CN109253320B - Multilayer composite pipe and preparation method thereof - Google Patents
Multilayer composite pipe and preparation method thereof Download PDFInfo
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- CN109253320B CN109253320B CN201810965499.8A CN201810965499A CN109253320B CN 109253320 B CN109253320 B CN 109253320B CN 201810965499 A CN201810965499 A CN 201810965499A CN 109253320 B CN109253320 B CN 109253320B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
- F16L9/121—Rigid pipes of plastics with or without reinforcement with three layers
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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
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/02—Protection of pipes or objects of similar shape against external or internal damage or wear against cracking or buckling
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/04—Protection of pipes or objects of similar shape against external or internal damage or wear against fire or other external sources of extreme heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
- F16L57/06—Protection of pipes or objects of similar shape against external or internal damage or wear against wear
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
- B29L2023/22—Tubes or pipes, i.e. rigid
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
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Abstract
The invention discloses a multilayer composite pipe and a preparation method thereof. The pipe is divided into an inner layer, a middle layer and an outer layer, wherein the inner layer is made of fluoroolefin polymer, the middle layer is made of polymer alloy containing a comb-shaped compatilizer, and the outer layer is made of random polyolefin. The pipe material adopts a three-layer co-extrusion one-step forming technology, the obtained pipe material has the advantages of low precipitation, tight interlayer combination, simple and convenient production process and the like, and on the basis, the pipe material also has the advantages of environmental protection, small precipitation and good chemical stability; the impact strength is high, the abrasion resistance is high, the creep resistance is high, and the mechanical strength and the toughness are good; the heat resistance is good, and the long-term use temperature is-20-100 ℃; smooth surface, small fluid resistance, outstanding oxygen resistance and other excellent qualities.
Description
Technical Field
The invention belongs to the technical field of pipes, and particularly relates to a multilayer composite pipe and a preparation method thereof.
Background
Polyvinylidene fluoride is a material with excellent performance, and has the advantages of environmental protection, small precipitation and good chemical stability; the impact strength is high, the abrasion resistance is high, the creep resistance is high, and the mechanical strength and the toughness are good; the heat resistance is good, the flame retardance is good, and the long-term use temperature is-40-150 ℃; the polyvinylidene fluoride has the excellent qualities of smooth surface, small fluid resistance, outstanding oxygen resistance and the like, and is particularly suitable for the field of pure water transportation and the like, but the high price of the polyvinylidene fluoride makes the material difficult to enter the civil field, so the polyvinylidene fluoride is not widely applied to the field of pipes. In order to expand the application range of polyvinylidene fluoride in the field of high-purity water delivery in medical, industrial and high-end living places and enable polyvinylidene fluoride to be widely applied, the development of a pipe which has similar performance to a polyvinylidene fluoride pure pipe and is low in cost is necessary to replace the pipe.
Generally speaking, in order to reduce the cost of the pipe, it is an effective method to use a slightly lower-priced material to manufacture a composite pipe with similar performance, and common pipe materials include polyvinyl chloride, polyethylene, atactic polypropylene and the like, wherein the polyvinyl chloride has poor heat resistance, the polyethylene is not easy to process, and the polyethylene is not easy to use hot-melt connection, so that the difficulty exists in the process of laying a pipeline system. From the aspect of performance and application, the random polypropylene is one of the materials most suitable for compounding with the polyvinylidene fluoride, from the aspect of compatibility, the polyvinylidene fluoride and the random polypropylene are two thermodynamically incompatible materials, the interface bonding force of the random polypropylene/polyvinylidene fluoride composite pipe is extremely poor, even if the random polypropylene/polyvinylidene fluoride alloy is prepared, the random polypropylene and the polyvinylidene fluoride are required to be respectively modified, the preparation process is complex, and the performances of the random polypropylene and the polyvinylidene fluoride are reduced in different degrees, so that the high-quality random polypropylene/polyvinylidene fluoride composite pipe is difficult to manufacture, and no commercial product with excellent quality exists in the market at present.
At present, companies at home and abroad do some related product research and development work. For example, patent CN201866421U discloses an anticorrosive oxygen-insulating self-cleaning random polypropylene composite tube, which is a three-layer structure with an inner layer, a middle layer and an outer layer, and is prepared by a three-layer co-extrusion method, wherein the inner layer is made of modified polyvinylidene fluoride/polyester alloy, the outer layer is made of random polypropylene material, the middle layer is made of an oxygen-insulating adhesive layer, i.e., a high-molecular composite adhesive layer with an oxygen-insulating function, and the oxygen-insulating adhesive layer is made of EVA (ethylene-vinyl acetate copolymer), EVOH (ethylene-vinyl alcohol copolymer) or acrylic ester and derivatives thereof. Although the composite pipe has a good self-cleaning function, the polyvinylidene fluoride/polyolefin alloy material of the inner layer is easy to separate out small molecular compounds, so that secondary pollution is caused to water quality. In addition, the polymer adhesive adopted by the middle oxygen-isolating adhesive has weaker interlayer bonding force between polyvinylidene fluoride and polyolefin, and is easy to absorb water, so that the interlayer of the composite pipe is easy to fall off, and the overall strength of the pipe is reduced.
The foreign patents US20080185065a1, US20060275572 and US20150252918a1 report composite pipes with similar three-layer structure, the inner layer material adopts polyvinylidene fluoride co-mixed gold, the middle bonding layer material adopts maleic anhydride grafted polyvinylidene fluoride, silane-based adhesive, epoxide, EVOH, acrylate polymer, polyurethane or the mixture of the above, etc., or the inner and outer layer materials are bonded by radiation crosslinking.
Although these composite pipes have some self-cleaning and barrier properties, the following disadvantages are common:
1. the inner layer is made of modified or composite polyvinylidene fluoride materials, so that small molecules are easy to separate out and are difficult to pass tests such as sanitation performance;
2. the inner and outer layers are not strong in binding power and are easy to separate, and hydrostatic tests for verifying the strength and service life of the pipe are difficult to verify through cold water internal pressure, hot water internal pressure, thermal cycle and the like;
3. cannot realize one-time coextrusion molding, and has complex production process.
Therefore, a novel composite pipe needs to be developed, which has the advantages of low precipitation, tight interlayer combination, simple and convenient production process and the like, and on the basis, the pure polyvinylidene fluoride pipe is environment-friendly, small in precipitation and good in chemical stability; the impact strength is high, the abrasion resistance is high, the creep resistance is high, and the mechanical strength and the toughness are good; the heat resistance is good, and the long-term use temperature is-20-100 ℃; smooth surface, small fluid resistance, outstanding oxygen resistance and other excellent qualities.
Disclosure of Invention
The invention aims to provide a multilayer composite pipe which has low precipitation, tight interlayer bonding, one-step co-extrusion molding and most of advantages of a polyvinylidene fluoride pure pipe, aiming at the defects of the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is a multilayer composite pipe, which is characterized in that:
a multilayer composite pipe, characterized in that: the alloy particle interlayer comprises a compatilizer and an outer layer of random polyolefin.
Further, the outer layer of the random polyolefin is an outer layer of random polypropylene, and the use amount is 100 parts by weight.
Further, the alloy granule intermediate layer is formed by interpenetrating and winding of a compatilizer, a fluoroolefin polymer and macromolecules of random polyolefin, and the intermediate layer is prepared by mixing and granulating, wherein the usage amount is 20-80 parts by weight, and the alloy granule intermediate layer comprises the following materials in parts by weight: 30-60% of polyvinylidene fluoride, 10-30% of compatilizer material and 30-60% of random polypropylene.
Furthermore, the mass fraction range of the compatilizer is 5-30%, the mass fraction range of the fluoroolefin polymer is 10-85%, and the mass fraction range of the random polyolefin is 10-85%, and the quality of the pipe is improved by controlling the mass fractions of the compatilizer, the fluoroolefin polymer and the random polyolefin.
Furthermore, the compatilizer is a comb polymer of which the side chain of the macromolecule simultaneously contains alkyl of C4 and above and ester of C4 and above.
Preferably, the compatilizer is C4 or above alkyl on the side chain of macromolecule.
Preferably, the compatilizer is acrylate with ester group of C4 or above on the side chain of macromolecule.
Further, the fluoroolefin polymer inner layer contains at least one of vinylidene fluoride homopolymer or copolymer mainly containing vinylidene fluoride, and the usage amount is 10-50 parts by weight.
A preparation method of a multilayer composite pipe is characterized by comprising the following steps: the method comprises the following steps:
s1, adding different materials into three extruders for extruding to form an inner layer, a middle layer and an outer layer respectively, wherein fluoroolefin polymer granules are added into the extruder for forming the inner layer, random polyolefin granules are added into the extruder for forming the outer layer, and alloy granules are added into the extruder for forming the middle layer;
s2, respectively extruding the inner layer, the middle layer and the outer layer by using three extruders under certain extrusion process conditions, and forming the three-layer composite pipe in one step by using the same composite extrusion die to obtain an unshaped three-layer composite pipe;
and S3, cutting the unshaped three-layer composite pipe into required length after vacuum sizing, and then carrying out heat setting by using an oven to obtain the three-layer composite pipe.
Further, the alloy pellet is obtained by mixing the compatilizer, the fluoroolefin polymer and the random polyolefin and then carrying out extrusion granulation.
Further, the barrels of the three extruders in step S2 are equally divided into 6 heating sections, and the heating temperature of each section of the barrel of the extruder for the inner layer is: the heating temperature of the 1 section is 220 +/-5 ℃, the heating temperature of the 2 section is 225 +/-5 ℃, the heating temperature of the 3 section is 230 +/-5 ℃, the heating temperature of the 4 section is 235 +/-5 ℃, the heating temperature of the 5 section is 240 +/-5 ℃, and the heating temperature of the 6 section is 245 +/-5 ℃; the heating temperature of each section of the machine barrel of the extruder used for the middle layer is as follows: the heating temperature of the 1 section is 220 +/-5 ℃, the heating temperature of the 2 section is 225 +/-5 ℃, the heating temperature of the 3 section is 230 +/-5 ℃, the heating temperature of the 4 section is 235 +/-5 ℃, the heating temperature of the 5 section is 240 +/-5 ℃, and the heating temperature of the 6 section is 245 +/-5 ℃; the heating temperature of each section of the machine barrel of the extruder used for the outer layer is as follows: the heating temperature of the 1 section is 195 +/-5 ℃, the heating temperature of the 2 section is 200 +/-5 ℃, the heating temperature of the 3 section is 205 +/-5 ℃, the heating temperature of the 4 section is 210 +/-5 ℃, the heating temperature of the 5 section is 215 +/-5 ℃, and the heating temperature of the 6 section is 220 +/-5 ℃.
Further, in step S2, 3 extruders share one composite extrusion die head, the composite extrusion die head is divided into 4 heating sections, and the heating temperature of each section is: the heating temperature of the 1 section is 235 +/-5 ℃, the heating temperature of the 2 section is 240 +/-5 ℃, the heating temperature of the 3 section is 235 +/-5 ℃, and the heating temperature of the 4 section is 235 +/-5 ℃.
Further, in step S3, the coextruded composite pipe is subjected to water cooling sizing at 20 ℃ in vacuum of 0.01-0.04, and then is placed in an oven for 24 hours to eliminate internal stress, and the multilayer composite pipe is obtained.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the invention solves the problems that the inner layer material is easy to separate out small molecules, the inner layer material and the outer layer material are easy to separate out, the processing technology is complex and the like in the polyvinylidene fluoride-polyolefin composite pipe, has the advantages of low separation, tight interlayer combination, simple and convenient production technology and the like, and has the advantages of environmental protection, small separation property and good chemical stability of the pure polyvinylidene fluoride pipe on the basis; the impact strength is high, the abrasion resistance is high, the creep resistance is high, and the mechanical strength and the toughness are good; the heat resistance is good, the incombustibility is good, and the long-term use temperature is-20-100 ℃; smooth surface, small fluid resistance, outstanding oxygen resistance and other excellent qualities.
Detailed Description
The invention relates to a multilayer composite pipe, which consists of an inner layer, an intermediate layer and an outer layer, wherein the intermediate layer is tightly attached to the outer side of the inner layer, the outer layer is tightly attached to the outer side of the intermediate layer, the inner layer is a fluoroolefin polymer inner layer, the fluoroolefin polymer inner layer contains at least one of vinylidene fluoride homopolymer or copolymer mainly containing vinylidene fluoride, the usage amount is 10-50 parts by weight, the intermediate layer is an alloy granule intermediate layer, the alloy granule intermediate layer contains a compatilizer, the alloy granule intermediate layer is formed by interpenetration of the compatilizer, the fluoroolefin polymer and macromolecules of random polyolefin, and the intermediate layer is prepared by mixing and granulating, the usage amount is 20-80 parts by weight, and the multilayer composite pipe comprises: 30-60% of polyvinylidene fluoride, 10-30% of a compatilizer material and 30-60% of random polypropylene, wherein the compatilizer is a comb polymer of which a macromolecule side chain simultaneously contains hydrocarbon groups of C4 and above and ester groups of C4 and above, the compatilizer is a comb polymer of which the hydrocarbon groups on the macromolecule side chain are alkyl groups of C4 and above, the ester groups on the macromolecule side chain are acrylate of which the ester groups are C4 and above, the outer layer is a random polyolefin outer layer, the random polyolefin outer layer is a random polypropylene outer layer, the using amount is 100 parts by weight, the mass fraction range of the compatilizer is 5-30%, the mass fraction range of the fluoroolefin polymer is 10-85%, and the mass fraction range of the random polyolefin is 10-85%.
A preparation method of a multilayer composite pipe comprises the following steps:
s1, adding different materials into three extruders for extruding to form an inner layer, a middle layer and an outer layer respectively, wherein fluoroolefin polymer granules are added into the extruder for forming the inner layer, random polyolefin granules are added into the extruder for forming the outer layer, alloy granules are added into the extruder for forming the middle layer, and the alloy granules are obtained by mixing a compatilizer, fluoroolefin polymer and random polyolefin and then extruding and granulating;
s2, respectively extruding the inner layer, the middle layer and the outer layer by using three extruders under certain extrusion process conditions, wherein machine barrels of the three extruders are equally divided into 6 heating sections, and the heating temperature of each section of the machine barrel of the extruder for the inner layer is as follows: the heating temperature of the 1 section is 220 +/-5 ℃, the heating temperature of the 2 section is 225 +/-5 ℃, the heating temperature of the 3 section is 230 +/-5 ℃, the heating temperature of the 4 section is 235 +/-5 ℃, the heating temperature of the 5 section is 240 +/-5 ℃, and the heating temperature of the 6 section is 245 +/-5 ℃; the heating temperature of each section of the machine barrel of the extruder used for the middle layer is as follows: the heating temperature of the 1 section is 220 +/-5 ℃, the heating temperature of the 2 section is 225 +/-5 ℃, the heating temperature of the 3 section is 230 +/-5 ℃, the heating temperature of the 4 section is 235 +/-5 ℃, the heating temperature of the 5 section is 240 +/-5 ℃, and the heating temperature of the 6 section is 245 +/-5 ℃; the heating temperature of each section of the machine barrel of the extruder used for the outer layer is as follows: the heating temperature of the 1 section is 195 +/-5 ℃, the heating temperature of the 2 section is 200 +/-5 ℃, the heating temperature of the 3 section is 205 +/-5 ℃, the heating temperature of the 4 section is 210 +/-5 ℃, the heating temperature of the 5 section is 215 +/-5 ℃, the heating temperature of the 6 section is 220 +/-5 ℃, and an unmolded three-layer composite pipe is obtained by one-step molding through the same composite extrusion die head, 3 extruders share one composite extrusion die head, the composite extrusion die head is divided into 4 heating sections, and the heating temperature of each section is respectively: the heating temperature of the 1 section is 235 +/-5 ℃, the heating temperature of the 2 section is 240 +/-5 ℃, the heating temperature of the 3 section is 235 +/-5 ℃, and the heating temperature of the 4 section is 235 +/-5 ℃;
s3, cutting the unmolded three-layer composite pipe into required length after vacuum sizing, performing heat setting by using an oven to obtain the three-layer composite pipe, performing water cooling sizing on the co-extruded composite pipe in vacuum of 0.01-0.04 at 20 ℃, and then placing the pipe in the oven for 24 hours to eliminate internal stress to obtain the multilayer composite pipe.
The present invention is further illustrated by the following specific examples, which are provided for illustrative purposes only and do not limit the scope of the present invention.
Example 1
The outer layer material is random polypropylene, and the use amount is 100 parts by weight; the intermediate layer material is made of polyvinylidene fluoride and random polypropylene alloy, the usage amount is 20 parts by weight, and the intermediate layer material comprises 45% of polyvinylidene fluoride, 10% of compatilizer material and 45% of random polypropylene by mass; the inner layer material is vinylidene fluoride homopolymer, and the usage amount is 20 parts by weight. The composite pipe is obtained by three-layer coextrusion and one-step forming.
Example 2
The outer layer material is random polypropylene, and the use amount is 100 parts by weight; the intermediate layer material is made of polyvinylidene fluoride and random polypropylene alloy, the usage amount is 40 parts by weight, and the intermediate layer material comprises 40% of polyvinylidene fluoride, 20% of compatilizer material and 40% of random polypropylene by mass; the inner layer material is vinylidene fluoride homopolymer, and the usage amount is 40 parts by weight. The composite pipe is obtained by three-layer coextrusion and one-step forming.
Example 3:
the outer layer material is random polypropylene, and the use amount is 100 parts by weight; the intermediate layer material is made of polyvinylidene fluoride and atactic polypropylene alloy, the usage amount is 60 parts by weight, and the intermediate layer material comprises 40% of polyvinylidene fluoride, 15% of compatilizer material and 45% of atactic polypropylene by mass; the inner layer material is vinylidene fluoride homopolymer, and the usage amount is 60 parts by weight. The composite pipe is obtained by three-layer coextrusion and one-step forming.
Example 4:
the outer layer material is random polypropylene, and the use amount is 100 parts by weight; the intermediate layer material is made of polyvinylidene fluoride and random polypropylene alloy, the usage amount is 80 parts by weight, and the intermediate layer material comprises 45% of polyvinylidene fluoride, 20% of compatilizer material and 35% of random polypropylene by mass; the inner layer material is vinylidene fluoride homopolymer, and the usage amount is 50 parts by weight. The composite pipe is obtained by three-layer coextrusion and one-step forming.
Example 5:
the outer layer material is random polypropylene, and the use amount is 100 parts by weight; the intermediate layer material is made of polyvinylidene fluoride and random polypropylene alloy, and the usage amount is 80 parts by weight, and the intermediate layer material comprises 45% of polyvinylidene fluoride, 10% of compatilizer material and 45% of random polypropylene by mass; the inner layer material is vinylidene fluoride copolymer, and the usage amount is 50 parts by weight. The composite pipe is obtained by three-layer coextrusion and one-step forming.
Comparative example 1:
the outer layer material is random polypropylene, and the use amount is 100 parts by weight; the intermediate layer material adopts EVOH, and the usage amount is 20 parts by weight; the inner layer material is vinylidene fluoride homopolymer, and the usage amount is 30 parts by weight. And extruding and forming for multiple times to obtain the composite pipe.
Comparative example 2:
the outer layer material is random polypropylene, and the use amount is 100 parts by weight; the intermediate layer material is made of polyvinylidene fluoride and random polypropylene alloy, the usage amount is 40 parts by weight, and the intermediate layer material comprises 45% of polyvinylidene fluoride, 10% of compatilizer material and 45% of random polypropylene by mass; the inner layer material is polymethyl methacrylate modified polyvinylidene fluoride, and the usage amount is 40 parts by weight. The composite pipe is obtained by three-layer coextrusion and one-step forming.
And (3) performance test results:
| numbering | Cold water internal pressure test | Hot water internal pressure test | Thermal cycling experiments | Experiment of hygiene Properties |
| Example 1 | No rupture leakage for 1h | No rupture leakage in 22h | No rupture leakage for 5000 times | By passing |
| Example 2 | No rupture leakage for 1h | No rupture leakage in 22h | No rupture leakage for 5000 times | By passing |
| Example 3 | No rupture leakage for 1h | No rupture leakage in 22h | No rupture leakage for 5000 times | By passing |
| Example 4 | No rupture leakage for 1h | No rupture leakage in 22h | No rupture leakage for 5000 times | By passing |
| Example 5 | No rupture leakage for 1h | No rupture leakage in 22h | No rupture leakage for 5000 times | By passing |
| Comparative example 1 | No rupture leakage for 1h | Leakage of 11h | 2533 number of ruptures | Do not pass through |
| Comparative example 2 | No rupture leakage for 1h | 9h break | 2052 times of fracture | Do not pass through |
Sample performance test criteria in the examples:
(1) internal pressure resistance test: GB/T6111-;
(2) thermal cycling experiments: GB/T18742.3-2002;
(3) hygiene performance experiments: GB/T17219-1998.
The invention solves the problems that the inner layer material is easy to separate out small molecules, the inner layer material and the outer layer material are easy to separate out, the processing technology is complex and the like in the polyvinylidene fluoride-polyolefin composite pipe, has the advantages of low separation, tight interlayer combination, simple and convenient production technology and the like, and has the advantages of environmental protection, small separation property and good chemical stability of the pure polyvinylidene fluoride pipe on the basis; the impact strength is high, the abrasion resistance is high, the creep resistance is high, and the mechanical strength and the toughness are good; the heat resistance is good, the incombustibility is good, and the long-term use temperature is-20-100 ℃; smooth surface, small fluid resistance, outstanding oxygen resistance and other excellent qualities.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple variations, equivalent substitutions or modifications based on the present invention to achieve substantially the same technical effects are within the scope of the present invention.
Claims (7)
1. A multilayer composite pipe, characterized in that: the alloy pellet interlayer is formed by interpenetrating and winding of a compatilizer, a fluoroolefin polymer and macromolecules of random polyolefin, wherein the mass fraction range of the compatilizer is 5% -30%, the mass fraction range of the fluoroolefin polymer is 10% -85%, and the mass fraction range of the random polyolefin is 10% -85%.
2. The multilayer composite pipe according to claim 1, wherein: the outer layer of random polyolefin is an outer layer of random polypropylene.
3. The multilayer composite pipe according to claim 1, wherein: the compatilizer is a comb polymer of which the side chain of a macromolecule simultaneously contains alkyl of C4 and above and ester group of C4 and above.
4. The multilayer composite pipe according to claim 1, wherein: the fluoroolefin polymer inner layer contains at least one of vinylidene fluoride homopolymer or copolymer mainly containing vinylidene fluoride.
5. A method of making a multilayer composite pipe as defined in claim 1, wherein: the method comprises the following steps:
s1, adding different materials into three extruders for extruding to form an inner layer, a middle layer and an outer layer respectively, wherein fluoroolefin polymer granules are added into the extruder for forming the inner layer, random polyolefin granules are added into the extruder for forming the outer layer, and alloy granules are added into the extruder for forming the middle layer;
s2, respectively extruding the inner layer, the middle layer and the outer layer by using three extruders, and forming the three-layer composite pipe in one step by using the same composite extrusion die to obtain an unshaped three-layer composite pipe; the composite extrusion die head is divided into 4 heating sections, and the heating temperature of each section is respectively as follows: the heating temperature of the 1 section is 235 +/-5 ℃, the heating temperature of the 2 section is 240 +/-5 ℃, the heating temperature of the 3 section is 235 +/-5 ℃, and the heating temperature of the 4 section is 235 +/-5 ℃;
and S3, cutting the unshaped three-layer composite pipe into required length after vacuum sizing, and then carrying out heat setting by using an oven to obtain the three-layer composite pipe.
6. The method of claim 5, wherein the method comprises the steps of: the alloy pellet is obtained by mixing a compatilizer, a fluoroolefin polymer and random polyolefin and then extruding and granulating.
7. The method of claim 6, wherein the method comprises the steps of: the barrels of the three extruders in the step S2 are equally divided into 6 heating sections, and the heating temperature of each section of the barrel of the extruder for the inner layer is as follows: the heating temperature of the 1 section is 220 +/-5 ℃, the heating temperature of the 2 section is 225 +/-5 ℃, the heating temperature of the 3 section is 230 +/-5 ℃, the heating temperature of the 4 section is 235 +/-5 ℃, the heating temperature of the 5 section is 240 +/-5 ℃, and the heating temperature of the 6 section is 245 +/-5 ℃; the heating temperature of each section of the machine barrel of the extruder used for the middle layer is as follows: the heating temperature of the 1 section is 220 +/-5 ℃, the heating temperature of the 2 section is 225 +/-5 ℃, the heating temperature of the 3 section is 230 +/-5 ℃, the heating temperature of the 4 section is 235 +/-5 ℃, the heating temperature of the 5 section is 240 +/-5 ℃, and the heating temperature of the 6 section is 245 +/-5 ℃; the heating temperature of each section of the machine barrel of the extruder used for the outer layer is as follows: the heating temperature of the 1 section is 195 +/-5 ℃, the heating temperature of the 2 section is 200 +/-5 ℃, the heating temperature of the 3 section is 205 +/-5 ℃, the heating temperature of the 4 section is 210 +/-5 ℃, the heating temperature of the 5 section is 215 +/-5 ℃, and the heating temperature of the 6 section is 220 +/-5 ℃.
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| CN109878175B (en) * | 2019-01-24 | 2021-03-19 | 武汉高正新材料科技有限公司 | PVDF pipe with anti-corrosion effect and processing technology thereof |
| CN110410589A (en) * | 2019-07-10 | 2019-11-05 | 袁睿 | A kind of impact-resistant pipe fitting |
| CN112223854A (en) * | 2020-09-18 | 2021-01-15 | 威海联桥新材料科技股份有限公司 | Three-layer composite PVC/PEX water delivery pipe and preparation method thereof |
| CN112373161B (en) * | 2020-10-15 | 2023-03-24 | 浙江巨化新材料研究院有限公司 | High-heat-conductivity and high-heat-resistance multilayer composite pipe and preparation method thereof |
| CN112277429A (en) * | 2020-11-05 | 2021-01-29 | 江苏申视新材料科技有限公司 | Bonding method for multilayer composite pipeline |
| CN113232373A (en) * | 2021-04-07 | 2021-08-10 | 临海伟星新型建材有限公司 | Multilayer composite pipe for direct drinking water conveying and preparation method thereof |
| WO2023218483A1 (en) * | 2022-05-09 | 2023-11-16 | Ashirvad Pipes Pvt. Ltd | Multilayer flexible pressure pipes |
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