CN110014696B - High-strength flame-retardant polypropylene pipe and preparation method thereof - Google Patents

High-strength flame-retardant polypropylene pipe and preparation method thereof Download PDF

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CN110014696B
CN110014696B CN201910155278.9A CN201910155278A CN110014696B CN 110014696 B CN110014696 B CN 110014696B CN 201910155278 A CN201910155278 A CN 201910155278A CN 110014696 B CN110014696 B CN 110014696B
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parts
flame retardant
polypropylene
poly
nucleating agent
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CN110014696A (en
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王军
杨浩佳
陈玉
汪磊
李白千
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Foshan Rifeng Enterprise Co Ltd
Rifeng Enterprise Group Co Ltd
Rifeng Technology Co Ltd
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Foshan Rifeng Enterprise Co Ltd
Rifeng Enterprise Group Co Ltd
Rifeng Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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    • B32—LAYERED PRODUCTS
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    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • 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
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to a high-strength flame-retardant polypropylene pipe and a preparation method thereof. The high-strength flame-retardant polypropylene pipe comprises an inner layer, a middle layer and an outer layer which are sequentially laminated from inside to outside; the inner layer is prepared from the following raw material components in parts by weight: polypropylene A: 100 parts of (A); color master batch A: 0-2 parts of a solvent; flame retardant A: 2-5 parts; alpha nucleating agent A: 0.01-0.2 parts; the middle layer is prepared from the following raw material components in parts by weight: polypropylene B: 100 parts of (A); glass fiber: 20-30 parts of a solvent; PP-g-MAH: 5-10 parts; and (3) a flame retardant B: 5-10 parts; alpha nucleating agent B: 0.01-0.2 parts; the outer layer is prepared from the following raw material components in parts by weight: polypropylene C: 100 parts of (A); color master batch C: 2-5 parts; and (3) a flame retardant C: 10-20 parts; alpha nucleating agent C: 0.01-0.2 portion. The polypropylene pipe has high strength and excellent flame retardance.

Description

High-strength flame-retardant polypropylene pipe and preparation method thereof
Technical Field
The invention relates to a pipe material, in particular to a high-strength flame-retardant polypropylene pipe and a preparation method thereof.
Background
At present, the fire fighting pipes applied to civil use and industry are mainly nodular cast iron pipes and galvanized steel pipes, and although the metal pipes have high compressive strength and good fireproof performance, the metal pipes are easy to corrode and break, have short service life and are troublesome in pipeline replacement. The polypropylene pipe not only has the advantages of light weight, no toxicity, corrosion resistance, higher strength, long service life, convenient installation, reliable connection, recyclability and the like, but also is widely applied to civil and industrial water supply and drainage as a novel green building energy-saving material.
However, the conventional polypropylene pipe has no flame retardancy, and cannot perform a function of extinguishing a fire in time in case of a fire, and the result is not obvious, so that the conventional polypropylene pipe is difficult to be used as a fire-fighting pipe. Research attempts are made to add flame retardant into the polypropylene pipe, but the flame retardant effect is not ideal, and the addition of the flame retardant easily causes the change of the processing performance of the polypropylene pipe and influences the strength of the polypropylene pipe.
Disclosure of Invention
Based on this, there is a need to provide a high strength flame retardant polypropylene tube. The polypropylene pipe has high strength and excellent flame retardance, and can be used as a fire fighting pipe.
A high-strength flame-retardant polypropylene pipe comprises an inner layer, a middle layer and an outer layer which are sequentially laminated from inside to outside;
the inner layer is prepared from the following raw material components in parts by weight:
polypropylene A: 100 parts of (A); color master batch A: 0-2 parts of a solvent; flame retardant A: 2-5 parts; alpha nucleating agent A: 0.01-0.2 parts;
the intermediate layer is prepared from the following raw material components in parts by weight:
polypropylene B: 100 parts of (A); glass fiber: 20-30 parts of a solvent; PP-g-MAH: 5-10 parts; and (3) a flame retardant B: 5-10 parts; alpha nucleating agent B: 0.01-0.2 parts;
the outer layer is prepared from the following raw material components in parts by weight:
polypropylene C: 100 parts of (A); color master batch C: 2-5 parts; and (3) a flame retardant C: 10-20 parts; alpha nucleating agent C: 0.01-0.2 parts;
wherein the flame retardant A, the flame retardant B and the flame retardant C are respectively selected from one or more of polyethylene diamine phosphorylphenyl ester, poly 4, 4-diaminobiphenyl phenyl methane dichlorophosphate, poly 4, 4-diaminobiphenyl sulfo-dichlorophosphate and poly 4, 4-diaminodiphenyl ether dichlorophosphate.
In one embodiment, the inner layer is prepared from the following raw material components in parts by weight:
polypropylene A: 100 parts of (A); color master batch A: 0-2 parts of a solvent; flame retardant A: 3-4 parts; alpha nucleating agent A: 0.1-0.2 parts;
the intermediate layer is prepared from the following raw material components in parts by weight:
polypropylene B: 100 parts of (A); glass fiber: 20-25; PP-g-MAH: 6-8 parts; and (3) a flame retardant B: 8-10 parts; alpha nucleating agent B: 0.1-0.2 parts;
the outer layer is prepared from the following raw material components in parts by weight:
polypropylene C: 100 parts of (A); color master batch C: 2-5 parts; and (3) a flame retardant C: 15-18 parts; alpha nucleating agent C: 0.1 to 0.2 portion.
In one embodiment, the flame retardant A, the flame retardant B and the flame retardant C are respectively selected from any one of:
the weight ratio is 0-1: 0-2: 1-3: 0-4 parts of poly (ethylenediamine-phosphorylphenyl ester), poly (4, 4-diaminodiphenyl phenylmethane) dichlorophosphate, poly (4, 4-diaminodiphenyl sulfodichlorophosphate) and poly (4, 4-diaminodiphenyl ether) dichlorophosphate.
In one embodiment, the flame retardant A, the flame retardant B and the flame retardant C are respectively selected from any one of:
the weight ratio is 1: 1.5-2: 1.5-2 parts of poly (ethylenediamine-phosphorylphenyl ester), poly (4, 4-diaminodiphenyl phenylmethane-dichlorophosphate) and poly (4, 4-diaminodiphenyl sulfodichlorophosphate); or the like, or, alternatively,
the weight ratio is 0.5-1.5: 0.5-1.5: 0.5 to 1.5 parts of poly-4, 4-diaminodiphenyl phenyl methane dichlorophosphate, poly-4, 4-diaminodiphenyl sulfo-dichlorophosphate and poly-4, 4-diaminodiphenyl ether dichlorophosphate.
In one embodiment, the PP-g-MAH has a grafting yield of 3% to 5%.
In one embodiment, the alpha nucleating agents a and C are each optionally organic salts.
In one embodiment, the glass fiber has a length of 0.3-0.6 mm.
In one embodiment, the thickness ratio of the inner layer, the middle layer and the outer layer is 1-2: 2-4: 1-2.
The invention also provides a preparation method of the high-strength flame-retardant polypropylene pipe, which comprises the following steps:
mixing the polypropylene A, the color master batch A, the flame retardant A and the alpha nucleating agent A, and then granulating through an extruder to obtain a formula material of the outer layer;
mixing the polypropylene B, the glass fiber, the PP-g-MAH, the flame retardant B and the alpha nucleating agent B, and then granulating through an extruder to obtain a formula material of the middle layer;
mixing the polypropylene C, the color master batch C, the flame retardant C and the alpha nucleating agent C, and then granulating through an extruder to obtain a formula material of the middle layer;
and co-extruding the formula material of the inner layer, the formula material of the middle layer and the formula material of the outer layer to form the inner layer, the middle layer and the outer layer which are sequentially laminated from inside to outside, thus obtaining the composite material.
In one embodiment, the granulation method comprises the following steps: a double-screw extruder is adopted, and the processing temperature is 170-200 ℃; the processing temperature of the co-extrusion is 180-220 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the high-strength flame-retardant polypropylene pipe adopts a three-layer pipe structure, raw materials of all layers are reasonably prepared, and the inner layer, the middle layer and the outer layer adopt certain flame retardants to be matched with the alpha nucleating agent, so that the alpha nucleating agent can change the crystallization behavior of polypropylene, improve the thermal deformation temperature of the polypropylene, increase the rigidity of the pipe, reduce the linear expansion coefficient of the pipe, and ensure that the flame retardants can be uniformly distributed in a polypropylene system to obtain excellent flame retardant performance; the middle layer is made of glass fiber reinforced polypropylene, and PP-g-MAH is adopted to ensure good compatibility among all components of the system, ensure the strength of the pipe and optimize the flame retardant property of the pipe. In conclusion, the polypropylene pipe has high strength, excellent flame retardance and low linear expansion coefficient, and can be used as a fire fighting pipe and applied to the field of fire fighting.
The preparation method of the high-strength flame-retardant polypropylene pipe is simple to operate, easy to control and convenient for large-scale production and application.
Drawings
FIG. 1 is a schematic structural view of a high strength flame retardant polypropylene tube as described in example 1;
wherein, 1-inner layer, 2-middle layer and 3-outer layer.
Detailed Description
The high-strength flame-retardant polypropylene tube and the method for preparing the same according to the present invention will be described in further detail with reference to the following examples.
The flame retardant used in the embodiment of the invention is poly (ethylenediamine phosphorylphenyl ester), poly (4, 4-diaminodiphenyl phenylmethane) dichlorophosphate, poly (4, 4-diaminodiphenyl sulfodichlorophosphate) and poly (4, 4-diaminodiphenyl ether) dichlorophosphate, which are purchased from Beijing limited flame retardant science and technology;
the grafting rate of the adopted PP-g-MAH is 3-5 percent; the length of the glass fiber is 0.3-0.6 mm;
the alpha nucleating agent is an organic salt nucleating agent and is purchased from Nap-50.
Example 1
The high-strength flame-retardant polypropylene pipe of the present embodiment has a structure shown in fig. 1, and includes an inner layer 1, an intermediate layer 2, and an outer layer 3 stacked in this order from inside to outside, in a specification S3.240 × 5.5. The thickness of the outer layer 3 is 1.5mm, the thickness of the middle layer 2 is 2.0mm, the thickness of the inner layer 1 is 2.0mm, the outer layer is red, the middle layer is colorless, and the inner layer is white. The preparation method comprises the following steps:
(1) the PP resin, the flame retardant, the color master batch and the alpha nucleating agent are mixed according to the mass part ratio of 100: 15: 3: 0.15, fully stirring for 5-10min by a high-speed stirrer, and then extruding and granulating by a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the outer layer formula material. Wherein the flame retardant is polyethylene phosphoroamidite, poly 4, 4-diaminodiphenyl phenyl methane dichlorophosphate and poly 4, 4-diaminodiphenyl sulfo dichlorophosphate according to the weight ratio of 1: 2: and 2, configuring in proportion.
(2) PPR resin, glass fiber, PP-g-MAH, flame retardant and alpha nucleating agent are mixed according to the mass part ratio of 100: 25: 8: 10: 0.15, fully stirring for 5-10min by a high-speed stirrer, and then extruding and granulating by a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the intermediate layer formula material. Wherein the flame retardant is polyethylene diamine phosphoryl phenyl ester, poly 4, 4-diaminodiphenyl phenyl methane dichloro phosphate and poly 4, 4-diaminodiphenyl sulfo dichloro phosphate according to the weight ratio of 1: 2: and 2, configuring in proportion.
(3) PPR resin, color master batch, flame retardant and alpha nucleating agent are mixed according to the mass part ratio of 100: 2: 4: 0.15, fully stirring for 5-10min by a high-speed stirrer, and then extruding and granulating by a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the outer layer formula material. Wherein the flame retardant is polyethylene diamine phosphoryl phenyl ester, poly 4, 4-diaminodiphenyl phenyl methane dichloro phosphate and poly 4, 4-diaminodiphenyl sulfo dichloro phosphate according to the weight ratio of 1: 2: and 2, configuring in proportion.
(4) And (3) configuring a three-layer co-extrusion die by using three single-screw extruders, feeding the formula materials of the layers into the extruders, respectively extruding the three layers, controlling the processing temperature at 180-220 ℃, and forming a pipe after vacuum sizing and cooling to obtain the high-strength flame-retardant polypropylene pipe.
The performance of the high-strength flame-retardant polypropylene pipe is tested as follows:
Figure BDA0001982698600000061
example 2
The high-strength flame-retardant polypropylene pipe of the embodiment, with the specification of S3.250 × 6.9, comprises an inner layer 1, an intermediate layer 2 and an outer layer 3 which are sequentially laminated from inside to outside. The outer thickness is 2.0mm, the intermediate level thickness is 2.5mm, the inlayer thickness is 2.4mm, outer red, the intermediate level is colourless, the inlayer is colourless. The preparation method comprises the following steps:
(1) the PP-RCT resin, the flame retardant and the color master batch are mixed according to the mass part ratio of 100: 18: 2, fully stirring for 5-10min by using a high-speed stirrer, and then extruding and granulating by using a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the outer layer formula material. Wherein the flame retardant is poly 4, 4-diaminodiphenyl phenyl methane dichlorophosphate, poly 4, 4-diaminodiphenyl sulfo-dichlorophosphate, poly 4, 4-diaminodiphenyl ether dichlorophosphate according to the weight ratio of 1: 1: 1 proportion configuration.
(2) The preparation method comprises the following steps of (1) mixing PP-RCT resin, glass fiber, PP-g-MAH and a flame retardant according to the mass part ratio of 100: 20: 6: 8, fully stirring for 5-10min by using a high-speed stirrer, and then extruding and granulating by using a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the intermediate layer formula material. Wherein the flame retardant is poly 4, 4-diaminodiphenyl phenyl methane dichlorophosphate, poly 4, 4-diaminodiphenyl sulfo-dichlorophosphate, poly 4, 4-diaminodiphenyl ether dichlorophosphate according to the weight ratio of 1: 1: 1 proportion configuration.
(3) The PP-RCT resin and the flame retardant are mixed according to the mass part ratio of 100: 3, fully stirring for 5-10min by using a high-speed stirrer, and then extruding and granulating by using a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the outer layer formula material. Wherein the flame retardant is poly 4, 4-diaminodiphenyl phenyl methane dichlorophosphate, poly 4, 4-diaminodiphenyl sulfo-dichlorophosphate, poly 4, 4-diaminodiphenyl ether dichlorophosphate according to the weight ratio of 1: 1: 1 proportion configuration.
(4) And (3) configuring a three-layer co-extrusion die by using three single-screw extruders, feeding the formula materials of the layers into the extruders, respectively extruding the three layers, controlling the processing temperature at 180-220 ℃, and forming a pipe after vacuum sizing and cooling to obtain the high-strength flame-retardant polypropylene pipe.
The performance of the high-strength flame-retardant polypropylene pipe is tested as follows:
Figure BDA0001982698600000071
example 3
The high-strength flame-retardant polypropylene pipe of the present embodiment has a structure shown in fig. 1, and includes an inner layer 1, an intermediate layer 2, and an outer layer 3 stacked in this order from inside to outside, in a specification S3.240 × 5.5. The thickness of the outer layer 3 is 1.5mm, the thickness of the middle layer 2 is 2.0mm, the thickness of the inner layer 1 is 2.0mm, the outer layer is red, the middle layer is colorless, and the inner layer is white. The preparation method comprises the following steps:
(1) the PP resin, the flame retardant, the color master batch and the alpha nucleating agent are mixed according to the mass part ratio of 100: 10: 5: 0.01, fully stirring for 5-10min by a high-speed stirrer, and then extruding and granulating by a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the outer layer formula material. Wherein the flame retardant is polyethylene phosphoroamidite, poly 4, 4-diaminodiphenyl phenyl methane dichlorophosphate and poly 4, 4-diaminodiphenyl sulfo dichlorophosphate according to the weight ratio of 1: 2: and 2, configuring in proportion.
(2) PPR resin, glass fiber, PP-g-MAH, flame retardant and alpha nucleating agent are mixed according to the mass part ratio of 100: 30: 10: 5: 0.01, fully stirring for 5-10min by a high-speed stirrer, and then extruding and granulating by a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the intermediate layer formula material. Wherein the flame retardant is polyethylene diamine phosphoryl phenyl ester, poly 4, 4-diaminodiphenyl phenyl methane dichloro phosphate and poly 4, 4-diaminodiphenyl sulfo dichloro phosphate according to the weight ratio of 1: 2: and 2, configuring in proportion.
(3) PPR resin, color master batch, flame retardant and alpha nucleating agent are mixed according to the mass part ratio of 100: 2: 5: 0.01, fully stirring for 5-10min by a high-speed stirrer, and then extruding and granulating by a double-screw extruder, wherein the processing temperature is controlled between 170 ℃ and 200 ℃ to obtain the outer layer formula material. Wherein the flame retardant is polyethylene diamine phosphoryl phenyl ester, poly 4, 4-diaminodiphenyl phenyl methane dichloro phosphate and poly 4, 4-diaminodiphenyl sulfo dichloro phosphate according to the weight ratio of 1: 2: and 2, configuring in proportion.
(4) And (3) configuring a three-layer co-extrusion die by using three single-screw extruders, feeding the formula materials of the layers into the extruders, respectively extruding the three layers, controlling the processing temperature at 180-220 ℃, and forming a pipe after vacuum sizing and cooling to obtain the high-strength flame-retardant polypropylene pipe.
The performance of the high-strength flame-retardant polypropylene pipe is tested as follows:
Figure BDA0001982698600000081
comparative example 1
The polypropylene pipe of the comparative example has the same raw materials and preparation method as example 1, except that: the flame retardant was replaced with morpholino thiourea.
The polypropylene pipe described above was tested for properties as follows:
Figure BDA0001982698600000091
the technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A high-strength flame-retardant polypropylene pipe is characterized by comprising an inner layer, a middle layer and an outer layer which are sequentially laminated from inside to outside;
the inner layer is prepared from the following raw material components in parts by weight:
polypropylene A: 100 parts of (A); color master batch A: 0-2 parts of a solvent; flame retardant A: 3-4 parts; alpha nucleating agent A: 0.1-0.2 parts;
the intermediate layer is prepared from the following raw material components in parts by weight:
polypropylene B: 100 parts of (A); glass fiber: 20-25; PP-g-MAH: 6-8 parts; and (3) a flame retardant B: 8-10 parts; alpha nucleating agent B: 0.1-0.2 parts;
the outer layer is prepared from the following raw material components in parts by weight:
polypropylene C: 100 parts of (A); color master batch C: 2-5 parts; and (3) a flame retardant C: 15-18 parts; alpha nucleating agent C: 0.1-0.2 parts;
wherein the flame retardant A, the flame retardant B and the flame retardant C are as follows:
the weight ratio is 1: 1.5-2: 1.5-2 parts of poly (ethylenediamine-phosphorylphenyl ester), poly (4, 4-diaminodiphenyl phenylmethane-dichlorophosphate) and poly (4, 4-diaminodiphenyl sulfodichlorophosphate); or the like, or, alternatively,
the weight ratio is 0.5-1.5: 0.5-1.5: 0.5 to 1.5 parts of poly-4, 4-diaminodiphenyl phenyl methane dichlorophosphate, poly-4, 4-diaminodiphenyl sulfo-dichlorophosphate and poly-4, 4-diaminodiphenyl ether dichlorophosphate.
2. The high strength, flame retardant polypropylene tube of claim 1 wherein the inner layer is made from the following raw material components in parts by weight:
polypropylene A: 100 parts of (A); color master batch A: 2 parts of (1); flame retardant A: 4 parts of a mixture; alpha nucleating agent A: 0.15 part;
the intermediate layer is prepared from the following raw material components in parts by weight:
polypropylene B: 100 parts of (A); glass fiber: 25; PP-g-MAH: 8 parts of a mixture; and (3) a flame retardant B: 10 parts of (A); alpha nucleating agent B: 0.15 part;
the outer layer is prepared from the following raw material components in parts by weight:
polypropylene C: 100 parts of (A); color master batch C: 3 parts of a mixture; and (3) a flame retardant C: 15 parts of (1); alpha nucleating agent C: 0.15 part.
3. The high strength, flame retardant polypropylene tube of claim 1 wherein the flame retardant a, flame retardant B and flame retardant C are in a weight ratio of 1: 2: 2 poly (ethylenediamine phosphorylphenyl ester), poly (4, 4-diaminodiphenyl phenylmethane dichlorophosphate) and poly (4, 4-diaminodiphenyl sulfodichlorophosphate).
4. The high strength, flame retardant polypropylene tube of claim 1 wherein the flame retardant a, flame retardant B and flame retardant C are in a weight ratio of 1: 1: 1 of poly-4, 4-diaminodiphenyl phenylmethane dichlorophosphate, poly-4, 4-diaminodiphenyl sulfodichlorophosphate and poly-4, 4-diaminodiphenyl ether dichlorophosphate.
5. The high strength, flame retardant polypropylene tube of claim 1 wherein the PP-g-MAH has a graft ratio of 3% to 5%.
6. The high strength, flame retardant polypropylene tube of claim 1 wherein the alpha nucleating agent a and the alpha nucleating agent C are each optionally selected from organic salts.
7. The high strength flame retardant polypropylene tube of any one of claims 1 to 5, wherein the glass fiber has a length of 0.3 to 0.6 mm.
8. The high strength, flame retardant polypropylene tube according to any one of claims 1 to 5 wherein the inner, middle and outer layers have a thickness ratio of 1 to 2: 2-4: 1-2.
9. The method for preparing a high strength flame retardant polypropylene tube according to any one of claims 1 to 8, comprising the steps of:
mixing the polypropylene A, the color master batch A, the flame retardant A and the alpha nucleating agent A, and then granulating through an extruder to obtain a formula material of the outer layer;
mixing the polypropylene B, the glass fiber, the PP-g-MAH, the flame retardant B and the alpha nucleating agent B, and then granulating through an extruder to obtain a formula material of the middle layer;
mixing the polypropylene C, the color master batch C, the flame retardant C and the alpha nucleating agent C, and then granulating through an extruder to obtain a formula material of the middle layer;
and co-extruding the formula material of the inner layer, the formula material of the middle layer and the formula material of the outer layer to form the inner layer, the middle layer and the outer layer which are sequentially laminated from inside to outside, thus obtaining the composite material.
10. The method for preparing the high-strength flame-retardant polypropylene tube according to claim 9, wherein the granulation method comprises the following steps: a double-screw extruder is adopted, and the processing temperature is 170-200 ℃; the processing temperature of the co-extrusion is 180-220 ℃.
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