CN109721807A - A kind of hdpe pipe of easy processing - Google Patents
A kind of hdpe pipe of easy processing Download PDFInfo
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- CN109721807A CN109721807A CN201711056861.1A CN201711056861A CN109721807A CN 109721807 A CN109721807 A CN 109721807A CN 201711056861 A CN201711056861 A CN 201711056861A CN 109721807 A CN109721807 A CN 109721807A
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Abstract
The invention discloses a kind of hdpe pipes of easy processing.It is a kind of ethylene polymer composition tubing；The melt index MFR of ethylene polymer composition2For 0.45-0.5g/10min, density 0.950-0.960g/cm3；It includes component A1 and component A2, and component A1 is the homopolymer of ethylene, and component A2 is the copolymer of the alpha-olefin of ethylene and at least two 4-10 carbon atom, and weight average molecular weight is higher than the weight average molecular weight of component A1；The hdpe pipe that the present invention obtains processing temperature in extrusion molding is 10-20 DEG C low compared with other similar tubing, and more similar tubing possesses longer service life and higher safety, can be widely applied in municipal water supply tubing and gas pipeline.
Description
Technical field
The present invention relates to a kind of hdpe pipes of easy processing, belong to macromolecule chemical industry technical field.
Background technique
Compared with traditional metal tube, pipe of cement, plastic pipe has light weight, corrosion-resistant, small flow resistance, comprehensive section
It can the advantages that property is good, easy to transportation and installation, long service life.The material that plastic pipe uses mainly has polyvinyl chloride (PVC), gathers
Ethylene (PE) and polypropylene (PP) etc..Compared with other plastic tubes (such as PVC), high density polyethylene (HDPE) (HDPE) tubing has density
Low, good toughness, corrosion-resistant, good insulation preformance, be easy to construct and install the features such as, be widely used in city have stable political situation building water supply and drainage,
The fields such as combustion gas, heat supply heating, wire and cable threading, agricultural water-saving irrigation.
Currently, plastic pipe has occupied the 54% of tubing market in the whole world.In developed countries and regions, PE is (main
It is HDPE) up to 90% or more, the market share shared by water supplying pipe reaches occupancy volume of the tubing in intercity steel gas pipe underground
60%, and mature construction and standard criterion are had been set up in terms of PE tubing.In China, as galvanized pipe is disabled,
HDPE pipe is in the fields such as building supply very competitive superiority.In fields such as combustion gas, industrial water supply and sewage, communication, agricultural irrigations, HDPE
Tubing is also in the situation increased rapidly.But due to the feature that HDPE molecular weight is high, melt index (MI) is less than normal, lead to its processing performance
It is poor, it needs to carry out process operation at high temperature, energy consumption is huge.
It is known in the art, for polyolefin, molecular weight and molecualr weight distribution greatly influence polymer mechanical performance and
Processing performance.Expanding polyacrylic molecular weight distribution may be implemented to improve rheological property while maintaining the mechanical performance of final products
Purpose；Wherein high molecular weight moieties guarantee that the mechanical performance of product, low molecular weight part help to improve the processability of product
Energy.
It is annular-pipe reactor that EP-B-517868, which describes first, and concatenated second is gas-phase fluidized-bed reactor, is made
Retarder thinner is that propane or iso-butane operate in the supercritical state, does not describe the hydrogen flashed off returning to endless tube
In；And it is impermissible for the MI for making to produce resin there are the hydrogen of higher concentration in a loop reactor2Within 140g/10min, gas
The MI of resin in phase reaction device5Also there was only 0.8g/10min, molecular weight not enough foot is high.
Summary of the invention
The shortcomings that in order to overcome existing high density polyethylene (HDPE), the object of the present invention is to provide a kind of high melt index easy processings
Hdpe pipe product.
Technical solution of the present invention is specifically described as follows.
The present invention provides a kind of hdpe pipe of easy processing, is ethylene polymer composition tubing；
The melt index MFR of ethylene polymer composition2For 0.45-0.5g/10min, density 0.950-0.960g/
cm3；The ethylene polymer composition includes component A1 and component A2, the component A1 are the homopolymers of ethylene, heavy to divide equally
Son amount is 80000-100000g/mol, and the component A2 is the copolymerization of the alpha-olefin of ethylene and at least two 4-10 carbon atom
Object, weight average molecular weight are higher than the weight average molecular weight of component A1；Based on the total amount of component A1 and A2, the content of component A1 is 30-
The content of 50wt%, component A2 are 50-70wt%.
In the present invention, the melt index MFR of ethylene polymer composition2For 0.49-0.50g/10min, density is
0.957-0.960g/cm3。
In the present invention, the weight average molecular weight of ethylene polymer composition is 120000-200000g/mol, molecular weight distribution
It is 8~20.
In the present invention, the component A2 of the ethylene polymer composition is the copolymer of ethylene and 1- butylene, 1- hexene.It is excellent
Choosing, the density of the component A1 is 0.950-0.965g/cm3, density of the density lower than component A1 of the component A2.
In the present invention, the weight of the component A1 son amount is 80000-100000g/mol, and the weight average molecular weight of component A2 is
150000-250000g/mol。
In the present invention, the wall thickness of the hdpe pipe is 1-10mm.
In the present invention, the ethylene polymer composition is prepared by following methods:
(1) ethylene, hydrogen, the polymerization containing transition metal component and triethyl aluminum activator are provided in the first polymeric area
Catalyst, the transition metal component include the metal of the 4th or 5 races in periodic table system, generate component A1 herein；
(2) ethylene, hydrogen, the polymerization catalyst and at least two 4-10 carbon atom are provided in the second polymeric area
Alpha-olefin comonomer generates the ethylene polymer component A2 of weight average molecular weight of the weight average molecular weight higher than component A1 herein；
Wherein: the first polymeric area and the second polymeric area are serially connected, and the polymer that the first polymeric area generates is present in second
In polymeric area, based on the total amount of component A1 and A2, component A1 accounts for 30-50wt%, and component A2 accounts for 50-70wt%.
In the present invention, first polymeric area uses annular-pipe reactor, and second polymeric area uses gas-phase reactor.
Composition of the invention can be mixed further with other components.This mixture, i.e. blend include defined above
Ethylene polymer composition and other components.Other components can be polymers compositions and/or additive, such as routinely
For the additive in polymer.It selects to depend on its final application with dosage.
Ethylene polymer composition of the invention can contain additive known in the art and auxiliary agent.Therefore it can be containing anti-
Oxidant and stabilizer, such as Irganox 1010 and Irgaphos 168, it can contain antistatic agent, such as ethoxyquin ammonium,
Ethoxylated amides and glyceryl monostearate, caking inhibiter, such as talcum or silica, slipping agent, such as oleamide and mustard
Sour amide, acid neutralizing agent, such as calcium stearate and zinc stearate, processing aid, such as fluoroelastomer and nucleating agent, such as benzene
Sodium formate.The suitable amounts of these additives are that this field is commonly known.One of skill in the art can select suitably to add
Add agent and its dosage with the required performance for the tubing realizing composition and being produced from it.
Ethylene polymer composition of the invention can pass through any polymerization known in the art, such as slurry, solution
Or gas-phase polymerization, produce the polymer composition.Polymerization can be single step or multistep polymerization.
In the present invention, it is preferable to use Ziegler-Natta polymerization catalyst.This catalyst includes transition metal group
Point and activator.Particularly preferred transition metal component includes halogenated titanium, the alkoxyalkyl of carrying on an inorganic
Magnesium compound and alkyl dihalides aluminium.Activator is the compound of energy activated transition metal component.Useful activator is especially
Alkyl aluminum and alkoxy aluminum compound.Particularly preferred activator is alkyl aluminum, especially trialkylaluminium, such as trimethyl aluminium, three
Aluminium ethide and triisobutyl aluminium.
In the present invention, if producing lower-molecular-weight component A1 in slurry, suitable pressure limit is 10-100Bar,
It is preferred that 20-80Bar.Then ethylene and inert liquid diluent are introduced together into reactor together with polymerization catalyst.By hydrogen
It is introduced into reactor, to control the weight average molecular weight of polymer.In addition, the density of comonomer control polymer can be used.
Hydrogen and final comonomer additional amount are set by the type and targeted weight average molecular weight and density of used catalyst
Exact amount.Suitably, the hydrogen in feed fluid phase and ethylene ratio are 50-100mol/kmol.In the present invention,
If being polymerize in the form of slurry polymerization, preferred annular-pipe reactor, because it is particularly conducive to critical-temperature and pressure in fluid
More than power, it is polymerize under so-called super critical condition.
The present invention is in production component A2 (polymeric segment of high molecular weight), the α-of ethylene and at least two 4-10 carbon atom
Olefin comonomer is copolymerized together.High molecular weight component A2 is produced in gas-phase reactor.In the case, list will be contained
Body, inert gas, hydrogen and optional comonomer gaseous fluid be introduced into reactor, polymerize herein.Typically,
The ratio between hydrogen and ethylene are 5-20mol/kmol in gaseous fluid and the ratio between comonomer and ethylene summation are 10-100mol/
kmol。
The beneficial effects of the present invention are: obtained hdpe pipe melt index is in 0.45-0.5g/10min
Between, tensile yield strength is 19MPa or so.In extrusion molding, processing temperature is 10~20 DEG C low compared with other similar tubing, easily
Processing；The resistance to Zernike annular polynomial time is not less than 525h, can be widely applied in municipal water supply tubing and gas pipeline.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Following method is used to test the structure or performance of the polyethylene produced in the embodiment:
Following method is used to test the performance of the polyethylene produced in the embodiment:
ASTM D1928 is used to test the density of polyethylene；
ASTM D1238 is used to test the melt index (MFR of polyethylene2, under 2.16Kg load, 190 DEG C)；
GB/T6111-2003 is used to test the resistance to hydrostatic performance of polyvinyl piping materials；
High-temperature gel permeation chromatography method (GPC) is used to test the molecular weight and its profile exponent of polyethylene.
Embodiment 1
Propane, ethylene and hydrogen are continually introduced into the annular-pipe reactor that volume is 250 liters.In addition, silica is born
The titanium-magnesium catalyst of load is introduced together into the reactor together with triethyl aluminum, and titanium rubs in the aluminium and solid component in activator
You are than being 20.The annular-pipe reactor is operated at 80 DEG C of temperature and the pressure of 20Bar.In annular-pipe reactor, in fluid phase
Interior ethylene contents are 1.8mol%, and the ratio between hydrogen and ethylene are 60mol/kmol.The speed of production of polymer is 14kg/h.?
The weight average molecular weight of the polymer produced in annular-pipe reactor is 80471g/mol, molecular weight distribution 6.81, and density is
0.963g/cm3。
Slurry is drawn from annular-pipe reactor to flash vessel, reduces pressure herein to 3Bar.Polymer is guided to stream again
Change in bed gas-phase reactor, also adds additional ethylene, 1- butylene, 1- hexene co-monomer and hydrogen herein and as inertia
Propane, the nitrogen of gas.Gas-phase reactor operates at 85 DEG C of temperature and the pressure of 2Bar.In the reactor, in circulating air
Middle ethylene partial pressure is 0.1Bar, and the ratio between hydrogen and ethylene are 10mol/kmol, and the ratio between 1- butylene and ethylene are 40mol/kmol, 1-
The ratio between hexene and ethylene are 105mol/kmol.The speed of production of polymer is 18kg/h in gas-phase reactor, so as in endless tube
It is 44/56 that production between gas-phase reactor, which is compared,.Total speed of production is 32kg/h.
The final densities of polymer masses are 0.959g/cm3, weight average molecular weight 140930g/mol, and molecular weight distribution is
13.1- butene content in polymer is 0.7wt%, and 1- ahexene content is 1.2wt%.
Embodiment 2
Propane, ethylene and hydrogen are continually introduced into the annular-pipe reactor that volume is 250 liters.In addition, silica is born
The titanium-magnesium catalyst of load is introduced together into the reactor together with triethyl aluminum, and titanium rubs in the aluminium and solid component in activator
You are than being 20.The annular-pipe reactor is operated at 80 DEG C of temperature and the pressure of 20Bar.In annular-pipe reactor, in fluid phase
Interior ethylene contents are 1.8mol%, and the ratio between hydrogen and ethylene are 60mol/kmol.The speed of production of polymer is 14kg/h.?
The weight average molecular weight of the polymer produced in annular-pipe reactor is 81387g/mol, molecular weight distribution 7.02, and density is
0.963g/cm3。
Slurry is drawn from annular-pipe reactor to flash vessel, reduces pressure herein to 3Bar.Polymer is guided to stream again
Change in bed gas-phase reactor, also adds additional ethylene, 1- butylene, 1- octene co-monomer and hydrogen herein and as inertia
Propane, the nitrogen of gas.Gas-phase reactor operates at 85 DEG C of temperature and the pressure of 2Bar.In the reactor, in circulating air
Middle ethylene partial pressure is 0.1Bar, and the ratio between hydrogen and ethylene are 10mol/kmol, and the ratio between 1- butylene and ethylene are 40mol/kmol, 1-
The ratio between octene and ethylene are 105mol/kmol.The speed of production of polymer is 18kg/h in gas-phase reactor, so as in endless tube
It is 44/56 that production between gas-phase reactor, which is compared,.Total speed of production is 32kg/h.
The final densities of polymer masses are 0.957g/cm3, weight average molecular weight 157850g/mol, and molecular weight distribution is
14.1.1- butene content in polymer is 0.7wt%, and 1- octene content is 1.1wt%.
Comparative example 1
By import ethylene general in the market/1- octene copolymer HDPE as a comparison case 1.
1 differing ethylene performance of copolymer index of table
This it appears that the performance indexes of two embodiments and ethylene/1- octene copolymer HDPE refer to from table 1
Mark very close to, and melt index be much higher than ethylene/1- octene copolymer HDPE, have better processing performance, can replace completely
For ethylene/1- octene copolymer HDPE product.
3 wall thickness of embodiment is the hdpe pipe A of 10mm
Ethylene copolymer 5kg obtained in Example 1 is added 1g antioxidant, and is uniformly mixed.
Extruder is heated to 185 DEG C, uniformly mixed raw material enters barrel from hopper, under the action of screw rotation, leads to
It crosses material tube inner wall and the effect of screw surface fricting shearing is fed forward to feeding section, be fed forward while being pressed in this bulk solids
It is real；In compression section, spiral groove depth shoals, and is further compacted, while in barrel external heat and screw rod and material tube inner wall fricting shearing
Effect, material temperature raising start to melt, and compression section terminates；Homogenizing zone keeps material uniform, and fixed temperature, quantitative, level pressure melt extrusion arrive machine
Head after form, be formed, cool down after obtain tubing article A.Results of property is as shown in table 2.
4 wall thickness of embodiment is the hdpe pipe B of 10mm
Ethylene copolymer 5kg obtained in Example 2 is added 1g antioxidant, and is uniformly mixed.
Extruder is heated to 185 DEG C, uniformly mixed raw material enters barrel from hopper, under the action of screw rotation, leads to
It crosses material tube inner wall and the effect of screw surface fricting shearing is fed forward to feeding section, be fed forward while being pressed in this bulk solids
It is real；In compression section, spiral groove depth shoals, and is further compacted, while in barrel external heat and screw rod and material tube inner wall fricting shearing
Effect, material temperature raising start to melt, and compression section terminates；Homogenizing zone keeps material uniform, and fixed temperature, quantitative, level pressure melt extrusion arrive machine
Head after form, be formed, cool down after obtain tubing article B.Results of property is as shown in table 2.
2 wall thickness of comparative example is the hdpe pipe C of 10mm
Ethylene copolymer 5kg obtained in comparative example 1 is taken, 1g antioxidant is added, and be uniformly mixed.
Extruder is heated to 200 DEG C (at 185 DEG C, raw material viscosity is excessive, can not process), uniformly mixed raw material is expected certainly
Bucket enters barrel, under the action of screw rotation, is fed forward to charging by material tube inner wall and the effect of screw surface fricting shearing
Section, is fed forward while being compacted in this bulk solids；In compression section, spiral groove depth shoals, and is further compacted, while in barrel
External heat and screw rod and material tube inner wall fricting shearing act on, and material temperature raising starts to melt, and compression section terminates；Homogenizing zone keeps material equal
It is even, fixed temperature, quantitative, level pressure melt extrusion, to head after form, be formed, cool down after obtain tubing article C.Results of property is such as
Shown in table 2.
The different hdpe pipe of table 2
By the comparison in table 2 it is found that the resistance to hydrostatic performance of hdpe pipe A, B, C are close, but it is high
The processing temperature of density polyethylene tubing C is apparently higher than hdpe pipe A, B, and process needs more energy consumptions.
This is because raw material of the melt index of the raw material of hdpe pipe A, B much higher than hdpe pipe C is molten
Melt index, there is better processing performance.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (9)
1. a kind of hdpe pipe of easy processing, it is characterised in that: it is ethylene polymer composition tubing；Ethylene is poly-
The melt index MFR of polymer composition2For 0.45-0.5g/10min, density 0.950-0.960g/cm3；The vinyl polymerization
Compositions include component A1 and component A2, the component A1 are the homopolymer of ethylene, weight average molecular weight 80000-
100000g/mol, the component A2 are the copolymer of the alpha-olefin of ethylene and at least two 4-10 carbon atom, Weight-average molecular
Amount is higher than the weight average molecular weight of component A1；Based on the total amount of component A1 and A2, the content of component A1 is 30-50wt%, component A2
Content be 50-70wt%.
2. hdpe pipe according to claim 1, which is characterized in that the melting of ethylene polymer composition refers to
Number MFR2For 0.49-0.50g/10min, density 0.957-0.960g/cm3。
3. hdpe pipe according to claim 1 again, which is characterized in that ethylene polymer composition is divided equally
Son amount is 120000-200000g/mol, and molecular weight distribution is 8~20.
4. the hdpe pipe of easy processing according to claim 1, which is characterized in that the ethene polymers group
The component A2 for closing object is the copolymer of ethylene and 1- butylene, 1- hexene.
5. the hdpe pipe of easy processing according to claim 1, it is characterised in that: the density of the component A1
For 0.950-0.965g/cm3, density of the density lower than component A1 of the component A2.
6. the hdpe pipe of easy processing according to claim 1, it is characterised in that: the Weight-average molecular of component A2
Amount is 150000-250000g/mol.
7. the hdpe pipe of easy processing according to claim 1, it is characterised in that: the high density polyethylene (HDPE)
The wall thickness of tubing is 1-10mm.
8. the hdpe pipe of easy processing according to claim 1, which is characterized in that the ethene polymers group
Object is closed to prepare by following methods:
(1) ethylene, hydrogen, polymerization catalyzed containing transition metal component and triethyl aluminum activator is provided in the first polymeric area
Agent, the transition metal component include the metal of the 4th or 5 races in periodic table system, generate component A1 herein；
(2) α-alkene of ethylene, hydrogen, the polymerization catalyst and at least two 4-10 carbon atom is provided in the second polymeric area
Hydrocarbon comonomer generates the ethylene polymer component A2 of weight average molecular weight of the weight average molecular weight higher than component A1 herein；
Wherein: the first polymeric area and the second polymeric area are serially connected, and the polymer that the first polymeric area generates is present in the second polymerization
In area, based on the total amount of component A1 and A2, component A1 accounts for 30-50wt%, and component A2 accounts for 50-70wt%.
9. the preparation method of ethylene polymer composition according to claim 8, it is characterised in that: first polymeric area
Using annular-pipe reactor, second polymeric area uses gas-phase reactor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711056861.1A CN109721807A (en) | 2017-10-27 | 2017-10-27 | A kind of hdpe pipe of easy processing |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711056861.1A CN109721807A (en) | 2017-10-27 | 2017-10-27 | A kind of hdpe pipe of easy processing |
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| CN1556834A (en) * | 2001-10-16 | 2004-12-22 | Pipe for hot fluids | |
| CN101238529A (en) * | 2005-06-30 | 2008-08-06 | 博里利斯技术公司 | Outer sheath layer for power or communication cable |
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