CN106496376B - A kind of catalytic component and catalyst for vinyl polymerization - Google Patents
A kind of catalytic component and catalyst for vinyl polymerization Download PDFInfo
- Publication number
- CN106496376B CN106496376B CN201510561127.5A CN201510561127A CN106496376B CN 106496376 B CN106496376 B CN 106496376B CN 201510561127 A CN201510561127 A CN 201510561127A CN 106496376 B CN106496376 B CN 106496376B
- Authority
- CN
- China
- Prior art keywords
- catalytic component
- titanium
- silane
- compound
- component according
- 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.)
- Active
Links
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a kind of catalytic components for vinyl polymerization, the catalytic component is in the presence of inert diluent, solution is formed by being dissolved in magnesium halide in the system containing organic epoxide, organic alcohol compound and organo-silicon compound, cyclodextrin or derivatives thereof reaction is added, is then obtained with the halide of titanium or derivatives thereof effect.The present invention also provides the preparation methods of the catalytic component, and the ethylene rolymerization catalyst based on the catalytic component.The preparation process of catalytic component of the present invention is simple, and catalyst activity keeps higher level, few with titanium amount, is conducive to simplify subsequent processing work.
Description
Technical field
The present invention relates to a kind of catalytic component for ethylene polymerization, the preparation method of the catalytic component,
And the application of ethylene rolymerization catalyst and the catalyst in vinyl polymerization containing the catalytic component, belong to alkene
Polymerized hydrocarbon field.
Background technique
It occupies an leading position it is well known that the caltalyst of the compound containing Ti/Mg ties up in the industrialized production of polyolefin,
Research core is quick nothing more than the hydrogen tune of the particle shape and particle diameter distribution, catalyst that are the polymerization activity of catalyst, catalyst
Perception and copolymerization performance etc..In the prior art, there is the catalyst of uniform particle diameter and preferable particle shape in order to obtain,
People generally use different magnesium raw materials to prepare catalyst.
First method is that homogeneous solution is obtained in certain solvents using magnesium chloride as dissolution of raw material, then again that this is molten
Liquid is mixed with titanium compound and optional electron donor, is obtained by the method for precipitating containing magnesium, titanium and optional electron donor
Solids, and catalyst granules is obtained after the solids is handled with excessive liquid titanium compound.Such as
Preparation method disclosed in CN1099041A, CN1229092, catalyst therein are that organic epoxy is dissolved in by magnesium halide
Compound, organic phosphorus compound add electron donor and form homogeneous solution, then golden at least one precipitation additive and transition
Belong to halide of titanium or derivatives thereof effect and obtains.The shortcomings that this conventional method, is: the partial size and partial size of catalyst granules
Distribution is entirely by precipitation process, i.e., for the recrystallization process of magnesium carrier ingredient come what is controlled, stability is more difficult to control.
Second method is directly carried on catalyst activity component on inert carrier (such as silica gel), due to silica gel
Particle diameter be easy to control, and particle shape is preferable, therefore evengranular catalyst particle can be obtained.But due to carrier
The load capacity of upper active component is restricted, therefore Ti content is lower in catalyst made from this method, and polymerization activity is not high.
Such as: using magnesium chloride, silica as carrier in CN1268520, titanium tetrachloride is active component, and the preparation method of catalyst is such as
Under: by MgCl2In tetrahydrofuran with TiCl4Reaction, then with through the processed SiO of alkyl aluminum2Mixing, after removing tetrahydrofuran
Catalytic component is made.When being used for vinyl polymerization, since the Ti content in catalyst is lower, so that polymerization activity is lower.Cause
This, although this catalyst system can be used for the gas-phase fluidized bed polymerization process of ethylene, but since lower catalytic activity is difficult
Suitable for the slurry polymerization processes of ethylene.
In the slurry polymerization processes of ethylene, except requiring catalyst to answer catalytic activity with higher and preferable partial size point
Outside cloth, bulk density with higher and preferable hydrogen response are also answered.Wherein, polymer bulk density height is to embody to urge
One of the index of agent comprehensive performance quality.The higher bulk density of polymer is conducive to the mobility for increasing powder, and waits
It is same as increasing the effective volume of polymeric kettle, is conducive to the produce load for improving device, reduces the production cost of resin, reach drop originally
The effect of synergy.And the bulk density of catalyst system made from above two method is not satisfactory yet.Although in addition, above-mentioned
Catalyst system all has a preferable performance for olefinic polymerization, but above-mentioned catalyst system is during the preparation process in order to obtain
Catalyst solid product, the method for all using addition precipitation additive, and a large amount of titanium tetrachloride has been used, in post-processing rank
Section can bring the relatively burden of liquid waste processing.
Summary of the invention
To solve the problems, such as that above-mentioned technology exists, the purpose of the present invention is to provide a kind of catalyst for vinyl polymerization
Component.
The present invention also provides the ethylene rolymerization catalysts based on the catalytic component.The catalyst is poly- for ethylene
Higher polymerization activity and preferable bulk density are shown when conjunction, particle has biggish partial size.The catalyst preparation side
Method is simple, few with titanium amount, is conducive to simplify subsequent processing work.
The catalytic component is in the presence of inert diluent, by being dissolved in magnesium halide containing organic epoxy compound
Solution is formed in the system of object, organic alcohol compound and organo-silicon compound, adds cyclodextrin or derivatives thereof reaction, then
It is obtained with the halide of titanium or derivatives thereof effect.
In a specific embodiment of the present invention, the catalytic component is in the presence of inert diluent, by by halogenation
Magnesium and organic epoxy compound object, organic alcohol compound and reactive organic silicon compound form homogeneous solution, add cyclodextrin or
Then its derivatives reaction is gradually precipitated and is formed particle with the halide of transition metals Ti or derivatives thereof effect, solid, remove
The solid for removing unreacted reactant and solvent and being washed using inert diluent, obtains catalytic component of the present invention.
The complex compound or dihalo- that the magnesium halide is selected from magnesium dihalide, magnesium dihalide and water, alcohol or electron donor are formed
Change at least one of the derivative of one of halogen atom formation replaced alkyl or alkoxy of magnesium.Specific compound
In, the magnesium dihalide is selected from least one of magnesium dichloride, magnesium dibromide, bifluoride magnesium and magnesium diiodide, preferably dichloro
Change magnesium；The complex compound that the magnesium dihalide and water, alcohol or electron donor are formed is selected from magnesium dihalide and water, methanol, ethyl alcohol, third
The complex compound that alcohol, butanol, amylalcohol, hexanol, isooctanol, ammonia, hydroxyl ammonia, ether or ester are formed；The magnesium halide can individually or
It is used in mixed way.
The organic epoxy compound object is selected from aliphatic olefin, alkadienes or the halogenated aliphatic that carbon atom number is 2-8
At least one of the oxide of alkene or alkadienes, glycidol ether and inner ether.Specific compound is selected from ethylene oxide, ring
Ethylene Oxide, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and two are shunk
At least one of glycerin ether；Wherein it is preferred that epoxychloropropane and/or tetrahydrofuran.
The organic alcohol compound is the alkylol that carbon atom number is 1-10 or carbon atom number is the fragrant and mellow of 6-20, described
Alkyl is straight chain, branch or naphthenic base, is optionally taken by halogen atom outside the hydrogen atom hydroxyl-removal in the organic alcohol compound
Generation.In specific compound, the alkylol be selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isobutanol, glycerine, oneself
At least one of alcohol, 2- methyl anyl alcohol, 2- ethyl butanol, n-heptanol, n-octyl alcohol, decyl alcohol, cyclohexanol and methyl cyclohexanol；Institute
It states aromatic alcohol and is selected from least one of benzyl alcohol, methylbenzyl alcohol, α-methylbenzylalcohol and alpha, alpha dimethyl benzyl alcohol.Wherein
At least one of preferred alcohol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol and glycerine.To the ratio of alcohol each in organic alcohol compound
It is not particularly limited.
The general formula of the organo-silicon compound is R1 xR2 ySi(OR3)z, wherein R1And R2Respectively carbon atom number is 1-10
Alkyl or halogen, R3The alkyl for being 1-10 for carbon atom number, wherein x, y and z are positive integer, 0≤x≤2,0≤y≤2, and 0
≤ z≤4, and x+y+z=4.Specific compound is selected from silicon tetrachloride, silicon bromide, tetramethoxy-silicane, tetraethoxy-silicane
Alkane, tetrapropoxysilane, four butoxy silanes, four (2- ethyl hexyl oxy) silane, ethyl trimethoxy silane, three ethoxy of ethyl
Base silane, methyltrimethoxysilane, methyltriethoxysilane, n-propyl triethoxysilane, n-propyl trimethoxy silicon
Alkane, ruthenium trimethoxysilane, ruthenium triethoxysilane, cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, 2-
Methylcyclopentyl trimethoxy silane, 2,3- dimethylcyclopentyl trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl
Triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyl triethoxysilane, vinyl trimethoxy
Base silane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltrimethoxysilane, three ethoxy of normal-butyl
Base silane, trimethoxysilane, isobutyl triethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trimethoxy
Base silane, phenyltrimethoxysila,e, phenyl triethoxysilane, a chlorine trimethoxy silane, a chlorine triethoxysilane, second
Three isopropoxy silane of base, vinyltributoxysilane, trimethyl phenoxysilane, methyl triolefin npropoxysilane, ethylene
Base triacyloxysilanes, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diisopropyl dimethoxy silane, two
Isopropyl diethoxy silane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tertiary pentyl methyl two
Ethoxysilane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, methylcyclopentyl diethoxy silane,
Methylcyclopentyl dimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, three cyclopenta methoxy silanes,
At least one in three cyclopenta Ethoxysilanes, dicyclopentylmethyl methoxy silane and cyclopenta dimethyl methoxy silane
Kind.It is preferred that at least one of tetraethoxysilane, tetramethoxy-silicane and four butoxy silanes.
Cyclodextrin is one that amylose generates under the cyclodextrin glycosyltransferase effect generated by bacillus
The general name of series of annular oligosaccharide usually contains 6-12 D- glucopyranose units.Wherein study more and there is weight
Want practical significance is to be referred to as α-, β-and gamma-cyclodextrin containing the molecule of 6,7,8 glucose units.It is brilliant according to X- line
Body diffraction, infrared spectroscopy and spectral analysis of the nuclear magnetic resonance as a result, determining each D (+)-glucopyra for constituting cyclodextrin molecular
Sugar is all chair conformation.Each glucose unit combines cyclization with Isosorbide-5-Nitrae-glycosidic bond.Due to connecting the glycosidic bond of glucose unit
It cannot rotate freely, cyclodextrin is not cylindric molecule but the annulus that tapers slightly.Cyclodextrin of the present invention or its spread out
Biology in alpha-cyclodextrin or derivatives thereof, beta-cyclodextrin or derivatives thereof and gamma-cyclodextrin or derivatives thereof at least one
Kind；Specific compound be selected from alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, Hydroxyproply-α-cyclodextrin, methyl-B-cyclodextrin,
Hydroxypropyl-β-cyclodextrin, hydropropyl-y-cyclodextrin, Sulfobutyl ether β _ cyclodextrin and above-mentioned cyclodextrin derivative in extremely
Few one kind；At least one of more preferable alpha-cyclodextrin, Hydroxyproply-α-cyclodextrin and hydroxypropyl-β-cyclodextrin.
The general formula of the titanium-containing compound is Ti (OR4)aX1 b, R in formula4The aliphatic alkyl for being 1-14 for carbon atom number
Or aromatic hydrocarbyl, X1For halogen, the integer that a 0,1 or 2, b are 0 to 4, and a+b=3 or 4.Specific compound is selected from four
Titanium chloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanium trichloride, dichloro two
At least one of one ethanolato-titanium of ethanolato-titanium and trichlorine, preferably titanium tetrachloride.
In order to keep dissolution more abundant, inert diluent can be optionally added during the preparation process, usual this inertia is dilute
Release the halides that agent includes arene compounds or alkane derivative or both the above compound.The arene compounds
And its halides are in benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene and monochlorotoluene and its derivative
At least one；The alkane derivative and its halides are selected from the linear paraffin and halogenated straight alkane that carbon atom number is 3-20
Hydrocarbon, branched paraffin and halogenated branched paraffin or at least one of cycloalkane and halogenated cycloalkane, such as butane, pentane, hexane, ring
Hexane, heptane, 1,2- dichloroethanes etc., as long as facilitating can using for organo-magnesium compound dissolution.Above-mentioned inertia is dilute
Releasing agent can be used alone, and also can be used in combination.
Ratio between each reactant is calculated with every mole of magnesium halide, and usually the dosage of organic epoxy compound object is
0.0001-1 moles, the dosage of organic alcohol compound is 0.0001-6 moles, and the dosage of organo-silicon compound is rubbed for 0.0001-1
You, the dosage of cyclodextrin or derivatives thereof is 0.0001-0.001 moles, and the dosage of titanium compound is 0.001-20 moles.
The present invention also provides a kind of preparation methods of catalytic component for vinyl polymerization, comprising the following steps:
Magnesium halide is dissolved in the body containing organic epoxide, organic alcohol compound and organo-silicon compound in the presence of inert diluent
Homogeneous solution is formed in system, solution temperature is 0-110 DEG C；Cyclodextrin or derivatives thereof reaction 0-6 hours is added, preferably 1-6 is small
Shi Hou is cooled to -40 to 10 DEG C, and above-mentioned solution and titanium compound are carried out haptoreaction and obtain mixture, and mixture is delayed
Slowly it is warming up to 50-120 DEG C, solids is gradually precipitated and forms particle；It, will be above-mentioned solid after reaction 0-10 hours, preferably 1-6 hours
Body object removes unreacted reactant and solvent, and is washed using inert diluent, obtains the catalytic component.
The present invention also provides a kind of catalyst for vinyl polymerization, comprising: (1) of the present invention poly- for ethylene
The catalytic component of conjunction；(2) organo-aluminum compound.
The general formula of the organo-aluminum compound is AlR5 nX2 3-n, R in formula5The alkyl for being 1-20 for hydrogen or carbon atom number, X2
For halogen, and 0≤n≤3.Specific compound is selected from triethyl aluminum, aluminium diethyl monochloride, one aluminium ethide of dichloro, sesquialter ethyl
In aluminium, dichloro aluminium isobutyl, triisobutyl aluminium, a chlorine diisopropyl aluminium, chloromethyl n-propyl aluminium and a chlorodiphenyl base aluminium
It is at least one.Wherein at least one of preferred aluminium diethyl monochloride, one aluminium ethide of dichloro and triethyl aluminum.
Slurry polymerization can be used when the catalyst is used for vinyl polymerization, gas-phase polymerization can also be used.
Slurry polymerization medium includes: iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, hydrogasoline, kerosene,
The atent solvents such as the aliphatic saturated hydrocarbons such as benzene,toluene,xylene or aromatic hydrocarbon.
In order to adjust the molecular weight of final polymer, molecular weight regulator is made using hydrogen.
Catalyst of the present invention has many advantages, such as that catalytic activity is high, hydrogen response is good, polymer bulk density is high, is suitable for
In the slurry polymerization processes and gas-phase polymerization process of ethylene.
Specific embodiment
Following embodiment is to describe to more detailed citing of the invention, but the invention is not limited to these embodiments.
Test mode
1, catalyst grain size distribution: enterprising in the MASTER SIZE2000 particles distribution instrument of Malvern company, Britain production
Row measurement, n-hexane is dispersing agent.D (10), D (50), D (90) are respectively 10%, 50% and 90%, and (particle from small arrival) is tired
The particle diameter of product granularity, Span value are the ratio of (D90-D10)/D (50).
2, it the bulk density of polymer: is measured according to ASTM-D1895 standard method.
Embodiment 1
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, 4.5g magnesium dichloride, toluene 120ml, ring are sequentially added
Oxygen chloropropane 10.0ml, 2-Ethylhexyl Alcohol 10.0ml, silester 3.0ml, are warming up to 100 DEG C under stirring, when solid is completely molten
After solution forms uniform solution, 3 hours are reacted at 100 DEG C, it is small to be then added Hydroxyproply-α-cyclodextrin 0.01g the reaction was continued 1
When.The reaction system is cooled to -5 DEG C, is slowly added dropwise 25ml titanium tetrachloride, constant temperature 0.5 hour, then 85 DEG C are to slowly warm up to,
Reaction 2 hours.Then stop stirring, stand, suspension is layered quickly, is extracted supernatant liquor, is washed four times with hexane, High Purity Nitrogen
Air-blowing is dry, obtains the ingredient of solid catalyst of good fluidity.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L, and after high pure nitrogen is sufficiently displaced from, the triethyl aluminum that concentration is 1M is added
Hexane solution 1L (contains triethyl aluminum 1.0ml), and the solid catalyst of above-mentioned preparation is added, is warming up to 70 DEG C, being passed through hydrogen makes kettle
Interior pressure reaches 0.28Mpa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73Mpa (gauge pressure), and it is small that 2 are polymerize under the conditions of 80 DEG C
When, polymerization result is shown in Table 1.
Embodiment 2
(1) in addition to epoxychloropropane is 12.5ml, 2-Ethylhexyl Alcohol 10.0ml, Hydroxyproply-α-cyclodextrin are 0.015g,
The synthesis of catalyst is the same as embodiment 1.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Embodiment 3
(1) except epoxychloropropane dosage is 10.0ml, 2-Ethylhexyl Alcohol dosage is 5.0ml, Hydroxyproply-α-cyclodextrin is
0.010g, solution temperature are increased to outside 105 DEG C, and the synthesis of catalyst is the same as embodiment 1.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Embodiment 4
(1) in addition to Hydroxyproply-α-cyclodextrin is changed to hydroxypropyl-β-cyclodextrin, the synthesis of catalyst is the same as embodiment 1.
(2) vinyl polymerization is the same as embodiment 1.Polymerization result is shown in Table 1.
Comparative example 1
(1) TiCl is removed4Dosage is changed to 60ml, and dropping temperature is -5 DEG C outer, and the synthesis of catalyst is the same as embodiment 1.
(2) for vinyl polymerization with embodiment 1, polymerization result is shown in Table 1.
Comparative example 2
(1) in the reactor being sufficiently displaced from by high pure nitrogen, sequentially add 4.5g magnesium dichloride, toluene 120ml,
Epoxychloropropane 10.0ml, 2-Ethylhexyl Alcohol 10.0ml, silester 3.0ml, are warming up to 100 DEG C under stirring, when solid is complete
After dissolution forms uniform solution, reacted 3 hours at 100 DEG C.The reaction system is cooled to -5 DEG C, 25ml tetra- is slowly added dropwise
Titanium chloride, constant temperature 0.5 hour, then 85 DEG C are to slowly warm up to, it reacts 2 hours.Then stop stirring, stand, suspension divides quickly
Layer extracts supernatant liquor, is washed four times with hexane, and high pure nitrogen drying obtains the ingredient of solid catalyst of good fluidity.
(2) for vinyl polymerization with embodiment 1, polymerization result is shown in Table 1.
1 catalyst grain size of table and size distribution
As can be seen from Table 1, it is compared with comparative example 1 and comparative example 2, the partial size of the catalyst obtained by the present invention
Increase, achievees the purpose that size tunable, while the particle diameter distribution of catalyst obviously narrows.
2 polymer performance of table
The preparation process that can be seen that catalyst of the present invention from the experimental data of 2 embodiment of table and comparative example is simple, preparation
Cyclodextrin added in the process or derivatives thereof play the role of control catalyst granules form so that catalyst maintain compared with
High activity, and resulting polymers bulk density increases significantly, polymer beads are concentrated, and fine powder is few, and it is poly- to be conducive to ethylene
Attach together the raising for setting load.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (22)
1. a kind of catalytic component for vinyl polymerization, the catalytic component be in the presence of inert diluent, pass through by
Magnesium halide, which is dissolved in the system containing organic epoxide, organic alcohol compound and organo-silicon compound, forms solution, then plus
Enter cyclodextrine derivatives reaction, is then obtained with the halide of titanium or derivatives thereof effect；The cyclodextrine derivatives choosing
From at least one of alpha-cyclodextrin derivative, beta-cyclodextrin derivative and gamma-cyclodextrin derivative；In terms of every mole of magnesium halide
It calculates, the dosage of organic epoxy compound object is 0.0001-1 moles, and the dosage of organic alcohol compound is 0.0001-6 moles, organosilicon
The dosage of compound is 0.0001-1 moles, and the dosage of cyclodextrin or derivatives thereof is 0.0001-0.001 moles, the halogenation of titanium
The dosage of object or derivatives thereof is 0.001-20 moles.
2. catalytic component according to claim 1, which is characterized in that the magnesium halide is selected from magnesium dihalide, dihalo-
The one of halogen atom for changing complex compound or magnesium dihalide that magnesium is formed with water, alcohol or electron donor is taken by alkyl or alkoxy
At least one of the derivative that generation is formed.
3. catalytic component according to claim 2, which is characterized in that the magnesium halide is selected from magnesium dichloride, dibromo
Change at least one of magnesium, bifluoride magnesium and magnesium diiodide.
4. catalytic component according to claim 3, which is characterized in that the magnesium halide is magnesium dichloride.
5. catalytic component according to claim 1, which is characterized in that the organic epoxy compound object is selected from carbon atom
It counts in the oxide, glycidol ether and inner ether of aliphatic olefin, alkadienes or the halogenated aliphatic alkene or alkadienes that are 2-8
At least one.
6. catalytic component according to claim 5, which is characterized in that the organic epoxy compound object is selected from epoxy second
In alkane, propylene oxide, epoxy butane, butadiene oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether
It is at least one.
7. catalytic component according to any one of claim 1 to 6, which is characterized in that the organic alcohol compound
For carbon atom number be 1-10 alkylol or carbon atom number be the fragrant and mellow of 6-20, the alkyl is straight chain, branch or naphthenic base, institute
It states and is optionally replaced by halogen atom outside the hydrogen atom hydroxyl-removal in organic alcohol compound.
8. catalytic component according to claim 7, which is characterized in that the organic alcohol compound is selected from ethyl alcohol, third
At least one of alcohol, butanol, 2-Ethylhexyl Alcohol and glycerine.
9. catalytic component according to any one of claim 1 to 6, which is characterized in that the cyclodextrine derivatives
Selected from Hydroxyproply-α-cyclodextrin, methyl-B-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydropropyl-y-cyclodextrin, sulphur butyl-β-
At least one of cyclodextrin.
10. catalytic component according to any one of claim 1 to 6, which is characterized in that the organo-silicon compound
General formula be R1 xR2 ySi(OR3)z, wherein R1And R2Respectively alkyl or halogen of the carbon atom number for 1-10, R3It is for carbon atom number
The alkyl of 1-10, wherein x, y and z are positive integer, 0≤x≤2,0≤y≤2,0≤z≤4, and x+y+z=4.
11. catalytic component according to claim 10, which is characterized in that the organo-silicon compound are selected from four chlorinations
Silicon, silicon bromide, tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2- ethyl hexyl oxygen
Base) silane, ethyl trimethoxy silane, n-propyl triethoxysilane, n-propyl trimethoxy silane, decyl trimethoxy silicon
Alkane, ruthenium triethoxysilane, cyclopentyl-trimethoxy-silane, cyclopenta triethoxysilane, 2- methylcyclopentyl trimethoxy
Base silane, 2,3- dimethylcyclopentyl trimethoxy silane, methyltrimethoxysilane, methyltriethoxysilane, ethyl three
Ethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, normal-butyl three
Methoxy silane, ne-butyltriethoxysilaneand, trimethoxysilane, isobutyl triethoxy silane, cyclohexyl three
Ethoxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, a chlorine trimethoxy
Silane, a chlorine triethoxysilane, three isopropoxy silane of ethyl, vinyltributoxysilane, trimethyl phenoxysilane,
Methyl triolefin npropoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, diisopropyl dimethoxy silicon
Alkane, diisopropyldiethoxysilane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tertiary pentyl
Methyldiethoxysilane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, methylcyclopentyl diethoxy
Silane, methylcyclopentyl dimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, three cyclopentylmethoxies
In silane, three cyclopenta Ethoxysilanes, dicyclopentylmethyl methoxy silane and cyclopenta dimethyl methoxy silane extremely
Few one kind.
12. catalytic component according to claim 11, which is characterized in that the organo-silicon compound are selected from four ethoxies
At least one of base silane, tetramethoxy-silicane and four butoxy silanes.
13. catalytic component according to any one of claim 1 to 6, which is characterized in that the halide of the titanium or
The general formula of its derivative is Ti (OR4)aX1 b, R in formula4The aliphatic alkyl or aromatic hydrocarbyl for being 1-14 for carbon atom number, X1For
Halogen, the integer that a 0,1 or 2, b are 0 to 4, and a+b=3 or 4.
14. catalytic component according to claim 13, which is characterized in that described halide of titanium or derivatives thereof choosing
From titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, titanium trichloride, two
At least one of one ethanolato-titanium of chlorine diethoxy titanium and trichlorine.
15. catalytic component according to claim 14, which is characterized in that described halide of titanium or derivatives thereof is
Titanium tetrachloride.
16. catalytic component according to any one of claim 1 to 6, which is characterized in that the inert diluent is virtue
The halides of hydrocarbon compound or alkane derivative or both the above compound.
17. catalytic component according to claim 16, which is characterized in that the arene compounds and its halides choosing
From benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, trichloro-benzene and at least one of monochlorotoluene and its derivative.
18. catalytic component according to claim 17, which is characterized in that the alkane derivative and its halides choosing
From linear paraffin and halogenated straight alkane, branched paraffin and halogenated branched paraffin or cycloalkane that carbon atom number is 3-20 and halogenated
At least one of cycloalkane.
19. catalytic component according to claim 18, which is characterized in that the alkane derivative and its halides choosing
From at least one of butane, pentane, hexane, hexamethylene, heptane and 1,2- dichloroethanes.
20. being included in inert diluent to the preparation method of catalytic component described in any one of 19 according to claim 1 and depositing
It is formed uniformly in lower magnesium halide is dissolved in the system containing organic epoxide, organic alcohol compound and organo-silicon compound
Solution, solution temperature are 0-110 DEG C；After cyclodextrine derivatives reaction being added 1-6 hours, -40 to 10 DEG C are cooled to, it will be above-mentioned molten
Liquid and titanium compound carry out haptoreaction and obtain mixture, and mixture is to slowly warm up to 50-120 DEG C, and solids is gradually analysed
Out and form particle；After reaction 1-6 hours, above-mentioned solids is removed into unreacted reactant and solvent, and wash using inert diluent
It washs, obtains the catalytic component.
21. a kind of catalyst for vinyl polymerization, comprising:
(1) catalytic component of vinyl polymerization is used for described in any one of claims 1 to 19；
(2) general formula is AlR5 nX2 3-nOrgano-aluminum compound, R in formula5The alkyl for being 1-20 for hydrogen or carbon atom number, X2For halogen,
And 0≤n≤3.
22. application of the catalyst described in claim 21 in ethylene homo or copolyreaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510561127.5A CN106496376B (en) | 2015-09-06 | 2015-09-06 | A kind of catalytic component and catalyst for vinyl polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510561127.5A CN106496376B (en) | 2015-09-06 | 2015-09-06 | A kind of catalytic component and catalyst for vinyl polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106496376A CN106496376A (en) | 2017-03-15 |
| CN106496376B true CN106496376B (en) | 2019-05-31 |
Family
ID=58286337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510561127.5A Active CN106496376B (en) | 2015-09-06 | 2015-09-06 | A kind of catalytic component and catalyst for vinyl polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106496376B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885791A (en) * | 2010-07-22 | 2010-11-17 | 中国石油天然气股份有限公司 | Wide/multimodal distribution polyolefin catalyst, its preparation and use |
-
2015
- 2015-09-06 CN CN201510561127.5A patent/CN106496376B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885791A (en) * | 2010-07-22 | 2010-11-17 | 中国石油天然气股份有限公司 | Wide/multimodal distribution polyolefin catalyst, its preparation and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106496376A (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6705779B2 (en) | High performance Ziegler-Natta catalyst system, process for making such supported catalysts and use thereof | |
| HU212801B (en) | Process for producing ziegler-natta type catalyst and olefin polymerization process carried out in the presence of said catalyst | |
| JP2011511135A (en) | Polyethylene materials prepared using mixed Ziegler-Natta catalyst systems | |
| US10836846B2 (en) | Olefin polymerization catalyst, preparation method thereof, olefin polymerization catalyst system, use thereof, and method of preparing polyolefin resin | |
| CN103665204B (en) | A kind of solid catalyst component for olefine polymerization and catalyzer | |
| CN108341900A (en) | Catalytic component for vinyl polymerization and preparation method thereof and catalyst for vinyl polymerization | |
| CN105384854B (en) | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof | |
| CN104710549B (en) | A kind of emulsion process prepares Ball shape ethylene polymerization solid titanium catalytic and its application | |
| CN106496377B (en) | A kind of catalytic component and catalyst for vinyl polymerization | |
| CN105199024B (en) | A kind of catalytic component for vinyl polymerization, catalyst and preparation method thereof | |
| CN106496376B (en) | A kind of catalytic component and catalyst for vinyl polymerization | |
| KR101735447B1 (en) | method of preparing polyolefin nanocomposite including dispersed carbon support on the polyolefin and nanocomposite prepared thereby | |
| CN104479055B (en) | A kind of dialkoxy-magnesium support type ingredient of solid catalyst and catalyst | |
| JP5118847B2 (en) | Solid catalyst component for α-olefin polymerization, catalyst for α-olefin polymerization, and method for producing α-olefin polymer | |
| CN104558287A (en) | Catalyst component for olefin polymerization as well as catalyst | |
| WO2013093930A1 (en) | A high surface area silicon derivative free magnesium- titanium catalyst system for ethylene polymerization and process of preparation thereof | |
| CN104448064B (en) | A kind of polyolefine resin composition and preparation method thereof | |
| CN106496375B (en) | A kind of catalytic component and catalyst for vinyl polymerization | |
| JP2008308558A (en) | SOLID CATALYST COMPONENT FOR alpha-OLEFIN POLYMERIZATION, METHOD FOR PRODUCING THE SAME, CATALYST FOR POLYMERIZING alpha-OLEFIN, AND METHOD FOR PRODUCING alpha-OLEFIN POLYMER | |
| CN105481999B (en) | For the catalytic component of ethylene homo conjunction or combined polymerization, catalyst and preparation method thereof | |
| CN103788260B (en) | A kind of preparation method of Noblen | |
| KR20190058775A (en) | Method for producing supporting particle | |
| JP2012193258A (en) | METHOD FOR PRODUCING SOLID CATALYST COMPONENT FOR α-OLEFIN POLYMERIZATION AND CATALYST FOR α-OLEFIN POLYMERIZATION | |
| KR20200061585A (en) | Preparing method of catalyst for polymerization of polyethylene having a small particle | |
| JP2013071955A (en) | SOLID CATALYST COMPONENT FOR α-OLEFIN POLYMERIZATION, PRODUCTION METHOD OF SOLID CATALYST COMPONENT FOR α-OLEFIN POLYMERIZATION, CATALYST FOR α-OLEFIN POLYMERIZATION, AND PRODUCTION METHOD OF α-OLEFIN POLYMER |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |