CN109253320A - A kind of MULTILAYER COMPOSITE tubing and preparation method thereof - Google Patents
A kind of MULTILAYER COMPOSITE tubing and preparation method thereof Download PDFInfo
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- CN109253320A CN109253320A CN201810965499.8A CN201810965499A CN109253320A CN 109253320 A CN109253320 A CN 109253320A CN 201810965499 A CN201810965499 A CN 201810965499A CN 109253320 A CN109253320 A CN 109253320A
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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
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- 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
- C08L2205/03—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)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a kind of MULTILAYER COMPOSITE tubing and preparation method thereof.Tubing be divided into, in, it is three layers outer, inner layer material is fluorolefin polymer, and intermediate layer material is the high polymer alloy comprising comb shape compatilizer, and cladding material is atactic polyolefin.Tubing uses three-layer co-extruded one-shaping technique, and gained tubing has a low precipitation, the advantages that Coating combination is close, and production technology is easy, also has that pure Kynoar tubing environmental protection, precipitation property is small, chemical stability is good on this basis；Excellent in cushion effect, abrasion performance, creep resistance, mechanical strength and good toughness；Heat resistance is good, -20-100 DEG C of long-term use temperature；The one's best qualities such as surface is smooth, and fluid resistance is small, and oxygen resistance is prominent.
Description
Technical field
The invention belongs to tubing technical fields, and in particular to a kind of MULTILAYER COMPOSITE tubing and preparation method thereof.
Background technique
Kynoar is a kind of material of function admirable, and with environmental protection, precipitation property is small, chemical stability is good；Shock resistance
Intensity height, abrasion performance, creep resistance, mechanical strength and good toughness；Heat resistance is good, noninflammability, -40-150 DEG C of long-term use temperature；
The one's best qualities such as surface is smooth, and fluid resistance is small, and oxygen resistance is prominent especially suitable for fields such as pure water conveyings, however gather inclined
Vinyl fluoride fancy price makes the material be difficult to enter civil field, also therefore is not used widely in pipe material field.For
Application range of the developing Kynoar in medical, the industrial and high-end life area high purity water transportation art, obtains it
A kind of and pure pipe similar performance of Kynoar is developed in widely application, and lower-cost tubing is used as and replaces being very
It is necessary to.
Typically, in order to reduce tubing cost, the composite pipe using the slightly lower material production similar performance of price is
Effective method, common pipe material have polyvinyl chloride, polyethylene and random polypropylene etc., and wherein polyvinyl chloride is heat-resisting
Performance is poor, and polyethylene is not easy to be processed, and hot-melt adhesive paste not easy to use, has difficulties during being laid with pipe-line system.
From performance and purposes, random polypropylene is to be best suited for carrying out compound one of material with Kynoar, and from compatible
Property angle see that Kynoar and random polypropylene are two kinds of thermodynamically incompatible materials, random polypropylene/Kynoar
The interface binding power of composite pipe is very poor, is usually needed preparing random polypropylene/polyvinylidene fluoride alloy to random poly-
Propylene and Kynoar make modification respectively, and preparation process is complicated, and the performance of random polypropylene and Kynoar is all
There is different degrees of decline, therefore the random polypropylene of high-quality/Kynoar composite pipe manufacture difficulty is very big, exists at present
It there is no commercially produced product of fine qualities on the market.
At this stage, some Related product research and developments have all been done by domestic and international company.It is public such as patent CN201866421U
A kind of oxygen barrier self-cleaning random polypropylene multiple tube of anti-corrosion is opened, which is inside and outside three-decker, passes through three-layer co-extruded side
Method preparation, internal layer is made of modified polyvinilidene fluoride/polyester alloy, and outer layer is made of random polypropylene material, middle layer by every
Oxygen glue-line is that there is the macromolecule composite layer of oxygen barrier function to constitute, and oxygen barrier glue-line is using EVA (ethene-vinyl acetate copolymerization
Object), EVOH (ethylene-vinyl alcohol copolymer) or acrylate and its derivative etc..Although the composite pipe has good self-cleaning
Function, but Kynoar/polyolefin alloy material of internal layer is easy that small molecule compound is precipitated, to cause two to water quality
Secondary pollution.The polymer latex used additionally, due to intermediate oxygen barrier glue to the interlayer adhesion between Kynoar and polyolefin compared with
It is weak and hygroscopic, it is be easy to cause the intermediate peeling of composite pipe, reduces tubing integral strength.
Foreign patent US20080185065A1, US20060275572 report similar three layers with US20150252918A1
The composite pipe of structure, inner layer material use polyvinylidene blending alloy, and intennediate bond layer material is grafted using maleic anhydride
Kynoar, silane-based binder, epoxides, EVOH, acrylate polymer, polyurethane or more than mixture etc. or
Person bonds layer materials by way of crosslinking with radiation.
Although these composite pipes have certain self-cleaning property and barrier property, generally existing own shortcomings:
1, internal layer must use modified or compound polyvinylidene fluoride material, easily precipitation small molecule, it is difficult to pass through wholesomeness
The test such as energy；
2, layer materials cohesive force is not strong, and ectonexine is easily detached from, it is difficult to pass through cold water internal pressure, hot water internal pressure and thermal cycle
Deng the hydrostatic test of verifying tubing intensity and service life；
3, it can not accomplish that a co-extrusion modling, production technology are complicated.
Therefore it needs to develop a kind of novel composite pipe, there is low precipitation, Coating combination is close, and production technology simplicity etc. is excellent
Point, also has that the environmental protection of pure Kynoar tubing, precipitation property is small, chemical stability is good on this basis；It is excellent in cushion effect, resistance to
Abrasion, creep resistance, mechanical strength and good toughness；Heat resistance is good, -20-100 DEG C of long-term use temperature；Surface is smooth, fluid resistance
It is small, the one's best qualities such as oxygen resistance protrusion.
Summary of the invention
Present invention aims at a kind of low precipitation is provided for deficiency of the prior art, interlaminar bonding is close,
A co-extrusion modling and there can be the MULTILAYER COMPOSITE tubing of the pure pipe major part of Kynoar.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is a kind of MULTILAYER COMPOSITE tubing, and feature exists
In:
A kind of MULTILAYER COMPOSITE tubing, it is characterised in that: by internal layer, the middle layer being tightly attached on the outside of internal layer and be tightly attached to centre
The outer layer composition in layer outside, internal layer are fluorolefin polymer internal layer, and middle layer is alloy granule middle layer, alloy granule middle layer
In include compatilizer, outer layer be atactic polyolefin outer layer.
Further, atactic polyolefin outer layer is random polypropylene outer layer, and usage amount is 100 parts by weight.
Further, alloy granule middle layer is twined by the macromolecular interpenetrating of compatilizer, fluorolefin polymer and atactic polyolefin
Around formation, middle layer is made via mixing granulation, and usage amount is 20-80 parts by weight, the material including following mass fraction:
30-60% Kynoar, the compatible agent material of 10-30%, 30-60% random polypropylene.
Further, the mass fraction range of compatilizer is 5%-30%, and the mass fraction range of fluorolefin polymer is
10%-85%, the mass fraction range of atactic polyolefin are 10%-85%, by controlling the mass fraction of this three, improve pipe
The quality of material.
Further, compatilizer is the comb of the ester group of the alkyl containing C4 or more and C4 or more simultaneously on macromolecule side chain
Shape polymer.
After it is preferred that, compatilizer is that alkyl is C4 and the above alkyl on macromolecule side chain.
After it is preferred that, compatilizer is that ester group is C4 and the above acrylate on macromolecule side chain.
Further, in the copolymer in fluorolefin polymer internal layer comprising vinylidene fluoride homopolymer or based on vinylidene
At least one, by weight usage amount be 10-50 parts.
Using a kind of preparation method of MULTILAYER COMPOSITE tubing as claimed in claim 1, characterized by the following steps:
(1) different material is separately added into three extruders for being extruded into internal layer, middle layer and outer layer, wherein being used for
It is formed and fluorolefin polymer pellet is added in the extruder of internal layer, be used to form addition atactic polyolefin grain in the extruder of outer layer
Material, is used to form in the extruder of middle layer and alloy granule is added；
(2) under the conditions of certain extrusion process, internal layer, middle layer and outer layer are squeezed out respectively using three extruders, and
Unshaped three-layer composite pipe material is obtained by same composite extrusion die head one-pass molding；
(3) unshaped three-layer composite pipe material is cut into required length after passing through vacuum sizing, then carries out heat with baking oven and determine
Three-layer composite pipe material is obtained after type.
Further, it after alloy granule is by the mixing of compatilizer, fluorolefin polymer and atactic polyolefin, is obtained through extruding pelletization
?.
Further, the machine barrel of three extruders in step (2) is divided into 6 bringing-up sections, the extruder for internal layer
Each section of heating temperature of machine barrel are as follows: 1 section of heating temperature 2 is 20 ± 5 DEG C, and 2 sections of heating temperatures are 225 ± 5 DEG C, and 3 sections of heating temperatures are
230 ± 5 DEG C, 4 sections of heating temperatures are 235 ± 5 DEG C, and 5 sections of heating temperatures are 240 ± 5 DEG C, and 6 sections of heating temperatures are 245 ± 5 DEG C；With
In each section of heating temperature of the machine barrel of the extruder of middle layer are as follows: 1 section of heating temperature is 220 ± 5 DEG C, 2 sections of heating temperatures are 225 ±
5 DEG C, 3 sections of heating temperatures are 230 ± 5 DEG C, and 4 sections of heating temperatures are 235 ± 5 DEG C, and 5 sections of heating temperatures are 240 ± 5 DEG C, 6 sections of heating
Temperature is 245 ± 5 DEG C；Each section of heating temperature of the machine barrel of extruder for outer layer are as follows: 1 section of heating temperature is 195 ± 5 DEG C, 2 sections
Heating temperature is 200 ± 5 DEG C, and 3 sections of heating temperatures are 205 ± 5 DEG C, and 4 sections of heating temperatures are 210 ± 5 DEG C, and 5 sections of heating temperatures are
215 ± 5 DEG C, 6 sections of heating temperatures are 220 ± 5 DEG C.
Further, 3 extruders share a composite extrusion die head in step (2), and composite extrusion die head is divided into 4 heating
Section, it is 235 ± 5 DEG C that every section of heating temperature, which is respectively as follows: 1 section of heating temperature, and 2 sections of heating temperatures are 240 ± 5 DEG C, 3 sections of heating temperatures
It is 235 ± 5 DEG C, 4 sections of heating temperatures are 235 ± 5 DEG C.
Further, in step (3), the composite pipe after coextrusion carries out water in the vacuum of 0.01-0.04 at 20 DEG C
After cool sizing, it is placed in baking oven and eliminates internal stress for 24 hours to get MULTILAYER COMPOSITE tubing of the present invention is arrived.
The present invention is by adopting the above-described technical solution, have the advantages that
The present invention solves the inner layer material present in Kynoar-polyolefin composite pipe in the past and is easily precipitated small point
The problems such as son, layer materials are easily detached from and processing technology is complicated, has low precipitation, and Coating combination is close, and production technology is easy
The advantages that, also have that the environmental protection of pure Kynoar tubing, precipitation property is small, chemical stability is good on this basis；Impact strength
High, abrasion performance, creep resistance, mechanical strength and good toughness；Heat resistance is good, noninflammability, long-term use temperature are at -20-100 DEG C；Table
The one's best qualities such as face is smooth, and fluid resistance is small, and oxygen resistance is prominent.
Specific embodiment
A kind of MULTILAYER COMPOSITE tubing of the present invention, by internal layer, the middle layer being tightly attached on the outside of internal layer and is tightly attached to outside middle layer
The outer layer of side forms, and internal layer is fluorolefin polymer internal layer, in fluorolefin polymer internal layer comprising vinylidene fluoride homopolymer or with
At least one of copolymer based on vinylidene, by weight usage amount are 10-50 parts, and middle layer is among alloy granule
Layer, it include compatilizer in alloy granule middle layer, alloy granule middle layer is by compatilizer, fluorolefin polymer and atactic polyolefin
Macromolecular interpenetrating be wound, middle layer is made via mixing granulation, and usage amount is 20-80 parts by weight, including following
The material of mass fraction: 30-60% Kynoar, the compatible agent material of 10-30%, 30-60% random polypropylene, compatilizer are
The comb polymer of the ester group of the alkyl containing C4 or more and C4 or more, compatilizer are macromolecular simultaneously on macromolecule side chain
Alkyl is C4 and the above alkyl on side chain, and compatilizer is that ester group is C4 and the above acrylate on macromolecule side chain, and outer layer is nothing
Polyolefinic outer layer is advised, atactic polyolefin outer layer is random polypropylene outer layer, and usage amount is 100 parts by weight, the matter of compatilizer
Amount fraction range is 5%-30%, and the mass fraction range of fluorolefin polymer is 10%-85%, the quality point of atactic polyolefin
Number range improves the quality of tubing by controlling the mass fraction of this three for 10%-85%.
Using a kind of preparation method of MULTILAYER COMPOSITE tubing as claimed in claim 1, include the following steps:
(1) different material is separately added into three extruders for being extruded into internal layer, middle layer and outer layer, wherein being used for
It is formed and fluorolefin polymer pellet is added in the extruder of internal layer, be used to form addition atactic polyolefin grain in the extruder of outer layer
Material, is used to form in the extruder of middle layer and alloy granule is added, and alloy granule is by compatilizer, fluorolefin polymer and random poly-
After olefin, obtained through extruding pelletization；
(2) under the conditions of certain extrusion process, internal layer, middle layer and outer layer are squeezed out respectively using three extruders, three
The machine barrel of platform extruder is divided into 6 bringing-up sections, each section of heating temperature of the machine barrel of the extruder for internal layer are as follows: 1 section of heating temperature
Degree 2 is 20 ± 5 DEG C, and 2 sections of heating temperatures are 225 ± 5 DEG C, and 3 sections of heating temperatures are 230 ± 5 DEG C, and 4 sections of heating temperatures are 235 ± 5
DEG C, 5 sections of heating temperatures are 240 ± 5 DEG C, and 6 sections of heating temperatures are 245 ± 5 DEG C；Each section of the machine barrel of extruder for middle layer adds
Hot temperature are as follows: 1 section of heating temperature is 220 ± 5 DEG C, and 2 sections of heating temperatures are 225 ± 5 DEG C, and 3 sections of heating temperatures are 230 ± 5 DEG C, 4
Section heating temperature is 235 ± 5 DEG C, and 5 sections of heating temperatures are 240 ± 5 DEG C, and 6 sections of heating temperatures are 245 ± 5 DEG C；For squeezing for outer layer
Each section of heating temperature of the machine barrel of machine out are as follows: 1 section of heating temperature is 195 ± 5 DEG C, and 2 sections of heating temperatures are 200 ± 5 DEG C, 3 sections of heating
Temperature is 205 ± 5 DEG C, and 4 sections of heating temperatures are 210 ± 5 DEG C, and 5 sections of heating temperatures are 215 ± 5 DEG C, 6 sections of heating temperatures are 220 ±
5 DEG C, and unshaped three-layer composite pipe material is obtained by same composite extrusion die head one-pass molding, 3 extruders share one
Composite extrusion die head, composite extrusion die head are divided into 4 bringing-up sections, and it is 235 ± 5 that every section of heating temperature, which is respectively as follows: 1 section of heating temperature,
DEG C, 2 sections of heating temperatures are 240 ± 5 DEG C, and 3 sections of heating temperatures are 235 ± 5 DEG C, and 4 sections of heating temperatures are 235 ± 5 DEG C；
(3) unshaped three-layer composite pipe material is cut into required length after passing through vacuum sizing, then carries out heat with baking oven and determine
Three-layer composite pipe material is obtained after type, it is fixed to carry out water cooling in the vacuum of 0.01-0.04 at 20 DEG C for the composite pipe after coextrusion
After diameter, it is placed in baking oven and eliminates internal stress for 24 hours to get MULTILAYER COMPOSITE tubing of the present invention is arrived.
The present invention is further explained below by specific embodiment, these embodiments are only used for the purpose of illustration,
It is not intended to limit protection scope of the present invention.
Embodiment 1
Cladding material uses random polypropylene, and usage amount by weight is 100 parts；Intermediate layer material uses Kynoar
With the alloy of random polypropylene, usage amount by weight is 20 parts, including mass fraction be 45% Kynoar, 10%
Compatible agent material and 45% random polypropylene；Inner layer material is vinylidene fluoride homopolymer, and usage amount is 20 parts by weight.Through
Three-layer co-extruded one-pass molding out obtains composite pipe.
Embodiment 2
Cladding material uses random polypropylene, and usage amount by weight is 100 parts；Intermediate layer material uses Kynoar
With the alloy of random polypropylene, usage amount by weight is 40 parts, including mass fraction be 40% Kynoar, it is 20% compatible
Agent material and 40% random polypropylene；Inner layer material is vinylidene fluoride homopolymer, and usage amount is 40 parts by weight.Altogether through three layers
It squeezes out one-pass molding and obtains composite pipe.
Embodiment 3:
Cladding material uses random polypropylene, and usage amount by weight is 100 parts；Intermediate layer material uses Kynoar
With the alloy of random polypropylene, usage amount by weight is 60 parts, including mass fraction be 40% Kynoar, it is 15% compatible
Agent material and 45% random polypropylene；Inner layer material is vinylidene fluoride homopolymer, and usage amount is 60 parts by weight.Altogether through three layers
It squeezes out one-pass molding and obtains composite pipe.
Embodiment 4:
Cladding material uses random polypropylene, and usage amount by weight is 100 parts；Intermediate layer material uses Kynoar
With the alloy of random polypropylene, usage amount by weight is 80 parts, including mass fraction be 45% Kynoar, it is 20% compatible
Agent material and 35% random polypropylene；Inner layer material is vinylidene fluoride homopolymer, and usage amount is 50 parts by weight.Altogether through three layers
It squeezes out one-pass molding and obtains composite pipe.
Embodiment 5:
Cladding material uses random polypropylene, and usage amount by weight is 100 parts；Intermediate layer material uses Kynoar
With the alloy of random polypropylene, usage amount by weight is 80 parts, including mass fraction be 45% Kynoar, it is 10% compatible
Agent material and 45% random polypropylene；Inner layer material is vinylidene fluoride copolymers, and usage amount is 50 parts by weight.Altogether through three layers
It squeezes out one-pass molding and obtains composite pipe.
Comparative example 1:
Cladding material uses random polypropylene, and usage amount by weight is 100 parts；Intermediate layer material uses EVOH, by weight
Meter usage amount is 20 parts；Inner layer material is vinylidene fluoride homopolymer, and usage amount is 30 parts by weight.It is formed through repeated processing
Obtain composite pipe.
Comparative example 2:
Cladding material uses random polypropylene, and usage amount by weight is 100 parts；Intermediate layer material uses Kynoar
With the alloy of random polypropylene, usage amount by weight is 40 parts, including mass fraction be 45% Kynoar, it is 10% compatible
Agent material and 45% random polypropylene；Inner layer material is polymethyl methacrylate modified polyvinilidene fluoride, is used by weight
Amount is 40 parts.Composite pipe is obtained through three-layer co-extruded one-pass molding out.
The performance test results:
Properties of sample testing standard in embodiment:
(1) internal pressure-resistant is tested: GB/T 6111-2003；
(2) thermal cycle experiment: GB/T 18742.3-2002；
(3) sanitation performance is tested: GB/T 17219-1998.
The present invention solves the inner layer material present in Kynoar-polyolefin composite pipe in the past and is easily precipitated small point
The problems such as son, layer materials are easily detached from and processing technology is complicated, has low precipitation, and Coating combination is close, and production technology is easy
The advantages that, also have that the environmental protection of pure Kynoar tubing, precipitation property is small, chemical stability is good on this basis；Impact strength
High, abrasion performance, creep resistance, mechanical strength and good toughness；Heat resistance is good, noninflammability, long-term use temperature are at -20-100 DEG C；Table
The one's best qualities such as face is smooth, and fluid resistance is small, and oxygen resistance is prominent.
The above is only specific embodiments of the present invention, but technical characteristic of the invention is not limited thereto.It is any with this hair
Based on bright, to realize essentially identical technical effect, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (10)
1. a kind of MULTILAYER COMPOSITE tubing, it is characterised in that: by internal layer, the middle layer being tightly attached on the outside of the internal layer and be tightly attached to institute
The outer layer composition on the outside of middle layer is stated, the internal layer is fluorolefin polymer internal layer, and the middle layer is alloy granule middle layer,
It include compatilizer in the alloy granule middle layer, the outer layer is atactic polyolefin outer layer.
2. a kind of MULTILAYER COMPOSITE tubing according to claim 1, it is characterised in that: the atactic polyolefin outer layer is random
Outer layer of polypropylene.
3. a kind of MULTILAYER COMPOSITE tubing according to claim 1, it is characterised in that: the alloy granule middle layer is by compatible
The macromolecular interpenetrating of agent, fluorolefin polymer and atactic polyolefin is wound.
4. a kind of MULTILAYER COMPOSITE tubing according to claim 3, it is characterised in that: the mass fraction range of the compatilizer
For 5%-30%, the mass fraction range of the fluorolefin polymer is 10%-85%, the mass fraction of the atactic polyolefin
Range is 10%-85%.
5. a kind of MULTILAYER COMPOSITE tubing according to claim 3, it is characterised in that: the compatilizer is on macromolecule side chain
The comb polymer of the ester group of alkyl containing C4 or more and C4 or more simultaneously.
6. a kind of MULTILAYER COMPOSITE tubing according to claim 1, it is characterised in that: wrapped in the fluorolefin polymer internal layer
Containing vinylidene fluoride homopolymer or at least one of the copolymer based on vinylidene.
7. using a kind of preparation method of MULTILAYER COMPOSITE tubing as described in claim 1, it is characterised in that: including walking as follows
It is rapid:
(1) different material is separately added into three extruders for being extruded into internal layer, middle layer and outer layer, wherein being used to form
Fluorolefin polymer pellet is added in the extruder of internal layer, is used to form addition atactic polyolefin pellet in the extruder of outer layer,
It is used to form in the extruder of middle layer and alloy granule is added；
(2) under the conditions of certain extrusion process, internal layer, middle layer and outer layer are squeezed out respectively using three extruders, and pass through
Same composite extrusion die head one-pass molding obtains unshaped three-layer composite pipe material；
(3) unshaped three-layer composite pipe material is by being cut into required length after vacuum sizing, then after carrying out thermal finalization with baking oven
Obtain three-layer composite pipe material.
8. a kind of preparation method of MULTILAYER COMPOSITE tubing according to claim 7, it is characterised in that: the alloy granule by
After compatilizer, fluorolefin polymer and atactic polyolefin mixing, obtained through extruding pelletization.
9. a kind of preparation method of MULTILAYER COMPOSITE tubing according to claim 7, it is characterised in that: in the step (2)
The machine barrels of three extruders be divided into 6 bringing-up sections, each section of heating temperature of the machine barrel of the extruder for internal layer are as follows: 1 section plus
Hot temperature 2 is 20 ± 5 DEG C, and 2 sections of heating temperatures are 225 ± 5 DEG C, and 3 sections of heating temperatures are 230 ± 5 DEG C, and 4 sections of heating temperatures are 235
± 5 DEG C, 5 sections of heating temperatures are 240 ± 5 DEG C, and 6 sections of heating temperatures are 245 ± 5 DEG C；The machine barrel of extruder for middle layer is each
Section heating temperature are as follows: 1 section of heating temperature is 220 ± 5 DEG C, and 2 sections of heating temperatures are 225 ± 5 DEG C, and 3 sections of heating temperatures are 230 ± 5
DEG C, 4 sections of heating temperatures are 235 ± 5 DEG C, and 5 sections of heating temperatures are 240 ± 5 DEG C, and 6 sections of heating temperatures are 245 ± 5 DEG C；For outer layer
Extruder each section of heating temperature of machine barrel are as follows: 1 section of heating temperature is 195 ± 5 DEG C, and 2 sections of heating temperatures are 200 ± 5 DEG C, 3 sections
Heating temperature is 205 ± 5 DEG C, and 4 sections of heating temperatures are 210 ± 5 DEG C, and 5 sections of heating temperatures are 215 ± 5 DEG C, and 6 sections of heating temperatures are
220±5℃。
10. a kind of preparation method of MULTILAYER COMPOSITE tubing according to claim 7, it is characterised in that: in the step (2)
Composite extrusion die head be divided into 4 bringing-up sections, it is 235 ± 5 DEG C that every section of heating temperature, which is respectively as follows: 1 section of heating temperature, 2 sections of heating
Temperature is 240 ± 5 DEG C, and 3 sections of heating temperatures are 235 ± 5 DEG C, and 4 sections of heating temperatures are 235 ± 5 DEG C.
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| WO2023218483A1 (en) * | 2022-05-09 | 2023-11-16 | Ashirvad Pipes Pvt. Ltd | Multilayer flexible pressure pipes |
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