CN109370001A - A kind of plastic-metal composite pipe and preparation method thereof - Google Patents
A kind of plastic-metal composite pipe and preparation method thereof Download PDFInfo
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- CN109370001A CN109370001A CN201811098473.4A CN201811098473A CN109370001A CN 109370001 A CN109370001 A CN 109370001A CN 201811098473 A CN201811098473 A CN 201811098473A CN 109370001 A CN109370001 A CN 109370001A
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- F16L9/14—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups
- F16L9/147—Compound tubes, i.e. made of materials not wholly covered by any one of the preceding groups comprising only layers of metal and plastics with or without reinforcement
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of plastic-metal composite pipes and preparation method thereof, belong to tubular object extruding field.α of the present invention, dealcoholized type crosslinking agent methoxyl group triethoxysilane and catalyst dibutyltin dilaurylate is added in alpha, omega-dihydroxy polymethylphenylsiloxane, the additive for forming the plastic tube base-material of silicone rubber kinds, improves its resistance to low temperature, increases the resistance to low temperature of plastic-metal composite pipe；It is modified through γ-(methacryloxypropyl) propyl trimethoxy silicane that gas-phase silica, kaolin is added, prevents crazing from being further developed into crackle, improves the shock resistance of material and the toughness of plastics and mechanical property；Adipic acid hexamethylene diamine salt, Decyldiamine sebacate is added as nylon mixture, just property effectively improves blend low temperature, and low-temperature impact is strong, so that plastics will not become fragile under cryogenic, toughness is preferable, enhances the resistance to low temperature of multiple tube.The present invention solves the problems, such as that the low temperature ability to bear of current aluminum plastic composite pipe is poor, poor mechanical property.
Description
Technical field
The present invention relates to tubular object extruding technical fields, and in particular to a kind of plastic-metal composite pipe and preparation method thereof.
Background technique
Aluminum plastic composite pipe is a kind of water supplying pipe of cast iron pipe of substitution earliest, basic structure be followed successively by from inside to outside plastics,
Hot melt adhesive, aluminium alloy, hot melt adhesive and plastics.Traditional aluminum plastic composite pipe is to close polyethylene, polyethylene hot melt adhesive special and aluminium
The five-layer structure composite pipe that goldleaf is formed and is combined into one by high temperature, high pressure basis, outermost layer and inner layer are high density
(specific gravity is greater than 0.95g/cm to polyethylene3), the second layer is hot melt adhesive, and third layer is aluminum pipe, and the 4th layer is also one layer of hot melt adhesive；It should
Tubing can not only increase compressive resistance due to containing metallic aluminum, can be with blocking oxygen, carbon dioxide and water etc. to keep away
The corrosion risk of cast iron pipe is exempted from, thermal conductivity is good and reduces hot spot concentration, antistatic and shielding is good, and has certain fire-retardant
Effect, it is often more important that, by the partition of metallic intermediate layer aluminium, the inner layer vinyon no added using safety and sanitation, outside
Allow to add safety and sanitation of the stabilizer for being enough to resist light, oxygen aging without influencing inner layer contacts water in layer, it is ensured that defeated
Water lines it is safe and reliable.In the prior art, the inside and outside layer of aluminum plastic composite pipe generallys use high density polyethylene (HDPE), but highly dense
It is more to spend double bond content in polyethylene, and the hydrogen atom on the alpha-carbon atom by double bond is easier to oxygen than the hydrogen atom on tertiary carbon atom
Change, therefore the ageing-resistant performance of high density polyethylene (HDPE) is poor, at high temperature under high pressure aging speed faster, and high density polyethylene (HDPE)
Intermolecular force is smaller, thus is easier to mutually slide between macromolecular chain, and under little mechanical stress effect, polyethylene is remained to
Carry out slow deformation.The low temperature ability to bear of aluminum plastic composite pipe is poor, and outer layer plastic is easy to appear brittle failure at low temperature, causes
Outer layer plastic peels off, and influences normally to use.
Summary of the invention
The technical problems to be solved by the invention: for current aluminum plastic composite pipe low temperature ability to bear is poor, mechanical property
Can difference problem, a kind of plastic-metal composite pipe and preparation method thereof is provided.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of plastic-metal composite pipe, including low-temperature resistant plastic base-material, hot melt adhesive adhesive layer；
The preparation method of the low-temperature resistant plastic base-material, includes the following steps:
S1. take α, alpha, omega-dihydroxy polymethylphenylsiloxane 20 ~ 30:5 in mass ratio ~ 9 that flexibilizer additive is added, is warming up to 110
~ 120 DEG C are stirred, and are cooled to room temperature, obtain cooled material, take cooled material 100 ~ 150:5 in mass ratio ~ 9:1 ~ 3 that methoxyl group is added
Triethoxysilane, dibutyl tin dilaurate are stirred in 25 ~ 30 DEG C, vacuumize 10 ~ 20min of holding, must be stirred
Object；
S2. according to the mass fraction, 20 ~ 40 parts of stirring mixtures, 100 ~ 200 parts of polyethylene, 30 ~ 50 parts of hydrogenated styrene-fourths are taken
Diene block copolymer, 20 ~ 30 parts of ethylene-octene copolymers are stirred to get low-temperature resistant plastic base-material.
In the step S1 flexibilizer additive the preparation method comprises the following steps:
A. take gas-phase silica 2 ~ 6:1 in mass ratio ~ 4:2 ~ 5 that kaolin mixing is added, it is dry, obtain dried object, take dried object by
Dehydrated alcohol is added in 1 ~ 4:10 of mass ratio ~ 15, adds γ-(methacryloxypropyl) propyl trimethoxy of dried object quality 2 ~ 5%
Base silane is stirred in 60 ~ 65 DEG C, is filtered, and suction filtration slag is taken to grind 200 ~ 400 meshes, collects sieving particle；
B. it takes lauryl sodium sulfate 1 ~ 4:10 in mass ratio ~ 20 that deionized water is added, is warming up to 50 ~ 60 DEG C and is stirred, obtain
Mixed liquor adjusts pH to 8 ~ 9 and takes 30 ~ 60 parts of sieving particles, 15 ~ 20 portions of mixed liquors, 6 ~ 9 parts of metering systems according to the mass fraction
Methyl esters, 4 ~ 7 parts of butyl acrylate mixing, ultrasound obtain ultrasonic liquid, are warming up to 40 ~ 50 DEG C, and the over cure of ultrasonic liquid quality 1 ~ 3% is added
Sour potassium is stirred in 70 ~ 75 DEG C, is cooled to room temperature, and filters, and takes and takes out filter residue and drying to get flexibilizer additive.
Low-temperature resistant plastic base-material is stirred condition in the step S2 are as follows: is stirred 1 ~ 3h in 150 ~ 200 DEG C.
The hot melt adhesive adhesive layer the preparation method comprises the following steps:
(1) it takes adipic acid hexamethylene diamine salt 2 ~ 4:1 in mass ratio ~ 3 that Decyldiamine sebacate mixing is added, mixture is obtained, by quality
Number meter takes 8 ~ 10 parts of mixtures, 4 ~ 6 parts of caprolactams, 0.4 ~ 0.8 part of stearic acid, 80 ~ 100 parts of water to be stirred, must stir
Mixture a, is passed through nitrogen protection, adds four [β-(3,5- di-t-butyl -4- hydroxy benzenes of stirring mixture a mass 2 ~ 6%
Base) propionic acid] pentaerythritol ester, 200 ~ 250 DEG C are warming up to, is stirred in 1.5MPa, is cooled to room temperature, is stood, extrusion granulation,
Obtain particulate matter；
(2) it takes particulate matter 4 ~ 7:4 in mass ratio ~ 6 that thermoplastic polyurethane is added, is stirred in 5000r/min, obtains mixture a,
The terminal epoxy wax of mixture a mass 10 ~ 15% is added, adds maleic anhydride grafted ethene-vinegar of mixture a mass 6 ~ 10%
Vinyl acetate melt blending, through twin-screw extrusion to get hot melt adhesive adhesive layer.
The condition of melt blending in the step (2) are as follows: in 180rmp/min, 150 ~ 160 DEG C of melt blendings.
A kind of preparation method of plastic-metal composite pipe, includes the following steps:
Low-temperature resistant plastic base-material is taken to be molded, cooling 15 ~ 20s keeps 40MPa20 ~ 30s, through twin-screw extrusion, vacuum sizing is fixed
Type, cooling drying, obtains plastic inner pipe, takes hot melt adhesive adhesive layer to melt in 150 ~ 200 DEG C, obtains bond vitrified layer, take adhesive layer packet
It is overlying on plastic inner pipe outer wall, obtains inner tube, aluminium strip aluminum pipe full circle is welded into, then bond vitrified layer is coated on aluminum pipe outer wall, obtained
Intermediate tube respectively enters outer tube that plastic inner pipe is used as, intermediate tube, inner tube in co-extrusion die together, forms, obtains plastics
Metal composite pipe.
The low-temperature resistant plastic base-material injecting condition are as follows: be warming up to 200 ~ 220 DEG C, keep injection pressure 20MPa injection molding 10 ~
15s。
The present invention is compared with other methods, and advantageous effects are:
(1) dealcoholized type crosslinking agent methoxyl group triethoxysilane is added in α, alpha, omega-dihydroxy polymethylphenylsiloxane by the present invention
With catalyst dibutyltin dilaurylate, the addition of crosslinking agent so that condensation reaction occurs for linear polysiloxane, crosslinking curing at
Tridimensional network forms the additive of the plastic tube base-material of silicone rubber kinds, and the small molecule by-product of removing is alcohol, to environment friend
It is good pollution-free, phenyl polar group is introduced in rubber molecular chain, changes rubber structure regularity, is reduced Tg and is inhibited crystallization,
Its resistance to low temperature is improved, is added in plastic tube and carries out reinforcement and filling, increase the lower temperature resistance of plastic-metal composite pipe
Energy；
(2) gas-phase silica is added in the present invention, kaolin is modified through γ-(methacryloxypropyl) propyl trimethoxy silicane, by
Hydrophily has become lipophilicity, surface introduce active group carbon-carbon double bond, it is lipophilic raising improve flexibilizer additive and
Compatibility between plastic polyethylene matrix, then polymerize with methyl methacrylate, butyl acrylate through causing, polymer is formed,
The heat resistance for improving multiple tube plastic material, functions simultaneously as stress raiser, and the matrix for inducing particle periphery generates largely
Crazing and shear band, while again prevent crazing be further developed into crackle, so that the shock resistance of material is improved, to plastics
Toughness and the raising played the role of of mechanical property；
(3) adipic acid hexamethylene diamine salt, Decyldiamine sebacate is added as nylon mixture in the present invention, add caprolactam,
Stearic acid etc. forms nylon type copolyamide substance, and terminal epoxy wax, maleic anhydride grafted ethene-vinylacetate is added and makees
For expanding material, improve the compatibility with thermoplastic polyurethane, form hydrogen bond, in copolyamide containing it is a large amount of it is highly polar-
CONH- group has good affinity to aluminium surface, forms preferable molecular separating force, it is made to have excellent glue to aluminum pipe
Performance is tied, so that bonding interface, which stretches, can continue transmitting stress, tensile strength and elongation at break are improved, with hydrogenation of benzene second
Alkene-butadiene block copolymer, ethylene-octene copolymer can cause a large amount of crazings and shear band, crazing as rubber particles
The formation of shear band needs to consume energy, therefore just property effectively improves blend low temperature, and low-temperature impact is strong, so that in cryogenic conditions
Lower plastics will not become fragile, and toughness is preferable, enhance the resistance to low temperature of multiple tube.
Specific embodiment
Flexibilizer additive the preparation method comprises the following steps:
A. it takes gas-phase silica 2 ~ 6:1 in mass ratio ~ 4:2 ~ 5 that kaolin mixing is added, in 100 ~ 110 DEG C of dry 1 ~ 3h, obtains dry
Dry object takes dried object 1 ~ 4:10 in mass ratio ~ 15 that dehydrated alcohol is added, adds the γ-(metering system of dried object quality 2 ~ 5%
Acyl-oxygen) propyl trimethoxy silicane, it is stirred 1 ~ 3h in 60 ~ 65 DEG C, is filtered, suction filtration slag is taken to grind 200 ~ 400 mesh
Sieve collects sieving particle；
B. take lauryl sodium sulfate 1 ~ 4:10 in mass ratio ~ 20 that deionized water is added, be warming up to 50 ~ 60 DEG C be stirred 20 ~
30min obtains mixed liquor, adjusts pH to 8 ~ 9 and takes 30 ~ 60 portions of sieving particles, 15 ~ 20 portions of mixed liquors, 6 ~ 9 parts according to the mass fraction
Methyl methacrylate, 4 ~ 7 parts of butyl acrylate mixing, 20 ~ 30min of ultrasound obtain ultrasonic liquid, are warming up to 40 ~ 50 DEG C, and ultrasound is added
The potassium peroxydisulfate of liquid quality 1 ~ 3% is stirred 3 ~ 5h in 70 ~ 75 DEG C, is cooled to room temperature, filter, take take out filter residue and drying to get
Flexibilizer additive.
Low-temperature resistant plastic base-material the preparation method comprises the following steps:
S1. take α, alpha, omega-dihydroxy polymethylphenylsiloxane 20 ~ 30:5 in mass ratio ~ 9 that flexibilizer additive is added, is warming up to 110
~ 120 DEG C are stirred 50 ~ 70min, are cooled to room temperature, obtain cooled material, and cooled material 100 ~ 150:5 in mass ratio ~ 9:1 ~ 3 is taken to add
Enter methoxyl group triethoxysilane, dibutyl tin dilaurate, be stirred 1 ~ 3h in 25 ~ 30 DEG C, vacuumize holding 10 ~
20min obtains stirring mixture；
S2. according to the mass fraction, 20 ~ 40 parts of stirring mixtures, 100 ~ 200 parts of polyethylene, 30 ~ 50 parts of hydrogenated styrene-fourths are taken
Diene block copolymer, 20 ~ 30 parts of ethylene-octene copolymers, are stirred 1 ~ 3h in 150 ~ 200 DEG C to get low-temperature resistant plastic
Base-material.
Hot melt adhesive adhesive layer the preparation method comprises the following steps:
(1) it takes adipic acid hexamethylene diamine salt 2 ~ 4:1 in mass ratio ~ 3 that Decyldiamine sebacate mixing is added, mixture is obtained, by quality
Number meter takes 8 ~ 10 parts of mixtures, 4 ~ 6 parts of caprolactams, 0.4 ~ 0.8 part of stearic acid, 80 ~ 100 parts of water, it is stirred 20 ~
30min must stir mixture a, be passed through nitrogen protection, add four [β-(3,5- bis- tertiary fourths of stirring mixture a mass 2 ~ 6%
Base -4- hydroxy phenyl) propionic acid] pentaerythritol ester, 200 ~ 250 DEG C are warming up to, 1 ~ 3h is stirred in 1.5MPa, is cooled to room
Temperature, stands 30 ~ 50min, and extrusion granulation obtains particulate matter；
(2) it takes particulate matter 4 ~ 7:4 in mass ratio ~ 6 that thermoplastic polyurethane is added, is stirred 3 ~ 8min in 5000r/min, obtains mixed
Object a is closed, the terminal epoxy wax of mixture a mass 10 ~ 15% is added, adds the maleic anhydride grafting of mixture a mass 6 ~ 10%
Ethylene-vinyl acetate, in 180rmp/min, 150 ~ 160 DEG C of melt blendings, through twin-screw extrusion to get hot melt adhesive adhesive layer.
A kind of preparation method of plastic-metal composite pipe, includes the following steps:
Low-temperature resistant plastic base-material is taken to be warming up to 200 ~ 220 DEG C, injection pressure 20MPa is kept to be molded 10 ~ 15s, cooling 15 ~ 20s is protected
Hold 40MPa20 ~ 30s, through twin-screw extrusion, vacuum sizing sizing, cooling drying obtains plastic inner pipe, take hot melt adhesive adhesive layer in
150 ~ 200 DEG C of meltings, obtain bond vitrified layer, take adhesive layer to be coated on plastic inner pipe outer wall, obtain inner tube, aluminium strip is welded into aluminum pipe
Full circle, then bond vitrified layer is coated on aluminum pipe outer wall, obtains intermediate tube, the outer tube that is respectively used as plastic inner pipe, intermediate tube,
Inner tube enters in co-extrusion die together, and molding obtains plastic-metal composite pipe.
Embodiment 1
Flexibilizer additive the preparation method comprises the following steps:
A. it takes gas-phase silica 2:1:2 in mass ratio that kaolin mixing is added, in 100 DEG C of dry 1h, obtains dried object, take dried object
Dehydrated alcohol is added in 1:10 in mass ratio, adds γ-(methacryloxypropyl) propyl trimethoxy silicon of dried object quality 2%
Alkane is stirred 1h in 60 DEG C, filters, and suction filtration slag is taken to grind 200 meshes, collects sieving particle；
B. it takes lauryl sodium sulfate 1:10 in mass ratio that deionized water is added, is warming up to 50 DEG C and is stirred 20min, must mix
Liquid adjusts pH to 8 and takes 30 parts of sieving particles, 15 portions of mixed liquors, 6 parts of methyl methacrylates, 4 parts of acrylic acid according to the mass fraction
Butyl ester mixing, ultrasonic 20min obtain ultrasonic liquid, are warming up to 40 DEG C, and the potassium peroxydisulfate of ultrasonic liquid quality 1% is added, stirs in 70 DEG C
3h is mixed, is cooled to room temperature, is filtered, takes and takes out filter residue and drying to get flexibilizer additive.
Low-temperature resistant plastic base-material the preparation method comprises the following steps:
S1. take α, alpha, omega-dihydroxy polymethylphenylsiloxane 20:5 in mass ratio that flexibilizer additive is added, is warming up to 110 DEG C and stirs
Mixing 50min is mixed, is cooled to room temperature, obtains cooled material, takes cooled material 100:5:1 in mass ratio that methoxy ethyl triethoxy silicane is added
Alkane, dibutyl tin dilaurate are stirred 1h in 25 DEG C, vacuumize and keep 10min, obtain stirring mixture；
S2. according to the mass fraction, take 20 parts of stirring mixtures, 100 parts of polyethylene, 30 parts of hydrogenated styrene-butadiene blocks total
Polymers, 20 parts of ethylene-octene copolymers are stirred 1h in 150 DEG C to get low-temperature resistant plastic base-material.
Hot melt adhesive adhesive layer the preparation method comprises the following steps:
(1) it takes adipic acid hexamethylene diamine salt 2:1 in mass ratio that Decyldiamine sebacate mixing is added, mixture is obtained, by mass fraction
Meter, takes 8 parts of mixtures, 4 parts of caprolactams, 0.4 part of stearic acid, 80 parts of water, is stirred 20min, must stir mixture a, leads to
Enter nitrogen protection, adds four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi of stirring mixture a mass 2%
Alcohol ester, is warming up to 200 DEG C, is stirred 1h in 1.5MPa, is cooled to room temperature, and stands 30min, and extrusion granulation obtains particulate matter；
(2) it takes particulate matter 4:4 in mass ratio that thermoplastic polyurethane is added, is stirred 3min in 5000r/min, obtains mixture a,
The terminal epoxy wax of mixture a mass 10% is added, adds maleic anhydride grafted ethene-vinyl acetate of mixture a mass 6%
Ester, in 180rmp/min, 150 DEG C of melt blendings, through twin-screw extrusion to get hot melt adhesive adhesive layer.
A kind of preparation method of plastic-metal composite pipe, includes the following steps:
Low-temperature resistant plastic base-material is taken to be warming up to 200 DEG C, injection pressure 20MPa injection molding 10s, cooling 15s is kept to keep
40MPa20s, through twin-screw extrusion, vacuum sizing sizing, cooling drying obtains plastic inner pipe, takes hot melt adhesive adhesive layer in 150 DEG C
Melting, obtains bond vitrified layer, takes adhesive layer to be coated on plastic inner pipe outer wall, obtain inner tube, aluminium strip is welded into aluminum pipe full circle, then will
Bond vitrified layer is coated on aluminum pipe outer wall, obtains intermediate tube, and the outer tube that is respectively used as plastic inner pipe, intermediate tube, inner tube are together
Into in co-extrusion die, molding obtains plastic-metal composite pipe.
Embodiment 2
Flexibilizer additive the preparation method comprises the following steps:
A. it takes gas-phase silica 6:4:5 in mass ratio that kaolin mixing is added, in 110 DEG C of dry 3h, obtains dried object, take dried object
Dehydrated alcohol is added in 4:15 in mass ratio, adds γ-(methacryloxypropyl) propyl trimethoxy silicon of dried object quality 5%
Alkane is stirred 3h in 65 DEG C, filters, and suction filtration slag is taken to grind 400 meshes, collects sieving particle；
B. it takes lauryl sodium sulfate 4:20 in mass ratio that deionized water is added, is warming up to 60 DEG C and is stirred 30min, must mix
Liquid adjusts pH to 9 and takes 60 parts of sieving particles, 20 portions of mixed liquors, 9 parts of methyl methacrylates, 7 parts of acrylic acid according to the mass fraction
Butyl ester mixing, ultrasonic 30min obtain ultrasonic liquid, are warming up to 50 DEG C, and the potassium peroxydisulfate of ultrasonic liquid quality 3% is added, stirs in 75 DEG C
5h is mixed, is cooled to room temperature, is filtered, takes and takes out filter residue and drying to get flexibilizer additive.
Low-temperature resistant plastic base-material the preparation method comprises the following steps:
S1. take α, alpha, omega-dihydroxy polymethylphenylsiloxane 30:9 in mass ratio that flexibilizer additive is added, is warming up to 120 DEG C and stirs
Mixing 70min is mixed, is cooled to room temperature, obtains cooled material, takes cooled material 150:9:3 in mass ratio that methoxy ethyl triethoxy silicane is added
Alkane, dibutyl tin dilaurate are stirred 3h in 30 DEG C, vacuumize and keep 20min, obtain stirring mixture；
S2. according to the mass fraction, take 40 parts of stirring mixtures, 200 parts of polyethylene, 50 parts of hydrogenated styrene-butadiene blocks total
Polymers, 30 parts of ethylene-octene copolymers are stirred 3h in 200 DEG C to get low-temperature resistant plastic base-material.
Hot melt adhesive adhesive layer the preparation method comprises the following steps:
(1) it takes adipic acid hexamethylene diamine salt 4:3 in mass ratio that Decyldiamine sebacate mixing is added, mixture is obtained, by mass fraction
Meter, takes 10 parts of mixtures, 6 parts of caprolactams, 0.8 part of stearic acid, 100 parts of water, is stirred 30min, must stir mixture a,
It is passed through nitrogen protection, adds four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta of stirring mixture a mass 6%
Four alcohol esters, are warming up to 250 DEG C, are stirred 3h in 1.5MPa, are cooled to room temperature, and stand 50min, and extrusion granulation obtains particle
Object；
(2) it takes particulate matter 7:6 in mass ratio that thermoplastic polyurethane is added, is stirred 8min in 5000r/min, obtains mixture a,
The terminal epoxy wax of mixture a mass 15% is added, adds maleic anhydride grafted ethene-acetic acid second of mixture a mass 10%
Enester, in 180rmp/min, 160 DEG C of melt blendings, through twin-screw extrusion to get hot melt adhesive adhesive layer.
A kind of preparation method of plastic-metal composite pipe, includes the following steps:
Low-temperature resistant plastic base-material is taken to be warming up to 220 DEG C, injection pressure 20MPa injection molding 15s, cooling 20s is kept to keep
40MPa30s, through twin-screw extrusion, vacuum sizing sizing, cooling drying obtains plastic inner pipe, take hot melt adhesive adhesive layer in 150 ~
200 DEG C of meltings, obtain bond vitrified layer, take adhesive layer to be coated on plastic inner pipe outer wall, obtain inner tube, it is whole that aluminium strip is welded into aluminum pipe
Circle, then is coated on aluminum pipe outer wall for bond vitrified layer, obtains intermediate tube, the outer tube that is respectively used as plastic inner pipe, intermediate tube, interior
Pipe enters in co-extrusion die together, and molding obtains plastic-metal composite pipe.
Embodiment 3
Flexibilizer additive the preparation method comprises the following steps:
A. it takes gas-phase silica 3:2:3 in mass ratio that kaolin mixing is added, in 105 DEG C of dry 2h, obtains dried object, take dried object
Dehydrated alcohol is added in 3:13 in mass ratio, adds γ-(methacryloxypropyl) propyl trimethoxy silicon of dried object quality 3%
Alkane is stirred 2h in 63 DEG C, filters, and suction filtration slag is taken to grind 300 meshes, collects sieving particle；
B. it takes lauryl sodium sulfate 3:16 in mass ratio that deionized water is added, is warming up to 55 DEG C and is stirred 25min, must mix
Liquid adjusts pH to 8.5 and takes 40 parts of sieving particles, 18 portions of mixed liquors, 8 parts of methyl methacrylates, 6 parts of propylene according to the mass fraction
Acid butyl ester mixing, ultrasonic 25min obtain ultrasonic liquid, are warming up to 45 DEG C, and the potassium peroxydisulfate of ultrasonic liquid quality 2% is added, stirs in 72 DEG C
Mixing 4h is mixed, is cooled to room temperature, is filtered, takes and takes out filter residue and drying to get flexibilizer additive.
Low-temperature resistant plastic base-material the preparation method comprises the following steps:
S1. take α, alpha, omega-dihydroxy polymethylphenylsiloxane 25:6 in mass ratio that flexibilizer additive is added, is warming up to 115 DEG C and stirs
Mixing 60min is mixed, is cooled to room temperature, obtains cooled material, takes cooled material 120:8:2 in mass ratio that methoxy ethyl triethoxy silicane is added
Alkane, dibutyl tin dilaurate are stirred 2h in 27 DEG C, vacuumize and keep 15min, obtain stirring mixture；
S2. according to the mass fraction, take 30 parts of stirring mixtures, 150 parts of polyethylene, 40 parts of hydrogenated styrene-butadiene blocks total
Polymers, 25 parts of ethylene-octene copolymers are stirred 2h in 170 DEG C to get low-temperature resistant plastic base-material.
Hot melt adhesive adhesive layer the preparation method comprises the following steps:
(1) it takes adipic acid hexamethylene diamine salt 3:2 in mass ratio that Decyldiamine sebacate mixing is added, mixture is obtained, by mass fraction
Meter, takes 9 parts of mixtures, 5 parts of caprolactams, 0.6 part of stearic acid, 90 parts of water, is stirred 25min, must stir mixture a, leads to
Enter nitrogen protection, adds four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] Ji Wusi of stirring mixture a mass 4%
Alcohol ester, is warming up to 220 DEG C, is stirred 2h in 1.5MPa, is cooled to room temperature, and stands 40min, and extrusion granulation obtains particulate matter；
(2) it takes particulate matter 5:5 in mass ratio that thermoplastic polyurethane is added, is stirred 5min in 5000r/min, obtains mixture a,
The terminal epoxy wax of mixture a mass 13% is added, adds maleic anhydride grafted ethene-vinyl acetate of mixture a mass 8%
Ester, in 180rmp/min, 155 DEG C of melt blendings, through twin-screw extrusion to get hot melt adhesive adhesive layer.
A kind of preparation method of plastic-metal composite pipe, includes the following steps:
Low-temperature resistant plastic base-material is taken to be warming up to 210 DEG C, injection pressure 20MPa injection molding 13s, cooling 18s is kept to keep
40MPa25s, through twin-screw extrusion, vacuum sizing sizing, cooling drying obtains plastic inner pipe, takes hot melt adhesive adhesive layer in 180 DEG C
Melting, obtains bond vitrified layer, takes adhesive layer to be coated on plastic inner pipe outer wall, obtain inner tube, aluminium strip is welded into aluminum pipe full circle, then will
Bond vitrified layer is coated on aluminum pipe outer wall, obtains intermediate tube, and the outer tube that is respectively used as plastic inner pipe, intermediate tube, inner tube are together
Into in co-extrusion die, molding obtains plastic-metal composite pipe.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking low-temperature resistant plastic base-material.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking hot melt adhesive adhesive layer.
Comparative example 3: the plastic-metal composite pipe of company of Hebei province production.
The plastic-metal composite pipe that above-described embodiment is obtained with comparative example is detected, is tried using high/low temperature Alternate hot and humid
Tryoff (LRHS-1000B-LJS Shanghai Linpin Equipment Co., Ltd.) is to the aluminum plastic composite pipe of above-described embodiment and contrast groups
High/low-temperature impact processing is carried out, hot conditions are 60 DEG C, 90%RH, and cryogenic conditions are -30 DEG C, and high/low temperature residence time is 1h, is followed
Ring 200 times, the test of hydrostatic strength is then carried out using GB/T 6111-2003 again, test temperature is 95 DEG C, test period
For 165h, hydrostatic tension 4.6Mpa, whether observation sample has leakage or fracture phenomena after the completion of test, if any then for not
Qualification is not then qualification；The test of peel strength: test method is carried out according to GB/T2790-1995 standard, obtained result
As shown in table 1.
Table 1:
In summary, plastic-metal composite pipe effect of the invention is more preferable as can be seen from Table 1, is worth of widely use.
Claims (7)
1. a kind of plastic-metal composite pipe, which is characterized in that including low-temperature resistant plastic base-material, hot melt adhesive adhesive layer；
The preparation method of the low-temperature resistant plastic base-material, includes the following steps:
S1. take α, alpha, omega-dihydroxy polymethylphenylsiloxane 20 ~ 30:5 in mass ratio ~ 9 that flexibilizer additive is added, is warming up to 110
~ 120 DEG C are stirred, and are cooled to room temperature, obtain cooled material, take cooled material 100 ~ 150:5 in mass ratio ~ 9:1 ~ 3 that methoxyl group is added
Triethoxysilane, dibutyl tin dilaurate are stirred in 25 ~ 30 DEG C, vacuumize 10 ~ 20min of holding, must be stirred
Object；
S2. according to the mass fraction, 20 ~ 40 parts of stirring mixtures, 100 ~ 200 parts of polyethylene, 30 ~ 50 parts of hydrogenated styrene-fourths are taken
Diene block copolymer, 20 ~ 30 parts of ethylene-octene copolymers are stirred to get low-temperature resistant plastic base-material.
2. plastic-metal composite pipe according to claim 1, which is characterized in that the system of flexibilizer additive in the step S1
Preparation Method are as follows:
A. take gas-phase silica 2 ~ 6:1 in mass ratio ~ 4:2 ~ 5 that kaolin mixing is added, it is dry, obtain dried object, take dried object by
Dehydrated alcohol is added in 1 ~ 4:10 of mass ratio ~ 15, adds γ-(methacryloxypropyl) propyl trimethoxy of dried object quality 2 ~ 5%
Base silane is stirred in 60 ~ 65 DEG C, is filtered, and suction filtration slag is taken to grind 200 ~ 400 meshes, collects sieving particle；
B. it takes lauryl sodium sulfate 1 ~ 4:10 in mass ratio ~ 20 that deionized water is added, is warming up to 50 ~ 60 DEG C and is stirred, obtain
Mixed liquor adjusts pH to 8 ~ 9 and takes 30 ~ 60 parts of sieving particles, 15 ~ 20 portions of mixed liquors, 6 ~ 9 parts of metering systems according to the mass fraction
Methyl esters, 4 ~ 7 parts of butyl acrylate mixing, ultrasound obtain ultrasonic liquid, are warming up to 40 ~ 50 DEG C, and the over cure of ultrasonic liquid quality 1 ~ 3% is added
Sour potassium is stirred in 70 ~ 75 DEG C, is cooled to room temperature, and filters, and takes and takes out filter residue and drying to get flexibilizer additive.
3. plastic-metal composite pipe according to claim 1, which is characterized in that low-temperature resistant plastic base-material in the step S2
Be stirred condition are as follows: be stirred 1 ~ 3h in 150 ~ 200 DEG C.
4. plastic-metal composite pipe according to claim 1, which is characterized in that the preparation method of the hot melt adhesive adhesive layer
Are as follows:
(1) it takes adipic acid hexamethylene diamine salt 2 ~ 4:1 in mass ratio ~ 3 that Decyldiamine sebacate mixing is added, mixture is obtained, by quality
Number meter takes 8 ~ 10 parts of mixtures, 4 ~ 6 parts of caprolactams, 0.4 ~ 0.8 part of stearic acid, 80 ~ 100 parts of water to be stirred, must stir
Mixture a, is passed through nitrogen protection, adds four [β-(3,5- di-t-butyl -4- hydroxy benzenes of stirring mixture a mass 2 ~ 6%
Base) propionic acid] pentaerythritol ester, 200 ~ 250 DEG C are warming up to, is stirred in 1.5MPa, is cooled to room temperature, is stood, extrusion granulation,
Obtain particulate matter；
(2) it takes particulate matter 4 ~ 7:4 in mass ratio ~ 6 that thermoplastic polyurethane is added, is stirred in 5000r/min, obtains mixture a,
The terminal epoxy wax of mixture a mass 10 ~ 15% is added, adds maleic anhydride grafted ethene-vinegar of mixture a mass 6 ~ 10%
Vinyl acetate melt blending, through twin-screw extrusion to get hot melt adhesive adhesive layer.
5. plastic-metal composite pipe according to claim 4, which is characterized in that the item of melt blending in the step (2)
Part are as follows: in 180rmp/min, 150 ~ 160 DEG C of melt blendings.
6. a kind of preparation method of the plastic-metal composite pipe as described in claim 1 ~ 5 any one, which is characterized in that the system
Preparation Method includes the following steps:
Low-temperature resistant plastic base-material is taken to be molded, cooling 15 ~ 20s keeps 40MPa20 ~ 30s, through twin-screw extrusion, vacuum sizing is fixed
Type, cooling drying, obtains plastic inner pipe, takes hot melt adhesive adhesive layer to melt in 150 ~ 200 DEG C, obtains bond vitrified layer, take adhesive layer packet
It is overlying on plastic inner pipe outer wall, obtains inner tube, aluminium strip aluminum pipe full circle is welded into, then bond vitrified layer is coated on aluminum pipe outer wall, obtained
Intermediate tube respectively enters outer tube that plastic inner pipe is used as, intermediate tube, inner tube in co-extrusion die together, forms, obtains plastics
Metal composite pipe.
7. the preparation method of plastic-metal composite pipe according to claim 6, which is characterized in that the low-temperature resistant plastic base
Expect injecting condition are as follows: be warming up to 200 ~ 220 DEG C, injection pressure 20MPa is kept to be molded 10 ~ 15s.
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| CN201811098473.4A CN109370001A (en) | 2018-09-20 | 2018-09-20 | A kind of plastic-metal composite pipe and preparation method thereof |
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| CN201811098473.4A CN109370001A (en) | 2018-09-20 | 2018-09-20 | A kind of plastic-metal composite pipe and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094619A (en) * | 2019-12-13 | 2020-12-18 | 上海铂淳胶粘技术有限公司 | Fiber composite hot melt adhesive and preparation method thereof |
| CN113650940A (en) * | 2021-08-13 | 2021-11-16 | 珠海市华鹰药用包装材料有限公司 | Medicinal aluminum-plastic combined cover and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104482324A (en) * | 2014-11-20 | 2015-04-01 | 江阴市南方造粒厂有限公司 | High-viscosity flame-retardant polyethylene-aluminum composite pipe |
| CN104482323A (en) * | 2014-11-19 | 2015-04-01 | 江阴市南方造粒厂有限公司 | High-viscosity anti-oxidization polyethylene-aluminum composite pipe |
| CN108329555A (en) * | 2017-12-21 | 2018-07-27 | 安徽中电气有限公司 | A kind of processing method of low temperature resistant aluminum plastic composite pipe |
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2018
- 2018-09-20 CN CN201811098473.4A patent/CN109370001A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104482323A (en) * | 2014-11-19 | 2015-04-01 | 江阴市南方造粒厂有限公司 | High-viscosity anti-oxidization polyethylene-aluminum composite pipe |
| CN104482324A (en) * | 2014-11-20 | 2015-04-01 | 江阴市南方造粒厂有限公司 | High-viscosity flame-retardant polyethylene-aluminum composite pipe |
| CN108329555A (en) * | 2017-12-21 | 2018-07-27 | 安徽中电气有限公司 | A kind of processing method of low temperature resistant aluminum plastic composite pipe |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112094619A (en) * | 2019-12-13 | 2020-12-18 | 上海铂淳胶粘技术有限公司 | Fiber composite hot melt adhesive and preparation method thereof |
| CN113650940A (en) * | 2021-08-13 | 2021-11-16 | 珠海市华鹰药用包装材料有限公司 | Medicinal aluminum-plastic combined cover and preparation process thereof |
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Application publication date: 20190222 |