CN103707482B - Possesses high-strength and high oxygen polyolefin pipe and preparation method thereof simultaneously - Google Patents

Possesses high-strength and high oxygen polyolefin pipe and preparation method thereof simultaneously Download PDF

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CN103707482B
CN103707482B CN201310703112.9A CN201310703112A CN103707482B CN 103707482 B CN103707482 B CN 103707482B CN 201310703112 A CN201310703112 A CN 201310703112A CN 103707482 B CN103707482 B CN 103707482B
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strength
polyolefin
preparation
pipe
polyamide
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CN103707482A (en
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聂敏
刘慰
白时兵
王琪
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Sichuan University
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Sichuan University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/926—Flow or feed rate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92761—Mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92904—Die; Nozzle zone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92933—Conveying, transporting or storage of articles
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
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    • C08L2207/00—Properties characterising the ingredient of the composition
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Abstract

The preparation method simultaneously possessing high-strength and high oxygen polyolefin pipe disclosed by the invention is that 100 parts of polyolefin substrates are even with 1 ~ 60 part of fibroblast phase resin alloy, then twin-screw extrusion is put into molten in melt zone temperature 180 ~ 280 DEG C, die temperature 170 ~ 280 DEG C, extrude and adopt rotary extrusion pattern, and in drawing and forming process, port mould diameter is 1.25 ~ 4 with calibration sleeve diameter ratio, extruded velocity is 20 ~ 200rpm:0.2 ~ 6.5m/min with hauling speed ratio, the hoop tensile strength of prepared tubing improves 7.9 ~ 69% than traditional extruding pipe material, OTR oxygen transmission rate have dropped 7 ~ 47% than traditional extruding pipe material.Because preparation method provided by the invention is on prior art basis, introduce " melt convergence traction-cooling sizing " mode, thus fibroblast is made deformation, merging, in-situ fibrillation can to occur in tubing mutually, obtain the fento of corresponding major diameter when content, make the hoop tensile strength of tubing and oxygen resistance obtain larger raising simultaneously.

Description

Possesses high-strength and high oxygen polyolefin pipe and preparation method thereof simultaneously
Technical field
The invention belongs to polyolefin pipe and preparing technical field thereof, be specifically related to one and possess high-strength and high oxygen polyolefin pipe and preparation method thereof simultaneously.
Background technology
Polyolefin (PO) Guan Yin has that as little in density, resistance to chemical attack, pyroconductivity are low, safe and sanitary, can hot-melt adhesive paste and being easy to the excellent performance such as to construct, and development rapidly, is widely used in various field of fluid.For polyethylene (PE), within 2012, China PE pipe consumption figure is more than 3,000,000 tons.Even so, but still there are two defects in polyolefin pipe prepared by existing expressing technique: 1) hoop intensity is lower, and axial strength exceedes hoop intensity, and the hoop of theory analysis witness tube stressed be more than 2 times of axially loaded.2) hinder oxygen ability weak, make to manage interior microbial growth, the dirt that its metabolite is formed, not only have a strong impact on the Long-Time Service of pipeline, and also can affect drinking water quality.
This kind of related defects both at home and abroad for polyolefin pipe has carried out large quantity research, develops the new method of much polyolefin pipe machine-shaping.As in order to improve hoop intensity, the people such as Morath (MorathC.C., WardI.M., Plastics, RubberAndComposites, 2006,35:447) in the extrusion of PA tube, expander is carried out to polypropylene pipe melt, make it in cold drawing process, be subject to axis and circumference stress to improve its annular orientation simultaneously, obtain the PA tube of epipodium to intensity.The people such as Ing, by being locally heated to melt temperature to tubing, are attached to pipeline outer wall with multiply fiber interweaving, and make it to permeate completely in embedding matrix, obtain fibre-reinforced plastic tube (DE102012005973) through controlled cooling model.In order to strengthen the resistance oxygen ability of tubing, the people such as Xu Weiran by three-layer co-extruded go out molding mode prepared internal layer and outer be PERT, intermediate layer is the PERT floor heating pipeline (CN201723857) with good oxygen resistance of β type PP.Plum is clearly then that three layers of compound extrusion moulding are carried out in the PVC intermediate layer of PE skin, nanon calcium carbonatefilled and EPS internal layer, and PE layer and layer of PVC not only isolate oxygen and the thermal capacitance undergauge problem (CN101907205) efficiently solved in plastic tube installation process preferably.
But regrettably, said method is unsatisfactory when solving relevant issues, the first can not realize the hoop intensity of plastic pipe and the raising of oxygen resistance simultaneously, even if its two optional equipment required for raising all more complicated (as needed the co-extrusion outlet mold of multiple stage extruder and complexity thereof) obtaining single hoop intensity or oxygen resistance, or be batch production, unstable product quality, difficult control etc., optional equipment is simultaneously expensive, production cost is higher, and degree of being practical is poor.
Summary of the invention
The object of the invention is for existing plastic pipe Problems existing, first improve a kind of preparation method simultaneously possessing high-strength and high oxygen performance polyolefin pipe.
Another object of the present invention be to provide a kind of prepared by said method while possess the polyolefin pipe of high-strength and high oxygen performance.
The preparation method simultaneously possessing the polyolefin pipe of high-strength and high oxygen performance provided by the invention, the process conditions of the method are as follows:
100 parts of polyolefin substrates are even with 1 ~ 60 part of fibroblast phase resin alloy, then double screw extruder melting is put into, according to fibroblast phase resin, screw rod melt zone temperature is 180 ~ 280 DEG C, die temperature is 170 ~ 280 DEG C, extrude and adopt plug to rotate relative to mouth mould or mouth mould to reversely rotate from mouth mould relative to Mandrel Rotating or plug or plug is different with mouth mould speed rotating Vortex pattern, and in drawing and forming process, port mould diameter is 1.25 ~ 4 with calibration sleeve diameter ratio, preferably 2 ~ 4, extruded velocity is 20 ~ 200rpm:0.2 ~ 6.5m/min with hauling speed ratio, preferably 30 ~ 60rpm:0.2 ~ 0.3m/min, wherein the number of material is mass parts.
The number preferably 5 ~ 40 parts of fibroblast phase resin used in said method, more preferably 10 ~ 30 parts.
In said method, polyolefin substrate is any one in high density polyethylene (HDPE), atactic copolymerized polypropene, block copolymerization polypropylene, isotactic polybutene; Fibroblast phase resin is polystyrene, polyamide 6, any one in polyamide 66, polyamide 11, polyamide 12 and PETG.
In said method when fibroblast phase resin is polystyrene, its screw rod melt zone temperature is arranged between 180 ~ 200 DEG C, and die temperature is 170 ~ 190 DEG C.
In said method when fibroblast phase resin be polyamide 11 and polyamide 12 time, its screw rod melt zone temperature is arranged between 180 ~ 200 DEG C, and die temperature is 190 ~ 200 DEG C.
In said method when fibroblast phase resin be polyamide 6 and polyamide 66 time, its screw rod melt zone temperature is arranged between 230 ~ 260 DEG C, and die temperature is 220 ~ 250 DEG C.
In said method when fibroblast phase resin is PETG, its screw rod melt zone temperature is arranged between 250 ~ 280 DEG C, and die temperature should control at 260 ~ 280 DEG C.
Rotary mode of extruding described in said method realizes by rotary extrusion system disclosed in ZL200810045785.9.
In the commercial process of reality, above-mentioned melt extrude in material can also add the known auxiliary agent of other prior aries, as heat stabilizer, antioxidant, plasticizer and bulking agent etc.If necessary, the filler (as calcium carbonate) that other contribute to improving pipe performance (as glass fibre) further or reducing production cost can also be added, prerequisite is the formation that such additive must not affect pipe structure of the present invention, and must not produce negative effect to tubing premium properties.
Provided by the invention prepared by said method while possess high-strength and high oxygen polyolefin pipe, polyolefin substrate 100 parts contained in this tubing, fibroblast phase resin 1 ~ 60 part, its hoop tensile strength improves 7.9 ~ 69% than traditional extruding pipe material, and OTR oxygen transmission rate have dropped 7 ~ 47% than traditional extruding pipe material.
Polyolefin substrate 100 parts contained in above tubing, preferred fibroblast phase resin 5 ~ 40 parts, more preferably 10 ~ 40 parts; Its hoop tensile strength improves 15 ~ 69% than traditional extruding pipe material, and OTR oxygen transmission rate have dropped 10 ~ 47% than traditional extruding pipe material.
The present invention compared with prior art, has the following advantages:
1, in polyolefin substrate, not only with the addition of fibroblast phase resin due to preparation method provided by the invention and have matched existing rotary extrusion system, and also in drawing and forming process, introduce " melt convergence traction-cooling sizing " mode, thus fibroblast is made deformation, merging, in-situ fibrillation can to occur in tubing mutually, obtain the fento of corresponding major diameter when content, make the hoop tensile strength of tubing and oxygen resistance obtain larger raising simultaneously, fill up the blank of prior art.
2, because preparation method provided by the invention not only can according to the different purposes of different demands and tubing, by selecting different matrixes and fibroblast phase resin, and mate different mouth mould and calibration sleeve internal diameter and melt shrinks draw ratio, just different tubing can be prepared easily, thus widely applicable.
3, the fibroblast phase resin price owing to using in preparation method provided by the invention is cheap, and wide material sources are easy to get, and thus not only can reduce tubing cost, increase economic efficiency, and easy to implement.
4, because present invention process automaticity is high, continuity is good, does not need to add optional equipment, and thus without the need to increasing investment, production cost is low, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the circumference stress strain curve figure that rotary extrusion PS/PB-1 in-situ micro-fibril pipe of the present invention and tradition extrude PB-1 pipe.
Fig. 2 is the stereoscan photograph that tradition extrudes PB-1 inside pipe wall (extruding direction vertical).
Fig. 3 is rotary extrusion PS/PB-1 in-situ micro-fibril inside pipe wall (extruding direction vertical) stereoscan photograph of the present invention.
Fig. 4 is Mandrel Rotating speed when being 6rpm, rotary extrusion PS/PB-1 in-situ micro-fibril inside pipe wall (extruding direction vertical) stereoscan photograph of the present invention.
Fig. 5 is Mandrel Rotating speed when being 4rpm, rotary extrusion PS/PB-1 in-situ micro-fibril pipe outer wall (extruding direction vertical) stereoscan photograph of the present invention.
Fig. 6 is Mandrel Rotating speed when being 8rpm, rotary extrusion PA11/PP in-situ micro-fibril inside pipe wall (extruding direction vertical) stereoscan photograph of the present invention.
Detailed description of the invention:
Below by embodiment, the present invention is specifically described.It is important to point out that following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to foregoing invention content to the present invention.
In addition, what deserves to be explained is, 1) number of following embodiment and comparative example gained material is mass parts.2) mechanic property test method of tubing is: tubing is circumferentially tailored into the wide annulus of 10cm, under room temperature, stretches in rate of extension 20cm/min.3) the oxygen resistance method of testing of following embodiment and comparative example gained tubing is: pipe one end that 15cm is long is closed, and the oxygen of the 0.1MPa that exerts pressure at another section, pipe outer circulation nitrogen, tests the oxygen concentration after 24 hours in nitrogen.
Embodiment 1
By evenly blended for 100 parts of HDPE and 1 part PET resin, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 250 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 32mm, and screw speed is 60rpm, and hauling speed is 0.3m/min.
The hoop tensile strength of gained tubing is 38.3MPa, and OTR oxygen transmission rate is 48.6mm 3/ m 2* 24h*0.1MPa.Compared with extruding HDPE pipe with tradition, its hoop tensile strength improves 7.9%, and OTR oxygen transmission rate have dropped 7%.
Embodiment 2
By evenly blended for 100 parts of PB-1 and 10 part PET resin, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 260 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 20mm, and screw speed is 30rpm, and hauling speed is 0.2m/min.
The hoop tensile strength of gained tubing is 36.9MPa, and OTR oxygen transmission rate is 12.3mm 3/ m 2* 24h*0.1MPa.Compared with extruding PB-1 pipe with tradition, its hoop tensile strength improves 15%, and OTR oxygen transmission rate have dropped 22%.
Embodiment 3
By evenly blended for 100 parts of PPR and 20 part PET resin, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 280 DEG C, die temperature is 280 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 16mm, and screw speed is 20rpm, and hauling speed is 0.3m/min.
The hoop tensile strength of gained tubing is 40.5MPa, and OTR oxygen transmission rate is 13.4mm 3/ m 2* 24h*0.1MPa.Compared with extruding PPR pipe with tradition, its hoop tensile strength improves 32%, and OTR oxygen transmission rate have dropped 28%.
Embodiment 4
By even for 100 parts of PB-1 and 60 part PA11 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 190 DEG C, die temperature is 185 DEG C, extrude and adopt plug to reversely rotate relative to mouth mould, the rotary speed of the two is 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 10mm, and screw speed is 200rpm, and hauling speed is 6.5m/min.
The hoop tensile strength of gained tubing is 38.6MPa, and OTR oxygen transmission rate is 8.4mm 3/ m 2* 24h*0.1MPa.Compared with extruding PB-1 pipe with tradition, its hoop tensile strength improves 57.6%, and OTR oxygen transmission rate have dropped 46.5%.
Embodiment 5
By even for 100 parts of PB-1 and 15 part PS resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 195 DEG C, die temperature is 190 DEG C, extrude and adopt plug relative to mouth mould rotating Vortex, the equal 6rpm of rotary speed of the two, and in drawing and forming process, port mould diameter is 160mm, calibration sleeve diameter is 100mm, and screw speed is 180rpm, and hauling speed is 0.3m/min.
The hoop tensile strength of gained tubing is 35.3MPa, and OTR oxygen transmission rate is 14.1mm 3/ m 2* 24h*0.1MPa.Compared with extruding PB-1 pipe with tradition, its hoop tensile strength improves 44.1%, and OTR oxygen transmission rate have dropped 10.2%.
Embodiment 6
By even for 100 parts of PB-1 and 30 part PA11 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 180 DEG C, die temperature is 170 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 12mm, and screw speed is 120rpm, and hauling speed is 2.4m/min.
The hoop tensile strength of gained tubing is 41.4MPa, and OTR oxygen transmission rate is 11.2mm 3/ m 2* 24h*0.1MPa.Compared with extruding PB-1 pipe with tradition, its hoop tensile strength improves 69%, and OTR oxygen transmission rate have dropped 28.7%.
Embodiment 7
By even for 100 parts of PB-1 and 40 part PA11 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 190 DEG C, die temperature is 185 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 20mm, and screw speed is 30rpm, and hauling speed is 0.2m/min.
The hoop tensile strength of gained tubing is 38.4MPa, and OTR oxygen transmission rate is 9.2mm 3/ m 2* 24h*0.1MPa.Compared with extruding PB-1 pipe with tradition, its hoop tensile strength improves 56.7%, and OTR oxygen transmission rate have dropped 41.4%.
Embodiment 8
By even for 100 parts of PB-1 and 5 part PA6 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 255 DEG C, extrude and adopt plug to reversely rotate relative to mouth mould, the rotary speed of the two is 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 20mm, and screw speed is 30rpm, and hauling speed is 0.2m/min.
The hoop tensile strength of gained tubing is 30.5MPa, and OTR oxygen transmission rate is 14.2mm 3/ m 2* 24h*0.1MPa.Compared with extruding PB-1 pipe with tradition, its hoop tensile strength improves 24.5%, and OTR oxygen transmission rate have dropped 10.6%.
Embodiment 9
By even for 100 parts of PPB and 8 part PA6 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 255 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 20mm, and screw speed is 30rpm, and hauling speed is 0.2m/min.
The hoop tensile strength of gained tubing is 44.5MPa, and OTR oxygen transmission rate is 16.2mm 3/ m 2* 24h*0.1MPa.Compared with extruding PPB pipe with tradition, its hoop tensile strength improves 17.7%, and OTR oxygen transmission rate have dropped 15.6%.
Embodiment 10
By even for 100 parts of PB-1 and 25 part PA6 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 255 DEG C, extrude and adopt mouth mould relative to Mandrel Rotating, mouth mould rotary speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 20mm, and screw speed is 30rpm, and hauling speed is 0.2m/min.
The hoop tensile strength of gained tubing is 41.4MPa, and OTR oxygen transmission rate is 9.2mm 3/ m 2* 24h*0.1MPa.Compared with extruding PB-1 pipe with tradition, its hoop tensile strength improves 67%, and OTR oxygen transmission rate have dropped 41.4%.
Embodiment 11
By evenly blended for 100 parts of HDPE and 35 part PET resin, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 250 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 6rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 32mm, and screw speed is 60rpm, and hauling speed is 0.3m/min.
The hoop tensile strength of gained tubing is 46.3MPa, and OTR oxygen transmission rate is 32.6mm 3/ m 2* 24h*0.1MPa.Compared with extruding HDPE pipe with tradition, its hoop tensile strength improves 30.4%, and OTR oxygen transmission rate have dropped 37.7%.
Embodiment 12
By even for 100 parts of HDPE and 30 part PA11 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 250 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 20mm, and screw speed is 60rpm, and hauling speed is 1.2m/min.
The hoop tensile strength of gained tubing is 50.5MPa, and OTR oxygen transmission rate is 35.6mm 3/ m 2* 24h*0.1MPa.Compared with extruding HDPE pipe with tradition, its hoop tensile strength improves 42.3%, and OTR oxygen transmission rate have dropped 31.9%.
Comparative example 1
100 parts of HDPE are put into double screw extruder melting, by traditional rotation mode extrusion molding, screw rod melt zone temperature is 260 DEG C, and die temperature is 250 DEG C, extrudes and adopts plug to rotate relative to mouth mould, Mandrel Rotating speed 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 40mm, screw speed is 60rpm, and hauling speed is 0.6m/min.
The hoop tensile strength of gained tubing is 35.5MPa, and OTR oxygen transmission rate is 52.3mm 3/ m 2* 24h*0.1MPa.
Comparative example 2
By even for 100 parts of HDPE and 30 part PA11 resin alloy, then put into double screw extruder melting, through the extrusion molding of rotary extrusion head, screw rod melt zone temperature is 260 DEG C, die temperature is 250 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 40mm, and screw speed is 60rpm, and hauling speed is 1.2m/min.
The hoop tensile strength of gained tubing is 30.5MPa, and OTR oxygen transmission rate is 47.6mm 3/ m 2* 24h*0.1MPa.Compared with extruding HDPE pipe with tradition, its hoop tensile strength have dropped 14.1%, and OTR oxygen transmission rate have dropped 9.0%.
Comparative example 3
By even for 100 parts of HDPE and 30 part PA11 resin alloy, then put into double screw extruder melting, through rotary extrusion head and " melt shrinks traction-cooling sizing " device extrusion molding, screw rod melt zone temperature is 260 DEG C, die temperature is 250 DEG C, extrude and adopt plug to rotate relative to mouth mould, Mandrel Rotating speed 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 20mm, and screw speed is 60rpm, and hauling speed is 0.6m/min.
The hoop tensile strength of gained tubing is 28.5MPa, and OTR oxygen transmission rate is 48.8mm 3/ m 2* 24h*0.1MPa.Compared with extruding HDPE pipe with tradition, its hoop tensile strength have dropped 19.7%, and OTR oxygen transmission rate have dropped 6.7%.
Comparative example 4
100 parts of PB-1 are put into double screw extruder melting, by traditional rotation mode extrusion molding, screw rod melt zone temperature is 260 DEG C, and die temperature is 250 DEG C, extrudes and adopts plug to rotate relative to mouth mould, Mandrel Rotating speed 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 40mm, screw speed is 60rpm, and hauling speed is 0.6m/min.
The hoop tensile strength of gained tubing is 24.5MPa, and OTR oxygen transmission rate is 15.7mm 3/ m 2* 24h*0.1MPa.
Comparative example 5
100 parts of PPR are put into double screw extruder melting, by traditional rotation mode extrusion molding, screw rod melt zone temperature is 260 DEG C, and die temperature is 250 DEG C, extrudes and adopts plug to rotate relative to mouth mould, Mandrel Rotating speed 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 40mm, screw speed is 60rpm, and hauling speed is 0.6m/min.
The hoop tensile strength of gained tubing is 30.7MPa, and OTR oxygen transmission rate is 18.6mm 3/ m 2* 24h*0.1MPa.
Comparative example 6
100 parts of PPB are put into double screw extruder melting, by traditional rotation mode extrusion molding, screw rod melt zone temperature is 260 DEG C, and die temperature is 250 DEG C, extrudes and adopts plug to rotate relative to mouth mould, Mandrel Rotating speed 4rpm, and in drawing and forming process, port mould diameter is 40mm, calibration sleeve diameter is 40mm, screw speed is 60rpm, and hauling speed is 0.6m/min.
The hoop tensile strength of gained tubing is 37.8MPa, and OTR oxygen transmission rate is 19.2mm 3/ m 2* 24h*0.1MPa.

Claims (10)

1. possess a preparation method for high-strength and high oxygen polyolefin pipe, processing step and the condition of the method are as follows simultaneously:
100 parts of polyolefin substrates are even with 1 ~ 60 part of fibroblast phase resin alloy, then double screw extruder melting is put into, according to fibroblast phase resin, screw rod melt zone temperature is 180 ~ 280 DEG C, die temperature is 170 ~ 280 DEG C, extrude and adopt plug to rotate relative to mouth mould or mouth mould to reversely rotate from mouth mould relative to Mandrel Rotating or plug or plug is different with mouth mould speed rotating Vortex pattern, and in drawing and forming process, port mould diameter is 1.25 ~ 4 with calibration sleeve diameter ratio, extruded velocity is 20 ~ 200rpm:0.2 ~ 6.5m/min with hauling speed ratio, wherein the number of material is mass parts.
2. possess the preparation method of high-strength and high oxygen polyolefin pipe as claimed in claim 1, in the method, the number of fibroblast phase resin used is 5 ~ 40 parts simultaneously.
3. possess the preparation method of high-strength and high oxygen polyolefin pipe as claimed in claim 1, in the method, the number of fibroblast phase resin used is 10 ~ 30 parts simultaneously.
4. possess the preparation method of high-strength and high oxygen polyolefin pipe while as described in claim 1 or 2 or 3, in the method, polyolefin substrate used is any one in high density polyethylene (HDPE), atactic copolymerized polypropene, block copolymerization polypropylene, isotactic polybutene.
5. while as described in claim 1 or 2 or 3, possesses the preparation method of high-strength and high oxygen polyolefin pipe, in the method, fibroblast phase resin used is polystyrene, polyamide 6, any one in polyamide 66, polyamide 11, polyamide 12 and PETG.
6. possesses the preparation method of high-strength and high oxygen polyolefin pipe as claimed in claim 4 simultaneously, in the method, fibroblast phase resin used is polystyrene, polyamide 6, any one in polyamide 66, polyamide 11, polyamide 12 and PETG.
7. possess the preparation method of high-strength and high oxygen polyolefin pipe while as described in claim 1 or 2 or 3, in the method, port mould diameter is 2 ~ 4 with calibration sleeve diameter ratio; Extruded velocity is 30 ~ 60rpm:0.2 ~ 0.3m/min with hauling speed ratio.
8. possess the preparation method of high-strength and high oxygen polyolefin pipe as claimed in claim 6, in the method, port mould diameter is 2 ~ 4 with calibration sleeve diameter ratio simultaneously; Extruded velocity is 30 ~ 60rpm:0.2 ~ 0.3m/min with hauling speed ratio.
9. one kind prepared by method described in claim 1 while possess high-strength and high oxygen polyolefin pipe, polyolefin substrate 100 parts contained in this tubing, fibroblast phase resin 1 ~ 60 part, its hoop tensile strength improves 7.9 ~ 69% than traditional extruding pipe material, and OTR oxygen transmission rate have dropped 7 ~ 47% than traditional extruding pipe material.
10. method possesses high-strength and high oxygen polyolefin pipe while preparing as claimed in claim 1, polyolefin substrate 100 parts contained in this tubing, fibroblast phase resin 5 ~ 40 parts, its hoop tensile strength improves 15 ~ 69% than traditional extruding pipe material, and OTR oxygen transmission rate have dropped 10 ~ 47% than traditional extruding pipe material.
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