CN116144158B - High-temperature-resistant flame-retardant PC/ABS composite material and preparation method thereof - Google Patents

High-temperature-resistant flame-retardant PC/ABS composite material and preparation method thereof Download PDF

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CN116144158B
CN116144158B CN202310136346.3A CN202310136346A CN116144158B CN 116144158 B CN116144158 B CN 116144158B CN 202310136346 A CN202310136346 A CN 202310136346A CN 116144158 B CN116144158 B CN 116144158B
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CN116144158A (en
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于艳芬
刘海晨
刘海波
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Shenzhen Chen Yufeng Plastic New Material Co ltd
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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention relates to the technical field of composite materials, in particular to a high-temperature-resistant flame-retardant PC/ABS composite material and a preparation method thereof. The high-temperature-resistant flame-retardant PC/ABS composite material comprises the following raw materials in parts by weight: 800-120 parts by weight of PC/ABS, 15-40 parts by weight of mica powder, 8-14 parts by weight of toughening agent, 0.1-0.5 part by weight of pentaerythritol stearate, 0.3-0.8 part by weight of antioxidant and 7-13 parts by weight of flame retardant. The flame retardant is formed by compounding flame retardant modified lignin and carboxylated polymer. The flame retardant prepared by the invention can be well applied to high-temperature-resistant flame-retardant PC/ABS composite materials, and has good flame retardant property and mechanical property.

Description

High-temperature-resistant flame-retardant PC/ABS composite material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-temperature-resistant flame-retardant PC/ABS composite material and a preparation method thereof.
Background
Polycarbonate (PC) is a thermoplastic engineering plastic with excellent comprehensive performance, high impact strength and light transmittance, good dimensional stability, easy coloring, aging resistance and excellent electrical insulation, but has the defects of poor wear resistance, poor processing fluidity and the like. Acrylonitrile-butadiene-styrene (ABS) resin is a thermoplastic polymer material with high strength, high toughness and easy processing. The PC/ABS composite material prepared by blending PC and ABS can complement the performances of the respective components and improve the comprehensive performance of the material. PC/ABS composite materials are widely applied to building materials, electronic and electric appliances, automobiles and ships, but the flammability limits the use of the PC/ABS composite materials, so that flame retardant treatment is necessary for the PC/ABS composite materials.
Chinese patent (application number 201911241497.5) discloses a high-rigidity flame-retardant PC/ABS composite material and a product thereof. The high-rigidity flame-retardant PC/ABS composite material comprises, per 100 parts by mass of PC/ABS composite material finished product, 32-84.4 parts of PC, 5-20 parts of ABS, 5-25 parts of mica, 2-10 parts of toughening agent and 3.6-13 parts of flame retardant. The high-rigidity flame-retardant PC/ABS composite material can be directly used for injection molding of high-rigidity products. The high-rigidity flame-retardant PC/ABS is adoptedThe product prepared from the composite material has high rigidity and high flame retardance and can be directly injection molded. Although the PC/ABS composite material prepared by the method has better flame retardant property, the PC/ABS composite material has poor mechanical property and has only 13kJ/m impact strength 2 There may be a reason that compatibility and dispersibility of the added phosphate flame retardant, the silicone flame retardant and the hypophosphite flame retardant with the matrix are poor, resulting in poor mechanical properties, and thus, it is necessary to develop a high temperature resistant flame retardant PC/ABS composite material having both high mechanical properties and better flame retardant properties, so as to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-temperature-resistant flame-retardant PC/ABS composite material and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the PC/ABS composite material is composed of the following raw materials in parts by weight: 800-120 parts by weight of PC/ABS, 15-40 parts by weight of mica powder, 8-14 parts by weight of toughening agent, 0.1-0.5 part by weight of pentaerythritol stearate, 0.3-0.8 part by weight of antioxidant and 7-13 parts by weight of flame retardant.
The toughening agent is any one of triethyl phosphate, dioctyl terephthalate and epoxidized soybean oil;
the antioxidant is at least one of phosphite antioxidants and hindered phenol antioxidants;
the phosphaphenanthrene flame retardant has the characteristics of high carbon content, lasting flame retardance and the like, and is halogen-free and environment-friendly. DOPO is used as an important phosphorus and murphy film intermediate, the P-H bond of the DOPO has high reactivity, and the DOPO can be subjected to addition reaction with unsaturated groups such as carbonyl, epoxy, carbon-carbon double bonds and the like, so that a series of reactive DOPO flame retardants are obtained. The reactive DOPO flame retardant can be used for modifying a matrix or other materials, DOPO groups can be connected to a polymer molecular chain in a covalent bond mode, the flame retardant efficiency is extremely high, and the flame retardant performance of the polymer can be improved, and meanwhile, the mechanical properties and other properties of the polymer matrix can be improved.
The lignin has the characteristics of excellent mechanical property, good thermal stability, good flame retardance, easiness in chemical modification and the like, and the hydroxyl groups on the surface of the lignin endow the lignin with the functionalization characteristics of easiness in chemical modification and the like, so that the lignin can generate a crosslinking effect with other chemical molecules or nano materials, and the mechanical property and flame retardance of the composite material can be effectively improved when the lignin is applied to PC/ABS composite materials. However, because of rich hydroxyl groups on the surface of lignin, the lignin is easy to aggregate into a highly ordered structure, so that the lignin has higher polarity, is directly applied to PC/ABS composite materials, has poor compatibility with most organic media in a matrix, is extremely easy to self-agglomerate in a polymer matrix, weakens interface interaction, and influences the mechanical properties of plastics. The combination of lignin and DOPO can be applied to the PC/ABS composite material to further improve the flame retardant property and the mechanical property of the composite material. The lignin and the diethylenetriamine propyl trimethoxy silane react to contain rich hydroxyl and amino, and the acrylic anhydride-DOPO and the aminosilane modified lignin are utilized to carry out chemical imidization reaction to obtain the flame retardant modified lignin, and an imide ring with rigidity and heat resistance and a DOPO flame retardant structure are introduced into the side chain of the lignin skeleton, so that the lignin is functionally modified, the dispersion performance of the lignin and a matrix is effectively improved, and meanwhile, the composite material modified by the DOPO flame retardant has higher flame retardant efficiency, the composite material can obtain higher flame retardant performance only by a small amount, and the mechanical property and the like of the composite material can be improved while the flame retardant performance of the composite material is improved.
The flame retardant modified lignin prepared by the method can effectively improve the dispersion performance of lignin, the compatibility of the lignin with PC/ABS is better after the lignin is subjected to DOPO grafting modification, the interface bonding strength is higher, the DOPO modified lignin contains a rigid and heat-resistant aromatic ring, a nitrogen-containing imide ring and a DOPO phosphorus-containing flame retardant structure, and a nitrogen-phosphorus synergistic compound flame retardant system is formed with the lignin, so that the mechanical property and the flame retardant property are improved.
The preparation method of the flame retardant comprises the following steps: under the nitrogen environment, adding 1-4 parts by weight of DOPO and 2-5 parts by weight of acrylic anhydride into 15-30 parts by weight of tetrahydrofuran, reacting for 10-20 hours at 80-90 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 3-5 parts by weight of modified lignin and 1-2 parts by weight of acrylic anhydride-DOPO into 40-80 parts by weight of dimethyl sulfoxide, stirring for 4-7 hours at room temperature and 500-700rpm, adding 4-8 parts by weight of benzylamine and 12-18 parts by weight of acetic anhydride, reacting for 16-28 hours at 40-60 ℃ and 300-500rpm, centrifuging, washing and drying to obtain the flame retardant.
The preparation method of the modified lignin comprises the following steps: adding 5-8 parts by weight of lignin into 100-200 parts by weight of 60-90wt% ethanol water solution, performing ultrasonic dispersion for 20-50min at ultrasonic power of 200-400W and ultrasonic frequency of 50-70kHz, adding 0.5-2 parts by weight of diethylenetriamine propyl trimethoxysilane, stirring for 24-48h at 70-900 ℃ and 600-1000rpm, centrifuging, and drying to obtain modified lignin.
In the experimental process, the inventor finds that the elasticity and mechanical property of the flame retardant can be improved by introducing the polymer chain of the carboxylated polymer containing halogen atoms into the flame retardant modified lignin, and meanwhile, the flame retardant property of DOPO can be further improved by the synergistic effect of DOPO and the halogen atoms in the carboxylated polymer, so that the mechanical property and flame retardant property of the composite of DOPO modified lignin and carboxylated polymer are more effective than those of DOPO modified lignin or carboxylated polymer alone.
The flame retardant prepared by the method can effectively improve the dispersion performance of the flame retardant in a matrix, and the polymer chain of the carboxylated polymer is introduced into the flame retardant modified lignin, so that compared with the single addition of the flame retardant modified lignin and PC/ABS, the compatibility of the flame retardant modified lignin and PC/ABS is better, the interface bonding strength is higher, and the prepared flame retardant contains flame retardant structures such as aromatic rings, nitrogen-containing imide rings, DOPO phosphorus, halogen and the like with rigidity and heat resistance, and forms a nitrogen-phosphorus-bromine synergistic compound flame retardant system with DOPO, so that the mechanical property and flame retardant property are improved. The flame retardant coating is applied to PC/ABS composite materials and has good flame retardant effect and mechanical property.
Specifically, the reaction mechanism: s1: the P-H bond in DOPO and the double bond in acrylic anhydride undergo an addition reaction to obtain acrylic anhydride-DOPO; carrying out substitution reaction on anhydride in acrylic anhydride-DOPO and amino in amino silanization modified lignin to obtain flame retardant modified lignin; s2: and (3) carrying out nucleophilic substitution reaction on chloromethylated polystyrene resin and 2-bromoterephthalic acid in an alkaline environment to obtain a carboxylated polymer. The nucleophilic substitution reaction is carried out under an alkaline condition, the alkaline environment is favorable for promoting the smooth progress of the nucleophilic substitution reaction, and the reaction process can remove small hydrogen chloride molecules; s3: the method is characterized in that flame retardant modified lignin and carboxylated polymer are used as main raw materials, and under the reaction condition that N, N' -carbonyl diimidazole is used as an activator and 4-methylbenzenesulfonic acid pyridine is used as a catalyst, the carboxyl in the carboxylated polymer and the hydroxyl in the flame retardant modified lignin are subjected to condensation reaction to obtain the DOPO-containing composite flame retardant, namely the flame retardant.
Preferably, the preparation method of the flame retardant comprises the following steps:
s1, adding 1-4 parts by weight of DOPO and 2-5 parts by weight of acrylic anhydride into 15-30 parts by weight of tetrahydrofuran in a nitrogen environment, reacting for 10-20 hours at 80-90 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 3-5 parts by weight of modified lignin and 1-2 parts by weight of acrylic anhydride-DOPO into 40-80 parts by weight of dimethyl sulfoxide, stirring for 4-7 hours at room temperature and 500-700rpm, adding 4-8 parts by weight of benzylamine and 12-18 parts by weight of acetic anhydride, reacting for 16-28 hours at 40-60 ℃ and 300-500rpm, centrifuging, washing and drying to obtain flame retardant modified lignin;
s2, adding 5-10 parts by weight of chloromethyl polystyrene into 80-140 parts by weight of dimethyl sulfoxide, stirring at room temperature and 200-400rpm for 6-12h, and adding 4-6 parts by weight of 2-bromoterephthalic acid and 2-4 parts by weight of K 2 CO 3 Stirring at 400-800rpm for 20-40min, heating to 90-110deg.C, stirring for 14-24 hr, washing, purifying with ethanol, and drying to obtain carboxylated polymer;
s3, adding 2-5 parts by weight of flame retardant modified lignin into 50-80 parts by weight of dimethyl sulfoxide solvent, stirring for 8-15min at 400-800rpm, adding 0.02-0.1 part by weight of N, N' -carbonyldiimidazole, and stirring at 300-500rpm for reaction for 6-12h at 20-30 ℃; adding 5-7 parts by weight of carboxylated polymer and 0.05-0.2 part by weight of 4-methylbenzenesulfonic acid pyridine, stirring at 50-70 ℃ and 400-800rpm for reaction for 30-60 hours, adding water for precipitation, filtering, washing and drying to obtain the flame retardant.
The preparation method of the high-temperature-resistant flame-retardant PC/ABS composite material comprises the following steps:
(1) Weighing PC/ABS, mica powder, a toughening agent, pentaerythritol stearate, an antioxidant and a flame retardant according to a proportion, uniformly mixing, mixing for 30-60min at 150-170 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
The invention has the beneficial effects that:
1. the invention provides a high-temperature-resistant flame-retardant PC/ABS composite material and a preparation method thereof, wherein a flame retardant is used for modifying lignin in raw materials, so that the dispersion performance of the lignin can be effectively improved, the compatibility of the lignin with PC/ABS is better after the lignin is subjected to DOPO grafting modification, the interface bonding strength is higher, the DOPO modified lignin contains a rigid and heat-resistant aromatic ring, a nitrogen-containing imide ring and a DOPO phosphorus-containing flame-retardant structure, and a nitrogen-phosphorus synergistic compound flame-retardant system is formed with the lignin, so that the mechanical performance and the flame retardant performance are improved.
2. The invention provides a high-temperature-resistant flame-retardant PC/ABS composite material and a preparation method thereof, wherein a flame retardant obtained by introducing a polymer chain of carboxylated polymer into flame-retardant modified lignin can effectively improve the dispersion performance of the flame retardant in a matrix, compared with the flame retardant modified lignin which is independently added with PC/ABS, the flame retardant has better compatibility and higher interface bonding strength, and the prepared flame retardant contains flame retardant structures such as aromatic rings, nitrogen-containing imide rings, DOPO phosphorus, halogen and the like with rigidity and heat resistance, and forms a nitrogen-phosphorus-bromine synergistic compound flame retardant system with DOPO, thereby improving the mechanical performance and flame retardant performance.
3. The invention provides a high-temperature-resistant flame-retardant PC/ABS composite material and a preparation method thereof, and the prepared high-temperature-resistant flame-retardant PC/ABS composite material has good flame retardant property and mechanical property.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Introduction of some of the raw materials in this application:
PC/ABS is purchased from Dongguan, syngron Plastic materials, inc., trade name: T-2830R, tensile modulus: 2250MPa, tensile stress: 52.0MPa, bending stress: 80.0MPa, flexural modulus: 2150MPa, tensile strain: 120%.
Lignin is purchased from the rapo chemical plant in great city county, model: RB-300.
Chloromethylated polystyrene was purchased from merck chemical technology Shanghai limited, cat: 63868-10G.
Example 1
The PC/ABS composite material is composed of the following raw materials in parts by weight: 100 parts of PC/ABS, 20 parts of mica powder, 10 parts of dioctyl terephthalate, 0.2 part of pentaerythritol stearate, 0.5 part of antioxidant 168 and 10 parts of flame retardant.
The flame retardant is DOPO.
The preparation method of the high-temperature-resistant flame-retardant PC/ABS composite material comprises the following steps:
(1) Uniformly mixing PC/ABS, mica powder, dioctyl terephthalate, pentaerythritol stearate, an antioxidant 168 and a flame retardant according to a proportion, mixing for 40min at 160 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
Example 2
The PC/ABS composite material is composed of the following raw materials in parts by weight: 100 parts of PC/ABS, 20 parts of mica powder, 10 parts of dioctyl terephthalate, 0.2 part of pentaerythritol stearate, 0.5 part of antioxidant 168 and 10 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps: under the nitrogen environment, adding 2 parts by weight of DOPO and 3.5 parts by weight of acrylic anhydride into 20 parts by weight of tetrahydrofuran, reacting for 14 hours at 85 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; 4 parts by weight of lignin and 1.5 parts by weight of acrylic anhydride-DOPO are added into 60 parts by weight of dimethyl sulfoxide, stirred at room temperature and 600rpm for 5 hours, 6 parts by weight of benzylamine and 15 parts by weight of acetic anhydride are added, and the mixture is reacted at 50 ℃ for 20 hours at 400rpm, centrifuged, washed and dried to obtain the flame retardant.
The preparation method of the high-temperature-resistant flame-retardant PC/ABS composite material comprises the following steps:
(1) Uniformly mixing PC/ABS, mica powder, dioctyl terephthalate, pentaerythritol stearate, an antioxidant 168 and a flame retardant according to a proportion, mixing for 40min at 160 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
Example 3
The PC/ABS composite material is composed of the following raw materials in parts by weight: 100 parts of PC/ABS, 20 parts of mica powder, 10 parts of dioctyl terephthalate, 0.2 part of pentaerythritol stearate, 0.5 part of antioxidant 168 and 10 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps: under the nitrogen environment, adding 2 parts by weight of DOPO and 3.5 parts by weight of acrylic anhydride into 20 parts by weight of tetrahydrofuran, reacting for 14 hours at 85 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 4 parts by weight of modified lignin and 1.5 parts by weight of acrylic anhydride-DOPO into 60 parts by weight of dimethyl sulfoxide, stirring for 5 hours at room temperature and 600rpm, adding 6 parts by weight of benzylamine and 15 parts by weight of acetic anhydride, reacting for 20 hours at 50 ℃ and 400rpm, centrifuging, washing and drying to obtain the flame retardant.
The preparation method of the modified lignin comprises the following steps: adding 6 parts by weight of lignin into 120 parts by weight of 80wt% ethanol water solution, performing ultrasonic dispersion for 30min at ultrasonic power of 300W and ultrasonic frequency of 60kHz, adding 1 part by weight of diethylenetriamine propyl trimethoxy silane, stirring at 80 ℃ and 800rpm for 36h, centrifuging, and drying to obtain modified lignin.
The preparation method of the high-temperature-resistant flame-retardant PC/ABS composite material comprises the following steps:
(1) Uniformly mixing PC/ABS, mica powder, dioctyl terephthalate, pentaerythritol stearate, an antioxidant 168 and a flame retardant according to a proportion, mixing for 40min at 160 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
Example 4
The PC/ABS composite material is composed of the following raw materials in parts by weight: 100 parts of PC/ABS, 20 parts of mica powder, 10 parts of dioctyl terephthalate, 0.2 part of pentaerythritol stearate, 0.5 part of antioxidant 168 and 10 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps:
s1, adding 2 parts by weight of DOPO and 3.5 parts by weight of acrylic anhydride into 20 parts by weight of tetrahydrofuran in a nitrogen environment, reacting for 14 hours at 85 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 4 parts by weight of modified lignin and 1.5 parts by weight of acrylic anhydride-DOPO into 60 parts by weight of dimethyl sulfoxide, stirring for 5 hours at room temperature and 600rpm, adding 6 parts by weight of benzylamine and 15 parts by weight of acetic anhydride, reacting for 20 hours at 50 ℃ and 400rpm, centrifuging, washing and drying to obtain flame retardant modified lignin; the preparation method of the modified lignin comprises the following steps: adding 6 parts by weight of lignin into 120 parts by weight of 80wt% ethanol water solution, performing ultrasonic dispersion for 30min at ultrasonic power of 300W and ultrasonic frequency of 60kHz, adding 1 part by weight of diethylenetriamine propyl trimethoxy silane, stirring at 80 ℃ and 800rpm for 36h, centrifuging, and drying to obtain modified lignin;
s2, adding 8 parts by weight of chloromethylated polystyrene into 100 parts by weight of dimethyl sulfoxide, stirring for 8 hours at room temperature and 300rpm, and adding 5 parts by weight of 2-bromoterephthalic acid and 3.5 parts by weight of K 2 CO 3 Stirring at 600rpm for 30min, heating to 100deg.C, stirring for 18 hr, washing, purifying with ethanol, and drying to obtain carboxylated polymer;
s3, adding 3 parts by weight of flame retardant modified lignin into 60 parts by weight of dimethyl sulfoxide solvent, stirring for 10min at 600rpm, adding 0.05 part by weight of N, N' -carbonyldiimidazole, and stirring at 25 ℃ and 400rpm for reaction for 8h; and adding 6 parts by weight of carboxylated polymer and 0.1 part by weight of 4-methylbenzenesulfonic acid pyridine, stirring at 60 ℃ and 600rpm for reaction for 40 hours, adding water for precipitation, filtering, washing and drying to obtain the flame retardant.
The preparation method of the high-temperature-resistant flame-retardant PC/ABS composite material comprises the following steps:
(1) Uniformly mixing PC/ABS, mica powder, dioctyl terephthalate, pentaerythritol stearate, an antioxidant 168 and a flame retardant according to a proportion, mixing for 40min at 160 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
Example 5
The PC/ABS composite material is composed of the following raw materials in parts by weight: 100 parts of PC/ABS, 20 parts of mica powder, 10 parts of dioctyl terephthalate, 0.2 part of pentaerythritol stearate, 0.5 part of antioxidant 168 and 10 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps:
s1, adding 2 parts by weight of DOPO and 3.5 parts by weight of acrylic anhydride into 20 parts by weight of tetrahydrofuran in a nitrogen environment, reacting for 14 hours at 85 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 4 parts by weight of lignin and 1.5 parts by weight of acrylic anhydride-DOPO into 60 parts by weight of dimethyl sulfoxide, stirring at room temperature and 600rpm for 5 hours, adding 6 parts by weight of benzylamine and 15 parts by weight of acetic anhydride, reacting at 50 ℃ for 20 hours at 400rpm, centrifuging, washing and drying to obtain flame retardant modified lignin;
s2, adding 8 parts by weight of chloromethylated polystyrene into 100 parts by weight of dimethyl sulfoxide, stirring for 8 hours at room temperature and 300rpm, and adding 5 parts by weight of 2-bromoterephthalic acid and 3.5 parts by weight of K 2 CO 3 Stirring at 600rpm for 30min, heating to 100deg.C, stirring for 18 hr, washing, purifying with ethanol, and drying to obtain carboxylated polymer;
s3, adding 3 parts by weight of flame retardant modified lignin into 60 parts by weight of dimethyl sulfoxide solvent, stirring for 10min at 600rpm, adding 0.05 part by weight of N, N' -carbonyldiimidazole, and stirring at 25 ℃ and 400rpm for reaction for 8h; and adding 6 parts by weight of carboxylated polymer and 0.1 part by weight of 4-methylbenzenesulfonic acid pyridine, stirring at 60 ℃ and 600rpm for reaction for 40 hours, adding water for precipitation, filtering, washing and drying to obtain the flame retardant.
The preparation method of the high-temperature-resistant flame-retardant PC/ABS composite material comprises the following steps:
(1) Uniformly mixing PC/ABS, mica powder, dioctyl terephthalate, pentaerythritol stearate, an antioxidant 168 and a flame retardant according to a proportion, mixing for 40min at 160 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
Example 6
The PC/ABS composite material is composed of the following raw materials in parts by weight: 100 parts of PC/ABS, 20 parts of mica powder, 10 parts of dioctyl terephthalate, 0.2 part of pentaerythritol stearate, 0.5 part of antioxidant 168 and 10 parts of flame retardant.
The preparation method of the flame retardant comprises the following steps:
s1, adding 8 parts by weight of chloromethylated polystyrene into 100 parts by weight of dimethyl sulfoxide, stirring for 8 hours at room temperature and 300rpm, and adding 5 parts by weight of 2-bromoterephthalic acid and 3.5 parts by weight of K 2 CO 3 Stirring at 600rpm for 30min, heating to 100deg.C, stirring for 18 hr, washing, purifying with ethanol, and drying to obtain carboxylated polymer;
s2, adding 3 parts by weight of DOPO into 60 parts by weight of dimethyl sulfoxide solvent, stirring for 10min at 600rpm, adding 0.05 part by weight of N, N' -carbonyl diimidazole, and stirring at 25 ℃ and 400rpm for reaction for 8h; and adding 6 parts by weight of carboxylated polymer and 0.1 part by weight of 4-methylbenzenesulfonic acid pyridine, stirring at 60 ℃ and 600rpm for reaction for 40 hours, adding water for precipitation, filtering, washing and drying to obtain the flame retardant.
The preparation method of the high-temperature-resistant flame-retardant PC/ABS composite material comprises the following steps:
(1) Uniformly mixing PC/ABS, mica powder, dioctyl terephthalate, pentaerythritol stearate, an antioxidant 168 and a flame retardant according to a proportion, mixing for 40min at 160 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
Test example 1
Flame retardant performance test: determination of the Combustion behavior by the oxygen index method for plastics, part 2, according to the national Standard GB/T2406.2-2009: testing in a room temperature test method; injection molding is carried out on the high-temperature-resistant flame-retardant PC/ABS composite material prepared in each embodiment by an injection molding machine, and the sample size is as follows: the test specimen has a length of 100mm, a width of 10mm and a thickness of 4mm and is conditioned at a temperature of 23℃and a humidity of 50% for 90 hours. Parallel to the 5 groups, the average was taken and the results are shown in Table 1.
Table 1, flame retardant test results of high temperature resistant flame retardant PC/ABS composite material
Test example 2
Tensile strength test: determination of Plastic tensile Properties, section 2, with reference to the national Standard GB/T1040.2-2022: test conditions for molding and extrusion molding plastics tensile properties were tested for the high temperature resistant flame retardant PC/ABS composites prepared in the examples. Before testing, the high-temperature-resistant flame-retardant PC/ABS composite material prepared in each example is prepared into a standard dumbbell-shaped injection molding piece through an injection molding machine, a test sample is of a 1A dumbbell type, the total length of the test sample=170 mm, the width=10 mm and the thickness of the test sample is 4mm, the test speed is 1mm/min, the temperature of the test sample is adjusted at 23 ℃ at a constant temperature of 50% relative humidity for 24 hours before testing, 6 groups are parallel, and the average value is obtained, and the result is shown in Table 2.
TABLE 2 mechanical property test results of high temperature resistant flame retardant PC/ABS composite material
Tensile strength, MPa Elongation at break%
Example 1 44.9 82
Example 2 49.3 97
Example 3 55.8 114
Example 4 57.9 131
Example 5 56.1 122
Example 6 53.2 105
Test example 3
Impact strength test: impact resistance of the high temperature resistant flame retardant PC/ABS composite material obtained by the embodiments of the invention was measured according to GB/T21189-2007 inspection of a pendulum impact tester for Plastic simple corbel, cantilever and tensile impact test. The high-temperature-resistant flame-retardant PC/ABS composite material is manufactured into a strip sample with the specification of 60mm multiplied by 10mm multiplied by 3mm by adopting a conventional processing mode, and the sample is subjected to impact test by adopting a simple beam impact tester; the impact strength was calculated from the drop height of the impact head at the time of breaking the test piece. The results of averaging the 6 groups are shown in Table 3.
Table 3 shock resistance test results of high temperature resistant flame retardant PC/ABS composite material
From the results, the high-temperature-resistant flame-retardant PC/ABS composite material prepared by the invention has good flame-retardant property and mechanical property. From examples 1-2, the flame retardant modified lignin and DOPO are combined in the example 3 to further improve the flame retardant property and mechanical property of the composite material. The lignin and the diethylenetriamine propyl trimethoxy silane react to contain abundant hydroxyl and amino, acrylic anhydride-DOPO and aminosilane modified lignin are utilized to carry out chemical imidization reaction to obtain flame retardant modified lignin, and an imide ring with rigidity and heat resistance and a DOPO flame-retardant structure are introduced into a side chain of a lignin skeleton, so that the lignin is functionally modified, the dispersion performance of the lignin and a matrix is effectively improved, meanwhile, the composite material modified by the DOPO flame retardant has higher flame-retardant efficiency, the flame retardant modified lignin can effectively improve the dispersion performance of the lignin, the compatibility of the lignin with PC/ABS is better after the DOPO grafting modification, the interface bonding strength is higher, the DOPO modified lignin contains a rigid and heat-resistant aromatic ring, a nitrogen-containing imide ring and a DOPO phosphorus-containing flame-retardant structure, and a nitrogen-phosphorus synergistic compound flame-retardant system is formed with the lignin, and the mechanical property and the flame-retardant performance are improved.
It can be seen from examples 3-4 and examples 5-6 that introducing the polymer chain of the carboxylated polymer containing halogen atoms into the flame retardant modified lignin can improve the elasticity of the flame retardant and the mechanical properties, and simultaneously, the synergistic effect of DOPO and the halogen atoms in the carboxylated polymer can further improve the flame retardant properties of DOPO, so that the mechanical properties and flame retardant properties of the composite of DOPO modified lignin and carboxylated polymer are more effective than those of DOPO modified lignin or carboxylated polymer alone. The flame retardant obtained by introducing the polymer chain of the carboxylated polymer into the flame retardant modified lignin can effectively improve the dispersion performance of the flame retardant in a matrix, compared with the flame retardant modified lignin which is independently added with PC/ABS, the flame retardant has better compatibility and higher interface bonding strength, and the prepared flame retardant contains rigid and heat-resistant flame retardant structures such as aromatic rings, nitrogen-containing imide rings, DOPO phosphorus, halogen and the like, and forms a nitrogen-phosphorus-bromine synergistic compound flame retardant system with DOPO, so that the mechanical property and the flame retardant performance are improved.

Claims (5)

1. The PC/ABS composite material is characterized by comprising the following raw materials in parts by weight: 100 parts by weight of PC/ABS, 20 parts by weight of mica powder, 10 parts by weight of dioctyl terephthalate, 0.2 part by weight of pentaerythritol stearate, 0.5 part by weight of antioxidant 168 and 10 parts by weight of flame retardant;
the preparation method of the flame retardant comprises the following steps:
s1, adding 2 parts by weight of DOPO and 3.5 parts by weight of acrylic anhydride into 20 parts by weight of tetrahydrofuran in a nitrogen environment, reacting for 14 hours at 85 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 4 parts by weight of modified lignin and 1.5 parts by weight of acrylic anhydride-DOPO into 60 parts by weight of dimethyl sulfoxide, stirring for 5 hours at room temperature and 600rpm, adding 6 parts by weight of benzylamine and 15 parts by weight of acetic anhydride, reacting for 20 hours at 50 ℃ and 400rpm, centrifuging, washing and drying to obtain flame retardant modified lignin; the preparation method of the modified lignin comprises the following steps: adding 6 parts by weight of lignin into 120 parts by weight of 80wt% ethanol water solution, performing ultrasonic dispersion for 30min at ultrasonic power of 300W and ultrasonic frequency of 60kHz, adding 1 part by weight of diethylenetriamine propyl trimethoxy silane, stirring at 80 ℃ and 800rpm for 36h, centrifuging, and drying to obtain modified lignin;
s2, adding 8 parts by weight of chloromethylated polystyrene into 100 parts by weight of dimethyl sulfoxide, stirring for 8 hours at room temperature and 300rpm, adding 5 parts by weight of 2-bromoterephthalic acid and 3.5 parts by weight of K2CO3, stirring for 30 minutes at 600rpm, heating to 100 ℃ and continuing stirring for 18 hours, washing, purifying with ethanol, and drying to obtain carboxylated polymer;
s3, adding 3 parts by weight of flame retardant modified lignin into 60 parts by weight of dimethyl sulfoxide solvent, stirring for 10min at 600rpm, adding 0.05 part by weight of N, N' -carbonyldiimidazole, and stirring at 25 ℃ and 400rpm for reaction for 8h; adding 6 parts by weight of carboxylated polymer and 0.1 part by weight of 4-methylbenzenesulfonic acid pyridine, stirring at 60 ℃ and 600rpm for reaction for 40 hours, adding water for precipitation, filtering, washing and drying to obtain a flame retardant;
the PC/ABS is purchased from Dongguan poly plastic raw material Co., ltd, brand: T-2830R, tensile modulus: 2250MPa, tensile stress: 52.0MPa, bending stress: 80.0MPa, flexural modulus: 2150MPa, tensile strain: 120%;
the lignin is purchased from the Rainbow chemical plant in great city county, model: RB-300;
the chloromethylated polystyrene was purchased from merck chemical technology Shanghai limited, cat: 63868-10G.
2. The high temperature resistant flame retardant PC/ABS composite material according to claim 1, wherein the preparation method of the high temperature resistant flame retardant PC/ABS composite material comprises the following steps:
(1) Uniformly mixing PC/ABS, mica powder, dioctyl terephthalate, pentaerythritol stearate, an antioxidant 168 and a flame retardant according to a proportion, mixing for 40min at 160 ℃, cooling to room temperature, and discharging to obtain a material;
(2) Extruding and granulating the materials to obtain the high-temperature-resistant flame-retardant PC/ABS composite material.
3. The preparation method of the flame retardant is characterized by comprising the following steps:
s1, adding 1-4 parts by weight of DOPO and 2-5 parts by weight of acrylic anhydride into 15-30 parts by weight of tetrahydrofuran in a nitrogen environment, reacting for 10-20 hours at 80-90 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 3-5 parts by weight of modified lignin and 1-2 parts by weight of acrylic anhydride-DOPO into 40-80 parts by weight of dimethyl sulfoxide, stirring for 4-7 hours at room temperature and 500-700rpm, adding 4-8 parts by weight of benzylamine and 12-18 parts by weight of acetic anhydride, reacting for 16-28 hours at 40-60 ℃ and 300-500rpm, centrifuging, washing and drying to obtain flame retardant modified lignin;
s2, adding 5-10 parts by weight of chloromethylated polystyrene into 80-140 parts by weight of dimethyl sulfoxide, stirring at room temperature and 200-400rpm for 6-12 hours, adding 4-6 parts by weight of 2-bromoterephthalic acid and 2-4 parts by weight of K2CO3, stirring at 400-800rpm for 20-40 minutes, heating to 90-110 ℃ and continuously stirring for 14-24 hours, washing, purifying with ethanol, and drying to obtain carboxylated polymer;
s3, adding 2-5 parts by weight of flame retardant modified lignin into 50-80 parts by weight of dimethyl sulfoxide solvent, stirring for 8-15min at 400-800rpm, adding 0.02-0.1 part by weight of N, N' -carbonyldiimidazole, and stirring at 300-500rpm for reaction for 6-12h at 20-30 ℃; adding 5-7 parts by weight of carboxylated polymer and 0.05-0.2 part by weight of 4-methylbenzenesulfonic acid pyridine, stirring at 50-70 ℃ and 400-800rpm for reaction for 30-60 hours, adding water for precipitation, filtering, washing and drying to obtain a flame retardant;
the preparation method of the modified lignin comprises the following steps: adding 5-8 parts by weight of lignin into 100-200 parts by weight of 60-90wt% ethanol water solution, performing ultrasonic dispersion for 20-50min at ultrasonic power of 200-400W and ultrasonic frequency of 50-70kHz, adding 0.5-2 parts by weight of diethylenetriamine propyl trimethoxysilane, stirring for 24-48h at 70-900 ℃ and 600-1000rpm, centrifuging, and drying to obtain modified lignin.
4. A method of preparing a flame retardant according to claim 3, comprising the steps of:
s1, adding 1-4 parts by weight of DOPO and 2-5 parts by weight of acrylic anhydride into 15-30 parts by weight of tetrahydrofuran in a nitrogen environment, reacting for 10-20 hours at 80-90 ℃, separating liquid, washing and drying to obtain acrylic anhydride-DOPO; adding 3-5 parts by weight of modified lignin and 1-2 parts by weight of acrylic anhydride-DOPO into 40-80 parts by weight of dimethyl sulfoxide, stirring for 4-7 hours at room temperature and 500-700rpm, adding 4-8 parts by weight of benzylamine and 12-18 parts by weight of acetic anhydride, reacting for 16-28 hours at 40-60 ℃ and 300-500rpm, centrifuging, washing and drying to obtain flame retardant modified lignin;
s2, adding 5-10 parts by weight of chloromethylated polystyrene into 80-140 parts by weight of dimethyl sulfoxide, stirring at room temperature and 200-400rpm for 6-12 hours, adding 4-6 parts by weight of 2-bromoterephthalic acid and 2-4 parts by weight of K2CO3, stirring at 400-800rpm for 20-40 minutes, heating to 90-110 ℃ and continuously stirring for 14-24 hours, washing, purifying with ethanol, and drying to obtain carboxylated polymer;
s3, adding 2-5 parts by weight of flame retardant modified lignin into 50-80 parts by weight of dimethyl sulfoxide solvent, stirring for 8-15min at 400-800rpm, adding 0.02-0.1 part by weight of N, N' -carbonyldiimidazole, and stirring at 300-500rpm for reaction for 6-12h at 20-30 ℃; adding 5-7 parts by weight of carboxylated polymer and 0.05-0.2 part by weight of 4-methylbenzenesulfonic acid pyridine, stirring at 50-70 ℃ and 400-800rpm for reaction for 30-60 hours, adding water for precipitation, filtering, washing and drying to obtain a flame retardant;
the preparation method of the modified lignin comprises the following steps: adding 5-8 parts by weight of lignin into 100-200 parts by weight of 60-90wt% ethanol water solution, performing ultrasonic dispersion for 20-50min at ultrasonic power of 200-400W and ultrasonic frequency of 50-70kHz, adding 0.5-2 parts by weight of diethylenetriamine propyl trimethoxysilane, stirring for 24-48h at 70-900 ℃ and 600-1000rpm, centrifuging, and drying to obtain modified lignin.
5. Use of a flame retardant according to claim 3 for the preparation of a high temperature resistant flame retardant PC/ABS composite.
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