CN114851669B - Nylon and fluoropolymer co-extrusion automobile fuel oil conveying multilayer pipe resistant to interlayer cracking - Google Patents

Nylon and fluoropolymer co-extrusion automobile fuel oil conveying multilayer pipe resistant to interlayer cracking Download PDF

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CN114851669B
CN114851669B CN202210347258.3A CN202210347258A CN114851669B CN 114851669 B CN114851669 B CN 114851669B CN 202210347258 A CN202210347258 A CN 202210347258A CN 114851669 B CN114851669 B CN 114851669B
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nylon
fluoropolymer
layer
amphiphilic branched
maleic anhydride
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CN114851669A (en
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张天赐
刘彪
高斌
王磊
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
    • 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
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses an interlayer-cracking-resistant nylon and fluoropolymer co-extrusion automobile fuel oil conveying multilayer pipe which adopts a five-layer composite structure and comprises a nylon outer layer, an amphiphilic branched polymer bonding layer 1, a fluoropolymer barrier layer, an amphiphilic branched polymer bonding layer 2 and a conductive nylon inner layer from outside to inside. Compared with the traditional automobile fuel oil conveying multilayer pipe adhesive layer, the adhesive layer can greatly improve the acting force between the nylon layer and the fluoropolymer barrier layer, effectively avoid interlayer cracking after the multilayer pipe works for a long time, and improve the safety of an automobile fuel oil conveying system.

Description

Nylon and fluoropolymer co-extrusion automobile fuel oil conveying multilayer pipe resistant to interlayer cracking
Technical Field
The invention relates to the field of automobile fuel oil conveying pipelines, in particular to an automobile fuel oil conveying multilayer pipe co-extruded by interlayer cracking resistant nylon and fluoropolymer.
Background
With the high-speed development of the automobile industry at home and abroad, the environment protection and safety call of the automobile industry are higher and higher, and further the requirements on automobile parts are stricter. Particularly, the development of automobile fuel oil conveying pipelines with good mechanical properties and low fuel oil permeability by various host factories is a relatively universal solution, and nylon with salt spray resistance, low precipitation, heat resistance and fuel oil resistance and a fluoropolymer with excellent fuel oil blocking property are coextruded, and the two polymer materials have large chemical structure difference and poor compatibility, and an amphiphilic compatibility bonding layer is required to be added, otherwise interlayer cracking risk exists in the use process. Therefore, the selection of tie layers is considered in the preparation of automotive fuel delivery multilayer tubes using nylon and fluoropolymer coextrusion to produce a multilayer tube resistant to interlayer cracking.
Disclosure of Invention
The invention aims to prepare an interlayer-cracking-resistant nylon and fluoropolymer co-extruded automobile fuel oil conveying multilayer pipe.
The main technical problem faced by the invention is to prepare an amphipathic bonding layer with good compatibility with a nylon layer and a fluoropolymer barrier layer of a multilayer pipe, and the existence of the bonding layer can serve as a bridge to improve the interlayer adhesion between the nylon layer and the fluoropolymer layer, so that the interlayer cracking resistance of the multilayer pipe is improved.
In order to solve the technical problems, the invention adopts the technical principle that: the amidation reaction mechanism is utilized to carry out amidation reaction on the amino-terminated nylon oligomer and the carboxyl of the fluoropolymer modified by grafting maleic anhydride, so as to prepare a branched copolymer which takes the fluoropolymer as a molecular main chain and takes the nylon oligomer as a branched side chain, and the branched copolymer simultaneously contains nylon and a fluoropolymer chain structure and can serve as an amphiphilic bonding layer to improve the acting force between a nylon layer and the fluoropolymer layer, thereby improving the interlayer cracking resistance of the multilayer pipe.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
An automobile fuel oil conveying multilayer pipe co-extruded by nylon and fluoropolymer with interlayer cracking resistance adopts a five-layer composite structure, and comprises the following components from outside to inside: the nylon comprises a nylon outer layer, an amphiphilic branched polymer bonding layer 1, a fluoropolymer barrier layer, an amphiphilic branched polymer bonding layer 2 and a conductive nylon inner layer.
In some examples, the nylon outer layer thickness is 0.35±0.02mm, the amphiphilic branched polymer tie layer 1 thickness is 0.1±0.02mm, the fluoropolymer barrier layer thickness is 0.20±0.02mm, the amphiphilic branched polymer tie layer 2 thickness is 0.1±0.02mm, and the conductive nylon inner layer thickness is 0.15±0.02mm.
In some examples, the nylon outer layer is blended modified nylon, and the modifier is one or more selected from plasticizer, toughening agent, antioxidant, light stabilizer, ultraviolet absorbent, lubricant, flow modifier and flame retardant. The nylon matrix is selected from the group consisting of PA12, PA6, PA11, PA56, PA66, PA610, PA612, PA1010, PA1012, PA1212, preferably PA12. The relative viscosity of the nylon 12 matrix in the blended modified nylon is 1.9-2.4 (ISO 307, m-cresol is solvent, concentration of 0.005 g/ml), preferably 2.1.
The conductive nylon inner layer is conductive modified nylon, the nylon matrix is preferably the same as the nylon outer layer, and the nylon matrix is selected from PA12, PA6, PA11, PA56, PA66, PA610, PA612, PA1010, PA1012 and PA1212, preferably PA12; the conductive filler is selected from one or more of carbon black, carbon fiber, carbon nano tube and graphene, the addition amount is 3-30%, and the volume resistivity is less than 10 6 ohm cm. In addition, the conductive nylon inner layer can also contain one or more of toughening agent, antioxidant, lubricant and flame retardant.
The amphiphilic branched polymer bonding layers 1 and 2 are amphiphilic branched copolymers formed by amidation reaction of monoamino-terminated nylon oligomer and maleic anhydride grafted modified fluoropolymer, and the preparation method comprises the following steps:
(1) Preparation of maleic anhydride graft modified fluoropolymer: firstly, soaking the fluoropolymer in a strong alkali solution (such as a 20wt% NaOH solution) for 1-3 hours, and then washing with pure water and suction filtering to obtain a pretreated fluoropolymer; secondly, uniformly mixing the pretreated fluoropolymer, a certain proportion of Maleic Anhydride (MAH) monomer and an initiator by using a high-speed mixer; finally, extruding by using a double-screw extruder with the length-diameter ratio of 58-78, wherein the extruding temperature is determined by the type of the fluorine polymer, the screw rotating speed is 80-120rpm, and the maleic anhydride grafted modified fluorine polymer is prepared by drawing, water cooling, granulating and drying the extruded material.
Preferably, the fluoropolymer is one of polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), more preferably polyvinylidene fluoride (PVDF);
preferably, the amount of MAH monomer added is determined by the maleic anhydride grafting ratio of the desired maleic anhydride graft modified fluoropolymer, and in some embodiments, the maleic anhydride grafting ratio is 1.5% to 8%, and the MA monomer added is 2 to 15% of the fluoropolymer;
preferably, the initiator is selected from at least one of Benzoyl Peroxide (BPO), azobisisobutyronitrile (AIBN), dicumyl peroxide (DCP), more preferably Benzoyl Peroxide (BPO);
preferably, the initiator is added in an amount of 0.2 to 0.5wt%, more preferably 0.3% of the fluoropolymer;
(2) Preparation of monoamino-terminated nylon oligomer: adding nylon monomer, monoamino end-capping agent, catalyst and water in a certain proportion into a reaction kettle, replacing nitrogen for multiple times, and heating to raise the temperature for reaction (in some examples, raising the temperature to 240-290 ℃ and keeping for 2-6 h); after the reaction is completed, pressure is released (in some examples, the pressure is released to 5-10 kPa), the pressure is released and the temperature is reduced (in some examples, the temperature is reduced to 220-240 ℃), and then the vacuum treatment is carried out for 60-120min, so that melt polycondensation is completed; stopping vacuumizing after the melt polycondensation is completed; adding nitrogen to 100-300kpa, stopping stirring, and cooling to 20-30 ℃;
Wherein the nylon monomer is a monomer for preparing PA12, PA6, PA11, PA56, PA66, PA610, PA612, PA1010, PA1012 and PA1212, for example, when preparing monoamino end-capped PA12 oligomer, the nylon monomer is laurolactam; dodecalactam is preferred;
preferably, the monoamino end-capping agent is one or more of tridecyl amine, lauryl amine and n-undecyl amine, and the addition amount is determined by the molecular weight of the nylon oligomer;
Preferably, the catalyst is at least one of phosphoric acid, hypophosphorous acid and sodium hypophosphite, more preferably phosphoric acid, and the addition amount is 0.005-0.02% of the mass of the nylon monomer;
preferably, the water is ultrapure water, and the addition amount is 8-40% of the mass of the nylon monomer, preferably 10-20%;
Preferably, the molecular weight of the prepared nylon oligomer is 1000-3000;
preferably, the amino-terminated content of the nylon oligomer is 0.3-1.0mmol/g;
(3) Preparation of amphiphilic branched polymers: putting the maleic anhydride grafted and modified fluoropolymer prepared in the step (1) into a reaction kettle filled with nylon oligomer according to a certain proportion, replacing nitrogen for a plurality of times, heating to 240-265 ℃, vacuumizing to reduce the absolute pressure of a reaction system to below 1kPa, continuing to react for 1-4h to make the maleic anhydride grafted and modified fluoropolymer and the nylon oligomer perform amidation reaction to obtain an amphiphilic branched copolymer, and then carrying out traction-water cooling-granulating to obtain amphiphilic branched polymer granules.
Taking PA12 oligomer as an example, the structure of the amphiphilic branched copolymer is schematically shown below:
Preferably, the monoamino-terminated nylon oligomer of step (3) comprises 10-45% of the total mass of the feedstock, more preferably 30%.
In some examples, the fluoropolymer used in the fluoropolymer barrier layer is consistent with the fluoropolymer used in the preparation of the amphiphilic branched polymer tie layer.
According to the invention, preferably, the amphiphilic branched polymer bonding layer 1 is consistent with the nylon of the nylon outer layer, and the amphiphilic branched polymer bonding layer 2 is consistent with the nylon of the conductive nylon inner layer, more preferably, the nylons are all PA12; the present invention can produce, for example, PA 6-tie layer-fluoropolymer-tie layer-PA 6 multilayer tube, PA 6-tie layer-fluoropolymer-tie layer-PA 12 multilayer tube, PA 612-tie layer-fluoropolymer-tie layer-PA 12 multilayer tube.
The automobile fuel oil conveying multilayer pipe can be prepared by utilizing a multilayer coextrusion pipe production line.
Compared with the prior art, the invention has the main advantages that: compared with the traditional adhesive layer, the existence of the adhesive layer can greatly improve the acting force of the nylon layer and the fluoropolymer barrier layer, effectively avoid the interlayer cracking of the multilayer pipe during working, prolong the service life of the multilayer pipe and improve the safety of an automobile fuel oil conveying system. And the scheme can be popularized to the fields of any multilayer pipe containing nylon and fluorine polymer and the fields of blending modification.
Drawings
FIG. 1 is a schematic cross-sectional view of an automotive fuel delivery multilayer tube according to the present invention;
FIG. 2 is a schematic cross-sectional view of an interlayer peel strength test specimen;
fig. 3 is a schematic diagram of a test specimen for peel strength between a nylon outer layer and a fluoropolymer barrier layer, and fig. 4 is a schematic diagram of a test specimen for peel strength between a conductive nylon inner layer and a fluoropolymer barrier layer.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The testing method comprises the following steps:
(1) Number average molecular weight test: the test was performed by a Gel Permeation Chromatography (GPC) system, equipment model number WATERS 1515;
(2) End amino content test: the test was performed by potentiometric titration (Metrohm 848 automatic potentiometric titration);
(3) Grafting rate test of maleic anhydride grafted and modified fluoropolymer: the maleic anhydride graft modified fluoropolymer prepared in proper amount is dissolved in dimethyl sulfoxide (DMSO) solvent, and precipitated by methanol, and the precipitated powder is repeatedly washed, filtered by suction for three times, and dried in a vacuum oven at 80 ℃ for 10 hours. Then weighing a certain amount of purified maleic anhydride grafted modified fluoropolymer powder by a balance, dissolving in Dimethylformamide (DMF), dripping thymol blue, titrating by using a calibrated KOH-ethanol solution, and finally calculating the grafting rate according to the following formula:
Wherein: wherein, C is the concentration (mol/L) of KOH-ethanol solution; v 0 is the volume of KOH-ethanol solution (ml) required to titrate the DMF solution without maleic anhydride graft modification of the fluoropolymer; v 1 is the volume (ml) of KOH-ethanol solution required to titrate the DMF solution containing the maleic anhydride-grafted fluoropolymer; m is the mass (g) of the maleic anhydride graft modified fluoropolymer.
(4) Melt volume flow rate test: according to the ISO 1133 test standard.
(5) Interlayer peel strength test: because the automobile fuel oil conveying multilayer pipe related to the patent is small in size, interlayer peeling strength test is not easy to directly carry out, and the test method is used for referencing GB/T8808-1988 soft composite plastic material peeling test method, and the specific operation is as follows:
a. sample preparation: a multilayer composite sheet was prepared by extrusion using a multilayer sheet coextrusion apparatus, the material and thickness of each layer of the sheet were as described in the examples herein, and a specimen having a width of 15mm and a length of 200mm was cut along the extrusion direction of the multilayer sheet (a schematic cross-sectional view is shown in FIG. 2), and the test layer was peeled off in advance by 50mm along the length direction of the specimen, and the adhesive layer between the peeled off portions of the test layer was removed, and the peeled off portions were not significantly damaged.
B. interlayer peel force test: the test specimen should be first placed at 23℃under 50% relative humidity for 48 hours, then T-type tensile test was performed at 23℃under 50% relative humidity by using an electronic peel tester (BLD-01, jinan electric device Co., ltd.) at a tensile speed of 300mm/min, and the test result was recorded.
[ Preparation example 1]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified PVDF: soaking PVDF (Arkema, kynar 721) in 20% NaOH strong alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated PVDF; 3.5kg of pretreated PVDF and 140g of MAH monomer and 10.5g of BPO initiator are uniformly mixed by a high mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm in sequence, and preparing the maleic anhydride grafting modified PVDF (PVDF-MA-1) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 2%.
B. preparation of monoamino-terminated nylon 12 oligomer: 1.5kg of laurolactam, 151g of laurylamine, 0.15g of phosphoric acid and 180g of ultrapure water are added into a 10L reaction kettle, nitrogen is replaced for three times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 230 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 2008, and the amino-terminated content is 0.5mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-1 is put into a reaction kettle filled with nylon 12 oligomer, nitrogen is substituted for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-1), wherein the amino content of the branched copolymer is 0mmol/g, and the fact that all the amino end groups of the monoamino-terminated nylon 12 oligomer react with PVDF-MA-1 carboxyl has the melt index MVR=5 cm 3/10 min (235 ℃,5 kg).
[ Preparation example 2]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified PVDF: firstly, soaking PVDF (Arkema, kynar 721) in a 20% NaOH strong alkali solution for 2 hours, and then washing with pure water and suction filtering to obtain pretreated PVDF; uniformly mixing 3.5kg of pretreated PVDF, 210g of MAH monomer and 7g of BPO initiator by using a high-speed mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, sequentially setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm, and preparing the maleic anhydride grafted modified PVDF (PVDF-MA-2) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 3.3%.
B. monoamino-terminated nylon 612 oligomer preparation: 503g of hexamethylenediamine, 997g of dodecanedioic acid and 1000g of ultrapure water were added to a 10L reaction vessel, the mixture was replaced with nitrogen three times, and the mixture was heated to 70℃to prepare an aqueous amide salt dispersion having a solid content of 60%. Then 0.15g of phosphoric acid and 143g of laurylamine are added, the reaction system is heated to 240 ℃ and the temperature and pressure are maintained for 2 hours. Then heating to 250 ℃, dehydrating and decompressing to 5kPa, vacuumizing for 60min, and finishing melt polycondensation; after the melt polycondensation was completed, the vacuum was stopped, nitrogen was added to 200kpa, stirring was stopped, and the temperature was lowered to 30 ℃. The number average molecular weight of the prepared nylon 612 oligomer is 2010, and the content of terminal amino groups is 0.5mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-2 is put into a reaction kettle filled with nylon 612 oligomer, nitrogen is substituted for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa by vacuumizing, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 612 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-2), wherein the amino content of the branched copolymer is 0mmol/g, and the fact that all the amino end groups of the monoamino-terminated nylon 612 oligomer react with PVDF-MA-2 carboxyl groups proves that the melt index MVR=5 cm 3/10 min (235 ℃,5 kg).
[ Preparation example 3]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified PVDF: soaking PVDF (Arkema, kynar 721) in 20% NaOH strong alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated PVDF; uniformly mixing 3.5kg of pretreated PVDF, 210g of MAH monomer and 7g of BPO initiator by using a high-speed mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, sequentially setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm, and preparing the maleic anhydride grafted modified PVDF (PVDF-MA-3) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 3.3%.
B. Preparation of monoamino-terminated nylon 12 oligomer: 1.5kg of laurolactam, 334g of laurylamine, 0.15g of phosphoric acid and 180g of ultrapure water are added into a 10L reaction kettle, nitrogen is replaced for three times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 1000, and the amino-terminated content is 1.0mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-3 is put into a reaction kettle filled with nylon 12 oligomer, nitrogen is replaced for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-3), wherein the amino content of the branched copolymer is 0mmol/g, and the fact that all the amino end groups of the monoamino-terminated nylon 12 oligomer react with PVDF-MA-3 carboxyl has the melt index MVR=6.5 cm 3/10 min (235 ℃,5 kg).
[ PREPARATION EXAMPLE 4]
The amphiphilic branched copolymer is prepared according to the following steps
A. preparation of maleic anhydride graft modified PVDF: soaking PVDF (Arkema, kynar 721) in 20% NaOH strong alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated PVDF; uniformly mixing 3.5kg of pretreated PVDF, 105g of MAH monomer and 10.5g of BPO initiator by using a high mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, sequentially setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm, and preparing the maleic anhydride grafted modified PVDF (PVDF-MA-4) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 1.5%.
B. Preparation of monoamino-terminated nylon 12 oligomer: adding 1.5kg of laurolactam, 98g of laurylamine, 0.15g of phosphoric acid and 180g of ultrapure water into a 10L reaction kettle, replacing nitrogen for three times, heating to 280 ℃ and maintaining for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 90 minutes, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 3004, and the amino-terminated content is 0.3mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-4 is put into a reaction kettle filled with nylon 12 oligomer, nitrogen is replaced for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-4), wherein the amino content of the branched copolymer is 0mmol/g, and the fact that all the amino end groups of the monoamino-terminated nylon 12 oligomer react with PVDF-MA-4 carboxyl groups proves that the melt index MVR=4.0 cm 3/10 min (235 ℃ and 5 kg).
[ Preparation example 5]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified PVDF: soaking PVDF (Arkema, kynar 721) in 20% NaOH strong alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated PVDF; 3.0kg of pretreated PVDF, 180g of MAH monomer and 9g of dicumyl peroxide (DCP) initiator are uniformly mixed by a high mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, sequentially setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃,200 ℃ and the screw rotating speed of 100rpm, and preparing the maleic anhydride grafted modified PVDF (PVDF-MA-5) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 3.5%.
B. Preparation of monoamino-terminated nylon 12 oligomer: 2kg of laurolactam, 219g of tridecyl amine, 0.2g of phosphoric acid and 240g of ultrapure water are added into a 10L reaction kettle, nitrogen is replaced for three times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 2002, and the amino-terminated content is 0.5mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.0kg PVDF-MA-5 is put into a reaction kettle filled with nylon 12 oligomer, nitrogen is replaced for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-5), wherein the amino content of the branched copolymer is 0mmol/g, and the fact that all the amino end groups of the monoamino-terminated nylon 12 oligomer react with PVDF-MA-5 carboxyl groups proves that the melt index MVR=4.5 cm 3/10 min (235 ℃,5 kg).
[ Preparation example 6]
The amphiphilic branched copolymer is prepared according to the following steps
A. preparation of maleic anhydride graft modified PVDF: firstly, soaking PVDF (Arkema, kynar 721) in a 20% NaOH strong alkali solution for 2 hours, and then washing with pure water and suction filtering to obtain pretreated PVDF; 3.5kg of pretreated PVDF and 525g of MAH monomer, 17.5g of Azobisisobutyronitrile (AIBN) initiator are mixed homogeneously by means of a high mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, sequentially setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm, and preparing the maleic anhydride grafted modified PVDF (PVDF-MA-6) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 8%.
B. preparation of monoamino-terminated nylon 12 oligomer: 1.5kg of laurolactam, 303g of n-undecylamine, 0.15g of phosphoric acid and 180g of ultrapure water are added into a 10L reaction kettle, nitrogen is replaced for three times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 1001, and the amino-terminated content is 1.0mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-6 is put into a reaction kettle filled with nylon 12 oligomer, nitrogen is replaced for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-6), wherein the amino content of the branched copolymer is 0mmol/g, and the fact that all the amino end groups of the monoamino-terminated nylon 12 oligomer react with PVDF-MA-6 carboxyl has the melt index MVR=5.5 cm 3/10 min (235 ℃,5 kg).
[ Preparation example 7]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified ETFE: soaking ETFE (AGC, fluon ETFE 800C) in 20% NaOH alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated ETFE; uniformly mixing 4.5kg of pretreated ETFE and 180g of MAH monomer and 13.5g of BPO initiator by using a high-speed mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, sequentially setting the temperature of a feeding section to a machine head at 200 ℃, 260 ℃, 270 ℃, 265 ℃ and 260 ℃ at the screw speed of 100rpm, and preparing maleic anhydride graft modified ETFE (ETFE-MA-7) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of maleic anhydride is 2%.
B. Preparation of monoamino-terminated nylon 12 oligomer: adding 0.5kg of laurolactam, 50g of laurylamine, 0.05g of phosphoric acid and 90g of ultrapure water into a 10L reaction kettle, replacing nitrogen for three times, heating to 280 ℃ and maintaining for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 2020, and the amino-terminated content is 0.5mmol/g;
c. Preparation of amphiphilic branched copolymer: adding 4.5kg of ETFE-MA-7 into a reaction kettle filled with nylon 12 oligomer, after 3 times of nitrogen replacement, heating to 265 ℃, vacuumizing to ensure that the absolute pressure of a reaction system is reduced to below 1kPa, continuously reacting for 60 minutes to ensure that the maleic anhydride grafted and modified ETFE and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then carrying out traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-7), wherein the amino content of the branched copolymer is 0mmol/g, and the fact that all amino end groups of the monoamino end-capped nylon 12 oligomer react with ETFE-MA-7 carboxyl groups proves that the melt index MVR=10.5 cm 3/10 minutes (275 ℃ and 5 kg).
[ Preparation example 8 ]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified PVDF: soaking PVDF (Arkema, kynar 721) in 20% NaOH strong alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated PVDF; uniformly mixing 3.5kg of pretreated PVDF, 20g of MAH monomer and 10.5g of BPO initiator by using a high mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, sequentially setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm, and preparing the maleic anhydride grafted modified PVDF (PVDF-MA-8) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 0.3%.
B. Preparation of monoamino-terminated nylon 12 oligomer: 1.5kg of laurolactam, 151g of laurylamine, 0.15g of phosphoric acid and 180g of ultrapure water are added into a 10L reaction kettle, nitrogen is replaced for three times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 2008, and the amino-terminated content is 0.5mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-8 is put into a reaction kettle filled with nylon 12 oligomer, nitrogen is substituted for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the PVDF grafted and modified by maleic anhydride and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-1'), wherein the amino content of the branched copolymer is 0.10mmol/g, which means that due to the lower grafting rate of PVDF-MA-8 maleic anhydride, part of the amino end of the mono-ammonia end capped nylon 12 oligomer does not participate in the reaction, and the melt index of the branched copolymer is MVR=9.5 cm 3/10 min (235 ℃,5 kg).
[ Preparation example 9 ]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified PVDF: soaking PVDF (Arkema, kynar 721) in 20% NaOH strong alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated PVDF; 3.5kg of pretreated PVDF and 140g of MAH monomer and 10.5g of BPO initiator are uniformly mixed by a high mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm in sequence, and preparing the maleic anhydride grafted modified PVDF (PVDF-MA-9) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 2%.
B. Preparation of a diamine-terminated nylon 12 oligomer: 1.5kg of laurolactam, 165g of dodecanediamine, 0.15g of phosphoric acid and 180g of ultrapure water are added into a 10L reaction kettle, nitrogen is replaced for three times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 oligomer is 2004, and the amino-terminated content is 1.0mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-9 is put into a reaction kettle filled with nylon 12 oligomer, nitrogen is substituted for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 12 oligomer undergo amidation reaction to obtain an amphiphilic branched copolymer, and then the amphiphilic branched copolymer is subjected to traction-water cooling-granulating to obtain amphiphilic branched copolymer granules (FPA-2'), wherein the amino content of the branched copolymer is 0.30mmol/g, the melt index of the branched copolymer is MVR=0.1 cm 3/10 minutes (235 ℃,5 kg), and the reason that the melt index is lower is that the diamino terminated nylon 12 oligomer and the PVDF-MA-9 undergo branched crosslinking reaction.
[ Preparation example 10 ]
The amphiphilic branched copolymer is prepared according to the following steps
A. Preparation of maleic anhydride graft modified PVDF: soaking PVDF (Arkema, kynar 721) in 20% NaOH strong alkali solution for 2h, washing with pure water, and suction filtering to obtain pretreated PVDF; 3.5kg of pretreated PVDF and 140g of MAH monomer and 10.5g of BPO initiator are uniformly mixed by a high mixer; extruding by using a double screw extruder with the length-diameter ratio of 68, setting the temperature of a feeding section to a machine head at 160 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃ and the screw rotating speed of 100rpm in sequence, and preparing the maleic anhydride grafting modified PVDF (PVDF-MA-10) by traction, water cooling, granulating and drying the extruded material, wherein the grafting rate of the maleic anhydride is 2%.
B. Preparation of monoamino-terminated nylon 12: 1.5kg of laurolactam, 9.3g of laurylamine, 0.15g of phosphoric acid and 180g of ultrapure water are added into a 10L reaction kettle, nitrogen is replaced for three times, and the mixture is heated to 280 ℃ and kept for 5 hours to complete the ring-opening reaction of the laurolactam; after the ring opening is completed, the pressure is released to 10kPa, the temperature is reduced to 240 ℃ at the same time, and then the vacuum pumping treatment is carried out for 120min, thus completing the melt polycondensation; after the melt polycondensation is completed, the vacuum pumping is stopped, nitrogen is added to 100kpa, stirring is stopped, and the temperature is reduced to 30 ℃. The number average molecular weight of the prepared monoamino-terminated nylon 12 is 30060, and the amino-terminated content is 0.033mmol/g;
c. Preparation of amphiphilic branched copolymer: 3.5kg PVDF-MA-10 is put into a reaction kettle filled with nylon 12, nitrogen is substituted for 3 times, then the temperature is raised to 240 ℃, the absolute pressure of a reaction system is reduced to below 1kPa, the reaction is continued for 60 minutes, the maleic anhydride grafted and modified PVDF and the nylon 12 are subjected to amidation reaction to obtain an amphipathic branched copolymer, and then the amphipathic branched copolymer is subjected to traction-water cooling-granulating to obtain amphipathic branched copolymer granules (FPA-3'), wherein the amino content of the branched copolymer is 0mmol/g, the melt index is MVR=0.5 cm 3/10 min (235 ℃,5 kg), and the melt index is lower because of relatively serious continuous entanglement of nylon 12 molecular chains with high molecular weight.
[ Preparation example 11 ]
Nylon 12 and maleic anhydride graft modified PVDF blends were prepared as follows: 3.5kg of nylon 12 particles (Evonik, VESTAMID L2140) and 1.5kg of maleic anhydride modified PVDF ((PVDF-MA-1) are uniformly mixed by a high mixer and then extruded by a double screw extruder with the length-diameter ratio of 48, the feeding section is sequentially set to 180 ℃, 220 ℃, 240 ℃, 220 ℃ from the temperature of a machine head, the extruded materials are subjected to traction, water cooling, granulating and drying to prepare a nylon 12 and maleic anhydride grafted modified PVDF blend (EPA-4'), the amino content of the branched copolymer is 0.14mmol/g, and the melt index is MVR=5 cm 3/10 min (235 ℃,5 kg) when only a small amount of nylon 12 terminal amino reacts with PVDF-MA-1 in the extrusion blending process.
[ Preparation example 12 ]
The multilayer Guan Nilong outer layer raw material was prepared according to the following steps
7.2Kg of nylon 12 particles (Evonik, VESTAMID L2140), 2kg of plasticizer N-butylbenzenesulfonamide (Zhejiang Pramolen chemical Co., ltd.), 0.8kg of toughening agent POE-g-MAH (DOW, N416), 15g of antioxidant Irgafox, 15g of antioxidant Irganox1098, 20g of light stabilizer Tinuvin 770DF,20g of ultraviolet absorbent Tinuvin 312 are uniformly mixed by a high mixer and then extruded by a double screw extruder with an aspect ratio of 48, the feeding section is sequentially set to the temperature of a machine head at 190 ℃, 215 ℃, 230 ℃, 215 ℃, and the extruded materials are subjected to traction, water cooling, granulating and drying to prepare a multi-layer nylon 12 outer layer raw material, wherein the melt index of the modified nylon 12 is MVR=10 cm 3/10 min (235 ℃,5 kg).
[ Preparation example 13 ]
The raw materials of the inner layer of the multi-layer tube conductive nylon 12 are prepared according to the following steps
7.5Kg of nylon 12 particles (Evonik, L2140), 0.5kg of a toughening agent POE-G-MAH (DOW, N416), 2kg of conductive carbon black (Ensaco 350G), 15G of an antioxidant Irgafox, 15G of an antioxidant Irganox1098 and 10G of a lubricant KAOWAX EB-FF are uniformly mixed by a high mixer and then extruded by a double screw extruder with an aspect ratio of 48, the temperature of a feeding section to a machine head is set to 180 ℃, 220 ℃, 240 ℃, 220 ℃, and the extrusion material is subjected to traction, water cooling, granulating and drying to prepare a multilayer pipe conductive nylon 12 inner layer raw material, wherein the melt index of the modified nylon 12 is MVR=4 cm 3/10 min (235 ℃,5 kg).
[ Preparation example 14 ]
The raw materials of the inner layer of the multilayer tube conductive nylon 612 are prepared according to the following steps
7.5Kg of nylon 612 particles (DuPont, 158NC 010), 0.5kg of toughener POE-G-MAH (DOW, N416), 2kg of conductive carbon black (Ensaco 350G), 15G of antioxidant Irgafox, 15G of antioxidant Irganox1098 and 10G of lubricant KAOWAX EB-FF are uniformly mixed by a high mixer and then extruded by a double screw extruder with the length-diameter ratio of 48, the temperature of a feeding section to a machine head is set to 180 ℃, 220 ℃, 250 ℃, 240 ℃, 220 ℃, and the temperature of the extruded materials are subjected to traction, water cooling, granulating and drying to prepare the inner layer raw material of the multilayer pipe conductive nylon 12, wherein the melt index of the modified nylon 612 is MVR=4 cm 3/10 min (235 ℃,5 kg).
[ Example 1]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the outer layer of a multilayer tube, the amphiphilic branched copolymer (FPA-1) prepared in preparation example 1 was the tie layers 1 and 2 of the multilayer tube, pvdf (armema, kynar 721) was the barrier layer of the multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was the inner layer of the multilayer tube.
[ Example 2]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the outer layer of a multilayer tube, the amphiphilic branched copolymer (FPA-3) prepared in preparation example 3 was the tie layers 1 and 2 of the multilayer tube, pvdf (armema, kynar 721) was the barrier layer of the multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was the inner layer of the multilayer tube.
[ Example 3]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the outer layer of a multilayer tube, the amphiphilic branched copolymer (FPA-4) prepared in preparation example 4 was the tie layers 1 and 2 of the multilayer tube, pvdf (armema, kynar 721) was the barrier layer of the multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was the inner layer of the multilayer tube.
[ Example 4]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the multilayer tube outer layer, the branched copolymer (FPA-5) prepared in preparation example 5 was the multilayer tube tie layers 1 and 2, pvdf (armema, kynar 721) was the multilayer tube barrier layer, and the conductive modified nylon 12 prepared in preparation example 13 was the multilayer tube inner layer.
[ Example 5]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the outer layer of the multilayer tube, the amphiphilic branched copolymer (FPA-6) prepared in preparation example 6 was the adhesive layers 1 and 2 of the multilayer tube, pvdf (armema, kynar 721) was the barrier layer of the multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was the inner layer of the multilayer tube.
[ Example 6]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the outer layer of the multilayer tube, the amphiphilic branched copolymer (FPA-7) prepared in preparation example 7 was the tie layers 1 and 2 of the multilayer tube, ETFE (AGC, fluon ETFE 800C) was the barrier layer of the multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was the inner layer of the multilayer tube.
[ Example 7]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the multilayer tube outer layer, the amphiphilic branched copolymer (FPA-1) prepared in preparation example 1 was the multilayer tube tie layer 1, pvdf (armema, kynar 721) was the multilayer tube barrier layer, the amphiphilic branched copolymer (FPA-2) prepared in preparation example 2 was the multilayer tube tie layer 2, and the conductive modified nylon 612 prepared in preparation example 14 was the multilayer tube inner layer.
Comparative example 1
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the outer layer of the multilayer tube, the amphiphilic branched copolymer (FPA-1') prepared in preparation example 7 was the adhesive layers 1 and 2 of the multilayer tube, pvdf (armema, kynar 721) was the barrier layer of the multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was the inner layer of the multilayer tube.
Comparative example 2
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the outer layer of the multilayer tube, the amphiphilic branched copolymer (FPA-2') prepared in preparation example 8 was the adhesive layers 1 and 2 of the multilayer tube, pvdf (armema, kynar 721) was the barrier layer of the multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was the inner layer of the multilayer tube.
[ Comparative example 3]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the multilayer tube outer layer, the branched copolymer (FPA-3') prepared in preparation example 9 was the multilayer tube tie layers 1 and 2, pvdf (armema, kynar 721) was the multilayer tube barrier layer, and the conductive modified nylon 12 prepared in preparation example 13 was the multilayer tube inner layer.
[ Comparative example 4]
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon 12 prepared in preparation example 12 was the multilayer tube outer layer, the blend (EPA-4') prepared in preparation example 10 was the multilayer tube tie layers 1 and 2, PVDF (Arkema, kynar 721) was the multilayer tube barrier layer, and the conductive modified nylon 12 prepared in preparation example 13 was the multilayer tube inner layer.
Comparative example 5
The automobile fuel oil conveying multilayer pipe comprises the following layers: the modified nylon prepared in preparation example 12 was an outer layer of a multilayer tube, PVDF (armema, kynar 721) was a barrier layer of a multilayer tube, and the conductive modified nylon 12 prepared in preparation example 13 was an inner layer of a multilayer tube.
To characterize the interlayer peel strength of the multilayer pipes of each scheme, each of the examples and comparative schemes was prepared by a multilayer coextrusion processing apparatus to give a multilayer composite sheet having the same thickness as the corresponding multilayer pipe, wherein the corresponding multilayer pipe had a nylon outer layer thickness of 0.35.+ -. 0.02mm, a corresponding tie layer 1 thickness of 0.1.+ -. 0.02mm, a corresponding fluoropolymer barrier layer thickness of 0.20.+ -. 0.02mm, a corresponding tie layer 2 thickness of 0.1.+ -. 0.02mm, and a corresponding conductive nylon inner layer thickness of 0.15.+ -. 0.02mm. The specific method comprises the following steps: five layers of the multilayer sheet were extruded using a single screw extruder with an aspect ratio of 28, with specific temperatures set for each section:
(1) Nylon outer layer: 180 ℃, 220 ℃, 240 ℃, 230 ℃;
(2) PVDF modified tie layers 1 and 2:180 ℃, 230 ℃, 240 ℃, 230 ℃;
(3) ETFE modified tie layers 1 and 2:200 ℃, 260 ℃,270 ℃ and 260 ℃;
(4) PVDF barrier layer: 160 ℃, 210 ℃, 220 ℃, 210 ℃;
(5) ETFE barrier layer: 200 ℃, 260 ℃, 270 ℃ and 260 ℃;
(6) Conductive nylon inner layer: 180 ℃, 230 ℃, 240 ℃, 220 ℃.
The prepared multilayered sheet was subjected to an interlayer peel strength test, and the results were as follows:
TABLE 1 results of test for peel strength between layers of multilayer tube
Nylon outer layer and barrier layer/N.15mm -1 Conductive nylon inner layer and barrier layer/N.15mm -1
Example 1 6.0 5.0
Example 2 5.5 4.7
Example 3 5.3 4.5
Example 4 4.8 4.0
Example 5 5.5 4.8
Example 6 4.5 3.7
Example 7 5.9 5.1
Comparative example 1 3.3 2.5
Comparative example 2 1.8 1.2
Comparative example 3 2.5 1.9
Comparative example 4 2.6 2.0
Comparative example 5 0.8 0.5
As can be seen from the test result data of the interlayer peel strength test of the examples and the comparative examples in the table 1, the amphiphilic branched copolymer bonding layer prepared by the invention can effectively improve the peel strength of the nylon layer and the fluoropolymer barrier layer, effectively avoid interlayer cracking of the multilayer pipe during working, prolong the service life of the multilayer pipe and improve the safety of an automobile fuel oil conveying system.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (8)

1. A nylon and fluoropolymer co-extruded automotive fuel delivery multilayer tube resistant to interlayer cracking comprising from the outside in: the nylon comprises a nylon outer layer, an amphiphilic branched polymer bonding layer 1, a fluoropolymer barrier layer, an amphiphilic branched polymer bonding layer 2 and a conductive nylon inner layer;
The amphiphilic branched polymer bonding layer 1 is consistent with nylon of the nylon outer layer, the amphiphilic branched polymer bonding layer 2 is consistent with nylon of the conductive nylon inner layer, and the fluoropolymer used by the fluoropolymer blocking layer is consistent with the fluoropolymer used in the preparation of the amphiphilic branched polymer bonding layers 1 and 2;
Wherein, the amphiphilic branched polymer bonding layers 1 and 2 are amphiphilic branched copolymers formed by amidation reaction of monoamino-terminated nylon oligomer and maleic anhydride grafted modified fluoropolymer, and the preparation method comprises the following steps:
(1) Preparation of maleic anhydride graft modified fluoropolymer:
soaking the fluoropolymer in a strong alkali solution, washing with pure water, and suction filtering to obtain a pretreated fluoropolymer;
uniformly mixing the pretreated fluoropolymer with a certain proportion of maleic anhydride monomer and initiator; the addition amount of the maleic anhydride monomer is 2-15% of that of the fluoropolymer;
extruding by using a double-screw extruder, and preparing maleic anhydride grafted modified fluoropolymer by traction, water cooling, granulating and drying the extruded material;
(2) Preparation of monoamino-terminated nylon oligomer: adding a nylon monomer, a monoamino blocking agent, a catalyst and water in a certain proportion into a reaction kettle, and heating to react; after the reaction is finished, pressure relief and temperature reduction are carried out, and then vacuum pumping treatment is carried out, so that melt polycondensation is finished; stopping vacuumizing after the melt polycondensation is completed; the molecular weight of the prepared nylon oligomer is 1000-3000;
(3) Preparation of amphiphilic branched polymers: and (3) adding a certain proportion of the maleic anhydride grafted and modified fluoropolymer prepared in the step (1) into a reaction kettle filled with nylon oligomer, heating, vacuumizing, continuing to react to obtain an amphiphilic branched copolymer, and then carrying out traction-water cooling-granulating to obtain amphiphilic branched polymer granules.
2. A multilayer pipe according to claim 1, wherein the nylon outer layer is blended modified nylon, and the nylon matrix is selected from PA12, PA6, PA11, PA56, PA66, PA610, PA612, PA1010, PA1012, PA1212;
The conductive nylon inner layer adopts conductive modified nylon, and the nylon matrix is selected from PA12, PA6, PA11, PA56, PA66, PA610, PA612, PA1010, PA1012 and PA1212;
The fluoropolymer used in the fluoropolymer barrier layer is polyvinylidene fluoride or ethylene-tetrafluoroethylene copolymer.
3. A multilayer pipe according to claim 2, wherein the nylon matrix of the nylon outer layer is PA12;
And the nylon matrix of the conductive nylon inner layer is PA12.
4. The multilayer tube according to claim 1, wherein in step (1),
The fluorine polymer is polyvinylidene fluoride or ethylene-tetrafluoroethylene copolymer;
The initiator is selected from benzoyl peroxide, azodiisobutyronitrile and dicumyl peroxide, and the addition amount of the initiator is 0.2-0.5wt% of the fluoropolymer.
5. A multilayer pipe according to claim 1, wherein the monoamino capping agent in step (2) is one or more of tridecyl amine, laurylamine, n-undecylamine;
The catalyst is at least one of phosphoric acid, hypophosphorous acid and sodium hypophosphite, and the addition amount is 0.005-0.02% of the mass of the nylon monomer;
The water is ultrapure water, and the addition amount is 8-40% of the mass of the laurolactam;
the amino end content of the nylon oligomer is 0.3-1.0mmol/g.
6. A multilayer pipe according to claim 1 or 5, wherein in step (2), the heating is carried out to 240-290 ℃ for 2-6 hours; decompression to 5-10kPa, cooling to 220-240 ℃; and after stopping vacuumizing, adding nitrogen to 100-300kPa, stopping stirring, and cooling to 20-30 ℃.
7. A multilayer pipe according to claim 1, wherein in step (3) nylon oligomer comprises 10-45% of the total mass of the feedstock.
8. The multilayer pipe according to claim 1 or 7, wherein in step (3), the temperature is raised to 240-265 ℃; and vacuumizing to reduce the absolute pressure of the reaction system to below 1 kPa.
CN202210347258.3A 2022-04-01 2022-04-01 Nylon and fluoropolymer co-extrusion automobile fuel oil conveying multilayer pipe resistant to interlayer cracking Active CN114851669B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10311461A (en) * 1997-05-12 1998-11-24 Asahi Glass Co Ltd Fuel hose
JP2004216779A (en) * 2003-01-16 2004-08-05 Tokai Rubber Ind Ltd Fuel hose for automobile
CN102072368A (en) * 2011-01-13 2011-05-25 天津鹏翎胶管股份有限公司 Antistatic automobile multilayer pipe for transmitting fuel oil
CN103629454A (en) * 2013-12-05 2014-03-12 天津鹏翎胶管股份有限公司 Nylon fuel oil pipe coated with polyurethane sheath and preparation method thereof
CN204312876U (en) * 2014-12-19 2015-05-06 长春亚大汽车零件制造有限公司 Multilayer tubing

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190001636A1 (en) * 2015-09-24 2019-01-03 Dow Global Technologies Llc Multilayer films, articles comprising the same, and methods of making multilayer films

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10311461A (en) * 1997-05-12 1998-11-24 Asahi Glass Co Ltd Fuel hose
JP2004216779A (en) * 2003-01-16 2004-08-05 Tokai Rubber Ind Ltd Fuel hose for automobile
CN102072368A (en) * 2011-01-13 2011-05-25 天津鹏翎胶管股份有限公司 Antistatic automobile multilayer pipe for transmitting fuel oil
CN103629454A (en) * 2013-12-05 2014-03-12 天津鹏翎胶管股份有限公司 Nylon fuel oil pipe coated with polyurethane sheath and preparation method thereof
CN204312876U (en) * 2014-12-19 2015-05-06 长春亚大汽车零件制造有限公司 Multilayer tubing

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