CN109438593A - A kind of production extrahigh-molecular weight polyolefins catalyst and its preparation method and application - Google Patents
A kind of production extrahigh-molecular weight polyolefins catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109438593A CN109438593A CN201811420544.8A CN201811420544A CN109438593A CN 109438593 A CN109438593 A CN 109438593A CN 201811420544 A CN201811420544 A CN 201811420544A CN 109438593 A CN109438593 A CN 109438593A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- molecular weight
- extrahigh
- reaction
- inorganic carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a kind of production extrahigh-molecular weight polyolefins catalyst and its preparation method and application, catalyst includes: the inorganic carrier that load has surfactant, and the catalyst component being supported on inorganic carrier, catalyst component is transition metal halide MX4With the organometallic reagent M ' R containing R basen(n=1-3) reaction forms catalyst component MR4.Compared with prior art, the catalyst bulk density that the present invention is prepared is high, particle is uniform, ultra-high molecular weight polyethylene product of the average grain diameter less than 200 μm, the preparation and application that can be used for middle-high density extrahigh-molecular weight polyolefins, particularly suitable for products such as high-performance ultra high molecular weight polyethylene fibers.
Description
Technical field
The present invention relates to a kind of catalyst, more particularly, to a kind of production extrahigh-molecular weight polyolefins catalyst and its system
Preparation Method and application.
Background technique
China's polyolefin industry is quickly grown, but still is not able to satisfy the demand of domestic market, especially high-performance polyene
Hydrocarbon material relies primarily on import.The high performance of the commodity polymers material such as polyethylene always is the hot spot of research.Alkene
Polymerization catalyst is the core of polyolefin polymerization technology.Traditional Ziegler-Natta catalyst loads to catalytic efficiency on carrier
It significantly improves, referred to as efficient Ziegler-Natta catalyst is rapidly developed polyolefin industry.Ultra-fine grain gathers
Ethylene purposes is very extensive, ultra-fine ultra-high molecular weight polyethylene, micronized polyethylene wax, the ultra-fine polyene such as superfine high-density degree polyethylene
Hydrocarbon product, downstream client are used to manufacture the products such as injection molding, extrusion molding, blow molding.
In patent CN102002124, middle petroleum, which discloses, a kind of prepares high-density ultra-fine polyethylene powders with slurry process
Production method, use granularity for magnesium ethylate/TiCl 4 catalyst of the poly- second of 0.2-5.0,75~85 DEG C of reaction temperature,
Under conditions of 0.8~1.0MPa of reaction pressure, 50~1500RPM of speed of agitator, the poly- second prepared after polymerization reaction occurs for monomer
Alkene powder size has reached 30-80 microns.
In patent CN106317562A and CN106319667A, chemistry is disclosed a series of about preparing supra polymer
Measure the preparation method of micronized polyethylene and its patent of the application in film and fiber art.By the polymerization temperature for controlling ethylene
Degree, monomer ethylene purity, adjust catalyst preparation step and decentralized medium is introduced in polymerization system, synthesized one kind
Solubilized type super high molecular weight ultra-fine grain diameter polyethylene.Traditional chlorination magnesium alcoholate that catalyst uses passes through titanium tetrachloride dealcoholysis
Preparation method.Do not have to propose the average grain diameter and its property of the catalyst prepared in patent claim and embodiment, in patent
Final gained polyethylene average grain diameter is 50-80 microns, and contains a certain amount of high boiling decentralized medium in polymer, is produced
Object heap density is extremely low, only 0.1-0.3g/mL, although residual fraction solvent in polymer, improves the performance of following process, can
To be used in diaphragm and fiber art.But extremely low polyethylene heap density brings difficulty to the collection and transport of product.
Liao Yang petrochemical company polyethylene device produces high density polyethylene (HDPE) using magnesium ethylate/titanium tetrachloride catalyst system,
Its catalyst grain size is mainly used for downstream user at 100-180 microns in 5 microns, polyethylene product granularity produced
Manufacture injection molding, extrusion molding, blow molded product.
Another method for preparing superfine polyethylene powder is deep cooling crush method, i.e., common polyethylene powders are prior
Freezing crushes again, and this method production cost is excessively high, increases burden for users.
Patent CN101906179B and before CN101633703A in, Beijing University of Chemical Technology discloses a kind of (super
High molecular weight) polyolefin catalyst preparation method, by carrier such as SiO2It is scattered in organic solvent；At -40-30 DEG C, to
Organolithium (such as butyl lithium) or Grignard Reagent are added in obtained dispersion liquid, add finish -20-30 DEG C reaction 0.5-3 hours,
It is warming up to 30-100 DEG C again, reaction obtains mixture in 0.5-5 hours；Mixture is filtered, washing remove superfluous organolithium or
Grignard Reagent；At -30-30 DEG C, organo-silicon compound (such as dimethyl diethoxy silicon) and titanium tetrachloride are then added
Close object, after adding -30-30 DEG C reaction 0.5-3 hours, then be warming up to 30-100 DEG C, reaction 1-5 hours；It is filtered and is washed
Superfluous titanium halide is removed, is dried, obtains major catalyst.Then in slurry reaction kettle, major catalyst is added and helps
Catalyst (such as triethyl aluminum), is passed through ethylene reaction, polyethylene product is prepared.This method by Grignard Reagent (butyl lithium) with
Silica gel reacts, it is therefore an objective to improve the load capacity of titanium tetrachloride；Grignard Reagent reacts the silica gel for also contributing to widening with silica gel
Activation temperature (100-1000 DEG C) range, lower silica gel activating temperature gained catalyst also show higher activity；Preparation master
The purpose of addition organosilicon is the copolymerization efficiency in order to improve ethylene and comonomer when catalyst.The patent is by being added grignard
Agent modifier silica gel improves silica gel activating efficiency, but the active component of the catalyst is still titanium tetrachloride, silica gel load
The shortcomings that titanium tetrachloride, is difficult to overcome, for example heap density is low, molecular weight of product distribution is wide, growth of reuniting in polymerizate polymerization,
Grain diameter is big and the disadvantages of being unevenly distributed, and increases the difficulty of ultra-high molecular weight polyethylene post-processing, leads to product application
Field is limited, it is difficult to use in field in high-end field such as spinning, diaphragm.
Summary of the invention
The object of the invention is to for overcome the deficiencies in the prior art, present invention employs urging unlike the prior art
Agent preparation method, one of problem to be solved are to provide a kind of catalysis that can produce ultra-fine extrahigh-molecular weight polyolefins
Agent.For polymerization reaction, catalytic activity is higher, and the partial size of gained polymerizate is thinner, and granularity is at 200 microns hereinafter, average mark
Regulatable ultra-high molecular weight polyethylene powder between son amount 100-1000 ten thousand.
The second technical problem to be solved by the present invention is to provide the preparation method of the ultra-fine loaded catalyst.
The third technical problem to be solved by the present invention is to provide application of the loaded catalyst in vinyl polymerization.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of production extrahigh-molecular weight polyolefins catalyst, comprising:
Load has the inorganic carrier of surfactant,
The catalyst component being supported on inorganic carrier,
The catalyst component is transition metal halide MX4With the organometallic reagent M ' R containing R basen(n=1-3) it reacts
Form catalyst component MR4。
The transition metal halide MX4Middle M is titanium, zirconium, vanadium or hafnium, and X is halogen, is fluorine, chlorine, bromine or iodine；Organic gold
Belong to reagent M ' RnIn M ' be Li, Mg, Zn or Al, R base be benzyl, alkyl silicon methyl, methylene naphthalene or neopentyl in one
Kind is a variety of.
The content of the catalyst component is calculated as the 0.1-10wt% of catalyst total amount with metal.
The inorganic carrier is selected from magnesia, silica, aluminium oxide, titanium dioxide, silica-alumina, dioxy
One or more of SiClx-magnesia, chain silicate, phyllosilicate, talcum or magnesium hydroxide-magnesium sulfate, average grain
Diameter is 0.01-100 microns, and hydroxyl and/or carboxyl are contained in surface.
The average grain diameter of the inorganic carrier is 0.1-30 microns, preferably 0.5-10 microns.
The surfactant is that molecular structure has amphiphilic component, and one end is hydrophilic radical, and the other end is hydrophobic
The molar ratio of group, surfactant and inorganic carrier is 0.01-100:1.
The surfactant is a kind of or several in fatty acid methyl ester, alkyl e pioic acid methyl ester or alkyl dienoic acid methyl ester
Kind, alkyl carbon chain number is selected as 10-24, preferably 12-18, in addition alkyl carbon chain can also have side chain, and/or hydroxyl and/or its
His group.
Produce the preparation method of extrahigh-molecular weight polyolefins catalyst, comprising the following steps:
(1) by least one inorganic carrier for sloughing molecular water ultrasonic disperse in organic solvent, it is living that surface is then added
Property agent, reacts at moderate temperatures, obtains modified inorganic carrier；
(2) in organic solvent, it stirs at moderate temperatures, by transition metal halide MX4Step (1) is immersed in obtain
Modified inorganic carrier on, reacted with carrier surface, make transition metal halide MX4Component reaction in-situ is carried on modified inorganic
On carrier；
(3) in organic solvent, the inorganic compounding carrier that step (2) obtain is added and forms suspension, is then added organic
Metallic compound M ' Rn, reaction in-situ is carried out at moderate temperatures；
(4) step (3) products therefrom is washed through filtering and solvent and removes superfluous organo-metallic compound, at drying
Reason obtains production extrahigh-molecular weight polyolefins catalyst.
Long-chain saturated alkane or halogenated aryl hydrocarbon or their mixing of step (1) organic solvent selected from C10-C20
Solvent；Reaction temperature is 20-200 DEG C；Reaction time is -10 hours 0.1 hour；The use of dosage of surfactant and inorganic carrier
The weight ratio of amount is 0.01-100:1；
Step (2) the transition metal halide MX4Weight ratio with modified inorganic carrier is 0.01-50:1；Reaction temperature
Degree is -40~200 DEG C；Reaction time is -10 hours 0.1 hour；Mixing speed 20-800rpm；
Step (3) organo-metallic compound M ' RnWith transition metal halide MX4Weight ratio be 0.01-50:1；Instead
Answering temperature is -120-80 DEG C, and the reaction time is -10 hours 0.1 hour.
As more preferred embodiment,
Preferred 50-180 DEG C of the reaction temperature of step (1), more preferably 80-160 DEG C, the reaction time is 0.5 hour -5 small
When, more preferably 1-3 hours, the weight ratio of surfactant and inorganic carrier was preferably 0.1-20:1, more preferably 0.5-5:
1, the organic solvent includes decane, dodecane, kerosene, dichloro-benzenes, trichloro-benzenes, trimethylbenzene, dimethylbenzene, toluene or benzyl chloride
One or more, preferably kerosene or dichloro-benzenes；
Step (2) the transition metal halide MX4Weight ratio with modified inorganic carrier is preferably 0.5-30:1, more excellent
It is selected as 1-10:1；Reaction temperature is preferably 60-160 DEG C, and more preferably 100-140 DEG C；Reaction time is preferably 1 hour -6 small
When, more preferably 2-4 hours；Mixing speed 150-400rpm；More preferably 200-300rpm；
Step (3) organo-metallic compound M ' RnWith transition metal halide MX4Weight ratio be preferably 0.1-20:
1, more preferably 0.5-5:1；Preferably -90-50 DEG C, more preferably -80-20 DEG C of the reaction temperature.Reaction time preferred 0.5-5
Hour, it is 1-3 hours more preferable.
The application for producing extrahigh-molecular weight polyolefins catalyst, in single-reactor or 2 and the above tandem reaction
In device, ethylene, alpha-olefin comonomer, catalyst and co-catalyst is added and carries out polymerization reaction, produces polyethylene, the α-
The molar ratio of olefin comonomer and ethylene is 0.01-1:1, and the additional amount of the catalyst is to make its concentration 0.01-
100ppm, the additional amount of the co-catalyst are to make its concentration 5-500ppm.
The alpha-olefin comonomer is the alpha-olefin of C1-C20, including propylene, 1- butylene, 1- amylene, 1- hexene, 1- be pungent
The molar ratio of alkene or 1- decene, the alpha-olefin comonomer and ethylene is 0.05-0.5:1, and the co-catalyst adds
Entering amount is to make its concentration 20-400ppm.
The polymerization reaction is olefin polymetiation process, including slurry autoclave, slurry loop or polymerisation in solution, and slurry autoclave is poly-
Reaction pressure is 0.1-5MPa when conjunction, and reaction temperature is 0-120 DEG C, preferably 40-90 DEG C, most preferably 60-80 DEG C；Slurry loop
Reaction pressure is 0.5-6MPa when polymerization, and reaction temperature is 30-150 DEG C, preferably 50-100 DEG C, most preferably 60-80 DEG C.
The polyethylene average grain diameter being prepared is 10-500 microns, and preferably 40-400 microns, most preferably 60-200 is micro-
Rice.Product glues equal average molecular weight 30-1000 ten thousand, preferably average molecular weight 100-900 ten thousand；Density is 0.918-0.950g/
cm3, preferred density 0.920-0.940g/cm3。
Compared with prior art, present invention improves over available carrier material, it is that it includes at surface-active agents
The inorganic carrier of reason.It is fatty acid methyl ester, alkyl e pioic acid methyl ester or the alkyl diene of 12-18 that the present invention, which selects alkyl carbon chain number,
Sour methyl esters is as surfactant, and there are two purpose and effects: first is that improving the dispersibility of inorganic carrier, and trying with organic-magnesium
The uniformity of agent reaction.The surfactant can occur in (150 DEG C of thermo-field thoery) and inorganic carrier surface at a higher temperature
Chemical reaction makes inorganic carrier surface generate the alkyl of long-chain, facilitates the dispersion of inorganic carrier, be conducive to modified inorganic
Carrier with organomagnesium reagent is full and uniform reacts；Second is that improving the resistance to deactivation temperature of catalyst component.When reaction temperature superelevation 100
DEG C, facilitate catalyst component and sufficiently reacted with inorganic carrier, activated centre non-inactivation, the catalytic active center for obtaining reaction exists
Carrier surface is uniformly dispersed.In polymerization, catalyst can uniformly disperse in polymerization, reduce the reunion of catalyst granules,
Finally prepare ultra-fine grain diameter polyethylene particle.By loading different activities center, the superelevation point of ultra-fine grain diameter can be prepared
Sub- weight northylen can be used for the high-end fields such as lithium battery diaphragm, fibre spinning.
Compared with prior art, transition metal halide MX is utilized4Reaction in-situ is supported on inorganic carrier surface, by adding
Enter organo-metallic compound M ' RnWith MX4Reaction, activated centre ligand introduce big functional group R, improve the activity of catalyst, and energy
Polymerization chain tra nsfer is reduced, the molecular weight of product polyethylene is improved.Since the surface-active agents that catalyst contains improve polymerization
The dispersion degree of polyolefin particles in the process helps to prepare granularity in 200 microns of ultra-high molecular weight polyethylene powder below.
Detailed description of the invention
Fig. 1 is the electromicroscopic photograph of embodiment 1a polyethylene specimen；
Fig. 2 is the electromicroscopic photograph of 1 polyethylene specimen of comparative example；
Fig. 3 is the catalyst ethylene kinetics of polymerization curve of embodiment 1a, embodiment 1b and comparative example 1.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
The performance indicator of each polymer measures as follows in embodiment.
ASTM D1238 is used to test the melt index (MI2.16, in 2.16kg load, 190 DEG C) of polyvinyl resin, stream
Dynamic index (FI, in 21.6kg load, 190 DEG C)
The measurement of polymer stacks density: it is measured according to ASTM-D1895.
Produce ultra-fine superhigh-molecular weight polyolefin catalyst composition
The present invention provides the catalyst for producing ultra-fine extrahigh-molecular weight polyolefins, modified it includes surface is supported on
Inorganic carrier on catalyst.
According to an embodiment, catalyst of the invention includes:
(1) inorganic carrier handled by surfactant is as carrier；
(2) by transition metal halide and carrier situ reaction load in carrier surface；
(3) organo-metallic compound M ' R is then addednWith MX4Reaction, in-situ preparation MR4Catalyst component；
The present invention synthesize it is a kind of it is suitable production ultra-fine grain diameter polyolefin catalyst, it is described as carrier without airborne
Body, including magnesia, silica, aluminium oxide, titanium dioxide, silica-alumina, silica-magnesia, chain silicon
The one or more of hydrochlorate, phyllosilicate, talcum, magnesium hydroxide-magnesium sulfate etc.；The functional inorganic carrier is averaged grain
Diameter is 0.01-100 microns.
It is amphipathic that the surfactant refers to that molecular structure has: one end is hydrophilic radical, and the other end is hydrophobic group
Group.Preferred fatty acid methyl esters, alkyl e pioic acid methyl ester and alkyl dienoic acid methyl ester etc. are one or more of.The surfactant is used
The molar ratio of amount and the dosage of the functional inorganic carrier is (0.01-50): 1.
The transition metal halide MX4Middle M be titanium, zirconium, vanadium or hafnium, X is halogen compounds, preferably fluorine, chlorine, bromine,
Iodine etc..
Organometallic reagent M ' the Rn(n=1-3) M ' in is Li, Mg, Zn, Al etc., and R is benzyl, alkyl silicon first
Base, methylene naphthalene, neopentyl etc. are one or more.
The catalyst component is the transition metal halide MX by being supported on inorganic carrier surface4With having containing R base
Machine metal reagent M ' RnReaction forms MR4.The content of catalyst component is calculated as the 0.1-10wt% of catalyst total amount with metal；
The functional inorganic material average grain diameter is 0.1-30 microns, preferably 0.5-10 microns；
According to a specific aspect of the embodiment, following preparation method can be used:
(1) by least one micro-nano inorganic carrier for sloughing molecular water ultrasonic disperse in organic solvent, table is then added
Face activating agent, reacts at moderate temperatures, obtains modified inorganic carrier；
(2) in organic solvent, at moderate temperatures, by transition metal halide MX4It is immersed in the function that step (2) obtains
On energy property inorganic compounding carrier, is reacted with carrier surface, be carried on catalytic component on inorganic compounding carrier；
(3) in organic solvent, by organo-metallic compound M ' RnThe functional inorganic that step (2) obtains is added to suspend
Liquid, at moderate temperatures reaction in-situ.
(4) step (3) products therefrom is washed through filtering and solvent and removes superfluous organo-metallic compound, at drying
Reason, obtaining catalyst component is MR4Solid catalyst.
Program dehydration is carried out to carrier first, selects following carrier but not limited to this, dry oxidation magnesium, titanium dioxide
Silicon, aluminium oxide, silica-magnesia, alumina-silica magnesium.Program dehydration treatment method is as follows: under inert gas protection
(nitrogen or argon gas) carries out fluidization treatment activation.Between 100 DEG C of temperature to 600 DEG C of highest, every 100 DEG C of constant temperature 2 hours, so
It is gradually cooled to room temperature afterwards, carrier encapsulation nitrogen saves.In organic solvent, including but not limited to, dichloro-benzenes is added dehydration and lives
Then the inorganic carrier of change, ultrasonic disperse are added surfactant, react at moderate temperatures, obtain modified functional nothing
Airborne body.
In organic solvent, including but not limited to, dichloro-benzenes, the function that transition metal halide addition above-mentioned steps are obtained
Can be in property inorganic carrier suspension, transition metal halide includes but is not limited to this, titanium tetrachloride, zirconium chloride, hafnium tetrachloride,
Vanadium tetrachloride etc., reaction temperature are -50~100 DEG C, react with carrier surface, make MX4Catalyst component is carried on inorganic compounding load
On body.Products therefrom is filtered and solvent washing removes superfluous catalyst component, is dried, nitrogen protection saves.
In organic solvent, including but not limited to, dichloro-benzenes, by organo-metallic compound M ' RnAbove-mentioned steps are added to obtain
The functional inorganic suspension arrived, at moderate temperatures reaction in-situ.Products therefrom is removed into surplus through filtering and solvent washing
Organo-metallic compound, be dried, obtain catalyst component be MR4Solid catalyst.
The co-catalyst that the present invention is used in vinyl polymerization is selected from alkyl aluminum compound, alkyl aluminum compound, halogen
Substituted alkyl aluminium compound, alkyl magnesium compound, alkyl zinc compound, alkyl boron compound or combinations thereof, preferably triethyl aluminum, one
Chlorodiethyl aluminium, ethyl aluminum dichloride, triisobutyl aluminium are most preferably triethyl aluminum or aluminium diethyl monochloride.Co-catalyst
Concentration is typically about 5~500ppm, preferably from about 20~400ppm, and most preferably from about 40~300ppm (ethylene based on use).
The present invention provides the method for preparing ultra-fine grain diameter polyolefin powder, this method includes under polymerization conditions, at this
In the presence of the catalyst of invention and corresponding co-catalyst for polymerize individual ethylene or with other olefin monomers, it is such as a kind of
Or the ethylene that a variety of high alpha-olefins combine.Its example is C3-C10Alpha-olefin, as propylene, 1- butylene, 1- amylene, 1- hexene,
4-methyl-1-pentene, 1- heptene and 1- octene, preferably 1- butylene, 1- amylene, 1- hexene or 4-methyl-1-pentene and most preferably
1- hexene.
Any suitable, conventional olefin polymerization technique can be used in polymerization, as slurry loop, autoclave, solution or gas phase are poly-
It closes and carries out, but preferably in slurry loop reactor or in tank reactor, especially carried out in slurry loop reactor.It is poly-
Close can interval, it is semicontinuous or be carried out continuously.The catalyst poison in polymerization reaction system is being eliminated, such as moisture, oxygen, an oxidation
Under carbon and acetylene, carried out under the temperature and pressure for being adequate to bring about polymerization reaction using the catalyst (composition) of catalytically effective amount
Reaction.The particularly desirable method for producing Inventive polymers is in slurry loop or tank reactor.
Above-mentioned polymerization reaction is conventional olefin polymerization technique, including slurry autoclave, slurry loop or polymerisation in solution are described
Slurry tank polymerization when reaction pressure be 0.1-5MPa, reaction temperature be 0-120 DEG C, preferably 40-90 DEG C, most preferably 60-
80℃；Reaction pressure is 0.5-6MPa when the described slurry loop po lymerisation, and reaction temperature is 30-150 DEG C, preferably 50-100 DEG C,
Most preferably 60-80 DEG C.
It, can be using polymerizing condition those of commonly employed in the art in polymerization of the invention.For example, in slurry
In loop po lymerisation, reaction pressure is in 0.5-6MPa, preferably 1-3MPa；Reaction temperature is preferably 60-120 DEG C, more excellent at 30-150 DEG C
Select 90-110 DEG C.Kettle-typed polymerization method generally arrives about 5.0MPa or higher, pressure of the preferably from about 0.5MPa to about 2.0MPa 0.1
It is operated at a temperature of power and 0 DEG C-about 120 DEG C, about 110 DEG C of preferably from about 30-, about 100 DEG C of more preferably from about 60-.
It using catalyst according to the invention, can adopt in a known manner, such as suitably be controlled by using hydrogen poly-
Close the molecular weight of object.For hydrogen as chain-transferring agent, other reaction conditions are identical, and greater amount of hydrogen leads to the lower of polymer
Average molecular weight.Hydrogen/ethylene molar ratio of use can dependent on polymer required average molecular weight and change, and can be with
It is determined by those skilled in the art according to specific situation.The present invention is not limited, the quantity of hydrogen is typically about 0.001- about 2.0
The every molar ethylene of mol of hydrogen, the preferably every molar ethylene of 0.01-0.5 mol of hydrogen.
Can be according to many factors, such as polymerization technique type to be used and polymer type to be prepared, by this field
Technical staff determines polymerization temperature and time.It is generally carried out, is gathered under bigger rate using higher temperature due to chemically reacting
Closing temperature should be sufficiently high to obtain acceptable rate of polymerization.Therefore, under normal circumstances, polymerization temperature is greater than about 30 DEG C, more
Usually above about 65 DEG C.On the other hand, polymerization temperature should be less high to cause, such as the deterioration of catalyst or polymer.Generally
In the case of, polymerization temperature is less than about 200 DEG C, preferably less than about 115 DEG C, more preferably less than about 100 DEG C.
Polymerization temperature part for technique is determined by the density for the polyvinyl resin to be produced.More particularly, resin
Fusing point depends on resin density.The density of resin is higher, its fusing point is higher.Ethene polymerization method through the invention, can be with
Density is produced in 0.918-0.950g/cm3In the range of, preferably 0.920-0.940g/cm3Range；Viscosity average molecular weigh exists
Polymer powder in 1000000-1,000 ten thousand ranges.Polymerization of the present invention can be with the polyvinyl resin of ultra-fine grain diameter, product
Range of the molecular weight distribution MWD in 3-20,10-500 μm of product average grain diameter, preferably 40-400 μm, most preferably 60-200 μ
m。
Embodiment 1:
It prepares Ti (TMSM)4/MgCl2/ MgO catalyst system；
Embodiment 1a
The preparation of catalyst:
The preparation (activation) of carrier: under the protection of nitrogen (nitrogen or argon gas), using small-sized fluidized bed to magnesia into
The activation of row fluidization treatment.It is added 100g waterless nano magnesia (10 microns of average grain diameter), carries out temperature programmed control activation processing.Journey
Sequence temperature control step are as follows: between 100 DEG C to 400 DEG C of temperature, every 100 DEG C of constant temperature 2 hours, be then gradually cooled to room temperature, obtain
The magnesium oxide carrier S of activation0, encapsulation nitrogen preservation.Then the nano magnesia S of 10g dehydration activation is taken0It is added in white oil, surpasses
Sound disperses 30 minutes, and-ten eight methyl carbonate of 20ml surfactant is then added, reacts 2 hours at 180 DEG C, utilizes 100ml
Dimethylbenzene washs three times, is dried to obtain modified functional inorganic carrier S1。
Under nitrogen protection, the S of 2g is added in a reaction flask with stirring1Carrier and 30ml titanium tetrachloride, 140 DEG C
Lower stirring 2 hours, revolving speed 250rpm.After reaction, it is washed 6 times with 100ml n-hexane, is dried to obtain solid particle Cat0.
Under nitrogen protection, 100ml toluene is added, while 5g solid particle Cat0 is added, under stirring state, is slowly added dropwise
(trimethyl silicon substrate) lithium methide Li (TMSM) of 10ml 1.0M, is stirred to react 1 hour, is warming up to 50 DEG C by -78 DEG C of reaction temperature,
It reacts again 1 hour.Finally, being washed 3 times with 100ml toluene and 100ml n-hexane, it is dried to obtain solid catalyst Ti (TMSM)4/
MgCl2/MgO。
Slurry polymerization: reaction unit is 2L steel pressure resistance water cycle temperature control reaction kettle, at 95 DEG C of elder generation at vacuum-nitrogen displacement
Reason reaction kettle 2-4 hours is finally separately added into 1L n-hexane, 50mg catalyst, mono- chlorine of 2ml under nitrogen protection full of nitrogen
Diethyl aluminum, then ethylene is replaced 4 times, is removed nitrogen, is filled into the ethylene of the pressure of 1.0MPa, carry out polymerization reaction at 70 DEG C.
When reaction temperature rises, heat exchanger collet heating steam or cooling water are adjusted, controls temperature of reactor at 70 DEG C or so.Reaction
After 2 hours, reaction is terminated, room temperature is cooled to, discharged, it is dry, polyethylene product is obtained, is finally weighed, heap density, test are measured
Particle diameter distribution calculates catalyst activity and is listed in Table 1 by the performance of the polyvinyl resin of above-mentioned test method test.
Embodiment 1b:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to surfactant is changed to cis- -9- 18
E pioic acid methyl ester.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and press above-mentioned test method
The performance of the polyvinyl resin of test is listed in Table 1.
Embodiment 1c:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to surfactant is changed to 13.16- cis- two
Dodecadienoic acid methyl esters.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and by above-mentioned
The performance of the polyvinyl resin of test method test is listed in Table 1.
Embodiment 1d:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to surfactant is changed to 18- methyl 19
Methyl carbonate.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and press above-mentioned test method
The performance of the polyvinyl resin of test is listed in Table 1.
Embodiment 1e:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to benzyl lithium.It presses
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the polyethylene tested by above-mentioned test method
The performance of resin is listed in Table 1.
Embodiment 1f:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to 1- methyl-1-
Naphthalene lithium.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and by above-mentioned test method survey
The performance of the polyvinyl resin of examination is listed in Table 1.
Embodiment 1g:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to neopentyl lithium.
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the poly- second tested by above-mentioned test method
The performance of olefine resin is listed in Table 1.
Embodiment 1h:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to (trimethyl silicane
Base) acetylene lithium.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and press above-mentioned test method
The performance of the polyvinyl resin of test is listed in Table 1.
Embodiment 1i:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to phenyl lithium.It presses
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the polyethylene tested by above-mentioned test method
The performance of resin is listed in Table 1.
Embodiment 1j:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to (trimethyl silicane
Base) methyl magnesium.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and press above-mentioned test method
The performance of the polyvinyl resin of test is listed in Table 1.
Embodiment 1k:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to benzyl magnesium.It presses
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the polyethylene tested by above-mentioned test method
The performance of resin is listed in Table 1.
Embodiment 1l:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to 1- methyl-1-
Naphthalene zinc.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and by above-mentioned test method survey
The performance of the polyvinyl resin of examination is listed in Table 1.
Embodiment 1m:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to neopentyl zinc.
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the poly- second tested by above-mentioned test method
The performance of olefine resin is listed in Table 1.
Embodiment 1n:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to (trimethyl silicane
Base) methyl zinc.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and press above-mentioned test method
The performance of the polyvinyl resin of test is listed in Table 1.
Embodiment 1o:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to benzyl zinc.It presses
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the polyethylene tested by above-mentioned test method
The performance of resin is listed in Table 1.
Embodiment 1p:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to 1- methyl-1-
Naphthalene aluminium.Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and by above-mentioned test method survey
The performance of the polyvinyl resin of examination is listed in Table 1.
Embodiment 1q:
Composite catalyst is prepared using method identical with embodiment 1a, in addition to organometallic reagent is changed to tribenzyl aluminium.
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the poly- second tested by above-mentioned test method
The performance of olefine resin is listed in Table 1.
Comparative example 1:
Catalyst is prepared using method identical with embodiment 1a, in addition to surfactant is changed to 0ml.According to embodiment
The identical program of 1a carries out slurry polymerization.The performance of the catalytic activity of calculating and the polyvinyl resin by the test of above-mentioned test method
It is listed in Table 1.
The electromicroscopic photograph of 1 polyethylene specimen of embodiment 1a and comparative example is as illustrated in fig. 1 and 2, and Fig. 1 shows the poly- of embodiment 1a
The electromicroscopic photograph of ethylene sample, Fig. 2 indicates the electromicroscopic photograph of the polyethylene specimen of comparative example 1, from electromicroscopic photograph as can be seen that adopting
The polyethylene particle prepared with this patent method is smaller, more regular, helps to promote and apply in post-processing, for example more evenly more
Thin particle is due to the efficiency of the dissolution swell process before improving fibre spinning and the quality of fiber product.In table 1, also find out
The heap density of embodiment 1a is greater than the heap density of comparative example 1, and particle is more uniform.
Embodiment 1a-1b and the catalyst ethylene kinetics of polymerization curve of comparative example 1 are as shown in Figure 3: wherein curve a table
Show the catalyst ethylene kinetics of polymerization curve graph in embodiment 1a, curve b indicates the catalyst ethylene polymerization in embodiment 1b
Dynamic curve diagram, curve c indicate the catalyst ethylene kinetics of polymerization curve of comparative example 1.From kinetic curve as can be seen that
Due to joined fatty acid methyl ester and (trimethyl silicon substrate) lithium methide in this patent, kinetics of polymerization shows becoming for more stable state
Gesture facilitates the homogeneity of polymerizate growth, facilitates molecular weight of product and uniformly grow, reduce the chain entanglement of strand,
Improve the processing performance of product.
Table 1
As can be seen from the table, the use of surfactant helps to improve the heap density of particle, reduces gained polyethylene
Average grain diameter.
Embodiment 2:
V (TMSM) the 4/ inorganic carrier catalyst system of preparation；
Embodiment 2a
The preparation of catalyst:
The preparation (activation) of carrier: under the protection of nitrogen, it is living that fluidization treatment is carried out to magnesia using small-sized fluidized bed
Change.It is added 100g sheet silicate (being preferably but not limited to 10.0 microns of montmorillonite average grain diameter), carries out at temperature programmed control activation
Reason.Temperature programmed control step are as follows: between 100 DEG C to 500 DEG C of temperature, every 100 DEG C of constant temperature 2 hours, it is then gradually cooled to room temperature,
The montmorillonite carrier S activated0, encapsulation nitrogen preservation.Then the montmorillonite S of 10g dehydration activation is taken0It is added in kerosene, surpasses
Sound disperses 30 minutes, and 18 methyl carbonate of 20ml surfactant is then added, reacts 2 hours at 140 DEG C, utilizes 100ml
Dimethylbenzene washs three times, is dried to obtain modified functional inorganic carrier S1。
Under nitrogen protection, the S of 2g is added in a reaction flask with stirring1Tetra- chlorination V (VCl4) of carrier and 30ml,
It is stirred 2 hours at 130 DEG C, revolving speed 250rpm.After reaction, it is washed 6 times with 100ml n-hexane, is dried to obtain solid particle
Cat1。
Under nitrogen protection, 100ml normal heptane is added, while 5g solid particle Cat1 is added, under stirring state, slowly drips
(trimethyl silicon substrate) the lithium methide Li (TMSM) for adding 10ml 1.0M, is stirred to react 1 hour, is warming up to 50 by -78 DEG C of reaction temperature
DEG C, then react 1 hour.Finally, being washed 3 times with 100ml toluene and 100ml n-hexane, it is dried to obtain solid catalyst V (TMSM)
4/MMT。
Slurry polymerization: reaction unit is 2L steel pressure resistance water cycle temperature control reaction kettle, at 95 DEG C of elder generation at vacuum-nitrogen displacement
Reason reaction kettle 2-4 hours is finally separately added into 1L n-hexane, 50mg catalyst, mono- chlorine of 2ml under nitrogen protection full of nitrogen
Diethyl aluminum, then ethylene is replaced 4 times, is removed nitrogen, is filled into the ethylene of the pressure of 1.0MPa, carry out polymerization reaction at 90 DEG C.
When reaction temperature rises, heat exchanger collet heating steam or cooling water are adjusted, controls temperature of reactor at 90 DEG C or so.Reaction
After 2 hours, reaction is terminated, room temperature is cooled to, discharged, it is dry, polyethylene product is obtained, is finally weighed, heap density, test are measured
Particle diameter distribution calculates catalyst activity and is listed in Table 2 by the performance of the polyvinyl resin of above-mentioned test method test.
Embodiment 2b:
Composite catalyst is prepared using method identical with embodiment 2a, in addition to inorganic carrier is changed to talcum (average grain diameter 5
μm).Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and by above-mentioned test method test
The performance of polyvinyl resin is listed in Table 1.
Embodiment 2c:
Composite catalyst is prepared using method identical with embodiment 2a, in addition to be changed to chain silicate (excellent for inorganic carrier
Select but be not limited to concave convex rod, flat equal 2 μm of the partial size of silica gel).Slurry polymerization is carried out according to program identical with embodiment 2a.It calculates
Catalytic activity and the performance for the polyvinyl resin tested by above-mentioned test method are listed in Table 1.
Embodiment 2d:
Composite catalyst is prepared using method identical with embodiment 2a, (is put down in addition to inorganic carrier is changed to nano aluminium oxide
Equal 0.1 μm of partial size).Slurry polymerization is carried out according to program identical with embodiment 2a.The catalytic activity of calculating and press above-mentioned test
The performance of the polyvinyl resin of method test is listed in Table 1.
Embodiment 2e:
Composite catalyst is prepared using method identical with embodiment 2a, in addition to inorganic carrier is changed to magnesium hydroxide-sulfuric acid
Magnesium (3 μm of average grain diameter).Slurry polymerization is carried out according to program identical with embodiment 2a.The catalytic activity of calculating and press above-mentioned survey
The performance of the polyvinyl resin of method for testing test is listed in Table 1.
Embodiment 2f:
Composite catalyst is prepared using method identical with embodiment 2a, in addition to inorganic carrier is changed to silica-zirconia
Aluminium composition (SiO2: Al2O3Weight ratio 1:4,4 μm of average grain diameter).It is poly- that slurry is carried out according to program identical with embodiment 2a
It closes.The catalytic activity of calculating and the performance for the polyvinyl resin tested by above-mentioned test method are listed in Table 1.
Embodiment 2g:
Composite catalyst is prepared using method identical with embodiment 2a, in addition to inorganic carrier is changed to silica-zirconia
Magnesium compositions (SiO2: MgO weight ratio 1:3,0.5 μm of average grain diameter).It is poly- that slurry is carried out according to program identical with embodiment 2a
It closes.The catalytic activity of calculating and the performance for the polyvinyl resin tested by above-mentioned test method are listed in Table 1.
Embodiment 2h:
Composite catalyst is prepared using method identical with embodiment 2a, in addition to inorganic carrier is changed to silica (averagely
30 μm of partial size).Slurry polymerization is carried out according to program identical with embodiment 2a.The catalytic activity of calculating and press above-mentioned test method
The performance of the polyvinyl resin of test is listed in Table 1.
Embodiment 2i:
Composite catalyst is prepared using method identical with embodiment 2a, in addition to inorganic carrier is changed to titanium dioxide (averagely
1.0 μm of partial size).Slurry polymerization is carried out according to program identical with embodiment 2a.The catalytic activity of calculating and press above-mentioned test side
The performance of the polyvinyl resin of method test is listed in Table 2.
Table 2
From Table 2, it can be seen that changing different inorganic carrier types, the activity of gained catalyst is also relatively high, in table
Under the action of face activating agent and organometallic reagent, gained polyethylene particle partial size is very thin, both less than 150 μm, meets industry
Change and requires.
Embodiment 3:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to zirconium chloride.According to implementation
The identical program of example 1a carries out slurry polymerization.The property of the catalytic activity of calculating and the polyvinyl resin by the test of above-mentioned test method
It can be listed in Table 3.
Embodiment 4:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to hafnium chloride.According to implementation
The identical program of example 1a carries out slurry polymerization.The property of the catalytic activity of calculating and the polyvinyl resin by the test of above-mentioned test method
It can be listed in Table 3.
Embodiment 5:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to titanium tetrabromide.According to reality
It applies the identical program of a 1a and carries out slurry polymerization.The catalytic activity of calculating and polyvinyl resin by the test of above-mentioned test method
Performance is listed in Table 3.
Embodiment 6:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to titanium tetrafluoride.According to reality
It applies the identical program of a 1a and carries out slurry polymerization.The catalytic activity of calculating and polyvinyl resin by the test of above-mentioned test method
Performance is listed in Table 3.
Embodiment 7:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to titanium tetra iodide.According to reality
It applies the identical program of a 1a and carries out slurry polymerization.The catalytic activity of calculating and polyvinyl resin by the test of above-mentioned test method
Performance is listed in Table 3.
Embodiment 8:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to methoxytitanium trichloride.It presses
Slurry polymerization is carried out according to program identical with embodiment 1a.The catalytic activity of calculating and the polyethylene tested by above-mentioned test method
The performance of resin is listed in Table 3.
Embodiment 9:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to Aryl titanium chloride.According to
Program identical with embodiment 1a carries out slurry polymerization.The catalytic activity of calculating and the polyethylene tree tested by above-mentioned test method
The performance of rouge is listed in Table 3.
Embodiment 10:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to metatitanic acid methyl esters.According to reality
It applies the identical program of a 1a and carries out slurry polymerization.The catalytic activity of calculating and polyvinyl resin by the test of above-mentioned test method
Performance is listed in Table 3.
Embodiment 11:
Catalyst is prepared using method identical with embodiment 1a, in addition to catalyst component is changed to pentamethylcyclopentadiene trichlorine
Change titanium.Slurry polymerization is carried out according to program identical with embodiment 1a.
Table 3
From table 3 it is observed that changing different catalyst components, in the effect of surfactant and organometallic reagent
Under, also the very thin polyethylene particle of available partial size, both less than 150 μm, meet industrial requirement.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (16)
1. a kind of production extrahigh-molecular weight polyolefins catalyst, which is characterized in that the catalyst includes:
Load has the inorganic carrier of surfactant,
The catalyst component being supported on inorganic carrier,
The catalyst component is transition metal halide MX4With the organometallic reagent M ' R containing R basen(n=1-3) reaction is formed
Catalyst component MR4。
2. according to claim 1 or a kind of production extrahigh-molecular weight polyolefins catalyst, which is characterized in that the mistake
Cross metal halide MX4Middle M is titanium, zirconium, vanadium or hafnium, and X is halogen, is fluorine, chlorine, bromine or iodine；Organometallic reagent M ' RnIn M '
For Li, Mg, Zn or Al, R base is one of benzyl, alkyl silicon methyl, methylene naphthalene or neopentyl or a variety of.
3. according to claim 1 or a kind of production extrahigh-molecular weight polyolefins catalyst, which is characterized in that described to urge
The content for changing component is calculated as the 0.1-10wt% of catalyst total amount with metal.
4. a kind of production extrahigh-molecular weight polyolefins catalyst according to claim 1, which is characterized in that described inorganic
Carrier is selected from magnesia, silica, aluminium oxide, titanium dioxide, silica-alumina, silica-magnesia, chain
One or more of silicate, phyllosilicate, talcum or magnesium hydroxide-magnesium sulfate, average grain diameter are 0.01-100 microns,
Contain hydroxyl and/or carboxyl in surface.
5. a kind of production extrahigh-molecular weight polyolefins catalyst according to claim 1, which is characterized in that described inorganic
The average grain diameter of carrier is 0.1-30 microns, preferably 0.5-10 microns.
6. a kind of production extrahigh-molecular weight polyolefins catalyst according to claim 1, which is characterized in that the surface
Activating agent is that molecular structure has amphiphilic component, and one end is hydrophilic radical, and the other end is hydrophobic grouping, surfactant with
The molar ratio of inorganic carrier is 0.01-100:1.
7. according to claim 1 or a kind of production extrahigh-molecular weight polyolefins catalyst, which is characterized in that the table
Face activating agent is one or more of in fatty acid methyl ester, alkyl e pioic acid methyl ester or alkyl dienoic acid methyl ester, alkyl carbon chain number
It is selected as 10-24, preferably 12-18.
8. according to claim 7 or a kind of production extrahigh-molecular weight polyolefins catalyst, which is characterized in that the alkane
Base carbochain has side chain, and/or hydroxyl and/or other groups.
9. the preparation method of production extrahigh-molecular weight polyolefins catalyst as described in claim 1, which is characterized in that the party
Method the following steps are included:
(1) by least one inorganic carrier for sloughing molecular water ultrasonic disperse in organic solvent, surfactant is then added,
It reacts at moderate temperatures, obtains modified inorganic carrier；
(2) in organic solvent, it stirs at moderate temperatures, by transition metal halide MX4Be immersed in that step (1) obtains changes
On property inorganic carrier, is reacted with carrier surface, make transition metal halide MX4Component reaction in-situ is carried on modified inorganic carrier
On；
(3) in organic solvent, the inorganic compounding carrier that step (2) obtain is added and forms suspension, organic metal is then added
Compound M ' Rn, reaction in-situ is carried out at moderate temperatures；
(4) step (3) products therefrom is filtered and solvent washing removes superfluous organo-metallic compound, be dried, obtain
To production extrahigh-molecular weight polyolefins catalyst.
10. according to claim 9 or a kind of preparation method for producing extrahigh-molecular weight polyolefins catalyst, feature
It is,
Long-chain saturated alkane or halogenated aryl hydrocarbon or their mixing of step (1) organic solvent selected from C10-C20 are molten
Agent；Reaction temperature is 20-200 DEG C；Reaction time is -10 hours 0.1 hour；The dosage of dosage of surfactant and inorganic carrier
Weight ratio be 0.01-100:1；
Step (2) the transition metal halide MX4Weight ratio with modified inorganic carrier is 0.01-50:1；Reaction temperature be-
40~200 DEG C；Reaction time is -10 hours 0.1 hour；Mixing speed 20-800rpm；
Step (3) organo-metallic compound M ' RnWith transition metal halide MX4Weight ratio be 0.01-50:1；Reaction temperature
Degree is -120-80 DEG C, and the reaction time is -10 hours 0.1 hour.
11. according to claim 10 or a kind of preparation method for producing extrahigh-molecular weight polyolefins catalyst, it is special
Sign is,
Preferred 50-180 DEG C of the reaction temperature of step (1), more preferably 80-160 DEG C, the reaction time is -5 hours 0.5 hour, more
Preferably 1-3 hours, the weight ratio of surfactant and inorganic carrier was preferably 0.1-20:1, and more preferably 0.5-5:1 is described
Organic solvent include decane, dodecane, kerosene, dichloro-benzenes, trichloro-benzenes, trimethylbenzene, dimethylbenzene, toluene or benzyl chloride one kind
Or several, preferably kerosene or dichloro-benzenes；
Step (2) the transition metal halide MX4Weight ratio with modified inorganic carrier is preferably 0.5-30:1, more preferably
1-10:1；Reaction temperature is preferably 60-160 DEG C, and more preferably 100-140 DEG C；Reaction time is preferably -6 hours 1 hour, more
Preferably 2-4 hours；Mixing speed 150-400rpm；More preferably 200-300rpm；
Step (3) organo-metallic compound M ' RnWith transition metal halide MX4Weight ratio be preferably 0.1-20:1, more
Preferably 0.5-5:1；Preferably -90-50 DEG C, more preferably -80-20 DEG C of the reaction temperature.Reaction time, preferred 0.5-5 was small
When, it is 1-3 hours more preferable.
12. as described in claim 1 production extrahigh-molecular weight polyolefins catalyst application, which is characterized in that by ethylene,
Alpha-olefin comonomer, catalyst and co-catalyst carry out polymerization reaction, produce polyethylene, the alpha-olefin comonomer with
The molar ratio of ethylene is 0.01-1:1, and the additional amount of the catalyst is to make its concentration 0.01-100ppm, and described helping is urged
The additional amount of agent is to make its concentration 5-500ppm.
13. according to claim 12 or a kind of application for producing extrahigh-molecular weight polyolefins catalyst, feature exist
In the alpha-olefin that, the alpha-olefin comonomer is C1-C20, including propylene, 1- butylene, 1- amylene, 1- hexene, 1- octene or
The molar ratio of 1- decene, the alpha-olefin comonomer and ethylene is 0.05-0.5:1, the additional amount of the co-catalyst
To make its concentration 20-400ppm.
14. according to claim 12 or a kind of application for producing extrahigh-molecular weight polyolefins catalyst, feature exist
In, the polymerization reaction be olefin polymetiation process, including slurry autoclave, slurry loop or polymerisation in solution, when slurry tank polymerization
Reaction pressure is 0.1-5MPa, and reaction temperature is 0-120 DEG C, preferably 40-90 DEG C, most preferably 60-80 DEG C；Slurry loop po lymerisation
When reaction pressure be 0.5-6MPa, reaction temperature be 30-150 DEG C, preferably 50-100 DEG C, most preferably 60-80 DEG C.
15. according to claim 12 or a kind of application for producing extrahigh-molecular weight polyolefins catalyst, feature exist
In the polyethylene average grain diameter is 10-500 microns, preferably 40-400 microns, most preferably 60-200 microns.
16. according to claim 12 or a kind of application for producing extrahigh-molecular weight polyolefins catalyst, feature exist
In the polyethylene glues equal average molecular weight 30-1000 ten thousand, preferably glues equal average molecular weight 150-800 ten thousand；Density is 0.918-
0.950g/cm3, preferred density 0.920-0.940g/cm3。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811420544.8A CN109438593B (en) | 2018-11-26 | 2018-11-26 | Catalyst for producing ultrahigh molecular weight polyolefin and preparation method and application thereof |
| PCT/CN2019/098641 WO2020107926A1 (en) | 2018-11-26 | 2019-07-31 | Catalyst used for producing ultra-high molecular weight polyolefin, preparation method therefor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811420544.8A CN109438593B (en) | 2018-11-26 | 2018-11-26 | Catalyst for producing ultrahigh molecular weight polyolefin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109438593A true CN109438593A (en) | 2019-03-08 |
| CN109438593B CN109438593B (en) | 2020-09-22 |
Family
ID=65554662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811420544.8A Active CN109438593B (en) | 2018-11-26 | 2018-11-26 | Catalyst for producing ultrahigh molecular weight polyolefin and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109438593B (en) |
| WO (1) | WO2020107926A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111101217A (en) * | 2020-01-19 | 2020-05-05 | 上海化工研究院有限公司 | High-thermal-conductivity ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN111172607A (en) * | 2020-01-19 | 2020-05-19 | 上海化工研究院有限公司 | Preparation method of creep-resistant ultra-high molecular weight polyethylene fiber |
| WO2020107926A1 (en) * | 2018-11-26 | 2020-06-04 | 上海化工研究院有限公司 | Catalyst used for producing ultra-high molecular weight polyolefin, preparation method therefor and application thereof |
| CN111848844A (en) * | 2019-04-26 | 2020-10-30 | 旭化成株式会社 | Ethylene polymer particles and molded body |
| CN115160458A (en) * | 2022-08-02 | 2022-10-11 | 上海欣鑫化工有限公司 | Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method thereof |
| CN115636893A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | High-density polyethylene resin and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4155324A3 (en) * | 2021-09-22 | 2023-05-03 | Sumitomo Chemical Company, Limited | Method for producing solid catalyst component for olefin polymerization, method for producing catalyst for olefin polymerization, and method for producing olefin polymer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004481A2 (en) * | 1978-03-29 | 1979-10-03 | Exxon Research And Engineering Company | Catalyst compositions containing a trialkyl aluminium co-catalyst and the use for the polymerization of olefins |
| EP0349146A2 (en) * | 1988-06-14 | 1990-01-03 | Nippon Oil Co. Ltd. | Process for preparing ultra-high molecular weight polyethylene |
| CN101906179A (en) * | 2010-07-23 | 2010-12-08 | 北京化工大学 | Preparation method and application of superhigh-molecular weight polyolefin catalyst |
| CN102039184A (en) * | 2009-10-26 | 2011-05-04 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst as well as preparation method and application thereof |
| CN103304702A (en) * | 2012-03-06 | 2013-09-18 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst, its preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL135065C (en) * | 1965-05-14 | |||
| KR101624164B1 (en) * | 2009-11-16 | 2016-05-26 | 에스케이이노베이션 주식회사 | Metallocene catalyst compositions and process for preparing polyolefines |
| EP2812362B1 (en) * | 2012-02-08 | 2017-08-09 | Reliance Industries Limited | Immobilization of single site catalyst on inorganic oxide support for preparation of uhmwpe |
| CN104558295A (en) * | 2015-02-09 | 2015-04-29 | 上海化工研究院 | Carrier catalyst for producing wear-resistant flame-retardant polyethylene as well as preparation method and application of carrier catalyst |
| CN109438593B (en) * | 2018-11-26 | 2020-09-22 | 上海化工研究院有限公司 | Catalyst for producing ultrahigh molecular weight polyolefin and preparation method and application thereof |
-
2018
- 2018-11-26 CN CN201811420544.8A patent/CN109438593B/en active Active
-
2019
- 2019-07-31 WO PCT/CN2019/098641 patent/WO2020107926A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0004481A2 (en) * | 1978-03-29 | 1979-10-03 | Exxon Research And Engineering Company | Catalyst compositions containing a trialkyl aluminium co-catalyst and the use for the polymerization of olefins |
| EP0349146A2 (en) * | 1988-06-14 | 1990-01-03 | Nippon Oil Co. Ltd. | Process for preparing ultra-high molecular weight polyethylene |
| CN102039184A (en) * | 2009-10-26 | 2011-05-04 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst as well as preparation method and application thereof |
| CN101906179A (en) * | 2010-07-23 | 2010-12-08 | 北京化工大学 | Preparation method and application of superhigh-molecular weight polyolefin catalyst |
| CN103304702A (en) * | 2012-03-06 | 2013-09-18 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst, its preparation method and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020107926A1 (en) * | 2018-11-26 | 2020-06-04 | 上海化工研究院有限公司 | Catalyst used for producing ultra-high molecular weight polyolefin, preparation method therefor and application thereof |
| CN111848844A (en) * | 2019-04-26 | 2020-10-30 | 旭化成株式会社 | Ethylene polymer particles and molded body |
| CN111101217A (en) * | 2020-01-19 | 2020-05-05 | 上海化工研究院有限公司 | High-thermal-conductivity ultra-high molecular weight polyethylene fiber and preparation method thereof |
| CN111172607A (en) * | 2020-01-19 | 2020-05-19 | 上海化工研究院有限公司 | Preparation method of creep-resistant ultra-high molecular weight polyethylene fiber |
| CN115636893A (en) * | 2021-07-20 | 2023-01-24 | 中国石油天然气股份有限公司 | High-density polyethylene resin and preparation method thereof |
| CN115160458A (en) * | 2022-08-02 | 2022-10-11 | 上海欣鑫化工有限公司 | Catalyst suitable for producing polyolefin with superfine grain diameter and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020107926A1 (en) | 2020-06-04 |
| CN109438593B (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109438593A (en) | A kind of production extrahigh-molecular weight polyolefins catalyst and its preparation method and application | |
| CN109535290A (en) | It is suitble to the catalyst and its preparation method and application of production ultra-fine grain diameter polyolefin | |
| CN100358923C (en) | Polymerization process using a metallocene catalyst system | |
| JP5301151B2 (en) | Method for controlling olefin polymerization | |
| JP2008509276A (en) | Spray-dried rugged Ziegler-Natta procatalyst and polymerization method using the same | |
| EP0991676A1 (en) | Multistage polymerization process using a catalyst having different catalytically active sites | |
| JP2001510212A (en) | Catalyst for producing polyethylene with broad or bimodal molecular weight distribution | |
| EP1778746A1 (en) | Robust spray-dried ziegler-natta procatalyst and polymerization process employing same | |
| CN108137718A (en) | For the method for olefinic polymerization | |
| CN108174605A (en) | For the method for olefinic polymerization | |
| JP2010215920A (en) | Precision fragmentation aggregate and olefin polymerization catalyst manufactured therefrom | |
| CN105482004B (en) | A kind of composite catalyst for being used to prepare wide/dual-peak distributed high density polyethylene | |
| CN101970508A (en) | A catalyst system and a process for the production of polyethylene in the presence of this catalyst system | |
| Teimoury et al. | The effect of SiO2 calcination temperature and [Si]/[Mg] molar ratio on the performance of bi-supported Ziegler-Natta catalysts in ethylene polymerizations | |
| US20190176118A1 (en) | A process for feeding a polymerisation catalyst | |
| CN102471401A (en) | Catalyst system and process for production of polyethylene | |
| CN101137677A (en) | Catalyst components for the polymerization of olefins | |
| CN100491418C (en) | Preparing method of catalyst for slurry polymerization of ethylene | |
| CN108137717A (en) | For the method for olefinic polymerization | |
| EP3856794A1 (en) | A multi-stage process for producing a c2 to c8 olefin polymer composition | |
| JPH08231631A (en) | Ethylene (co)polymerization catalyst and method of polymerization by using the same | |
| US10266618B2 (en) | Chromium-based catalyst compositions for olefin polymerization | |
| CN108690152A (en) | A kind of alkoxyl magnesium microsphere particle and its solid polyethylene catalytic component of preparation | |
| CN106866848A (en) | Ethylene polymerization main catalyst, preparation method thereof and ethylene polymerization catalyst containing main catalyst | |
| US8247342B2 (en) | Polymer supported chrome catalyst for olefins polymerization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |