击强度：根据ASTM D256-2010标准下测试3.0mm IZOD冲击强度，放在室温为25℃湿度为50％的环境下进行调节48h以上，然后进行测试并记录结果，记录为常温冲击强度。Impact strength: 3.0mm IZOD impact strength was tested according to ASTM D256-2010 standard. The specimen was placed in an environment with room temperature of 25℃ and humidity of 50% for more than 48 hours, and then tested and the results were recorded as room temperature impact strength.
低温冲击强度：根据ASTM D256-2010标准下测试3.0mm IZOD冲击强度，放在预设温度为-30℃的环境调节箱中调节8h以上，然后进行测试并记录结果，记录为低温冲击强度；测试结果数值越高，韧性越好。Low-temperature impact strength: According to the ASTM D256-2010 standard, the 3.0mm IZOD impact strength is tested in an environmental conditioning box with a preset temperature of -30°C for more than 8 hours, and then tested and the results are recorded as low-temperature impact strength. The higher the test result value, the better the toughness.
外观：固定注塑温度为280℃注塑速度为85％，注塑压力为85％成型1.0mm厚度100mm边长的方板，通过目测连续注塑10块样板的表面进行外观评级，若10片均无任何缺陷为A级，若有1～3片出现轻微的水花或银丝等缺陷为B级，若有＞3片出现轻微的水花或银丝等缺陷为C级，若至少1片出现了严重的水花银丝则为D级。Appearance: The injection molding temperature is fixed at 280℃, the injection molding speed is 85%, and the injection molding pressure is 85% to form a square plate with a thickness of 1.0mm and a side length of 100mm. The appearance is graded by visually inspecting the surface of 10 samples continuously. If all 10 samples have no defects, they are rated as Grade A. If 1 to 3 samples have slight defects such as water splashes or silver threads, they are rated as Grade B. If more than 3 samples have slight defects such as water splashes or silver threads, they are rated as Grade C. If at least 1 sample has serious water splashes or silver threads, it is rated as Grade D.
本发明各实施例的缓燃聚碳酸酯复合材料和各对比例提供的对比聚碳酸酯复合材料的制备工艺如下：按照配比称取各组分后，加入高混机中搅拌共混，得到预混料，然后在双螺杆挤出机中进行挤出，熔融造粒工序后即得缓燃聚碳酸酯复合材料/对比聚碳酸酯复合材料。其中，搅拌的转速为65转/min，双螺杆挤出机的长径比为40:1，螺筒温度为220～260℃，螺杆转速为250～650转/min。The preparation process of the slow-burning polycarbonate composite material of each embodiment of the present invention and the comparative polycarbonate composite material provided in each comparative example is as follows: weigh each component according to the ratio, add it into a high mixer, stir and blend it, obtain a premix, and then extrude it in a twin-screw extruder, and obtain the slow-burning polycarbonate composite material/comparative polycarbonate composite material after the melt granulation process. Among them, the stirring speed is 65 rpm, the aspect ratio of the twin-screw extruder is 40:1, the barrel temperature is 220-260°C, and the screw speed is 250-650 rpm.
实施例1～17Examples 1 to 17
实施例1～17提供一系列缓燃聚碳酸酯复合材料，其配方如表1、表2所示。Examples 1 to 17 provide a series of slow-burning polycarbonate composite materials, the formulations of which are shown in Tables 1 and 2.
表1实施例1～6的配方(重量份)

Table 1 Formula of Examples 1 to 6 (parts by weight)

表2实施例7～17的配方(重量份)
Table 2 Formulas of Examples 7 to 17 (parts by weight)
对比例1Comparative Example 1
本对比例提供一种对比聚碳酸酯复合材料，其配方与实施例1的不同之处在于：改性高成碳树脂1#替换成改性高成碳树脂6#。This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that modified high carbon content resin 1# is replaced by modified high carbon content resin 6#.
对比例2 Comparative Example 2
本对比例提供一种对比聚碳酸酯复合材料，其配方与实施例1的不同之处在于：改性高成碳树脂1#替换成改性高成碳树脂7#。This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that modified high carbon content resin 1# is replaced by modified high carbon content resin 7#.
对比例3Comparative Example 3
本对比例提供一种对比聚碳酸酯复合材料，其配方与实施例1的不同之处在于：不加入改性高成碳树脂8#。This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that: modified high carbon resin 8# is not added.
对比例4Comparative Example 4
本对比例提供一种对比聚碳酸酯复合材料，其配方与实施例1的不同之处在于：不加入改性高成碳树脂1#。This comparative example provides a comparative polycarbonate composite material, the formula of which is different from that of Example 1 in that: modified high carbon resin 1# is not added.
性能测试Performance Testing
按上述提及的测试方法对各实施例的缓燃聚碳酸酯复合材料和各对比例提供的对比聚碳酸酯复合材料的性能进行测定，测试结果如表3。The performance of the slow-burning polycarbonate composite material of each embodiment and the comparative polycarbonate composite material provided by each comparative example was tested according to the above-mentioned test method. The test results are shown in Table 3.
表3各实施例的缓燃聚碳酸酯复合材料和各对比例提供的对比聚碳酸酯复Table 3 The slow-burning polycarbonate composite materials of each embodiment and the comparative polycarbonate composite materials provided in each comparative example
合材料的性能测试结果

Composite material performance test results

从表3可知，实施例1～17的缓燃聚碳酸酯复合材料不仅具有较低的燃烧速率(燃烧速率≤56mm/min)，而且保持了优异的冲击强度(包括低温冲击强度)和良好的外观。从实施例1～5对比可知，各组分的用量对燃烧速率、冲击强度、低温冲击强度和外观都有一定的影响。具体地，由于聚碳酸酯对燃烧速率的影响较大，故在一定范围内聚碳酸酯的用量较大时，缓燃聚碳酸酯复合材料的燃烧速率较低，故实施例2的燃烧速率低于实施例4，实施例5的燃烧速率低于实施例3；冲击强度和低温冲击强度除受到聚碳酸酯和改性高成碳树脂的影响外，其他组分用量的影响也有一定影响，在各组分的综合调控下，实施例1的冲击强度和低温冲击强度最好，实施例4和5的低温冲击强度分别优于实施例2和3的低温冲击强度。It can be seen from Table 3 that the slow-burning polycarbonate composite materials of Examples 1 to 17 not only have a lower burning rate (burning rate ≤ 56 mm/min), but also maintain excellent impact strength (including low-temperature impact strength) and good appearance. From the comparison of Examples 1 to 5, it can be seen that the amount of each component has a certain influence on the burning rate, impact strength, low-temperature impact strength and appearance. Specifically, since polycarbonate has a greater influence on the burning rate, when the amount of polycarbonate is large within a certain range, the burning rate of the slow-burning polycarbonate composite material is lower, so the burning rate of Example 2 is lower than that of Example 4, and the burning rate of Example 5 is lower than that of Example 3; in addition to being affected by polycarbonate and modified high carbon resin, the impact strength and low-temperature impact strength are also affected by the amount of other components. Under the comprehensive regulation of each component, the impact strength and low-temperature impact strength of Example 1 are the best, and the low-temperature impact strength of Examples 4 and 5 are better than the low-temperature impact strength of Examples 2 and 3, respectively.
从实施例1、9～11可知，当选用苯乙烯-丙烯腈共聚物时，苯乙烯-丙烯腈共聚物的丙烯腈的含量在28～40wt％的范围下，得到的缓燃聚碳酸酯复合材料具有更低的燃烧速率。It can be seen from Examples 1 and 9 to 11 that when styrene-acrylonitrile copolymer is used and the acrylonitrile content of the styrene-acrylonitrile copolymer is in the range of 28 to 40 wt %, the obtained slow-burning polycarbonate composite material has a lower burning rate.
从实施例9、12可知，若选用苯乙烯-丁二烯-苯乙烯共聚物(实施例12)，由于引入丁二烯链段成分，则对聚碳酸酯复合材料的缓燃效果起到负面作用，虽然在常温冲击强度以及低温冲击强度和外观可以保持相似的质量等级，但燃烧速率较高。It can be seen from Examples 9 and 12 that if styrene-butadiene-styrene copolymer (Example 12) is selected, the introduction of butadiene chain segments will have a negative effect on the slow-burning effect of the polycarbonate composite material. Although the room-temperature impact strength, low-temperature impact strength and appearance can maintain similar quality grades, the burning rate is higher.
从实施例1、14～17可知，改性高成碳树脂中高成碳树脂的残碳量越高，得到的缓燃聚碳酸酯复合材料的燃烧速率越小(比如实施例14～16)。从实施例1、14～16可知，而当高成碳树脂选用PPE(聚苯醚树脂)时(实施例1和实施例14)，得到的缓燃聚碳酸酯复合材料在满足燃烧速率≤56mm/min的情况下，能保持较 好的冲击强度和低温冲击强度。From Examples 1, 14 to 17, it can be seen that the higher the residual carbon content of the high carbon content resin in the modified high carbon content resin, the lower the combustion rate of the obtained slow-burning polycarbonate composite material (such as Examples 14 to 16). From Examples 1, 14 to 16, it can be seen that when the high carbon content resin is PPE (polyphenylene ether resin) (Examples 1 and 14), the obtained slow-burning polycarbonate composite material can maintain a relatively high combustion rate while satisfying the combustion rate of ≤56mm/min. Good impact strength and low temperature impact strength.
对比例1加入的是改性高成碳树脂6#，得到的对比聚碳酸酯复合材料的燃烧速率较高。对比例2加入的是改性高成碳树脂7#，燃烧速率较高，且冲击强度(包括低温冲击强度)较低，外观等级差；对比例3加入的是改性高成碳树脂8#，燃烧速率的减缓效果不佳，且冲击强度(包括低温冲击强度)较低，外观等级差；对比例4不加入改性高成碳树脂，燃烧速率较高。In Comparative Example 1, modified high carbon resin 6# was added, and the obtained comparative polycarbonate composite material had a higher combustion rate. In Comparative Example 2, modified high carbon resin 7# was added, and the combustion rate was higher, and the impact strength (including low-temperature impact strength) was lower, and the appearance grade was poor; in Comparative Example 3, modified high carbon resin 8# was added, and the effect of slowing down the combustion rate was poor, and the impact strength (including low-temperature impact strength) was lower, and the appearance grade was poor; in Comparative Example 4, no modified high carbon resin was added, and the combustion rate was higher.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。 Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

  1. 一种缓燃聚碳酸酯复合材料，其特征在于，包括如下重量份数的组分：
    A slow-burning polycarbonate composite material, characterized by comprising the following components in parts by weight:
    所述改性高成碳树脂通过柠檬酸对高成碳树脂改性得到，所述高成碳树脂在惰性氛围、升温速率为20℃/min和计算温度固定为750℃的条件下的残碳量≥18％；The modified high carbon content resin is obtained by modifying the high carbon content resin with citric acid, and the high carbon content resin has a residual carbon content of ≥18% under the conditions of an inert atmosphere, a heating rate of 20°C/min, and a calculated temperature fixed at 750°C;
    所述苯乙烯类树脂为苯乙烯-丙烯腈共聚物或苯乙烯-丁二烯-苯乙烯共聚物中的至少一种。The styrene resin is at least one of styrene-acrylonitrile copolymer and styrene-butadiene-styrene copolymer.
  2. 根据权利要求1所述缓燃聚碳酸酯复合材料，其特征在于，所述高成碳树脂为聚苯醚树脂、聚亚苯基硫醚树脂、新料聚碳酸酯树脂或聚对亚苯基对苯二甲酰胺树脂中的至少一种。The slow-burning polycarbonate composite material according to claim 1 is characterized in that the high carbon resin is at least one of polyphenylene ether resin, polyphenylene sulfide resin, new material polycarbonate resin or polyparaphenylene terephthalamide resin.
  3. 根据权利要求2所述缓燃聚碳酸酯复合材料，其特征在于，所述高成碳树脂为聚苯醚树脂。The slow-burning polycarbonate composite material according to claim 2, characterized in that the high carbon content resin is polyphenylene ether resin.
  4. 根据权利要求1所述缓燃聚碳酸酯复合材料，其特征在于，所述苯乙烯类树脂为苯乙烯-丙烯腈共聚物。The slow-burning polycarbonate composite material according to claim 1, characterized in that the styrene resin is a styrene-acrylonitrile copolymer.
  5. 根据权利要求1所述缓燃聚碳酸酯复合材料，其特征在于，所述苯乙烯-丙烯腈共聚物中丙烯腈的含量为28～40wt％。The slow-burning polycarbonate composite material according to claim 1, characterized in that the content of acrylonitrile in the styrene-acrylonitrile copolymer is 28 to 40 wt%.
  6. 根据权利要求1所述缓燃聚碳酸酯复合材料，其特征在于，所述高成碳树脂的残碳量为28～52％。The slow-burning polycarbonate composite material according to claim 1 is characterized in that the residual carbon content of the high carbon content resin is 28-52%.
  7. 根据权利要求1所述缓燃聚碳酸酯复合材料，其特征在于，所述聚碳酸酯树脂为新料聚碳酸酯树脂和/或回收聚碳酸酯树脂。The slow-burning polycarbonate composite material according to claim 1, characterized in that the polycarbonate resin is new polycarbonate resin and/or recycled polycarbonate resin.
  8. 根据权利要求1所述缓燃聚碳酸酯复合材料，其特征在于，所述增韧剂为核壳结构增韧剂。The slow-burning polycarbonate composite material according to claim 1, characterized in that the toughening agent is a core-shell structure toughening agent.
  9. 权利要求1～8任一所述聚碳酸酯合金材料的制备方法，其特征在于，包如下步骤：将各组分混合，熔融挤出，造粒，即得所述缓燃聚碳酸酯复合材料。The method for preparing the polycarbonate alloy material according to any one of claims 1 to 8 is characterized in that it comprises the following steps: mixing the components, melt-extruding, and granulating to obtain the slow-burning polycarbonate composite material.
  10. 权利要求1～8任一所述聚碳酸酯合金材料在制备通信网络设备产品或电 子电器制件产品中的应用。 The polycarbonate alloy material according to any one of claims 1 to 8 is used in the preparation of communication network equipment products or electrical appliances Application in electronic and electrical products.
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