CN111849117A - Flame-retardant plastic and processing technology thereof - Google Patents
Flame-retardant plastic and processing technology thereof Download PDFInfo
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- CN111849117A CN111849117A CN202010689282.6A CN202010689282A CN111849117A CN 111849117 A CN111849117 A CN 111849117A CN 202010689282 A CN202010689282 A CN 202010689282A CN 111849117 A CN111849117 A CN 111849117A
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- 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
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The application relates to a flame-retardant plastic and a processing technology thereof, belonging to the technical field of macromolecules, and the flame-retardant plastic is prepared from the following raw materials in parts by weight: 60-100 parts of ABS, 4-10 parts of coupling agent modified magnesium hydroxide whisker, 1-5 parts of graphene oxide, 0.5-4 parts of dispersant, 0.5-7 parts of flexibilizer, 1-6 parts of antioxidant and 0.3-1.3 parts of poly-di-melamine dihydrogen aluminum phosphate salt. The preparation method comprises the following steps: the raw materials are evenly mixed, melted and blended at 195-220 ℃, extruded and granulated to obtain the flame-retardant plastic. The application improves the flame retardant property of the plastic, reduces harmful substances such as hydrogen halide and the like generated in the plastic combustion process, and improves the safety effect of the plastic.
Description
Technical Field
The application relates to the field of macromolecules, in particular to flame-retardant plastic and a processing technology thereof.
Background
Various products made of plastics have been widely used in various aspects of people's life and work due to their characteristics of light weight, excellent chemical stability, excellent electrical insulation, and the like.
However, most plastics are flammable substances, and the combustion speed is high, so that a large amount of toxic gas is generated. According to statistics, the casualties caused by suffocation and smoke poisoning in the fire accounts for 50-80% of the total casualties of the fire. In recent years, with the continuous development of science and technology and economy, daily necessities produced by plastics play an increasingly important role in daily life, and "high-quality safe life" will gradually become an indispensable important factor in life. Therefore, flame retardant plastic materials have become the favorite of the market. The flame-retardant plastic is not easy to burn, has low flame propagation rate, low mass loss rate and heat release rate and certain self-extinguishing property, and is suitable for the fields of garbage cans, plastic trays, wall switches, sockets, pipes, molded case circuit breakers, motor parts, plates and the like. In recent years, more and more enterprises have started to research and develop flame retardant plastics.
However, the performance of the currently used flame-retardant plastic cannot meet the requirements, and most of the flame-retardant plastic adopts halogen flame retardants, so that toxic substances such as hydrogen halide and the like can be generated in the long-term use process, especially in the combustion process, and the flame-retardant plastic can cause great harm to the health of people and the environment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the flame-retardant plastic which has the effects of improving the flame-retardant property of the plastic, reducing harmful substances such as hydrogen halide and the like generated in the combustion process of the plastic and improving the safety of the plastic.
The invention also aims to provide a processing technology of the flame-retardant plastic, which has the advantage of simple technology.
In order to achieve the first object, the invention provides the following technical scheme:
the flame-retardant plastic is prepared from the following raw materials in parts by weight: 60-100 parts of ABS, 4-10 parts of coupling agent modified magnesium hydroxide whisker, 1-5 parts of graphene oxide, 0.5-4 parts of dispersant, 0.5-7 parts of flexibilizer, 1-6 parts of antioxidant and 0.3-1.3 parts of poly-di-melamine dihydrogen aluminum phosphate salt.
By adopting the technical scheme, the magnesium oxide generated after the magnesium hydroxide is decomposed and dehydrated can play the roles of flame retardance and smoke abatement, and meanwhile, the magnesium oxide with high activity can absorb a plurality of substances such as free radicals, carbon and the like to promote the polymer to form carbon. In addition, the magnesium hydroxide can neutralize acidic and corrosive gases generated in the combustion process, and reduce the harm of toxic gases in the combustion to human bodies and the environment. However, magnesium hydroxide is required as a flame retardant in a large amount, and the mechanical properties of the plastic are easily impaired.
The magnesium hydroxide whisker modified by the coupling agent is used as a flame retardant, and the magnesium hydroxide whisker has a reinforcing effect while ensuring the flame retardant and smoke abatement effects of the magnesium hydroxide, so that the mechanical property of the plastic is improved.
In addition, the coupling agent is adsorbed and coated on the surface of the magnesium hydroxide whisker in a chemical and physical mode through the magnesium hydroxide whisker modified by the coupling agent, so that the hydrophilic and oleophobic properties of the magnesium hydroxide whisker before modification are changed into the oleophilic and hydrophobic properties after modification, the polarity and the surface energy are greatly reduced, and the compatibility of the magnesium hydroxide whisker and an ABS matrix is improved. Meanwhile, the coupling agent is coated on the surface of the magnesium hydroxide whisker, so that the repulsive force among the magnesium hydroxide whiskers is increased, the magnesium hydroxide whisker is easier to disperse, the dispersity of the magnesium hydroxide whisker is improved, the flame retardant property of the magnesium hydroxide is effectively improved, and the addition amount of the magnesium hydroxide can be reduced.
During the combustion process of the graphene oxide, the heat absorption, viscosity and dripping performance of the polymer can be changed, namely the graphene can improve the thermal stability and delay the ignition time of the polymer. In addition, the graphene oxide can form one or more compact and stable carbon layers, and the carbon layers have the functions of oxygen isolation and heat insulation on the surface of the ABS matrix, so that the further thermal decomposition of the ABS matrix is effectively inhibited or prevented, the thermal decomposition speed of the material is reduced, and the continuous diffusion of combustible gas is prevented. The graphite can promote the crosslinking and carbonizing action of the ABS matrix by heating, and can effectively protect the carbonizing product and increase the carbonizing quantity, thereby improving the flame retardant effect.
The poly-di-melamine dihydrogen phosphate aluminum salt contains three flame retardant elements of phosphorus, nitrogen and aluminum, and the synergistic effect of the three flame retardant elements ensures that the poly-di-melamine dihydrogen phosphate aluminum salt has higher char forming efficiency and better flame retardant effect; the flame retardant usually needs a larger addition amount to play a higher flame retardant role, but excessive flame retardant is unevenly dispersed in the plastic, partial agglomeration or debonding and layering phenomena can occur, so that the bonding force of each component in the plastic is weakened, and the mechanical property of the plastic is reduced, therefore, the magnesium hydroxide whisker modified by the poly-di-melamine aluminum dihydrogen phosphate salt and the coupling agent has a synergistic flame retardant effect, a lower addition amount can be used to play a higher flame retardant role, the flame retardant property of the plastic is improved, and the mechanical property of the plastic is improved.
In conclusion, the specific raw materials are selected in the formula and the proportion of the raw materials is limited, so that the raw materials are mutually matched and act synergistically, and the flame retardant property and the mechanical property of the plastic can be effectively improved; meanwhile, the raw materials in the formula of the invention do not contain halogen, the generation of hydrogen halide can be reduced in the combustion process, the invention is friendly to the environment and the health of people, and the safety in use is improved.
Further, the feed additive is prepared from the following raw materials in parts by weight: 85-95 parts of ABS, 5-8 parts of coupling agent modified magnesium hydroxide whisker, 2-4 parts of graphene oxide, 1-3 parts of dispersant, 1-5 parts of flexibilizer, 2-5 parts of antioxidant and 0.5-1 part of poly-di-melamine ammonium dihydrogen phosphate aluminum salt.
By adopting the technical scheme, experiments show that in the range, the plastic prepared from the raw materials has better flame retardant property and mechanical property, and when the reason of the plastic is possibly analyzed, in the range, the proportion of the coupling agent modified magnesium hydroxide whisker, the poly-di-melamine aluminum dihydrogen phosphate salt and the graphene oxide is more reasonable, so that the synergistic cooperation effect among the three materials and other raw materials is better, the flame retardant property of the plastic can be improved, and the mechanical property of the plastic can be improved.
Further, the modification method of the magnesium hydroxide whisker comprises the following steps:
s1: adding a coupling agent into absolute ethyl alcohol, and uniformly mixing at 60-75 ℃ to obtain a modifier, wherein the weight ratio of the coupling agent to the absolute ethyl alcohol is 1 (3-5);
s2: adding the magnesium hydroxide whisker into the modifier in S1, performing ultrasonic vibration for 1.5-2h, performing suction filtration, and drying to obtain the modified magnesium hydroxide whisker, wherein the weight ratio of the magnesium hydroxide whisker to the coupling agent is 55-75.
By adopting the technical scheme and using ultrasonic vibration, the structure of the magnesium hydroxide whisker is protected to the maximum extent, and the reduction of the length-diameter ratio of the magnesium hydroxide whisker can be obviously prevented.
Further, the coupling agent comprises a borate coupling agent and a silane coupling agent, and the weight ratio of the borate coupling agent to the silane coupling agent is 0.8-1.8.
By adopting the technical scheme, the silane coupling agent contains more alkoxy groups and reactive groups, the alkoxy groups are changed into silicon hydroxyl groups through hydrolysis and are subjected to chemical reaction with hydroxyl groups on the surface of the magnesium hydroxide whisker, and the reactive groups are bonded with the borate coupling agent through reaction, so that the silane coupling agent is matched with the borate coupling agent to form a coating layer on the surface of the magnesium hydroxide whisker, the surface energy of the magnesium hydroxide whisker is greatly reduced, the dispersity of the magnesium hydroxide whisker is improved, the flame retardant property of the plastic is improved, and the strength of the plastic can be improved. In addition, the silane coupling agent is matched with the borate coupling agent, so that the connection strength with the ABS matrix can be further increased, the bonding strength of the borate whisker and the ABS matrix is further improved, and the strength of the plastic is improved.
In addition, the boric acid ester coupling agent contains boron element, the boron element and phosphorus element and nitrogen element in the poly-di-melamine ammonium dihydrogen phosphate aluminum salt form a P-N-B flame retardant system, and the boric acid ester coupling agent and the poly-di-melamine ammonium dihydrogen phosphate aluminum salt have synergistic flame retardant property in the combustion process, so that the flame retardant effect of the plastic is greatly improved, and the flame retardant property of the plastic can be further improved.
Further, the weight ratio of the magnesium hydroxide whiskers modified by the coupling agent to the poly-aluminum dihydrogen melamine phosphate is 9-12.
By adopting the technical scheme, experiments show that when the weight ratio of the magnesium hydroxide whisker modified by the coupling agent to the poly-dicyan ammonium dihydrogen phosphate aluminum salt is 9-12, the P-N-B flame-retardant system formed by the boron element in the coupling agent and the phosphorus element and the nitrogen element in the poly-dicyan ammonium dihydrogen phosphate aluminum salt has better flame-retardant effect, so that the prepared plastic has better flame-retardant property. When the reason is possible, the synergistic effect between the magnesium hydroxide whisker modified by the coupling agent and the poly-dicyan ammonium dihydrogen phosphate aluminum salt is better in the range, so that the flame retardant property of the plastic is further improved.
Furthermore, the silane coupling agent adopts one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane and hexamethylene diamine methyl triethoxysilane.
By adopting the technical scheme, the gamma-aminopropyltriethoxysilane, the gamma-aminopropyltrimethoxysilane and the hexamethylene diamine methyl triethoxysilane all contain N atoms, and can be mutually bonded with the borate coupling agent through N-B coordination, so that a compact and uniform coating thin layer is formed on the periphery of the magnesium hydroxide whisker, the agglomeration phenomenon of the magnesium hydroxide whisker is effectively reduced, the dispersity of the magnesium hydroxide whisker is improved, the flame retardant property of the plastic is improved, and the mechanical property of the plastic is effectively improved.
Further, the graphene oxide is modified graphene oxide, and the modification method comprises the following steps:
a. mixing 6-15 parts of 3-isocyanatopropyl trimethoxy silane and 1-1.5 parts of graphene oxide, adding the mixture into 300-500ml of anhydrous ethanol, and performing ultrasonic vibration to obtain a mixture;
b. and (b) adding 3-5 parts of polyethylene glycol into the mixture obtained in the step (a), then carrying out ultrasonic vibration, filtering and drying to obtain the modified graphene oxide.
By adopting the technical scheme, the 3-isocyanate propyl trimethoxy silane and the polyethylene glycol are used for modifying the graphene oxide, so that the graphene oxide has good lipophilicity and good hydrophilicity, and the dispersibility and the adhesion with an ABS (acrylonitrile butadiene styrene) matrix of the graphene oxide are improved, so that the flame retardant property and the mechanical property of the plastic are improved; in addition, the modified graphene oxide has double effects of solid particles and chemical surfactants, can play a role of a dispersing agent, improves the dispersibility of raw materials, fully exerts the self effect of each raw material and can reduce the using amount of the dispersing agent.
Further, the dispersing agent adopts one or more of liquid paraffin, glyceryl tristearate and stearic acid.
Object two of the present invention: provides a processing technology of flame retardant plastic, which comprises the steps of uniformly mixing raw materials, then carrying out melt blending at 195-220 ℃, carrying out extrusion granulation, and obtaining the flame retardant plastic.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the formula, specific raw materials are selected and matched in proportion, and the prepared plastic has good flame retardant property and mechanical property by utilizing the mutual synergistic effect of the raw materials; in addition, the formula of the invention does not contain halogen elements, thereby reducing the generation of hydrogen halide in the combustion process and reducing the harm to human bodies and environment.
2. The magnesium hydroxide whisker is modified by a coupling agent, so that the compatibility of the magnesium hydroxide whisker and an ABS matrix is improved, the magnesium hydroxide whisker is easier to disperse, and the binding force of the magnesium hydroxide whisker and the ABS matrix can be increased, thereby improving the flame retardant property and the mechanical property of the plastic.
3. The modified graphene oxide has the double effects of solid particles and chemical surfactants, can play the role of a dispersing agent, and improves the dispersibility of raw materials, so that the flame retardant property and the mechanical property of plastics are improved, and the using amount of the dispersing agent can be reduced.
4. The coupling agent adopts the matching of a borate coupling agent and a silane coupling agent to modify the magnesium hydroxide whisker, the borate coupling agent contains boron element, the boron element and phosphorus element and nitrogen element in the poly-di-melamine dihydrogen phosphate aluminum salt form a P-N-B flame retardant system, and the borate coupling agent and the poly-di-melamine dihydrogen phosphate aluminum salt have synergistic flame retardance in the combustion process, thereby greatly improving the flame retardant effect of the plastic and further increasing the flame retardant property of the plastic.
Detailed Description
The present invention will be described in further detail with reference to examples and comparative examples.
In the following preparations, examples and comparative examples:
the magnesium hydroxide whisker is purchased from Yingkoukangkan chemical Co., Ltd;
graphene oxide was purchased from lake nan feng materials development ltd;
the poly (aluminium dihydrogen cyanurate) phosphate is purchased from Xiongding chemical Co., Ltd, Totai city;
preparation example 1
The modification method of the magnesium hydroxide whisker comprises the following steps:
s1: adding a coupling agent into absolute ethyl alcohol, and uniformly mixing at 60 ℃ to obtain a modifier, wherein the weight ratio of the coupling agent to the absolute ethyl alcohol is 1: 3;
s2: adding the magnesium hydroxide whisker into the modifier in S1, performing ultrasonic vibration for 1.5h, performing suction filtration, and drying at 95 ℃ for 3h to obtain the modified magnesium hydroxide whisker, wherein the weight ratio of the magnesium hydroxide whisker to the coupling agent is 55; wherein the coupling agent comprises a borate coupling agent and hexamethylenediamine methyl triethoxysilane, and the weight ratio of the borate coupling agent to the hexamethylenediamine methyl triethoxysilane is 0.8.
Preparation example 2
The modification method of the magnesium hydroxide whisker comprises the following steps:
s1: adding a coupling agent into absolute ethyl alcohol, and uniformly mixing at 70 ℃ to obtain a modifier, wherein the weight ratio of the coupling agent to the absolute ethyl alcohol is 1: 4;
S2: adding the magnesium hydroxide whisker into the modifier in S1, performing ultrasonic vibration for 1.8h, performing suction filtration, and drying at 95 ℃ for 3h to obtain the modified magnesium hydroxide whisker, wherein the weight ratio of the magnesium hydroxide whisker to the coupling agent is 65; wherein the coupling agent comprises borate coupling agent and gamma-aminopropyl trimethoxy silane, and the weight ratio of the borate coupling agent to the gamma-aminopropyl trimethoxy silane is 1.3.
Preparation example 3
The modification method of the magnesium hydroxide whisker comprises the following steps:
s1: adding a coupling agent into absolute ethyl alcohol, and uniformly mixing at 75 ℃ to obtain a modifier, wherein the weight ratio of the coupling agent to the absolute ethyl alcohol is 1: 5;
s2: adding the magnesium hydroxide whisker into the modifier in S1, performing ultrasonic vibration for 2h, performing suction filtration, and drying at 95 ℃ for 3h to obtain the modified magnesium hydroxide whisker, wherein the weight ratio of the magnesium hydroxide whisker to the coupling agent is 75; wherein the coupling agent comprises a borate coupling agent and gamma-aminopropyltriethoxysilane, and the weight ratio of the borate coupling agent to the gamma-aminopropyltriethoxysilane is 1.8.
Preparation example 4
The modification method of the magnesium hydroxide whisker is different from the preparation example 2 in that the borate coupling agent is replaced by the same amount of silane coupling agent.
Preparation example 5
The modification method of the magnesium hydroxide whisker is different from the preparation example 2 in that the same amount of borate coupling agent is used for replacing gamma-aminopropyl trimethoxy silane.
Preparation example 6
The magnesium hydroxide whisker modification method is different from the preparation example 2 in that the weight ratio of the borate coupling agent to the gamma-aminopropyltrimethoxysilane is 0.5.
Preparation example 7
The magnesium hydroxide whisker modification method is different from the preparation example 2 in that the weight ratio of the borate coupling agent to the gamma-aminopropyltrimethoxysilane is 2.2.
Preparation example 8
The graphene oxide modification method comprises the following steps:
a. mixing 6 parts of 3-isocyanatopropyl trimethoxy silane and 1.5 parts of graphene oxide, adding the mixture into 300ml of absolute ethyl alcohol, and then performing ultrasonic vibration for 1 hour to obtain a mixture;
b. and (b) adding 5 parts of polyethylene glycol into the mixture obtained in the step (a), then carrying out ultrasonic vibration filtration, and carrying out vacuum drying to obtain the modified graphene oxide.
Preparation example 9
The graphene oxide modification method comprises the following steps:
a. mixing 10 parts of 3-isocyanatopropyl trimethoxy silane and 1.2 parts of graphene oxide, adding the mixture into 400ml of absolute ethyl alcohol, and then performing ultrasonic vibration for 1 hour to obtain a mixture;
b. and (b) adding 4 parts of polyethylene glycol into the mixture obtained in the step (a), then carrying out ultrasonic vibration, filtering, and carrying out vacuum drying to obtain the modified graphene oxide.
Preparation example 10
The graphene oxide modification method comprises the following steps:
a. mixing 15 parts of 3-isocyanatopropyl trimethoxy silane and 1 part of graphene oxide, adding the mixture into 500ml of absolute ethyl alcohol, and then performing ultrasonic vibration for 1 hour to obtain a mixture;
b. and (b) adding 3 parts of polyethylene glycol into the mixture obtained in the step (a), then carrying out ultrasonic vibration, filtering, and carrying out vacuum drying to obtain the modified graphene oxide.
Example 1
A flame retardant plastic prepared by a process comprising:
a. adding 60g of ABS, 10g of coupling agent modified magnesium hydroxide whisker, 1g of graphene oxide, 4g of liquid paraffin, 0.5g of toughening agent, 6g of antioxidant and 0.3g of poly-di-melamine dihydrogen aluminum phosphate salt into a high-speed mixer, and mixing at the rotating speed of 900r/min for 10min to obtain a mixture;
b. and adding the mixture into a double-screw extruder, carrying out melt blending at 195 ℃, and carrying out extrusion granulation to obtain the flame-retardant plastic, wherein the extrusion temperature of a machine head is 200 ℃.
Wherein, the magnesium hydroxide whisker modified by the coupling agent adopts the modified magnesium hydroxide whisker prepared in the preparation example 1, the toughening agent adopts methyl methacrylate-butadiene-styrene copolymer, and the antioxidant adopts 1010 type hindered phenol antioxidant.
Example 2
A flame retardant plastic prepared by a process comprising:
a. adding 85g of ABS, 8g of coupling agent modified magnesium hydroxide whisker, 2g of graphene oxide, 3g of glyceryl tristearate, 1g of toughening agent, 5g of antioxidant and 0.5g of poly-di-melamine dihydrogen aluminum phosphate salt into a high-speed mixer, and mixing for 9min at the rotating speed of 1000r/min to obtain a mixture;
b. and adding the mixture into a double-screw extruder, carrying out melt blending at the temperature of 200 ℃, and carrying out extrusion granulation to obtain the flame-retardant plastic, wherein the extrusion temperature of a machine head is 210 ℃.
Wherein, the magnesium hydroxide whisker modified by the coupling agent adopts the modified magnesium hydroxide whisker prepared in the preparation example 2, the toughening agent adopts methyl methacrylate-butadiene-styrene copolymer, and the antioxidant adopts 1010 type hindered phenol antioxidant.
Example 3
A flame retardant plastic prepared by a process comprising:
a. adding 80g of ABS, 7g of coupling agent modified magnesium hydroxide whisker, 3g of graphene oxide, 2.2g of stearic acid, 3.7g of toughening agent, 3.5g of antioxidant and 0.8g of poly-dicyan ammonium dihydrogen phosphate aluminum salt into a high-speed mixer, and mixing for 8min at the rotating speed of 1100r/min to obtain a mixture;
b. and adding the mixture into a double-screw extruder, carrying out melt blending at 215 ℃, and carrying out extrusion granulation to obtain the flame-retardant plastic, wherein the extrusion temperature of a machine head is 220 ℃.
Wherein, the magnesium hydroxide whisker modified by the coupling agent adopts the modified magnesium hydroxide whisker prepared in the preparation example 3, the toughening agent adopts methyl methacrylate-butadiene-styrene copolymer, and the antioxidant adopts 1010 type hindered phenol antioxidant.
Example 4
A flame retardant plastic prepared by a process comprising:
a. adding 95g of ABS, 5g of coupling agent modified magnesium hydroxide whisker, 4g of graphene oxide, 1g of stearic acid, 5g of toughening agent, 2g of antioxidant and 1g of aluminium polydicyanamide dihydrogen phosphate salt into a high-speed mixer, and mixing for 7min at the rotating speed of 1200r/min to obtain a mixture;
b. and adding the mixture into a double-screw extruder, carrying out melt blending at 220 ℃, extruding and granulating to obtain the flame-retardant plastic, wherein the extrusion temperature of a machine head is 220 ℃.
Wherein, the magnesium hydroxide whisker modified by the coupling agent adopts the modified magnesium hydroxide whisker prepared in the preparation example 3, the toughening agent adopts methyl methacrylate-butadiene-styrene copolymer, and the antioxidant adopts 1010 type hindered phenol antioxidant.
Example 5
A flame retardant plastic prepared by a process comprising:
a. 100g of ABS, 4g of coupling agent modified magnesium hydroxide whisker, 5g of graphene oxide, 0.5g of stearic acid, 7g of toughening agent, 1g of antioxidant and 1.3g of poly-di-melamine dihydrogen aluminum phosphate salt are added into a high-speed mixer and mixed for 6min at the rotating speed of 1300r/min to obtain a mixture;
b. And adding the mixture into a double-screw extruder, carrying out melt blending at 220 ℃, extruding and granulating to obtain the flame-retardant plastic, wherein the extrusion temperature of a machine head is 220 ℃.
Wherein, the magnesium hydroxide whisker modified by the coupling agent adopts the modified magnesium hydroxide whisker prepared in the preparation example 3, the toughening agent adopts methyl methacrylate-butadiene-styrene copolymer, and the antioxidant adopts 1010 type hindered phenol antioxidant.
Example 6
A flame-retardant plastic prepared by the following method was different from example 3 in that 9g of magnesium hydroxide whiskers modified with a coupling agent and 1g of aluminum dihydrogen polydicyanamide phosphate salt were used, i.e., the weight ratio of the magnesium hydroxide whiskers modified with the coupling agent to the aluminum dihydrogen polydicyanamide phosphate salt was 9.
Example 7
A flame-retardant plastic was produced by the following method, which was different from example 3 in that 4.2g of magnesium hydroxide whiskers modified with a coupling agent and 0.4g of aluminum dihydrogen polydicyanammophosphate, i.e., the weight ratio of the magnesium hydroxide whiskers modified with a coupling agent to the aluminum dihydrogen polydicyanammophosphate was 10.5.
Example 8
A flame-retardant plastic prepared by the following method was different from example 3 in that 6g of magnesium hydroxide whiskers modified with a coupling agent and 0.5g of aluminum dihydrogen polydicyanamide phosphate salt were used, i.e., the weight ratio of the magnesium hydroxide whiskers modified with a coupling agent to the aluminum dihydrogen polydicyanamide phosphate salt was 12.
Example 9
A flame retardant plastic prepared by the following method was different from example 3 in that the same amount of modified graphene oxide prepared in preparation example 8 was used instead of graphene oxide.
Example 10
A flame retardant plastic prepared by the following method was different from example 3 in that the same amount of modified graphene oxide prepared in preparation example 9 was used instead of graphene oxide.
Example 11
A flame retardant plastic prepared by the following method was different from example 3 in that the same amount of modified graphene oxide prepared in preparation example 10 was used instead of graphene oxide.
Comparative example 1
The flame-retardant plastic prepared by the following method is different from the flame-retardant plastic prepared in example 3 in that 50g of ABS, 12g of coupling agent modified magnesium hydroxide whisker, 0.5g of graphene oxide, 5g of stearic acid, 0.3g of toughening agent, 8g of antioxidant and 0.1g of poly-di-melamine dihydrogen aluminum phosphate salt are adopted.
Comparative example 2
A flame-retardant plastic prepared by the following method is different from the flame-retardant plastic prepared in example 3 in that 120g of ABS, 2g of coupling agent modified magnesium hydroxide whisker, 7g of graphene oxide, 0.3g of stearic acid, 7g of toughening agent, 0.5g of antioxidant and 1.5g of poly-di-melamine aluminum dihydrogen phosphate salt.
Comparative example 3
A flame retardant plastic prepared by the following method was different from example 3 in that the modified magnesium hydroxide whiskers of preparation example 4 were used.
Comparative example 4
A flame retardant plastic prepared by the following method was different from example 3 in that the modified magnesium hydroxide whiskers of preparation example 5 were used.
Comparative example 5
A flame retardant plastic prepared by the following method was different from example 3 in that the modified magnesium hydroxide whiskers of preparation example 6 were used.
Comparative example 6
A flame retardant plastic prepared by the following method was different from example 3 in that the modified magnesium hydroxide whiskers of preparation example 7 were used.
Comparative example 7
A flame-retardant plastic prepared by the following method was different from example 7 in that 4g of magnesium hydroxide whiskers modified with a coupling agent and 2g of aluminum dihydrogen polydicyanamide phosphate salt were used, i.e., the weight ratio of the magnesium hydroxide whiskers modified with the coupling agent to the aluminum dihydrogen polydicyanamide phosphate salt was 2.
Comparative example 8
A flame-retardant plastic prepared by the following method was different from example 7 in that 14g of the coupling agent-modified magnesium hydroxide whiskers and 0.4g of the aluminum polydicyanamide dihydrogen phosphate salt were used, i.e., the weight ratio of the coupling agent-modified magnesium hydroxide whiskers to the aluminum polydicyanamide dihydrogen phosphate salt was 35.
Performance detection
Mechanical property, flame retardant property and smoke density tests are carried out on the samples 1 to 11 and the samples 1 to 8,
flame retardant property: the flame retardant performance is tested by adopting a test method in UL94 combustion test Standard, and the thickness of a test sample strip is 1.6 mm;
the oxygen index (%) is determined according to GB/T2406-1993 'oxygen index method for testing the combustion performance of plastics';
smoke density the smoke density in the presence of flame was determined according to ASTM-E662;
the mechanical property is measured according to GB/T1040-2006 determination of tensile property of plastics; the impact strength was determined according to GB/T1843-2008 "determination of impact Strength of Plastic Izod".
The test results are shown in table 1:
TABLE 1 flame retardant plastics test results
| Item | Flame retardant properties | Oxygen index (%） | Density of smoke | Tensile strength (MPa) | Impact Strength (J/m) |
| Example 1 | V-0 | 37.8 | 57.1 | 166 | 169 |
| Example 2 | V-0 | 38.2 | 56.7 | 167 | 171 |
| Example 3 | V-0 | 38.4 | 56.2 | 168 | 172 |
| Example 4 | V-0 | 38.1 | 57 | 167 | 171 |
| Example 5 | V-0 | 37.9 | 56.4 | 166 | 170 |
| Example 6 | V-0 | 38.9 | 55.6 | 170 | 174 |
| Example 7 | V-0 | 39.1 | 55.2 | 171 | 175 |
| Example 8 | V-0 | 38.8 | 55.7 | 170 | 174 |
| Example 9 | V-0 | 39.2 | 55.1 | 172 | 176 |
| Example 10 | V-0 | 39.3 | 54.9 | 172 | 176 |
| Example 11 | V-0 | 39.7 | 55.0 | 174 | 178 |
| Comparative example 1 | V-1 | 32.2 | 61.7 | 141 | 145 |
| Comparative example 2 | V-1 | 31.1 | 59.6 | 137 | 140 |
| Comparative example 3 | V-1 | 32.1 | 61.5 | 141 | 144 |
| Comparative example 4 | V-1 | 33.5 | 64.2 | 147 | 150 |
| Comparative example 5 | V-1 | 35.2 | 67.4 | 154 | 158 |
| Comparative example 6 | V-1 | 34.9 | 66.9 | 153 | 157 |
| Comparative example 7 | V-1 | 31.4 | 60.2 | 138 | 141 |
| Comparative example 8 | V-1 | 31.8 | 61.0 | 140 | 143 |
As shown in Table 1, compared with comparative examples 1-2, in examples 1-5, the test results of the flame retardant property, the oxygen index, the smoke density, the tensile strength and the impact strength in examples 1-5 are superior to those in comparative examples 1-2, which shows that the raw materials and the proportion among the raw materials selected in the invention are scientific and reasonable, and the flame retardant property and the mechanical property of the plastic can be effectively improved.
It can be seen by combining example 3 and comparative examples 3-4 that the test results of flame retardant property, oxygen index, smoke density, tensile strength and impact strength in example 3 are all superior to those in comparative examples 3-4, which shows that the silane coupling agent and the borate coupling agent cooperate to form a dense coating layer on the surface of the magnesium hydroxide whisker, thereby greatly reducing the surface energy of the magnesium hydroxide whisker, improving the dispersibility of the magnesium borate whisker, and further increasing the connection strength with the ABS matrix, thereby improving the impact strength and tensile strength of the plastic. Meanwhile, a P-N-B flame-retardant system is formed by boron elements in the borate coupling agent and phosphorus elements and nitrogen elements in the poly-di-melamine dihydrogen aluminum phosphate salt, and the borate coupling agent and the poly-di-melamine dihydrogen aluminum phosphate salt have synergistic flame retardance in the combustion process, so that the flame-retardant effect of the plastic is greatly improved, and the flame retardant property of the plastic can be further improved. And by combining the comparison between example 3 and comparative examples 5-6, the flame retardant property and the mechanical property of the plastic can be further increased when the weight ratio of the borate coupling agent to the silane coupling agent is 0.8-1.8.
By combining the example 3 and the examples 9 to 11, it can be seen that the test results of the flame retardant property, the oxygen index, the smoke density, the tensile strength and the impact strength in the examples 9 to 11 are better than those in the example 3, which shows that the modified graphene oxide has the dual effects of the solid particles and the chemical surfactant, can play a role of a dispersant, improve the dispersibility of the raw materials, and can increase the bonding force between the modified graphene oxide and the ABS matrix, so that the flame retardant property and the mechanical property of the plastic can be improved.
Combining example 3 with examples 6-8 and comparative examples 7-8, it can be seen that the results of the tests on flame retardant property, oxygen index, smoke density, tensile strength and impact strength in examples 6-8 are all better than those in example 3, which shows that the flame retardant property and mechanical property of plastics are improved more obviously when the weight ratio of the coupling agent modified magnesium hydroxide whiskers to the poly (aluminium dihydrogen dicyanamide phosphate) is in the range of 9-12.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (9)
1. A flame retardant plastic characterized by: the feed is prepared from the following raw materials in parts by weight: 60-100 parts of ABS, 4-10 parts of coupling agent modified magnesium hydroxide whisker, 1-5 parts of graphene oxide, 0.5-4 parts of dispersant, 0.5-7 parts of flexibilizer, 1-6 parts of antioxidant and 0.3-1.3 parts of poly-di-melamine dihydrogen aluminum phosphate salt.
2. A fire retardant plastic according to claim 1, wherein: the feed is prepared from the following raw materials in parts by weight: 85-95 parts of ABS, 5-8 parts of coupling agent modified magnesium hydroxide whisker, 2-4 parts of graphene oxide, 1-3 parts of dispersant, 1-5 parts of flexibilizer, 2-5 parts of antioxidant and 0.5-1 part of poly-di-melamine ammonium dihydrogen phosphate aluminum salt.
3. A flame retardant plastic according to claim 1 or 2, wherein: the modification method of the magnesium hydroxide whisker comprises the following steps:
s1: adding a coupling agent into absolute ethyl alcohol, and uniformly mixing at 60-75 ℃ to obtain a modifier, wherein the weight ratio of the coupling agent to the absolute ethyl alcohol is 1 (3-5);
s2: adding the magnesium hydroxide whisker into the modifier in S1, performing ultrasonic vibration for 1.5-2h, performing suction filtration, and drying to obtain the modified magnesium hydroxide whisker, wherein the weight ratio of the magnesium hydroxide whisker to the coupling agent is 55-75.
4. A flame retardant plastic according to claim 3, wherein the coupling agent comprises a borate coupling agent and a silane coupling agent, and the weight ratio of the borate coupling agent to the silane coupling agent is 0.8 to 1.8.
5. A fire retardant plastic according to claim 4, wherein: the weight ratio of the coupling agent modified magnesium hydroxide whisker to the poly-di-melamine dihydrogen aluminum phosphate salt is 9-12.
6. A fire retardant plastic according to claim 4, wherein: the silane coupling agent adopts one of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane and hexamethylene diamine methyl triethoxysilane.
7. A fire retardant plastic according to claim 1, wherein: the graphene oxide is modified graphene oxide, and the modification method comprises the following steps:
a. mixing 6-15 parts of 3-isocyanatopropyl trimethoxy silane and 1-1.5 parts of graphene oxide, adding the mixture into 300-500ml of anhydrous ethanol, and performing ultrasonic vibration to obtain a mixture;
b. and (b) adding 3-5 parts of polyethylene glycol into the mixture obtained in the step (a), and then drying after ultrasonic vibration filtration to obtain the modified graphene oxide.
8. A fire retardant plastic according to claim 1, wherein: the dispersant is one or more of liquid paraffin, glyceryl tristearate and stearic acid.
9. A process for the manufacture of a fire retardant plastic according to any one of claims 1 to 8, comprising the steps of: the raw materials are evenly mixed, melted and blended at 195-220 ℃, extruded and granulated to obtain the flame-retardant plastic.
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