CN105985490A - Heat-resistant polyethylene copolymer preparation method, heat-resistant polyethylene copolymer and pipe - Google Patents
Heat-resistant polyethylene copolymer preparation method, heat-resistant polyethylene copolymer and pipe Download PDFInfo
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Abstract
The invention discloses a heat-resistant polyethylene copolymer preparation method, a heat-resistant polyethylene copolymer and a pipe. According to the heat-resistant polyethylene copolymer preparation method, the steps that a magnesium chloride loaded TiCl4 Ziegler-Natta catalyst serves as a main catalyst, aluminum alkyl serves as an auxiliary catalyst, ethylene and alpha-olefin are catalyzed for copolymerization in an inert hydrocarbon solvent, and ethylene homopolymerization and copolymerization reaction of ethylene and alpha-olefin are conducted stage by stage through two serial connected reaction kettles; by changing the technological conditions of polymerization reaction, the polyethylene copolymer with good heat resistance can be obtained, and the copolymer can be extruded and formed easily to serve as a heat-resistant pipe material.
Description
Technical field
The present invention relates to preparation method and the heat-proof polythene copolymer of a kind of heat-proof polythene copolymer.
Background technology
Heat-resistant flexible polyethylene, is a kind of to use what special MOLECULE DESIGN and synthesis technique produced may be used for
The non-cross-linked polyvinyl that hot-water line produces.Owing to having molecular chain structure and the crystallographic configurations of uniqueness, therefore have
Having good pliability and processing characteristics, excellent cryogenic property and resistance to chemical corrosion, in hot conditions
Under have a good resistance to hydrostatic performance, also light weight, be prone to transport and installation, the advantage such as recyclable.
It is mainly used in home-use hot and cold water conveying pipe, including floor heating, heating installation connection, heat exchanger, solar energy
Plate and heat circulating system etc..
Dow Chemical (WOP 03/020821 A1, USP 2007/0112160 A1, USP 7250473
B2, USP 2010/0003439 A1) first with solution polymerization technique, use ethylene and octene copolymer
Method, develops pipeline PE-RT resin, within 1991, develops DOWLEX 2344 resin, and it is PE-RT
I type resin, is the copolymer of ethylene and octene, and density is 0.933g/mL.Calendar year 2001, the said firm pushes away again
Having gone out another trade mark Dowlex2388 (PE-RT II type), it is also ethylene and the copolymer of 1-octene, close
Degree is 0.941g/mL.Patent CN 101796085 A, CN 102325810 A disclose employing metallocene urge
Change the heat-proof polythene copolymer prepared with hexene-1 copolymerization of ethylene, there is high zero-shear viscosity and higher
Shear shinning degree.Patent CN 1906220A provides and a kind of is total to for the based on ethylene of non-crosslinked feed pipe
Polymers.Use ethylene to prepare with hexene-1 copolymerization, there is high comonomer access amount and copolymerization evenly
Monomer distribution, has bimodal or wide molecular weight distribution, has the machinability of excellence, anti-intrinsic pressure under high temperature
Creep properties and environmental stress crack resistance.This copolymer uses supported metallocene catalyst to prepare.Li Ande
Company of Basel (US 2010/0076136 A1, CN 101400933A, CN 1162453C, CN 102712715
A, CN 102325811 A, CN 102282182 A) utilize three still tandem process to produce PE-RT PP Pipe Compound (second
Alkene and the copolymer of butylene), regulate and control poly-second by controlling the addition of comonomer and catalyst in different still
The molecular structure of alkene.Its production technology is that the first still produces low molecular weight polyethylene, and the second still and the 3rd still are equal
Add comonomer, control the distribution of copolymer, obtain the polyethylene pipe material product of pressure-and heat-resistance.CN
101353387A provides a kind of ethylene and a-alkene carries out combined polymerization preparation and has the side of highly-branched copolymer
Method.The method uses the mixed modifier of Conjugated Diolefin and alkoxy silane composition, to improve comonomer
Insertion rate and distributing homogeneity.CN 101472950A discloses what under high pressure ethylene was polymerized with comonomer
Technique and equipment, use radical polymerization mechanism.Raise sub-petrochemical industry (CN 101654494A) and disclose a kind of profit
The ethylene copolymer manufactured with specific load type non-metallocene catalyst, and the manufacture of this ethylene copolymer
Method.This copolymer is mainly for the manufacture of peroxide crosslinking heat-resisting polyethylene tube.CN 101688033A reports
Road employing metallocene or Ziegler-Natta catalyst, prepare multimodal polyethylene altogether by fluid bed and moving bed
The technique of copolymer resin composition.Patent CN201210445946.X discloses a kind of by series polymerizations system
The method of standby ethylene copolymer, the salicylic alidehyde imine metalloid different by two kinds of catalytic performances of use continuously is urged
Agent co-catalysis ethylene polymerization, can obtain ethylene copolymer in the case of using single ethylene monomer
Thing, its advantage is the step removing added comonomer from, it is possible to be directly synthesized ethylene copolymer, but product
Heat resistance is poor.
Up to now, the method preparing heat-proof polythene copolymer of report disclosed in science and patent documentation
In, it is usually present one or more lower column defects: (1) uses polyethylene prepared by metallocene catalyst, by
In Narrow Molecular Weight Distribution, there is poor machinability.(2) use expensive comonomer, cause production
Relatively costly.(3) reactions steps of series polymerizations is more.(4) polyethylene and ethylene copolymers hot property and mechanics
Performance can not meet the performance requirement of hot water tubing long term high temperature.(5) tubing cannot be made.
Summary of the invention
Present invention aim at providing the preparation method of a kind of heat-proof polythene copolymer, heat-proof polythene
Copolymer and tubing, to solve the problem that art methods has poor machinability.
For achieving the above object, the present invention proposes the preparation method of a kind of heat-proof polythene copolymer, its feature
Being, use major catalyst and promoter catalysis, described major catalyst is titanium, the load of vanadium halogen compounds
Solid to magnesium chloride, silica supports contains transition-metal catalyst, and employing alkyl aluminum is promoter,
Under hydrogen regulates, carry out ethylene homo by two cascade reaction still segmentations and ethylene copolymer reacts, including
Following steps:
A) in the first reactor inject organic solvent, be separately added in described organic solvent major catalyst and
Promoter, adds a certain amount of hydrogen, and ethylene homo reaction is in temperature between 50～100 DEG C, pressure
Power is 0.5～1.0MPa, reacts 0.1～1 hour prepared Natene；And
B) aaerosol solution containing Natene Yu organic solvent step a prepared, injects second
In reactor, add a certain amount of hydrogen, at 50～100 DEG C, be passed through ethylene and C4-C12Aliphatic alpha-
The gaseous mixture of alkene, holding pressure is 0.1-3.0MPa, reacts 0.1-10 hour, prepares polyethylene copolymer
Thing.
Wherein, described organic solvent is toluene, pentane, normal hexane, hexamethylene or the one of heptane inertia hydro carbons
Plant or several.
Wherein, major catalyst described in step a is by magnesium chloride load TiCl4Ziegler-Natta catalyst.
Wherein, the hydrogen usage described in step a is hydrogen/ethylene pressure than for 0-10.
Wherein, the hydrogen usage described in step b is that hydrogen/ethene-alpha-olefin gaseous mixture intrinsic standoff ratio is
0-10。
Wherein, ethylene described in step b and described C4-C12Aliphatic alpha-olefin gaseous mixture be ethylene/C4-C12
Aliphatic alpha-olefin intrinsic standoff ratio be 0.01-1.0.
Wherein, the molecular weight distribution of described polyethylene and ethylene copolymers is for having unimodal wide distribution, and melt index is
0.08-0.9g/10min (190 DEG C, 2.16kg), fusing point > 133 DEG C.
Wherein, the branch lengths of gained polyethylene and ethylene copolymers is 1-10 carbon atom, the relative degree of branching
0.06-0.6。
And, for achieving the above object, the present invention provides the preparation method of above-mentioned polyethylene and ethylene copolymers made
The polyethylene and ethylene copolymers obtained.
Wherein, the molecular weight distribution of described polyethylene and ethylene copolymers is for having unimodal wide distribution, and melt index is
0.08-0.9g/10min (190 DEG C, 2.16kg), fusing point > 133 DEG C.
Wherein, the branch lengths of gained polyethylene and ethylene copolymers is 1-10 carbon atom, the relative degree of branching
0.06-0.6。
And, for achieving the above object, the present invention proposes a kind of polyethylene and ethylene copolymers tubing, uses above-mentioned
Polyethylene and ethylene copolymers is made.
The invention provides a kind of employing Conventional Ziegler-Natta catalyst and be catalyzed second with organo-aluminium promoter
Alkene and low cost alpha-olefin copolymer, in a mild condition, by relatively simple step, prepare resistance to hot polymerization second
The method of alkene.By the adjustment to polymerization technique, being allowed to produce broad peak distribution, different molecular weight component is with common
Performance under polymers respective material different temperatures, thus meet the performance requirement of heat-proof polythene tube material.
The molecular weight distribution of the polyethylene and ethylene copolymers obtained by the present invention has unimodal, and molecular weight distribution index is
5-18, melt index is 0.08-0.9g/10min (190 DEG C, 2.16kg), it is possible to keep preferable intensity and processing
Mobility, beneficially extrusion molding are tubing.It addition, fusing point > 133 DEG C and branch lengths be 1-10
Individual carbon atom, relative degree of branching 0.06-0.6, it is provided that moderate wafer thickness with opposing cracks can spread is
Band strand, its structure is conducive to improving heat distortion temperature, polyethylene and ethylene copolymers fine heat-resisting performance, therefore,
Can serve as heat-resisting pipes aspect.
Detailed description of the invention
The process for copolymerization of the present invention relates to two-stage polymerization method, and wherein a step is to manufacture Alathon, another
Step is to manufacture ethylene copolymer.All polyreaction and copolymerizations are to implement continuously, first in the first reaction
Device is formed homopolymer, then this homopolymer is fed in the second reactor, in homopolymer and the existence of hydrogen
Under carry out ethylene and C4-C12The copolymerization of aliphatic alpha-olefin.
The preparation method of the heat-proof polythene copolymer of the present invention, uses major catalyst and promoter catalysis,
Described major catalyst is titanium, vanadium halogen compounds loads to magnesium chloride, the solid of silica supports contains transition
Metallic catalyst, employing alkyl aluminum is promoter, under hydrogen regulates, is divided by two cascade reaction stills
Duan Jinhang ethylene homo and ethylene copolymer reaction, comprise the following steps:
A) in the first reactor inject organic solvent, be separately added in described organic solvent major catalyst and
Promoter, adds a certain amount of hydrogen, and ethylene homo reaction is in temperature between 50～100 DEG C, pressure
Power is 0.5～1.0MPa, reacts 0.1～1 hour prepared Natene；And
B) aaerosol solution containing Natene Yu organic solvent step a prepared, injects second
In reactor, add a certain amount of hydrogen, at 50～100 DEG C, be passed through ethylene and C4-C12Aliphatic alpha-
The gaseous mixture of alkene, holding pressure is 0.1-3.0MPa, reacts 0.1-10 hour, prepares polyethylene copolymer
Thing.
Wherein, major catalyst described in step a is by magnesium chloride load TiCl4Ziegler-Natta catalyst.
Wherein, the hydrogen usage described in step a is hydrogen/ethylene pressure than for 0-10.
Wherein, the hydrogen usage described in step b is that hydrogen/ethene-alpha-olefin gaseous mixture intrinsic standoff ratio is
0-10。
Wherein, ethylene described in step b and described C4-C12Aliphatic alpha-olefin gaseous mixture be ethylene/C4-C12
Aliphatic alpha-olefin intrinsic standoff ratio be 0.01-1.0.
Wherein, the molecular weight distribution of described polyethylene and ethylene copolymers is for having unimodal wide distribution, and melt index is
0.08-0.9g/10min (190 DEG C, 2.16kg), fusing point > 133 DEG C.
Wherein, the branch lengths of gained polyethylene and ethylene copolymers is 1-10 carbon atom, the relative degree of branching
0.06-0.6。
And, the present invention provides the polyethylene copolymer obtained by the preparation method of above-mentioned polyethylene and ethylene copolymers
Thing.
Wherein, the molecular weight distribution of described polyethylene and ethylene copolymers is for having unimodal wide distribution, and melt index is
0.08-0.9g/10min (190 DEG C, 2.16kg), fusing point > 133 DEG C.
Wherein, the branch lengths of gained polyethylene and ethylene copolymers is 1-10 carbon atom, the relative degree of branching
0.06-0.6。
And, the present invention proposes a kind of polyethylene and ethylene copolymers tubing, uses above-mentioned polyethylene and ethylene copolymers to make.
Specifically, the preparation method of heat-proof polythene of the present invention, polyreaction is organic in inertia
Carrying out in solvent, selectable solvent is alkane, aromatic hydrocarbons, halogenated hydrocarbons.Typical solvent include toluene, pentane,
One or more mixture of the inertia hydro carbons such as normal hexane, hexamethylene or heptane.
The preparation method of heat-proof polythene of the present invention, the catalyst system of employing is by containing transition metal
Compound and organo-aluminium cocatalyst compound composition.Contained transition metal catalyst component by solid-state and had
The high-activity catalyst systems that machine aluminum cocatalyst component is formed is particularly well-suited to the inventive method.
The catalyst of heat-proof polythene preparation method of the present invention is the halogen compounds such as titanium, vanadium, load
The solid obtained on the carrier such as magnesium chloride, silicon dioxide contains transition-metal catalyst.It is preferably magnesium chloride to bear
Carry titanium tetrachloride.
The alkyl aluminum that promoter is following formula (1) of heat-proof polythene preparation method of the present invention:
AlRmX3-mFormula (1)
In formula, R is selected from Cl-C10 alkyl, and X is selected from halogen, or Cl-6 alkoxy base, and m is 1,2,
3.Representational organo-aluminum compound includes triethyl aluminum, three n-butylaluminum, diethyl aluminum chloride, dibutyl
Aluminum chloride, sesquialter ethylmercury chloride aluminum, diethylaluminum ethoxide etc..
Catalyst and promoter are usually dispersed in unreactive hydrocarbons and add after metering in reactor, catalyst
It is transformable with the consumption of promoter.The usual consumption of catalyst is to contain in every liter of diluent
The transition metal of 0.001～0.06 mM, and the consumption of promoter is usually in every liter of diluent and contains
0.02～10 mM of aluminum.
This method use polymerizing condition and step can be conventional, temperature between 0～150 DEG C, pressure
Be 0.5～2.0MPa, react 0.1～10 hour, preferable temperature between 50～100 DEG C, pressure be 0.5～
1.0MPa, reacts 0.1～1 hour prepared Natene.
The aaerosol solution containing Natene Yu organic solvent prepared, injects in the second reactor.Add
Entering hydrogen, be passed through ethylene and alpha-olefin gaseous mixture at 0～150 DEG C, keeping pressure is 0.5～2.0MPa,
Reacting 0.1～10 hour, preferable temperature is between 50～100 DEG C, and pressure is 0.5～1.0MPa, reaction
0.1-1 hour prepared polyethylene and ethylene copolymers.
During two step series polymerizations, Molecular regulator amount can be carried out by adding hydrogen.In the first reactor
Make the major amount of Alathon with higher density and higher MI value, and make in the second reactor
Have compared with low-density and the ethylene/butylene-1 of relatively low MI value, ethylene/hexene-1 or ethylene/octene-1 copolymer.
In order to reach this purpose, the hydrogen used in the first reactor is 0～10 with the mol ratio of ethylene, optimum
It is 0.1～5；The hydrogen used in the second reactor is 0.01～1 with the mol ratio of ethylene gaseous mixture,
Excellent is 0.1～0.2.When implementing converging operationJu Hecaozuo in a series arrangement, may must empty before transfer homopolymer
Hydrogen is so that the second reactor reaches the ratio of required hydrogen and ethylene.
The aliphatic olefin that alpha-olefin is C4～C12 used by heat-proof polythene preparation method of the present invention
Hydrocarbon.Representational have butene-1, hexene-1 or octene-1.
Ethylene described in heat-proof polythene preparation method of the present invention and α-alkene in alpha-olefin gaseous mixture
Hydrocarbon/ethylene partial pressure ratio is 0.01～1, and preferably alpha-olefin/ethylene partial pressure ratio is 0.05～0.5.
In the first reactor preparation the MI of polymer and density is respectively 1～1000 gram/10 minutes and
0.955～0.975 gram/cc, and the MI of the copolymer prepared in the second reactor and density are respectively
It it is 0.001～10 gram/10 minutes and 0.915～0.940 gram/cc.In the present invention, second is anti-
Answering the density optimum of the copolymer of preparation in device is 0.925～0.938 gram/cc, and MI is 0.01～5
Gram/10 minutes.
The molecular weight distribution of gained polyethylene and ethylene copolymers has a unimodal wide characteristic distributions, moderate melt index,
Can keep preferable intensity and processing fluidity, beneficially extrusion molding is tubing.It addition, fusing point > 133 DEG C,
And branch lengths is 2-10 carbon atom, relative degree of branching 0.06-0.6, it is provided that moderate wafer is thick
Degree and the tie molecule chain of opposing cracks can spread, its structure is conducive to improving heat distortion temperature, therefore can use
Make heat-resisting pipes aspect.
A kind of method preparing heat-resisting ethylene copolymer that the present invention proposes.Use by the magnesium chloride of a kind of routine
Load TiCl4Ziegler-Natta catalyzed, cheap alkyl aluminum is promoter, molten at inertia hydro carbons
In agent, catalyzed ethylene and alpha-olefin copolymer, by two cascade reaction stills, segmentation carries out ethylene homo and second
Alkene copolyreaction, under hydrogen regulates, changes the process conditions of polyreaction, and availability can excellent, processing
Property is good, meet the ethylene copolymer of heat-proof polythene tubing performance requirement.
Hereinafter use embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiments.
The polymerization activity of catalyst calculates in accordance with the following methods: after polyreaction terminates, by reactor
Polymerizate (ethylene copolymer) filters and is dried, and then weighs the quality of this polymerizate, with this polymerization
The ratio of product quality and load type non-metallocene catalyst quality used represents the polymerization activity of catalyst
(unit is kgPE/gCat).
Polymer stacks density measurement reference standard GB 1636-79 carries out that (unit is g/cm3)。
Density polymer measures reference standard GB/T 1033-86 and carries out that (unit is g/cm3)。
Polymer particle size distributional analysis uses sieve method, is sieved by different-grain diameter screen cloth by the powder of this polymer
Point, after sieving, each constituent mass measures divided by the gross mass of polymer.
Melt flow rate measures reference standard GB/T 3682-2000 to be carried out.
Fusing point and percent crystallinity: differential scanning calorimetry, ASTM D 3418-03.
Molecular weight: the weight average molecular weight of copolymer is to be measured by high-temperature gel permeation chromatography method (GPC).Use
Measure equipped with mix-B chromatographic column PL220 high-temperature gel permeation chromatography method.Sample is by by 10 milligrams of resins
It is dissolved in the 1,2,4-trichloro-benzenes of 10mL and making.The nominal flow rate of flowing phase is 1.0 ml/min, temperature
It it is 155 DEG C.Molecular weight is by using Narrow distribution polystyrene calibration trace to be calculated.
Embodiment 1
In 5L reactor, nitrogen is replaced 3 times, adds 2L hexamethylene, adds the triethyl aluminum of 3mmol,
Add 0.48MPa hydrogen, 10mg magnesium chloride load TiCl4Ziegler-Natta catalyst, is warming up to 70 DEG C,
Being passed through ethylene, holding pressure is 0.8MPa, reacts 0.5 hour.Afterwards by hanging containing Natene
Supernatant liquid, is injected in the second reactor.Add 0.08MPa hydrogen, at 80 DEG C, be passed through ethylene/alpha-olefin
Being the gaseous mixture of 0.06/1, holding pressure is 0.3MPa, reacts 0.5 hour, prepares polyethylene and ethylene copolymers
114g.The performance test results is shown in Table 1.
Embodiment 2
In 5L reactor, nitrogen is replaced 3 times, adds 2L hexamethylene, adds the triethyl aluminum of 3mmol,
Add 0.58MPa hydrogen, 10mg magnesium chloride load TiCl4Ziegler-Natta catalyst, is warming up to 70 DEG C,
Being passed through ethylene, holding pressure is 0.8MPa, reacts 0.5 hour.Afterwards by hanging containing Natene
Supernatant liquid, injects in the second reactor.Adding 0.08MPa hydrogen, being passed through ethylene/alpha-olefin at 80 DEG C is
0.06/1 gaseous mixture, holding pressure is 0.3MPa, reacts 0.5 hour, prepares polyethylene and ethylene copolymers 117g.
The performance test results is shown in Table 1.
Embodiment 3
In 5L reactor, nitrogen is replaced 3 times, adds 2L hexamethylene, adds the triethyl aluminum of 3mmol,
Add 0.18MPa hydrogen, 10mg magnesium chloride load TiCl4Ziegler-Natta catalyst, is warming up to 70 DEG C,
Being passed through ethylene, holding pressure is 0.8MPa, reacts 0.5 hour.Afterwards by hanging containing Natene
Supernatant liquid, injects in the second reactor.Adding 0.08MPa hydrogen, being passed through ethylene/alpha-olefin at 80 DEG C is
0.06/1 gaseous mixture, holding pressure is 0.3MPa, reacts 0.5 hour, prepares polyethylene and ethylene copolymers 103g.
The performance test results is shown in Table 1.
Embodiment 4
In 5L reactor, nitrogen is replaced 3 times, adds 2L hexamethylene, adds the triethyl aluminum of 3mmol,
Add 0.48MPa hydrogen, 10mg magnesium chloride load TiCl4Ziegler-Natta catalyst, is warming up to 70 DEG C,
Being passed through ethylene, holding pressure is 0.8MPa, reacts 0.5 hour.Afterwards by hanging containing Natene
Floating, inject in the second reactor.Adding 0.08MPa hydrogen, being passed through ethylene/alpha-olefin at 80 DEG C is 0.1/1
Gaseous mixture, holding pressure is 0.3MPa, reacts 0.5 hour, prepares polyethylene and ethylene copolymers 123g.Performance is surveyed
Test result is shown in Table 1.
Embodiment 5
In 5L reactor, nitrogen is replaced 3 times, adds 2L hexamethylene, adds the triethyl aluminum of 3mmol,
Add 0.48MPa hydrogen, 10mg magnesium chloride load TiCl4Ziegler-Natta catalyst, is warming up to 70 DEG C,
Being passed through ethylene, holding pressure is 0.8MPa, reacts 0.5 hour.Afterwards by hanging containing Natene
Floating, inject in the second reactor.Adding 0.08MPa hydrogen, being passed through ethylene/alpha-olefin at 80 DEG C is
0.01/1 gaseous mixture, holding pressure is 0.3MPa, reacts 0.5 hour, prepares polyethylene and ethylene copolymers 102g.
The performance test results is shown in Table 1.
Embodiment 6
In 5L reactor, nitrogen is replaced 3 times, adds 2L hexamethylene, adds the triethyl aluminum of 3mmol,
Add 0.48MPa hydrogen, 10mg magnesium chloride load TiCl4Ziegler-Natta catalyst, is warming up to 70 DEG C,
Being passed through ethylene, holding pressure is 0.8MPa, reacts 0.5 hour.Afterwards by hanging containing Natene
Floating, inject in the second reactor.Adding 0.18MPa hydrogen, being passed through ethylene/alpha-olefin at 80 DEG C is 0.1/1
Gaseous mixture, holding pressure is 0.3MPa, reacts 0.5 hour, prepares polyethylene and ethylene copolymers 121g.Performance is surveyed
Test result is shown in Table 1.
The invention provides a kind of employing Conventional Ziegler-Natta catalyst and be catalyzed second with organo-aluminium promoter
Alkene and low cost alpha-olefin copolymer, in a mild condition, by relatively simple step, prepare resistance to hot polymerization second
The method of alkene.By the adjustment to polymerization technique, being allowed to produce broad peak distribution, different molecular weight component is with common
Performance under polymers respective material different temperatures, thus meet the performance requirement of heat-proof polythene tube material.
The molecular weight distribution of the polyethylene and ethylene copolymers obtained by the present invention has unimodal wide characteristic distributions, moderate
Melt index, it is possible to keeping preferable intensity and processing fluidity, beneficially extrusion molding is tubing.It addition,
Fusing point > 133 DEG C and branch lengths be 1-10 carbon atom, relative degree of branching 0.06-0.6, it is provided that suitable
In wafer thickness and opposing cracks can spread tie molecule chain, its structure is conducive to improving heat distortion temperature,
Polyethylene and ethylene copolymers fine heat-resisting performance, therefore, it can as heat-resisting pipes aspect.
Certainly, the present invention also can have other various embodiments, without departing substantially from present invention spirit and the feelings of essence thereof
Under condition, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but this
A little corresponding changes and deformation all should belong to the protection domain of the claims in the present invention.
Claims (12)
1. the preparation method of a heat-proof polythene copolymer, it is characterised in that use major catalyst and help
Catalyst, described major catalyst is that titanium, vanadium halogen compounds load to magnesium chloride, silica supports
Solid containing transition-metal catalyst, employings alkyl aluminum is promoter, under hydrogen regulation, by two
Cascade reaction still segmentation carries out ethylene homo and ethylene copolymer reaction, comprises the following steps:
A) in the first reactor inject organic solvent, be separately added in described organic solvent major catalyst and
Promoter, adds a certain amount of hydrogen, and ethylene homo reaction is in temperature between 50～100 DEG C, pressure
It is 0.5～1.0MPa, reacts 0.1～1 hour prepared Natene；And
B) aaerosol solution containing Natene Yu organic solvent step a prepared, injects second
In reactor, add a certain amount of hydrogen, at 50～100 DEG C, be passed through ethylene and C4-C12Aliphatic alpha-
The gaseous mixture of alkene, holding pressure is 0.1-3.0MPa, reacts 0.1-10 hour, prepares polyethylene and ethylene copolymers.
The preparation method of heat-proof polythene copolymer the most according to claim 1, it is characterised in that institute
State one or more that organic solvent is toluene, pentane, normal hexane, hexamethylene or heptane inertia hydro carbons.
The preparation method of heat-proof polythene copolymer the most according to claim 1, it is characterised in that
Major catalyst described in step a is by magnesium chloride load TiCl4Ziegler-Natta catalyst.
The preparation method of heat-proof polythene copolymer the most according to claim 1, it is characterised in that
Hydrogen usage described in step a is hydrogen/ethylene pressure than for 0-10.
The preparation method of heat-proof polythene copolymer the most according to claim 1, it is characterised in that
Hydrogen usage described in step b be hydrogen/ethene-alpha-olefin gaseous mixture intrinsic standoff ratio be 0-10.
The preparation method of heat-proof polythene copolymer the most according to claim 1, it is characterised in that
Ethylene described in step b and described C4-C12Aliphatic alpha-olefin gaseous mixture be ethylene/C4-C12Aliphatic
Alpha-olefin intrinsic standoff ratio is 0.01-1.0.
The preparation method of heat-proof polythene copolymer the most according to claim 1, it is characterised in that
The molecular weight distribution of described polyethylene and ethylene copolymers is unimodal for having, and molecular weight distribution index is 5-18,
190 DEG C, melt index is 0.08-0.9g/10min in the case of 2.16kg, fusing point > 133 DEG C.
The preparation method of heat-proof polythene copolymer the most according to claim 1, it is characterised in that
The branch lengths of gained polyethylene and ethylene copolymers is 1-10 carbon atom, relative degree of branching 0.06-0.6.
9. poly-obtained by the preparation method of polyethylene and ethylene copolymers described in any one in claim 1-8
Ethylene copolymer.
Polyethylene and ethylene copolymers the most according to claim 9, it is characterised in that described polyethylene copolymer
The molecular weight distribution of thing is unimodal for having, and molecular weight distribution index is 5-18,190 DEG C, 2.16kg situation
Lower melt index is 0.08-0.9g/10min, fusing point > 133 DEG C.
11. polyethylene and ethylene copolymers according to claim 9, it is characterised in that gained polyethylene copolymer
The branch lengths of thing is 1-10 carbon atom, relative degree of branching 0.06-0.6.
12. 1 kinds of polyethylene and ethylene copolymers tubing, it is characterised in that use the poly-second described in claim 9
Alkene copolymer is made.
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| CN113912756A (en) * | 2020-07-08 | 2022-01-11 | 中国科学院化学研究所 | Catalyst system for improving fluidity of polyethylene melt and application thereof |
| CN114133489A (en) * | 2021-12-28 | 2022-03-04 | 中国石油天然气股份有限公司 | Blow molding material for hollow container and preparation method and application thereof |
| CN114181349A (en) * | 2021-12-28 | 2022-03-15 | 中国石油天然气股份有限公司 | Polyethylene pipe material and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1350552A (en) * | 1999-03-09 | 2002-05-22 | 巴塞尔技术有限公司 | Multi-stage process for the (co) polymerization of olefins |
| CN1390235A (en) * | 1999-09-10 | 2003-01-08 | 巴塞尔技术有限公司 | Catalyst for the polymerization of olefins |
| CN1788024A (en) * | 2003-05-12 | 2006-06-14 | 联合碳化化学及塑料技术公司 | Process for control of polymer fines in a gas-phase polymerization |
| CN1798774A (en) * | 2003-05-29 | 2006-07-05 | 巴塞尔聚烯烃意大利有限责任公司 | Process for the preparation of a catalyst component and components therefrom obtained |
| CN1860136A (en) * | 2003-10-15 | 2006-11-08 | 尤尼威蒂恩技术有限责任公司 | Polymerization process and control of polymer composition properties |
| CN1898274A (en) * | 2003-12-19 | 2007-01-17 | 巴塞尔聚烯烃股份有限公司 | Process for the (co)polymerization of ethylene |
| CN101885795A (en) * | 2010-07-14 | 2010-11-17 | 中国石油天然气股份有限公司 | Electron donor catalyst and preparation and application |
| CN101891849A (en) * | 2010-06-25 | 2010-11-24 | 中国石油天然气股份有限公司 | Polyolefin catalyst, preparation thereof and application thereof |
| CN1980959B (en) * | 2004-07-07 | 2011-03-30 | 陶氏环球技术公司 | Multistage process for producing ethylene polymer compositions |
| CN102333798A (en) * | 2009-02-27 | 2012-01-25 | 巴塞尔聚烯烃股份有限公司 | Multistage process for the polymerization of ethylene |
| CN103476810A (en) * | 2011-03-28 | 2013-12-25 | 陶氏环球技术有限责任公司 | Process to produce enhanced melt strength ethylene/alpha-olefin copolymers and articles thereof |
-
2015
- 2015-02-16 CN CN201510085095.6A patent/CN105985490A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1350552A (en) * | 1999-03-09 | 2002-05-22 | 巴塞尔技术有限公司 | Multi-stage process for the (co) polymerization of olefins |
| CN1390235A (en) * | 1999-09-10 | 2003-01-08 | 巴塞尔技术有限公司 | Catalyst for the polymerization of olefins |
| CN1788024A (en) * | 2003-05-12 | 2006-06-14 | 联合碳化化学及塑料技术公司 | Process for control of polymer fines in a gas-phase polymerization |
| CN1798774A (en) * | 2003-05-29 | 2006-07-05 | 巴塞尔聚烯烃意大利有限责任公司 | Process for the preparation of a catalyst component and components therefrom obtained |
| CN1860136A (en) * | 2003-10-15 | 2006-11-08 | 尤尼威蒂恩技术有限责任公司 | Polymerization process and control of polymer composition properties |
| CN1898274A (en) * | 2003-12-19 | 2007-01-17 | 巴塞尔聚烯烃股份有限公司 | Process for the (co)polymerization of ethylene |
| CN1980959B (en) * | 2004-07-07 | 2011-03-30 | 陶氏环球技术公司 | Multistage process for producing ethylene polymer compositions |
| CN102333798A (en) * | 2009-02-27 | 2012-01-25 | 巴塞尔聚烯烃股份有限公司 | Multistage process for the polymerization of ethylene |
| CN101891849A (en) * | 2010-06-25 | 2010-11-24 | 中国石油天然气股份有限公司 | Polyolefin catalyst, preparation thereof and application thereof |
| CN101885795A (en) * | 2010-07-14 | 2010-11-17 | 中国石油天然气股份有限公司 | Electron donor catalyst and preparation and application |
| CN103476810A (en) * | 2011-03-28 | 2013-12-25 | 陶氏环球技术有限责任公司 | Process to produce enhanced melt strength ethylene/alpha-olefin copolymers and articles thereof |
Non-Patent Citations (1)
| Title |
|---|
| 孔媛: ""改性负载Ziegler-Natta催化体系催化乙烯/高级α-烯烃共聚合的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535532A (en) * | 2018-10-09 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of production method of 1- hervene copolymer linear polyethylene resin |
| CN110183558A (en) * | 2019-05-31 | 2019-08-30 | 上海化工研究院有限公司 | A kind of back end hydrogenation technique for vinyl polymerization |
| CN110183558B (en) * | 2019-05-31 | 2022-01-28 | 上海化工研究院有限公司 | Post-hydrogenation process for ethylene polymerization |
| CN113912756A (en) * | 2020-07-08 | 2022-01-11 | 中国科学院化学研究所 | Catalyst system for improving fluidity of polyethylene melt and application thereof |
| CN113912756B (en) * | 2020-07-08 | 2022-09-09 | 中国科学院化学研究所 | Catalyst system for improving fluidity of polyethylene melt and application thereof |
| CN114133489A (en) * | 2021-12-28 | 2022-03-04 | 中国石油天然气股份有限公司 | Blow molding material for hollow container and preparation method and application thereof |
| CN114181349A (en) * | 2021-12-28 | 2022-03-15 | 中国石油天然气股份有限公司 | Polyethylene pipe material and preparation method and application thereof |
| CN114181349B (en) * | 2021-12-28 | 2023-11-17 | 中国石油天然气股份有限公司 | Polyethylene pipe material and preparation method and application thereof |
| CN114133489B (en) * | 2021-12-28 | 2024-02-02 | 中国石油天然气股份有限公司 | Blow molding material for hollow container, preparation method and application thereof |
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