CN115386162A - Halogen-free flame-retardant material and preparation method thereof - Google Patents

Halogen-free flame-retardant material and preparation method thereof Download PDF

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Publication number
CN115386162A
CN115386162A CN202210794063.3A CN202210794063A CN115386162A CN 115386162 A CN115386162 A CN 115386162A CN 202210794063 A CN202210794063 A CN 202210794063A CN 115386162 A CN115386162 A CN 115386162A
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parts
flame retardant
halogen
modified
flame
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Inventor
袁文博
刘振振
张晓通
赵明雷
刘朋
徐宾
马韵升
赵永臣
王耀伟
栾波
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Shandong Chambroad Petrochemicals Co Ltd
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Shandong Chambroad Petrochemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

The invention provides a halogen-free flame-retardant PP material capable of replacing flame-retardant ABS, which comprises the following components: 49-74 parts of PP resin, 10-20 parts of nitrogen and phosphorus flame retardant, 0.1-0.8 part of anti-dripping agent, 10-15 parts of modified basalt fiber, 10-15 parts of modified hollow glass bead, 1-5 parts of compatilizer, 2-5 parts of azido trimethoxy silane coupling agent, 0.1-1 part of antioxidant, 1-2 parts of lubricant, 0.5-1 part of light stabilizer and 0.5-1 part of antistatic agent. The new material provided by the invention can replace flame-retardant ABS in a certain range, has obvious advantages in the aspects of thermal deformation temperature, temperature resistance, flame retardance and impact resistance, solves the environmental protection problem of the flame-retardant ABS and reduces the cost. The invention also provides a preparation method of the halogen-free flame retardant material.

Description

Halogen-free flame-retardant material and preparation method thereof
Technical Field
The invention belongs to the technical field of flame retardant materials, particularly relates to a halogen-free flame retardant material and a preparation method thereof, and particularly relates to a halogen-free flame retardant PP material capable of replacing flame retardant ABS and a preparation method thereof.
Background
The ABS material is a terpolymer of three monomers of acrylonitrile, butadiene and styrene, and the relative contents of the three monomers can be changed at will to prepare resins with various properties. Acrylonitrile makes it resistant to chemical corrosion and heat, improves the surface hardness, butadiene makes it have high elasticity and toughness, and styrene makes it have the processing and forming characteristics of thermoplastic plastics; therefore, the flame retardant ABS material is widely applied to the fields of electronic and electric products, industrial parts and the like, but the flame retardant ABS material is an important classification of ABS materials in the occasions using ABS, most of the flame retardant ABS materials in China at present are halogenated, the price is high, the environment is not protected, and the mechanical reduction of the ABS material is very obvious along with the increase of the addition amount of the flame retardant.
Polypropylene (PP) has excellent mechanical properties, heat resistance, chemical stability, electrical insulation, low density, low price and extremely high cost performance, and is widely applied to the fields of household appliances, automobiles, smart homes, building materials and the like. However, the PP oxygen index is only about 18 percent, the PP is a flammable material, a large amount of heat and smoke are released in the combustion process, and the PP is accompanied by molten drops, so that surrounding articles are easily ignited, and great damage is caused to life and property. In order to avoid fire, flame retardancy is required in many fields, and a halogen flame retardant has an excellent flame retardant effect, but generates a large amount of smoke and corrosive gas during combustion, thereby causing harm to human health. The halogen-free flame retardant has low smoke, low toxicity, environmental protection and high efficiency, is an ideal flame retardant, but the existing flame retardant has great influence on the mechanical properties of PP.
Disclosure of Invention
In view of the above, the present invention provides a halogen-free flame retardant material and a preparation method thereof, and the halogen-free flame retardant material provided by the present invention has good mechanical properties, low cost and environmental protection.
The invention provides a halogen-free flame-retardant material which comprises the following components in parts by weight:
Figure BDA0003734929940000011
Figure BDA0003734929940000021
preferably, the flame retardant PP particles comprise, by weight:
Figure BDA0003734929940000022
preferably, the antistatic agent is selected from at least one of lauric diethanolamide, N-bis (hydroxyethyl) cocoamide;
the lubricant is selected from one or more of ethylene bis stearamide, calcium stearate and EBS.
Preferably, the nitrogen-phosphorus flame retardant is a piperazine pyrophosphate composite flame retardant;
the anti-dripping agent is polytetrafluoroethylene anti-dripping agent.
Preferably, the modified hollow glass beads are modified by azido trimethoxy silane coupling agent;
the modified basalt fiber is a basalt fiber modified by an azido trimethoxy silane coupling agent.
The invention provides a preparation method of the halogen-free flame retardant material, which comprises the following steps:
and mixing the flame-retardant PP particles, the modified basalt fibers, the modified hollow glass microspheres, the compatilizer and the azido trimethoxy silane coupling agent, and then extruding and granulating to obtain the halogen-free flame-retardant material.
Preferably, the preparation method of the flame retardant PP particles comprises the following steps:
and mixing PP resin, a nitrogen-phosphorus flame retardant, an anti-dripping agent, an antioxidant, a lubricant, an antistatic agent and a light stabilizer, and then extruding and granulating to obtain the flame-retardant PP particles.
Preferably, the temperature of a machine barrel in the extrusion granulation process is 180-200 ℃, and the temperature of a machine head is 170-180 ℃.
Preferably, the temperature of a cylinder in the extrusion granulation process is 170-190 ℃, and the temperature of a machine head is 170-180 ℃.
Preferably, the preparation method of the modified hollow glass bead comprises the following steps:
soaking hollow glass beads in an azido trimethoxy silane coupling agent and then drying to obtain modified hollow glass beads;
the preparation method of the modified basalt fiber comprises the following steps:
and (3) soaking the basalt fiber in an azido trimethoxy silane coupling agent, and drying to obtain the modified basalt fiber.
The invention provides a halogen-free flame-retardant PP material capable of replacing flame-retardant ABS and a preparation method thereof, effectively solves the problems that in the prior art, ABS materials are high in price and not environment-friendly, and mechanics is remarkably reduced, and also solves the problem that the existing flame retardant still has great influence on the mechanical properties of PP.
The invention adopts a two-step method to prepare a halogen-free flame retardant PP material which can replace flame retardant ABS, and in the first step, PP resin, a flame retardant and other additives are mixed and extruded and granulated in a double screw extruder, so that the raw materials can be uniformly mixed to obtain uniformly dispersed flame retardant PP particles; and secondly, uniformly mixing the flame-retardant PP particles obtained in the first step with the modified basalt fibers, the modified hollow glass beads, the compatilizer and the azido trimethoxy silane coupling agent, adding the mixture into a single-screw extruder, and extruding and granulating to obtain the uniformly dispersed halogen-free flame-retardant PP material capable of replacing flame-retardant ABS.
On one hand, in the invention, the azido trimethoxy silane coupling agent is interpenetrated in the gaps between PP and the modified basalt fiber and the modified hollow glass bead filler to play a role for a long time, thereby improving the size stability of the product; on the other hand, the structure of the modified hollow glass beads and the modified basalt fibers is prevented from being damaged under the shearing action of the double screws, the impact resistance, the temperature resistance and the flame retardance of the product are improved, and the phenomenon of fiber exposure can be eliminated by adding the modified hollow glass beads.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a halogen-free flame-retardant material which comprises the following components in parts by weight:
Figure BDA0003734929940000031
Figure BDA0003734929940000041
in the present invention, the weight part of the flame retardant PP (polypropylene) particles is preferably 65 to 75 parts, more preferably 68 to 72 parts, and most preferably 70 parts.
In the present invention, the flame retardant PP particles preferably include, in parts by weight:
Figure BDA0003734929940000042
in the present invention, the weight part of the PP resin is preferably 40 to 60 parts, more preferably 45 to 55 parts, and most preferably 50 parts.
In the invention, the PP resin is preferably selected from homopolymerized PP, copolymerized PP or blended PP, and more preferably selected from one or more of T30S, Z S, SP179, K8003 and S1003.
In the invention, the weight part of the nitrogen-phosphorus flame retardant is preferably 12 to 18 parts, more preferably 14 to 16 parts, and most preferably 15 parts.
In the present invention, the nitrogen-phosphorus flame retardant is preferably a piperazine pyrophosphate-based composite flame retardant.
In the present invention, the anti-dripping agent is preferably 0.2 to 0.7 part by weight, more preferably 0.3 to 0.6 part by weight, and most preferably 0.4 to 0.5 part by weight.
In the present invention, the anti-dripping agent is preferably a polytetrafluoroethylene anti-dripping agent.
In the present invention, the azido trimethoxysilane coupling agent is preferably present in the flame retardant PP particles in an amount of 3 to 4 parts by weight, more preferably 3.5 parts by weight.
In the present invention, the antioxidant is preferably 0.2 to 0.8 part by weight, more preferably 0.3 to 0.6 part by weight, and most preferably 0.4 to 0.5 part by weight.
In the invention, the antioxidant is preferably selected from one or more of antioxidant 1010, antioxidant 168, antioxidant 245, antioxidant 1098, DLTP and DSTP.
In the present invention, the weight part of the lubricant is preferably 1.2 to 1.8 parts, more preferably 1.4 to 1.6 parts, and most preferably 1.5 parts.
In the present invention, the lubricant is preferably selected from one or more of ethylene bis stearamide, calcium stearate, and EBS.
In the present invention, the light stabilizer is preferably 0.6 to 0.9 part by weight, more preferably 0.7 to 0.8 part by weight.
In the present invention, the light stabilizer is preferably selected from one or more of BAD, OPS, UV-327 and UV-326.
In the present invention, the weight part of the antistatic agent is preferably 0.6 to 0.9 part, more preferably 0.7 to 0.8 part.
In the present invention, the antistatic agent is preferably at least one selected from lauric acid diethanolamide, N-bis (hydroxyethyl) cocamide.
In the present invention, the method for preparing the flame retardant PP particles preferably comprises:
and mixing PP resin, a nitrogen-phosphorus flame retardant, an anti-dripping agent, an antioxidant, a lubricant, an antistatic agent and a light stabilizer, and then extruding and granulating to obtain the flame-retardant PP particles.
In the present invention, the mixing is preferably uniform; the extrusion granulation in the process of preparing the flame-retardant PP particles is preferably carried out in a double-screw extruder; the cylinder temperature in the extrusion granulation process of the double-screw extruder is preferably 180-200 ℃, more preferably 185-195 ℃, and most preferably 190 ℃; the head temperature is preferably 170 to 180 deg.C, more preferably 175 deg.C.
In the present invention, the modified basalt fiber is preferably 11 to 14 parts by weight, more preferably 12 to 13 parts by weight.
In the invention, the modified basalt fiber is preferably the basalt fiber modified by azido trimethoxy silane coupling agent; the preparation method of the modified basalt fiber preferably comprises the following steps:
and (3) soaking the basalt fiber in an azido trimethoxy silane coupling agent, and drying to obtain the modified basalt fiber.
In the invention, the dipping temperature in the process of preparing the modified basalt fiber is preferably 70-80 ℃, and more preferably 75 ℃; the time for immersion is preferably 5 to 10 minutes, more preferably 6 to 9 minutes, most preferably 7 to 8 minutes; the drying temperature is preferably 110-130 ℃, more preferably 115-125 ℃, and most preferably 120 ℃; the drying time is preferably 5 to 10 minutes, more preferably 6 to 9 minutes, and most preferably 7 to 8 minutes; drying is preferably carried out in an oven.
In the present invention, the modified hollow glass bead is preferably 11 to 14 parts by weight, more preferably 12 to 13 parts by weight.
In the invention, the modified hollow glass bead is preferably a hollow glass bead modified by an azido trimethoxy silane coupling agent; the preparation method of the modified hollow glass bead preferably comprises the following steps:
and (3) soaking the hollow glass beads in an azido trimethoxy silane coupling agent, and drying to obtain the modified hollow glass beads.
In the invention, the dipping temperature in the process of preparing the modified hollow glass bead is preferably 70-80 ℃, and more preferably 75 ℃; the time for immersion is preferably 5 to 10 minutes, more preferably 6 to 9 minutes, most preferably 7 to 8 minutes; the drying temperature is preferably 110-130 ℃, more preferably 115-125 ℃, and most preferably 120 ℃; the drying time is preferably 5 to 10 minutes, more preferably 6 to 9 minutes, and most preferably 7 to 8 minutes; drying is preferably carried out in an oven.
In the present invention, the weight part of the compatibilizer is preferably 2 to 4 parts, and more preferably 3 parts.
In the present invention, the compatibilizer is preferably at least one selected from the group consisting of PP-g-ST and PP-g-MAH.
In the invention, the weight portion of the azido trimethoxy silane coupling agent in the halogen-free flame retardant material is preferably 3 to 4 portions, and more preferably 3.5 portions.
The invention provides a preparation method of the halogen-free flame retardant material, which comprises the following steps:
and mixing the flame-retardant PP particles, the modified basalt fibers, the modified hollow glass beads, the compatilizer and the azido trimethoxy silane coupling agent, and then extruding and granulating to obtain the halogen-free flame-retardant material.
In the present invention, the mixing is preferably uniform; the extrusion granulation in the process of preparing the halogen-free flame retardant material is preferably carried out in a single-screw extruder; the barrel temperature in the extrusion process of the single-screw extruder is preferably 170-190 ℃, more preferably 175-185 ℃, and most preferably 180 ℃; the head temperature is preferably 170 to 180 deg.C, more preferably 175 deg.C.
The invention adopts a two-step method to prepare a halogen-free flame retardant PP material which can replace flame retardant ABS, and in the first step, PP resin, a flame retardant and other additives are mixed and extruded and granulated in a double screw extruder, so that the raw materials can be uniformly mixed to obtain uniformly dispersed flame retardant PP particles; and secondly, uniformly mixing the flame-retardant PP particles obtained in the first step with the modified basalt fibers, the modified hollow glass beads, the compatilizer and the azido trimethoxy silane coupling agent, adding the mixture into a single-screw extruder, and extruding and granulating to obtain the uniformly dispersed halogen-free flame-retardant PP material capable of replacing flame-retardant ABS. In the invention, on one hand, the azido trimethoxy silane coupling agent is interpenetrated in the gaps between PP and the modified basalt fiber and the modified hollow glass bead filler to play a role for a long time, thereby improving the size stability of the product; on the other hand, the structure of the modified hollow glass beads and the modified basalt fibers is prevented from being damaged under the shearing action of the double screws, the impact resistance and the temperature resistance and the flame retardance of the product are improved, and the phenomenon of fiber exposure can be eliminated by adding the modified hollow glass beads.
Comparative example 1
The flame-retardant ABS particles comprise the following components in parts by weight: 60 parts of Jilin petrochemical ABS 0215A, 12 parts of national Qiao Gao rubber powder 60P, 18 parts of decabromodiphenyl ether, 6 parts of antimony trioxide, 0.2 part of antioxidant, 168.1 part of antioxidant, 1 part of EBS (N, N' -ethylene bis stearamide) and 0.5 part of UV-327.
The preparation method comprises the following steps: uniformly mixing ABS resin with decabromodiphenyl ether, antimony trioxide, anti-dripping agent, toughening agent, antioxidant, EBS and UV-327, and extruding and granulating by using a double-screw extruder at the cylinder temperature of 200-220 ℃ and the head temperature of 180 ℃ to obtain the flame-retardant ABS particles.
Comparative example 2
The flame-retardant ABS particles comprise the following components in parts by weight: jilin petrochemical ABS 0215A 54 parts, national Qiao Gao rubber powder 60P 14 parts, pentabromodiphenyl ether 20 parts, antimony trioxide 10 parts, antioxidant 1010.2 parts, antioxidant 168.1 parts, ethylene bis-oleamide 2 parts, and UV-327 0.5 part.
The preparation method comprises the following steps: uniformly mixing ABS resin with pentabromobiphenyl ether, antimony trioxide, high rubber powder, an antioxidant, ethylene bisoleic acid amide and UV-327, and extruding and granulating by a double-screw extruder at the cylinder temperature of 200-220 ℃ and the head temperature of 180 ℃ to obtain the flame-retardant ABS particles.
Comparative example 3
The flame-retardant PP particles comprise the following components in parts by weight: 78 parts of Yanshan petrochemical PP K7726H, 18 parts of pestle EPFR-100A, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of UV-327 and 0.5 part of N, N-di (hydroxyethyl) cocamide.
The preparation method comprises the following steps: K7726H, EPFR-100A, an antioxidant, EBS, N-di (hydroxyethyl) cocoamide and UV-327 are uniformly mixed, and extruded and granulated by a double-screw extruder at the cylinder temperature of 190 ℃ and the head temperature of 175 ℃ to obtain the flame-retardant PP granules.
Example 1
The halogen-free flame retardant material comprises the following components in parts by weight: 52 parts of PP resin, 16 parts of nitrogen-phosphorus flame retardant, 0.5 part of anti-dripping agent, 5 parts of PP-g-MAH, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of light stabilizer, 0.5 part of N, N-di (hydroxyethyl) cocamide, 10 parts of modified basalt fiber, 10 parts of modified hollow glass microsphere and 3 parts of azido trimethoxy silane coupling agent.
The preparation method comprises the following steps:
the PP resin, a nitrogen and phosphorus flame retardant, an anti-dripping agent, an antioxidant, EBS, N-di (hydroxyethyl) cocoamide and a light stabilizer are uniformly mixed, and extruded and granulated by a double screw extruder at the cylinder temperature of 190 ℃ and the head temperature of 175 ℃ to obtain the flame-retardant PP granules.
Uniformly mixing the flame-retardant PP particles, modified basalt fibers, modified hollow glass microspheres, PP-g-MAH and azido trimethoxy silane coupling agent, adding the mixture into a single-screw extruder, and extruding and granulating at the temperature of 180 ℃ of a machine barrel and 190 ℃ of a machine head to obtain a halogen-free flame-retardant material;
the preparation method of the modified basalt fiber comprises the following steps: and (3) soaking the basalt fiber in an azido trimethoxy silane coupling agent, and drying to obtain the modified basalt fiber. The dipping temperature in the process of preparing the modified basalt fiber is 75 ℃; the dipping time is 7 to 8 minutes; the drying temperature is 120 ℃; the drying time is 7 to 8 minutes; drying treatment is carried out in an oven.
The preparation method of the modified hollow glass bead comprises the following steps: and (3) soaking the hollow glass beads in an azido trimethoxy silane coupling agent, and drying to obtain the modified hollow glass beads. The dipping temperature in the process of preparing the modified hollow glass microspheres is 75 ℃; the dipping time is 7 to 8 minutes; the drying temperature is 120 ℃; the drying time is 7 to 8 minutes; drying treatment is carried out in an oven.
Example 2
The halogen-free flame retardant material comprises the following components in parts by weight: 50 parts of PP resin, 18 parts of nitrogen-phosphorus flame retardant, 0.5 part of anti-dripping agent, 5 parts of PP-g-MAH, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of light stabilizer, 0.5 part of N, N-bis (hydroxyethyl) cocamide, 10 parts of modified basalt fiber, 10 parts of modified hollow glass microsphere and 3 parts of azido trimethoxy silane coupling agent.
The preparation method is the same as example 1.
Example 3
The halogen-free flame retardant material comprises the following components in parts by weight: 41 parts of PP resin, 20 parts of nitrogen-phosphorus flame retardant, 0.5 part of anti-dripping agent, 5 parts of PP-g-MAH, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of light stabilizer, 0.5 part of N, N-di (hydroxyethyl) cocamide, 10 parts of modified basalt fiber, 10 parts of modified hollow glass microsphere and 3 parts of azido trimethoxy silane coupling agent.
The preparation method is the same as example 1.
Example 4
The halogen-free flame retardant material comprises the following components in parts by weight: 49 parts of PP resin, 18 parts of nitrogen and phosphorus flame retardant, 0.5 part of anti-dripping agent, 5 parts of PP-g-MAH, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of light stabilizer, 0.5 part of N, N-di (hydroxyethyl) cocamide, 10 parts of modified basalt fiber, 11 parts of modified hollow glass microsphere and 3.5 parts of azido trimethoxy silane coupling agent.
The preparation method is the same as example 1.
Example 5
The halogen-free flame retardant material comprises the following components in parts by weight: 47 parts of PP resin, 18 parts of nitrogen-phosphorus flame retardant, 0.5 part of anti-dripping agent, 5 parts of PP-g-MAH, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of light stabilizer, 0.5 part of N, N-di (hydroxyethyl) cocamide, 10 parts of modified basalt fiber, 12 parts of modified hollow glass microsphere and 4 parts of azido trimethoxy silane coupling agent.
The preparation method is the same as example 1.
Example 6
The halogen-free flame retardant material comprises the following components in parts by weight: 46 parts of PP resin, 18 parts of nitrogen-phosphorus flame retardant, 0.5 part of anti-dripping agent, 5 parts of PP-g-MAH, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of light stabilizer, 0.5 part of N, N-bis (hydroxyethyl) cocamide, 10 parts of modified basalt fiber, 13 parts of modified hollow glass microsphere and 4 parts of azido trimethoxy silane coupling agent.
The preparation method is the same as example 1.
Example 7
The halogen-free flame retardant material comprises the following components in parts by weight: 43 parts of PP resin, 18 parts of nitrogen-phosphorus flame retardant, 0.5 part of anti-dripping agent, 5 parts of PP-g-MAH, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of EBS, 0.5 part of light stabilizer, 0.5 part of N, N-di (hydroxyethyl) cocamide, 10 parts of modified basalt fiber, 15 parts of modified hollow glass microsphere and 5 parts of azido trimethoxy silane coupling agent.
The preparation method is the same as example 1.
Performance detection
The products prepared in the examples and comparative examples were tested for their performance according to the test methods in the following table, with the following results:
Figure BDA0003734929940000101
the detection results show that the halogen-free flame-retardant PP material prepared in the embodiment is obviously superior to the flame-retardant material of the comparative example in the aspects of thermal deformation temperature, temperature resistance, flame resistance, impact resistance and the like. The flame-retardant PP plastic prepared by the embodiment of the invention achieves V-0 of flame-retardant UL94 grade, has excellent flame-retardant performance and can pass a water resistance test of UL 746C; the tensile strength is above 44MPa, and the highest tensile strength can reach 54MPa; the bending strength is over 55MPa, and the highest bending strength can reach 64MPa; the IZOD notch impact strength is 12kJ/m 2 Above that, the maximum can be 17kJ/m 2 (ii) a The thermal deformation temperature is far higher than that of the flame-retardant ABS, the glow wire temperature is far higher than that of the flame-retardant ABS, and the flame-retardant ABS has good temperature resistance and flame retardance.
According to the detection results, the addition of the modified basalt fibers and the modified hollow glass beads can improve the mechanical property of the halogen-free flame-retardant PP material, improve the dimensional stability of the PP material, and effectively improve the temperature resistance and flame retardance of the halogen-free flame-retardant PP material; in addition, the addition of the modified hollow glass beads can eliminate the phenomenon of fiber exposure.
The new material provided by the invention can replace flame-retardant ABS in a certain range, and has obvious advantages in the aspects of thermal deformation temperature, temperature resistance, flame retardance and impact resistance, thereby not only solving the environmental protection problem of the flame-retardant ABS, but also reducing the cost.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form, material, composition of matter, substance, method or process may be made without departing from the true spirit and scope of the invention as defined in the appended claims to adapt it to the objective, spirit and scope of the application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (10)

1. A halogen-free flame retardant material comprises the following components in parts by weight:
Figure FDA0003734929930000011
2. the halogen-free flame retardant material of claim 1, wherein the flame retardant PP particles comprise, in parts by weight:
Figure FDA0003734929930000012
3. halogen free flame retardant material according to claim 2, characterized in that the antistatic agent is selected from at least one of lauric diethanolamide, N-bis (hydroxyethyl) cocamide;
the lubricant is selected from one or more of ethylene bis stearamide, calcium stearate and EBS.
4. The halogen-free flame retardant material according to claim 2, wherein the nitrogen-phosphorus flame retardant is a piperazine pyrophosphate-based composite flame retardant;
the anti-dripping agent is polytetrafluoroethylene anti-dripping agent.
5. The halogen-free flame retardant material according to claim 1, wherein the modified hollow glass microspheres are hollow glass microspheres modified by an azido-trimethoxysilane coupling agent;
the modified basalt fiber is modified by azido trimethoxy silane coupling agent.
6. A method for preparing the halogen-free flame retardant material of claim 1, comprising:
and mixing the flame-retardant PP particles, the modified basalt fibers, the modified hollow glass beads, the compatilizer and the azido trimethoxy silane coupling agent, and then extruding and granulating to obtain the halogen-free flame-retardant material.
7. The method according to claim 6, characterized in that the method for preparing flame retardant PP particles comprises:
and mixing PP resin, a nitrogen-phosphorus flame retardant, an anti-dripping agent, an antioxidant, a lubricant, an antistatic agent and a light stabilizer, and then extruding and granulating to obtain the flame-retardant PP particles.
8. The method of claim 6, wherein the barrel temperature during the extrusion granulation process is 180-200 ℃ and the head temperature is 170-180 ℃.
9. The method of claim 7, wherein the barrel temperature during the extrusion granulation process is 170-190 ℃ and the head temperature is 170-180 ℃.
10. The method according to claim 6, wherein the modified hollow glass microsphere is prepared by a method comprising:
soaking hollow glass beads in an azido trimethoxy silane coupling agent and then drying to obtain modified hollow glass beads;
the preparation method of the modified basalt fiber comprises the following steps:
and (3) soaking the basalt fiber in an azido trimethoxy silane coupling agent, and drying to obtain the modified basalt fiber.
CN202210794063.3A 2022-07-07 2022-07-07 Halogen-free flame-retardant material and preparation method thereof Pending CN115386162A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103467851A (en) * 2013-09-11 2013-12-25 成都硕屋科技有限公司 Halogen-free flame-retardant PP (polypropylene) fiber material capable of replacing flame-retardant ABS (acrylonitrile-butadiene-styrene) and preparation method of halogen-free flame-retardant PP fiber material
CN108530848A (en) * 2018-04-25 2018-09-14 横店集团得邦工程塑料有限公司 High thermal deformation basalt fibre enhancing halogen-free flameproof PET material and preparation method thereof
CN110283384A (en) * 2019-07-17 2019-09-27 苏州禾润昌新材料有限公司 A kind of high glaze high-strength basalt reinforced polypropylene compound material and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103467851A (en) * 2013-09-11 2013-12-25 成都硕屋科技有限公司 Halogen-free flame-retardant PP (polypropylene) fiber material capable of replacing flame-retardant ABS (acrylonitrile-butadiene-styrene) and preparation method of halogen-free flame-retardant PP fiber material
CN108530848A (en) * 2018-04-25 2018-09-14 横店集团得邦工程塑料有限公司 High thermal deformation basalt fibre enhancing halogen-free flameproof PET material and preparation method thereof
CN110283384A (en) * 2019-07-17 2019-09-27 苏州禾润昌新材料有限公司 A kind of high glaze high-strength basalt reinforced polypropylene compound material and preparation method

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