CN110885498A - Flame-retardant toughened polypropylene material and preparation method thereof - Google Patents
Flame-retardant toughened polypropylene material and preparation method thereof Download PDFInfo
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention discloses a flame-retardant toughened polypropylene material which comprises the following components in parts by weight: 40-70 parts of polypropylene, 10-20 parts of flame retardant, 3-8 parts of toughening agent, 0.5-2 parts of antioxidant, 2-6 parts of montmorillonite and 3-5 parts of compatilizer, wherein the polypropylene is prepared from the following components in parts by weightThe weight ratio of the homopolymerization polypropylene to the copolymerization polypropylene is 1: 1-5. According to the invention, homopolymerization type polypropylene and copolymerization type polypropylene are compounded, and the flame retardant modified by silicone oil and montmorillonite are added for synergistic flame retardance, so that the prepared material has excellent flame retardance, toughness and low temperature resistance, the flame retardance is V-0 grade, and the notch impact strength at-25 ℃ is more than or equal to 9.2kJ/m2The tensile strength is more than or equal to 68MPa, and the prepared polypropylene can be applied to various fields, such as automobiles, daily necessities, aerospace, military fields and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant toughened polypropylene material and a preparation method thereof.
Background
The polypropylene has the advantages of no toxicity, no smell, small density, light weight, easy processing, good electrical insulation, chemical corrosion resistance and the like, and has wide application in the fields of household appliances, automobile interior and exterior trimming parts, body building equipment, office supplies, daily necessities and the like. With the continuous development of the industry, polypropylene occupies an important position in the production and processing industry. However, it has been found that polypropylene has some disadvantages in application, such as strength, flame retardancy and low temperature resistance, and further improvement of polypropylene is required, thereby widening its application in various industries.
Patent CN109651749A discloses a low-temperature impact-resistant cracking-resistant flame-retardant polypropylene material, a preparation method and an application thereof, wherein the low-temperature impact-resistant cracking-resistant flame-retardant polypropylene material comprises the following components in parts by weight: 40-75 parts of polypropylene resin, 2-20 parts of ethylene-octene copolymer, 0-30 parts of mineral filler, 5-30 parts of bromine-containing flame retardant, 5-15 parts of synergistic flame retardant, 0.3-3.5 parts of stabilizer and 0.5-2 parts of toner. The polypropylene material has good flame retardance and low-temperature impact resistance, but due to the addition of the halogen flame retardant, hydrogen halide with large smoke and strong toxicity and other halogen-containing organic matters can be generated during combustion, so that the polypropylene material has great harm to human bodies.
Patent CN101974195A discloses a flame-retardant low-temperature-resistant polypropylene material, a preparation method and an application thereof, the flame-retardant low-temperature-resistant polypropylene material is composed of 50-75 parts by weight of polypropylene, 15-25 parts by weight of flame retardant, 10-25 parts by weight of thermoplastic elastomer and 0.2-0.5 part by weight of antioxidant, the polypropylene material has good flame retardance, but the notch impact strength is lower and the low-temperature impact performance is poorer.
Because many polypropylene materials are used in severe cold regions with severe weather, higher requirements are provided for the performance of the polypropylene materials, but the existing polypropylene materials have the problems of poor impact strength at low temperature, short service life, poor strength and flame retardance and the like, and cannot be suitable for the use in the severe cold regions, so that the polypropylene materials need to be modified to improve the low-temperature resistance, toughness and flame retardance.
Disclosure of Invention
The object of the present invention is to overcome the disadvantages of the prior art and to provide a polypropylene material with excellent mechanical properties, such as toughness, low temperature resistance and flame retardancy.
In order to solve the technical problems, the invention adopts the technical scheme that:
the flame-retardant toughened polypropylene material comprises the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene in a weight ratio of 1: 1-5.
Further, the flame-retardant toughened polypropylene material can comprise the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene in a weight ratio of 1: 1-3.
Further, the flame retardant toughened polypropylene material may further add some common components to further provide the corresponding properties of the polypropylene material, such as light stabilizer, heat stabilizer, lubricant, pigment, and ultraviolet absorber, etc.
The homopolymerized polypropylene is a single propylene monomer polymer, a molecular chain does not contain an ethylene monomer, the regularity of the molecular chain is high, the crystallinity of the material is high, the strength is good, but the impact resistance is poor and the toughness is poor.
The copolymer polypropylene has the advantages of good impact resistance, good impact strength and high toughness, but has poor oxidation resistance. Therefore, the homo-polypropylene and the co-polypropylene are compounded for use, so that the advantages and the disadvantages of the homo-polypropylene and the co-polypropylene can be integrated, and the polypropylene material with excellent strength, impact resistance and toughness is provided.
Preferably, the homo-polypropylene has a melt index of 8-12g/10min and a number average molecular weight of 8-15 ten thousand at 190 ℃. Further, at 190 ℃, the melt index of the homopolymerization type polypropylene is 10-12g/10min, and the number average molecular weight is 10-12 ten thousand. Furthermore, the homopolymerized polypropylene needs to be dried for 2-3h at 80-90 ℃, and the water content is controlled to be below 0.1%.
Preferably, the copolymer polypropylene is a block copolymer of ethylene and propylene, and has a melt index of 5-6g/10min and a number average molecular weight of 3-8 ten thousand at 190 ℃. Further, at 190 ℃, the copolymerization type polypropylene is a block copolymer of ethylene and propylene, the melt index of the copolymer is 5-6g/10min, and the number average molecular weight of the copolymer is 5-8 ten thousand. Furthermore, the copolymerization type polypropylene needs to be dried for 2 to 3 hours at a temperature of between 80 and 90 ℃, and the moisture content of the copolymerization type polypropylene is controlled to be below 0.1 percent.
Preferably, the flame retardant is obtained by mixing a nitrogen flame retardant and a phosphorus flame retardant and carrying out surface treatment on silicone oil. More preferably, the silicone oil is an amino silicone oil.
Preferably, the flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to the weight ratio of 1:1-3 to obtain a mixture;
mixing the obtained mixture with silicone oil, and carrying out heat treatment at the temperature of 120-200 ℃ for 1-3 hours to obtain the flame retardant.
More specifically, the flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant at normal temperature according to the weight ratio of 1:1-3 to obtain a mixture;
mixing the obtained mixture with silicone oil, and carrying out heat treatment at 150-180 ℃ for 2 hours, wherein the mass of the added silicone oil accounts for 0.1-1% of the mass of the mixture, and thus obtaining the flame retardant.
The silicone oil has good heat resistance, weather resistance, lubricating property and flame resistance, and the flame retardant effect can be further improved by adopting the silicone oil to modify the nitrogen flame retardant and the phosphorus flame retardant.
Further, the nitrogen-based flame retardant may be one or more selected from melamine, dicyandiamide and melamine cyanurate salt.
Further, the phosphorus flame retardant can be one or more selected from melamine polyphosphate, trimethyl phosphate, triethyl phosphate and triphenyl phosphate.
Preferably, the toughening agent is selected from one or more of maleic acid grafted polyolefin elastic resin, polyethylene octene co-elastomer and maleic anhydride grafted ethylene-octene polymer.
Preferably, the antioxidant is selected from at least one of hindered phenol antioxidants and phosphite antioxidants.
Further, the hindered phenol antioxidant can be one or more selected from antioxidant 1010, antioxidant 1222, antioxidant 1076, antioxidant 1135, antioxidant 54, antioxidant 730 and 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol.
Further, the phosphite antioxidant may be one or more selected from the group consisting of antioxidant 618, antioxidant 852, tris (2, 4-di-t-butylphenyl) phosphite, octaethylpentaerythritol tetraphosphite, bis (benzyl alcohol) pentaerythritol diphosphite, bis (cetyl alcohol) pentaerythritol diphosphite and bis (bisphenol a) pentaerythritol diphosphite.
Preferably, the particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent. Further, the silane coupling agent is selected from a silane coupling agent KH 550.
The montmorillonite has a unique layered structure and an ultra-large specific surface area, so that the montmorillonite is endowed with some excellent mechanical properties such as thermal properties and mechanical properties, and the tensile strength, bending strength, wear resistance and stability of the polymer can be improved by adding the montmorillonite into the polymer. The montmorillonite also has flame retardance, and can perform flame retardant effect together with nitrogen flame retardant and phosphorus flame retardant.
The invention also provides a preparation method of the flame-retardant toughened polypropylene material, which comprises the following steps:
mixing the homopolymerized polypropylene, the flame retardant, the toughening agent, the antioxidant and the montmorillonite, and performing melt extrusion to obtain master batches;
and mixing the master batch with the copolymerization type polypropylene, adding a compatilizer, and then performing melt extrusion granulation to obtain the flame-retardant toughening polypropylene material.
In the invention, the homopolymerization polypropylene, the flame retardant, the toughening agent, the antioxidant and the montmorillonite are melted and extruded to obtain the master batch, and then the master batch and the copolymerization polypropylene are extruded and granulated, so that the copolymerization polypropylene with excellent impact resistance and toughness wraps the homopolymerization polypropylene, thereby further indirectly improving the impact resistance and toughness of the polypropylene material.
Preferably, the homopolymerization type polypropylene, the flame retardant, the flexibilizer, the antioxidant and the montmorillonite are mixed in a high-speed mixer at the rotating speed of 500-1000r/min for 5-10min and are melted and extruded at the temperature of 200-280 ℃; mixing the obtained master batch and the copolymerization type polypropylene in a low-speed mixer at the rotating speed of 200 plus 400r/min for 5-8min, adding a compatilizer, and then performing melt extrusion granulation at the temperature of 220-300 ℃.
The invention has the beneficial effects that: according to the invention, homopolymerization type polypropylene and copolymerization type polypropylene are compounded, and the flame retardant modified by silicone oil and montmorillonite are added for synergistic flame retardance, so that the prepared material has excellent flame retardance, toughness and low temperature resistance, the flame retardance is V-0 grade, and the notch impact strength at-25 ℃ is more than or equal to 9.2kJ/m2The tensile strength is more than or equal to 68MPa, and the prepared polypropylene can be applied to various fields, such as automobiles, daily necessities, aerospace, military fields and the like, and is suitable for being applied to low-temperature environments.
Detailed Description
The technical solution of the present invention is further described in detail by the following examples.
Example 1
The flame-retardant toughened polypropylene material comprises the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene with the weight ratio of 1: 1.
The flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to a weight ratio of 1:1 to obtain a mixture;
mixing the obtained mixture with silicone oil, and performing heat treatment at 150 ℃ for 1 hour, wherein the mass of the added silicone oil is 0.1% of that of the mixture, and the flame retardant is obtained.
The toughening agent is selected from maleic acid grafted polyolefin elastic resin.
The antioxidant is selected from antioxidant 1010.
The particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent KH 550.
The preparation method of the flame-retardant toughened polypropylene material comprises the following steps:
mixing homopolymerized polypropylene, a flame retardant, a toughening agent, an antioxidant and montmorillonite in a high-speed mixer at the rotating speed of 500-1000r/min for 5-10min, and performing melt extrusion at the temperature of 200-280 ℃ to obtain master batches;
mixing the master batch and the copolymerization type polypropylene in a low-speed mixer at the rotating speed of 200 plus 400r/min for 5-8min, adding a compatilizer, and then performing melt extrusion granulation at the temperature of 220-300 ℃ to obtain the flame-retardant toughening polypropylene material.
Example 2
The flame-retardant toughened polypropylene material comprises the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene with the weight ratio of 1: 2.
The flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to a weight ratio of 1:1 to obtain a mixture;
mixing the obtained mixture with silicone oil, and performing heat treatment at 150 ℃ for 1.5 hours, wherein the mass of the added silicone oil is 0.5 percent of that of the mixture, and the flame retardant is obtained.
The toughening agent is selected from polyethylene octene co-elastomer and maleic anhydride grafted ethylene-octene polymer (mass ratio 1: 1).
The antioxidant is selected from antioxidant 1010 and antioxidant 618 (mass ratio 1: 1).
The particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent KH 550.
The preparation method of the flame retardant toughened polypropylene material of the embodiment 2 is the same as that of the flame retardant toughened polypropylene material of the embodiment 1.
Example 3
The flame-retardant toughened polypropylene material comprises the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene with the weight ratio of 1: 3.
The flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to a weight ratio of 1:2 to obtain a mixture;
mixing the obtained mixture with silicone oil, and performing heat treatment at 180 ℃ for 2 hours, wherein the mass of the added silicone oil is 0.5% of that of the mixture, and the flame retardant is obtained.
The toughening agent is selected from maleic anhydride grafted ethylene-octene polymers.
The antioxidant is selected from an oxidant 1010 and tris (2, 4-di-tert-butylphenyl) phosphite (mass ratio 1: 1).
The particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent KH 550.
The preparation method of the flame retardant toughened polypropylene material of the embodiment 3 is the same as that of the flame retardant toughened polypropylene material of the embodiment 1.
Example 4
The flame-retardant toughened polypropylene material comprises the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene with the weight ratio of 1: 4.
The flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to a weight ratio of 1:3 to obtain a mixture;
mixing the obtained mixture with silicone oil, and performing heat treatment at 120 ℃ for 3 hours, wherein the mass of the added silicone oil is 0.5 percent of that of the mixture, and the flame retardant is obtained.
The toughening agent is selected from polyethylene octene co-elastomers.
The antioxidant is selected from 2, 6-di-tert-butyl-4 (dimethylaminomethyl) phenol.
The particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent KH 550.
The preparation method of the flame retardant toughened polypropylene material of the embodiment 4 is the same as that of the flame retardant toughened polypropylene material of the embodiment 1.
Comparative example 1
A polypropylene material comprises the following components in parts by weight:
the flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to a weight ratio of 1:2 to obtain a mixture;
mixing the obtained mixture with silicone oil, and performing heat treatment at 180 ℃ for 2 hours, wherein the mass of the added silicone oil is 0.5% of that of the mixture, and the flame retardant is obtained.
The toughening agent is selected from maleic anhydride grafted ethylene-octene polymers.
The antioxidant is selected from an oxidant 1010 and tris (2, 4-di-tert-butylphenyl) phosphite (mass ratio 1: 1).
The particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent KH 550.
The preparation method of the polypropylene material comprises the following steps:
the homopolymerization type polypropylene, the flame retardant, the toughening agent, the antioxidant and the montmorillonite are mixed in a compatilizer high-speed mixer at the rotating speed of 500-1000r/min for 5-10min, and the mixture is melted and extruded at the temperature of 200-280 ℃ to obtain the flame-retardant toughening polypropylene material.
Comparative example 2
A polypropylene material comprises the following components in parts by weight:
the flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to a weight ratio of 1:2 to obtain a mixture;
mixing the obtained mixture with silicone oil, and performing heat treatment at 180 ℃ for 2 hours, wherein the mass of the added silicone oil is 0.5% of that of the mixture, and the flame retardant is obtained.
The toughening agent is selected from maleic anhydride grafted ethylene-octene polymers.
The antioxidant is selected from an oxidant 1010 and tris (2, 4-di-tert-butylphenyl) phosphite (mass ratio 1: 1).
The particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent KH 550.
The preparation method of the polypropylene material comprises the following steps:
mixing the copolymerization type polypropylene, the flame retardant, the toughening agent, the antioxidant and the montmorillonite in a compatilizer high-speed mixer at the rotating speed of 500-1000r/min for 5-10min, and performing melt extrusion at the temperature of 200-280 ℃ to obtain the flame-retardant toughening polypropylene material.
Comparative example 3
A polypropylene material comprises the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene with the weight ratio of 1: 3.
The flame retardant is a nitrogen flame retardant.
The toughening agent is selected from maleic anhydride grafted ethylene-octene polymers.
The antioxidant is selected from an oxidant 1010 and tris (2, 4-di-tert-butylphenyl) phosphite (mass ratio 1: 1).
The particle size of the montmorillonite is 300-600 meshes; the compatilizer is a silane coupling agent KH 550.
The preparation method of the polypropylene material of the comparative example 3 is the same as that of the flame retardant toughened polypropylene material of the example 1.
The performance of the flame retardant toughened polypropylene materials prepared in examples 1-4 and the polypropylene materials prepared in comparative examples 1-3 was measured, and the results are shown in the following table.
As can be seen from the above table, compared with the polypropylene materials in comparative examples 1 to 3, the flame retardant toughened polypropylene materials prepared in examples 1 to 4 of the present invention have good flame retardant property, notch impact strength and tensile strength, and are suitable for use in low temperature environments.
Claims (10)
1. The flame-retardant toughened polypropylene material is characterized by comprising the following components in parts by weight:
the polypropylene is compounded by homopolymerization type polypropylene and copolymerization type polypropylene in a weight ratio of 1: 1-5.
2. The flame retardant toughened polypropylene material as claimed in claim 1, wherein the homo-polypropylene has a melt index of 8-12g/10min and a number average molecular weight of 8-15 ten thousand at 190 ℃.
3. The flame retardant toughened polypropylene material as claimed in claim 1, wherein the copolymer polypropylene is a block copolymer of ethylene and propylene, and has a melt index of 5-6g/10min and a number average molecular weight of 3-8 ten thousand at 190 ℃.
4. The flame-retardant toughened polypropylene material as claimed in claim 1, wherein the flame retardant is prepared by mixing a nitrogen flame retardant and a phosphorus flame retardant and subjecting the mixture to surface treatment with silicone oil.
5. The flame-retardant toughened polypropylene material as claimed in claim 4, wherein the flame retardant is prepared by the following preparation method:
mixing a nitrogen flame retardant and a phosphorus flame retardant according to the weight ratio of 1:1-3 to obtain a mixture;
mixing the obtained mixture with silicone oil, and carrying out heat treatment at the temperature of 120-200 ℃ for 1-3 hours to obtain the flame retardant.
6. The flame retardant toughened polypropylene material as claimed in claim 1, wherein the toughening agent is selected from one or more of maleic acid grafted polyolefin elastomer resin, polyethylene octene co-elastomer and maleic anhydride grafted ethylene-octene polymer.
7. The flame retardant toughened polypropylene material as claimed in claim 1, wherein the antioxidant is at least one selected from hindered phenol antioxidants and phosphite antioxidants.
8. The flame retardant toughened polypropylene material as claimed in claim 1, wherein the particle size of the montmorillonite is 300-600 mesh; the compatilizer is a silane coupling agent.
9. The method for preparing the flame retardant toughened polypropylene material as claimed in any one of claims 1 to 8, wherein the method comprises the following steps:
mixing the homopolymerized polypropylene, the flame retardant, the toughening agent, the antioxidant and the montmorillonite, and performing melt extrusion to obtain master batches;
and mixing the master batch with the copolymerization type polypropylene, adding a compatilizer, and then performing melt extrusion granulation to obtain the flame-retardant toughening polypropylene material.
10. The method as claimed in claim 9, wherein the homo-polypropylene, the flame retardant, the toughening agent, the antioxidant and the montmorillonite are mixed in a high-speed mixer at a rotation speed of 500-1000r/min for 5-10min and melt-extruded at a temperature of 200-280 ℃; mixing the obtained master batch and the copolymerization type polypropylene in a low-speed mixer at the rotating speed of 200 plus 400r/min for 5-8min, adding a compatilizer, and then performing melt extrusion granulation at the temperature of 220-300 ℃.
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