CN114702749A - Flame-retardant polyolefin and preparation method thereof - Google Patents
Flame-retardant polyolefin and preparation method thereof Download PDFInfo
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- CN114702749A CN114702749A CN202210407415.5A CN202210407415A CN114702749A CN 114702749 A CN114702749 A CN 114702749A CN 202210407415 A CN202210407415 A CN 202210407415A CN 114702749 A CN114702749 A CN 114702749A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses flame-retardant polyolefin and a preparation method thereof, wherein the flame-retardant polyolefin comprises the following components: polyolefin, composite flame retardant, aluminum diethylphosphinate, compatilizer, lubricant and antioxidant; the composite flame retardant comprises polyhedral oligomeric silsesquioxane, modified nano magnesium hydroxide and nano aluminum hydroxide. According to the invention, the POSS, the magnesium hydroxide and the aluminum hydroxide are compounded into the composite flame retardant, so that the flame retardant effect is greatly improved and the addition amounts of the magnesium hydroxide and the aluminum hydroxide are reduced through the synergistic effect of the POSS, the magnesium hydroxide and the aluminum hydroxide; by adding the compatilizer, the compatibility of the inorganic flame retardant and the polyolefin is improved, and the adverse effects of the inorganic flame retardant (magnesium hydroxide and aluminum hydroxide) on the mechanical property and the processability of the polyolefin are further reduced; in addition, the flame retardant property is further improved by adding aluminum diethylphosphinate. Therefore, the flame-retardant polyolefin provided by the invention has good flame-retardant effect and excellent mechanical property.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to flame-retardant polyolefin and a preparation method thereof.
Background
The polyester material is a polymer obtained by polycondensation of polyhydric alcohol and polybasic acid, is an economic and effective thermosetting material, is easy to process, has excellent performance, and is widely applied to daily life. However, polyester has flammability, which limits its application in important fields such as electronic and electric appliances, transportation and construction.
In order to improve the flame retardant performance of polyolefin materials, flame retardants are often added to the raw materials. The common flame retardants at present mainly include metal hydroxides, antimony series, and the like. Among them, magnesium hydroxide and aluminum hydroxide are widely used because they have functions such as a filler, a flame retardant and a smoke suppressant. In order to meet the requirement of flame retardance, a large amount of magnesium hydroxide and aluminum hydroxide are added to the polyolefin material, but the operation causes the mechanical property of the polyolefin material to be reduced, so that the stability of the polyolefin material is reduced.
Therefore, how to make the composite material have excellent mechanical properties while simultaneously considering the flame retardancy of the polyolefin composite material is a problem to be solved at present.
Disclosure of Invention
The invention mainly aims to provide flame-retardant polyolefin and a preparation method thereof, and aims to provide flame-retardant polyolefin with good flame-retardant effect and excellent mechanical property.
In order to achieve the above object, the present invention provides a flame retardant polyolefin, comprising the following components:
polyolefin, composite flame retardant, aluminum diethylphosphinate, compatilizer, lubricant and antioxidant;
the composite flame retardant comprises polyhedral oligomeric silsesquioxane, modified nano magnesium hydroxide and nano aluminum hydroxide.
Optionally, in the flame-retardant polyolefin, the mass parts of the components are as follows:
50-70 parts of polyolefin, 30-45 parts of composite flame retardant, 2-5 parts of aluminum diethylphosphinate, 3-7 parts of compatilizer, 0.1-3 parts of lubricant and 0.1-5 parts of oxidant.
Optionally, the polyolefin comprises at least one of polyethylene, ethylene-octene copolymer, and ethylene-vinyl acetate copolymer.
Optionally, the compatibilizing agent comprises a maleic anhydride grafted polyolefin.
Optionally, the lubricant comprises at least one of methyl vinyl silicone rubber, stearic acid, zinc stearate, and polyethylene wax.
Optionally, the antioxidant comprises at least one of antioxidant 1010, 1024, 1076, 168, KY-405, and antioxidant DLTDP.
Based on the above object, the present invention also provides a method for preparing the flame retardant polyolefin, the method comprising the steps of:
uniformly mixing polyolefin, a composite flame retardant, aluminum diethylphosphinate, a lubricant and an antioxidant in a high-speed stirrer to obtain a mixture;
banburying the mixture and a compatilizer at 110-140 ℃ to form a mass to obtain an intermediate;
and extruding, granulating and cooling the intermediate to obtain the flame-retardant polyolefin.
Optionally, before the step of uniformly mixing the polyolefin, the composite flame retardant, the aluminum diethylphosphinate, the lubricant and the antioxidant in a high-speed stirrer to obtain a mixture, the method further comprises the following steps of:
uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material;
spraying a modifier to the powder material, drying and sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide;
and uniformly mixing the polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and the nano aluminum hydroxide to obtain the composite flame retardant.
Optionally, the mass ratio of the nano magnesium hydroxide to the nano aluminum hydroxide to the polyhedral oligomeric silsesquioxane is 20-30: 20-30: 10 to 20.
Optionally, the addition amount of the modifier is 1-3% of the mass of the powder material; and/or the presence of a gas in the gas,
the modifier comprises gamma-aminopropyltriethoxysilane or gamma- (2,3 epoxypropyl) propyltrimethoxysilane.
In the technical scheme provided by the invention, polyhedral oligomeric silsesquioxane (POSS) has good flame retardance, smoke suppression and thermal stability, and can improve the processability and mechanical property of polyolefin, magnesium hydroxide and aluminum hydroxide are inorganic flame retardants and can desorb heat by heating, metal oxide generated by reaction covers the surface of polyolefin, and the metal oxide can also enable the polyolefin to generate thermo-oxidative crosslinking reaction to form a compact carbon layer on the surface of the polyolefin, so that oxygen isolation and heat insulation are realized; by adding the compatilizer, the compatibility of the inorganic flame retardant and the polyolefin is improved, and the adverse effects of the inorganic flame retardant on the mechanical property and the processability of the polyolefin are further reduced; in addition, the flame retardant performance is further improved by adding the diethyl aluminum phosphinate serving as a synergistic flame retardant. Therefore, the flame-retardant polyolefin provided by the invention has good flame-retardant effect and excellent mechanical property.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that those who do not specify specific conditions in the examples were performed under the conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The common flame retardants at present mainly include metal hydroxides, antimony series, and the like. Among them, magnesium hydroxide and aluminum hydroxide are widely used because they have functions such as a filler, a flame retardant and a smoke suppressant. In order to meet the requirement of flame retardance, a large amount of magnesium hydroxide and aluminum hydroxide are added to the polyolefin material, but the operation causes the mechanical property of the polyolefin material to be reduced, so that the stability of the polyolefin material is reduced.
In view of the above, the present invention provides a flame retardant polyolefin, which in one embodiment comprises the following components: polyolefin, composite flame retardant, aluminum diethylphosphinate, compatilizer, lubricant and antioxidant; the composite flame retardant comprises polyhedral oligomeric silsesquioxane, modified nano magnesium hydroxide and nano aluminum hydroxide.
Polyhedral oligomeric silsesquioxane (POSS) is a low-toxicity environment-friendly substance, and by adding POSS, the problems of violent fuming and melt dripping during polyolefin combustion can be obviously improved, the flammability of polyolefin is reduced, and the mechanical property and the processability of a polyolefin material are improved. Specifically, the mechanism of action of POSS is: when the flame-retardant polyolefin material is combusted, POSS can migrate to the surface of the material to generate a Si-C compact barrier layer, so that the oxygen and heat insulation are realized, the melt is prevented from dripping, and the flame-retardant effect is excellent.
Magnesium hydroxide and aluminum hydroxide belong to inorganic flame retardants, and are decomposed and absorb heat at high temperature to generate metal oxides and water vapor, so that the surface temperature of polyolefin is reduced, combustible gas on the surface of a combustion product is diluted, and the metal oxides can also enable the polyolefin to generate a thermal-oxygen crosslinking reaction to form a compact carbon layer on the surface of the polyolefin, thereby isolating the transfer of heat and oxygen and preventing the continuous combustion of the polyolefin.
Furthermore, compared with micron-sized aluminum hydroxide and magnesium hydroxide, the nano-sized magnesium hydroxide and aluminum hydroxide are selected, so that the flame retardant property and the mechanical property are better. In addition, the nano magnesium hydroxide and the nano aluminum hydroxide can be synergistic, so that the addition amount of the inorganic flame retardant is reduced when the same flame retardant effect is realized, and the adverse effect of the inorganic flame retardant on the mechanical property and the processing flowability of the polyolefin material is reduced.
According to the technical scheme provided by the invention, the composite flame retardant comprises POSS, and modified nano magnesium hydroxide and nano aluminum hydroxide, wherein the POSS has good flame retardance, smoke suppression and thermal stability, and can also improve the processability and mechanical property of polyolefin; by adding the compatilizer, the compatibility of the inorganic flame retardant and the polyolefin is improved, and the adverse effects of the inorganic flame retardant on the mechanical property and the processability of the polyolefin are further reduced; in addition, the flame retardant performance is further improved by adding the diethyl aluminum phosphinate serving as a synergistic flame retardant. Therefore, the flame-retardant polyolefin provided by the invention has good flame-retardant effect and excellent mechanical property.
The present invention does not limit the specific kind of the polyolefin, and the polyolefin may be added according to the actual application scenario of the prepared flame retardant polyolefin, and in an embodiment, the polyolefin includes at least one of ethylene-vinyl acetate copolymer (EVA), Polyethylene (PE), and ethylene-octene copolymer (POE). It is understood that the specific addition amount of each of the above polyolefins is determined according to the actual application scenario. For example: when the wire and cable insulation and sheath with high voltage resistance and high hardness needs to be prepared, the polyolefin is a mixture of PE and POE, and the mass ratio of the PE to the POE is 40: 15.
further, the melt flow rate of EVA, PE and POE at 190 ℃ under a load of 2.16kg is 0.5-20 g/10min, the polyolefin extrusion at the melt flow rate is stable and does not deform, and the finally prepared flame-retardant polyolefin has high strength.
The compatibility of the inorganic flame retardant with the polyolefin is improved by the addition of a compatibilizer, which in this embodiment comprises a maleic anhydride grafted polyolefin, thereby further reducing the adverse effects of the inorganic flame retardant on the mechanical properties and processability of the polyolefin. Further, the maleic anhydride grafted polyolefin includes maleic anhydride grafted PE or maleic anhydride grafted POE.
The lubricant can reduce the cohesive force among polymer molecules, thereby improving the internal friction and the fluidity of the polyolefin, reducing the melt viscosity and ensuring good processability of the polyolefin. In this embodiment, the lubricant includes at least one of methyl vinyl silicone rubber, stearic acid, zinc stearate, and polyethylene wax, and the lubricant is selected to improve the processability, thereby facilitating the preparation of the flame retardant polyolefin.
By adding the antioxidant, the aging speed of the prepared flame-retardant polyolefin can be slowed down, so that the service life of the flame-retardant polyolefin is prolonged. In the embodiment, the antioxidant comprises at least one of antioxidants 1010, 1024, 1076, 168, KY-405 and DLTDP, so that the flame-retardant polyolefin has good ageing resistance.
Preferably, in the flame-retardant polyolefin, the components in parts by mass are as follows: 50-70 parts of polyolefin, 30-45 parts of composite flame retardant, 2-5 parts of aluminum diethylphosphinate, 3-7 parts of compatilizer, 0.1-3 parts of lubricant and 0.1-5 parts of oxidant, and the flame retardant effect and the mechanical property of the prepared flame retardant polyolefin are better in proportion.
The present invention also provides a method for preparing the flame retardant polyolefin, which comprises the following steps:
and step S10, uniformly mixing the polyolefin, the composite flame retardant, the aluminum diethylphosphinate, the lubricant and the antioxidant in a high-speed stirrer to obtain a mixture.
The invention does not limit the concrete preparation method of the composite flame retardant, as long as the composite flame retardant contains POSS, modified nano magnesium hydroxide and nano aluminum hydroxide. Preferably, before step S10, the method further includes the following steps:
step A1, uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material;
a2, spraying a modifier to the powder material, drying and sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide;
step A3, uniformly mixing polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and the modified nano aluminum hydroxide to obtain the composite flame retardant.
Preferably, the mass ratio of the nano magnesium hydroxide to the nano aluminum hydroxide to the polyhedral oligomeric silsesquioxane is 20-30: 20-30: 10-20, so that the prepared flame-retardant polyolefin has better comprehensive performance.
In order to further improve the compatibility of the composite flame retardant and polyolefin, the invention carries out modification treatment on the nano magnesium hydroxide and the aluminum hydroxide, wherein the modifier is a silane coupling agent. Specifically, the modifier includes gamma-aminopropyltriethoxysilane (i.e., silane coupling agent KH-550) or gamma- (2,3 epoxypropyl) propyltrimethoxysilane (i.e., silane coupling agent KH-560). Preferably, the addition amount of the modifier is 1-3% of the mass of the powder material, and the modification effect is good at the addition amount.
In order to ensure that the modifier is sufficiently absorbed and the powder material is sufficiently dried, so that the powder material is not agglomerated, in the embodiment, the drying temperature of the drying is 100-130 ℃.
And step S20, banburying the mixture and a compatilizer at 110-140 ℃ to form a mass, and obtaining an intermediate.
And step S30, extruding, granulating and cooling the intermediate to obtain the flame-retardant polyolefin.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
The amounts of the respective raw materials added in examples 1 to 6 were weighed in the following table 1.
TABLE 1 amounts (parts) of components added
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Polyolefins | 55 | 64 | 70 | 50 | 56 |
| Composite flame retardant | 40 | 34 | 30 | 45 | 40 |
| Aluminium diethylphosphinate | 5 | 2 | 3 | 5 | 4 |
| Compatilizer | 5 | 7 | 7 | 3 | 4 |
| Lubricant agent | 2 | 3 | 0.1 | 1 | 2.5 |
| Antioxidant agent | 3 | 2 | 4 | 0.1 | 5 |
Example 1
(1) Uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material; spraying a modifier (gamma-aminopropyltriethoxysilane) to the powder material, drying at 120 ℃, and then sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide; and uniformly mixing polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and nano aluminum hydroxide to obtain the composite flame retardant, wherein the mass ratio of the nano magnesium hydroxide to the nano aluminum hydroxide to the polyhedral oligomeric silsesquioxane is 25: 24: 15, the addition amount of the modifier is 3% of the mass of the powder material;
(2) weighing the raw material components according to the formula shown in table 1, and then uniformly mixing polyolefin (POE and PE), a composite flame retardant, aluminum diethylphosphinate, a lubricant (methyl vinyl silicone rubber) and an antioxidant (antioxidant 1076) in a high-speed stirrer to obtain a mixture;
(3) adding the mixture and a compatilizer (maleic anhydride grafted PE) into an internal mixer, and internally mixing and agglomerating at 120 ℃ to obtain an intermediate;
(4) and adding the intermediate into a double-screw extruder, extruding, granulating and cooling to obtain the flame-retardant polyolefin.
Example 2
(1) Uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material; spraying a modifier (gamma-aminopropyltriethoxysilane) to the powder material, drying at 100 ℃, and then sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide; and uniformly mixing polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and nano aluminum hydroxide to obtain the composite flame retardant, wherein the mass ratio of the nano magnesium hydroxide to the nano aluminum hydroxide to the polyhedral oligomeric silsesquioxane is 20: 20: 10, wherein the addition amount of the modifier is 2% of the mass of the powder material;
(2) weighing the raw material components according to the formula shown in table 1, and then uniformly mixing polyolefin (EVA and POE), composite flame retardant, aluminum diethylphosphinate, lubricant (polyethylene wax) and antioxidant (antioxidant 168 and antioxidant 1010) in a high-speed mixer to obtain a mixture;
(3) adding the mixture and a compatilizer (maleic anhydride grafted POE) into an internal mixer, and internally mixing and agglomerating at 130 ℃ to obtain an intermediate;
(4) and adding the intermediate into a double-screw extruder, extruding, granulating and cooling to obtain the flame-retardant polyolefin.
Example 3
(1) Uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material; spraying a modifier (gamma-aminopropyltriethoxysilane) to the powder material, drying at 130 ℃, and then sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide; and uniformly mixing polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and nano aluminum hydroxide to obtain the composite flame retardant, wherein the mass ratio of the nano magnesium hydroxide to the nano aluminum hydroxide to the polyhedral oligomeric silsesquioxane is 30: 30: 20, wherein the addition amount of the modifier is 1 percent of the mass of the powder material;
(2) weighing the raw material components according to the formula shown in Table 1, and then uniformly mixing Polyolefin (PE), a composite flame retardant, aluminum diethylphosphinate, a lubricant (stearic acid) and an antioxidant (antioxidant 1024) in a high-speed stirrer to obtain a mixture;
(3) adding the mixture and a compatilizer (maleic anhydride grafted PE) into an internal mixer, and carrying out internal mixing at 140 ℃ to form a mass to obtain an intermediate;
(4) and adding the intermediate into a double-screw extruder, extruding, granulating and cooling to obtain the flame-retardant polyolefin.
Example 4
(1) Uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material; spraying a modifier (gamma- (2,3 epoxypropyl) propyl trimethoxy silane) to the powder material, drying at 120 ℃, and then sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide; and uniformly mixing polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and nano aluminum hydroxide to obtain the composite flame retardant, wherein the mass ratio of the nano magnesium hydroxide to the nano aluminum hydroxide to the polyhedral oligomeric silsesquioxane is 20: 30: 14, the addition amount of the modifier is 2% of the mass of the powder material;
(2) weighing the raw material components according to the formula shown in table 1, and then uniformly mixing polyolefin (EVA and POE), a composite flame retardant, aluminum diethylphosphinate, a lubricant (zinc stearate) and an antioxidant (antioxidant 1010) in a high-speed stirrer to obtain a mixture;
(3) adding the mixture and a compatilizer (maleic anhydride grafted POE) into an internal mixer, and internally mixing and agglomerating at 110 ℃ to obtain an intermediate;
(4) and adding the intermediate into a double-screw extruder, extruding, granulating and cooling to obtain the flame-retardant polyolefin.
Example 5
(1) Uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material; spraying a modifier (gamma-aminopropyl triethylsilane) to the powder material, drying at the temperature of 100-130 ℃, and then sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide; uniformly mixing polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and the modified nano aluminum hydroxide to obtain the composite flame retardant, wherein the mass ratio of the nano magnesium hydroxide to the nano aluminum hydroxide to the polyhedral oligomeric silsesquioxane is 30: 25: 17, the addition amount of the modifier is 3% of the mass of the powder material;
(2) weighing the raw material components according to the formula shown in Table 1, and then uniformly mixing the polyolefin, the composite flame retardant, the aluminum diethylphosphinate, the lubricant and the antioxidant in a high-speed stirrer to obtain a mixture;
(3) adding the mixture and a compatilizer into an internal mixer, and carrying out internal mixing at 120 ℃ to form a mass to obtain an intermediate;
(4) and adding the intermediate into a double-screw extruder, extruding, granulating and cooling to obtain the flame-retardant polyolefin.
Comparative example 1
The same procedure as in example 1 was repeated except that the composite flame retardant was replaced with polyhedral oligomeric silsesquioxane;
namely, the preparation method of the flame retardant polyolefin comprises the following steps:
(1) weighing the raw material components according to the formula shown in Table 1, and then uniformly mixing polyolefin, polyhedral oligomeric silsesquioxane, aluminum diethylphosphinate, a lubricant and an antioxidant in a high-speed stirrer to obtain a mixture;
(2) adding the mixture and a compatilizer into an internal mixer, and carrying out internal mixing at 120 ℃ to form a mass to obtain an intermediate;
(3) and adding the intermediate into a double-screw extruder, extruding, granulating and cooling to obtain the flame-retardant polyolefin.
Comparative example 2
The procedure was the same as in example 1 except that no modified aluminum hydroxide was added.
Namely, the preparation method of the flame retardant polyolefin comprises the following steps:
(1) spraying a modifier (vinyl triethoxysilane) to the nano magnesium hydroxide, drying at 120 ℃, and sieving to obtain modified nano magnesium hydroxide; and uniformly mixing polyhedral oligomeric silsesquioxane with the modified nano magnesium hydroxide to obtain the composite flame retardant, wherein the mass ratio of the nano magnesium hydroxide to the polyhedral oligomeric silsesquioxane is 25: 15, the addition amount of the modifier is 3% of the mass of the nano magnesium hydroxide;
(2) weighing the raw material components according to the formula shown in table 1, and then uniformly mixing polyolefin (EVA and PE), a composite flame retardant, aluminum diethylphosphinate, a lubricant (methyl vinyl silicone rubber) and an antioxidant (antioxidant 1076) in a high-speed mixer to obtain a mixture;
(3) adding the mixture and a compatilizer (maleic anhydride grafted PE) into an internal mixer, and internally mixing and agglomerating at 120 ℃ to obtain an intermediate;
(4) and adding the intermediate into a double-screw extruder, extruding, granulating and cooling to obtain the flame-retardant polyolefin.
Comparative example 3
The procedure was the same as in example 1 except that no compatibilizer was added.
The flame-retardant polyolefin injection molding layer test sample strips prepared in the example 1 and the comparative examples 1 to 3 are subjected to mechanical property, flame retardant property and smoke density tests, wherein the mechanical property is tensile strength determined according to GB/T1040-.
TABLE 1 test results
| Limiting oxygen index (%) | Flame retardant rating | Tensile Strength (MPa) | |
| Example 1 | 36.6 | V-0 | 28.5 |
| Comparative example 1 | 23.1 | V-2 | 28.4 |
| Comparative example 2 | 31.2 | V-0 | 28.1 |
| Comparative example 3 | 30.1 | V-0 | 24.1 |
As can be seen from Table 1, the limited oxygen index of the flame-retardant polyolefin prepared in example 1 of the invention is 36.6%, the flame-retardant rating is V-0, and the tensile strength is 28.5MPa, which indicates that the flame-retardant polyolefin prepared in the invention has good flame-retardant property and excellent mechanical property.
The flame retardant property of the flame retardant polyolefin prepared in comparative example 1 was inferior to that of example 1, presumably because the polyhedral oligomeric silsesquioxane had no multi-carbon structure and was not easily char-formed, and thus the effect was poor when used alone. Meanwhile, compared with the comparative examples 1-2, the polyhedral oligomeric silsesquioxane in the composite flame retardant, the modified nano magnesium hydroxide and the nano aluminum hydroxide can play a synergistic role, and even if one of the polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and the modified nano aluminum hydroxide is absent, the performance of the flame-retardant polyolefin is obviously weakened.
The same tests as those in example 1 were carried out on examples 2 to 5, and the results show that the flame-retardant polyolefins obtained in examples 2 to 5 are as good in flame retardancy and excellent in mechanical properties.
The above are only preferred embodiments of the present invention, and do not limit the scope of the present invention, and it is obvious to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A flame retardant polyolefin comprising the following components:
polyolefin, composite flame retardant, aluminum diethylphosphinate, compatilizer, lubricant and antioxidant;
the composite flame retardant comprises polyhedral oligomeric silsesquioxane, modified nano magnesium hydroxide and nano aluminum hydroxide.
2. The flame-retardant polyolefin according to claim 1, wherein the flame-retardant polyolefin comprises the following components in parts by mass:
50-70 parts of polyolefin, 30-45 parts of composite flame retardant, 2-5 parts of aluminum diethylphosphinate, 3-7 parts of compatilizer, 0.1-3 parts of lubricant and 0.1-5 parts of oxidant.
3. The flame retardant polyolefin of claim 1, wherein the polyolefin comprises at least one of polyethylene, ethylene-octene copolymer, and ethylene-vinyl acetate copolymer.
4. The flame retardant polyolefin of claim 1, wherein the compatibilizer comprises a maleic anhydride grafted polyolefin.
5. The flame retardant polyolefin of claim 1, wherein said lubricant comprises at least one of methyl vinyl silicone rubber, stearic acid, zinc stearate, and polyethylene wax.
6. The flame retardant polyolefin of claim 1, wherein the antioxidant comprises at least one of the antioxidants 1010, 1024, 1076, 168, KY-405 and DLTDP.
7. Process for the preparation of a flame-retardant polyolefin according to any of claims 1 to 6, characterized in that it comprises the following steps:
uniformly mixing polyolefin, a composite flame retardant, aluminum diethylphosphinate, a lubricant and an antioxidant in a high-speed stirrer to obtain a mixture;
banburying the mixture and a compatilizer at 110-140 ℃ to form a mass to obtain an intermediate;
and extruding, granulating and cooling the intermediate to obtain the flame-retardant polyolefin.
8. The method of claim 7, wherein prior to the step of uniformly mixing the polyolefin, the composite flame retardant, the aluminum diethylphosphinate, the lubricant, and the antioxidant in a high-speed mixer to obtain a mixture, the method further comprises the steps of:
uniformly mixing nano magnesium hydroxide and nano aluminum hydroxide to obtain a powder material;
spraying a modifier to the powder material, drying and sieving to obtain modified nano magnesium hydroxide and nano aluminum hydroxide;
and uniformly mixing the polyhedral oligomeric silsesquioxane, the modified nano magnesium hydroxide and the nano aluminum hydroxide to obtain the composite flame retardant.
9. The preparation method of the flame-retardant polyolefin according to claim 8, wherein the mass ratio of the nano magnesium hydroxide, the nano aluminum hydroxide and the polyhedral oligomeric silsesquioxane is 20-30: 20-30: 10 to 20.
10. The preparation method of the flame-retardant polyolefin as claimed in claim 8, wherein the addition amount of the modifier is 1-3% of the mass of the powder material; and/or the presence of a gas in the gas,
the modifier comprises gamma-aminopropyltriethoxysilane or gamma- (2,3 epoxypropyl) propyltrimethoxysilane.
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