CN104231140B - A kind of ethene-alpha-olefin catalyst for copolymerization and preparation thereof and application - Google Patents
A kind of ethene-alpha-olefin catalyst for copolymerization and preparation thereof and application Download PDFInfo
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- CN104231140B CN104231140B CN201310248115.8A CN201310248115A CN104231140B CN 104231140 B CN104231140 B CN 104231140B CN 201310248115 A CN201310248115 A CN 201310248115A CN 104231140 B CN104231140 B CN 104231140B
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Abstract
The present invention relates to a kind of ethylene and the catalyst of alhpa olefin copolymerization and preparation thereof and application；Magnesium compound is dissolved in hydrocarbon solvent, adds alcoholic solvent, react 2～4 hours under 70～90 DEG C of stirring conditions；It is subsequently adding electron donor I, reacts 1～2 hour under stirring condition, add electron donor II, react 1～2 hour under stirring condition；It is cooled to room temperature, drips titanium compound, dripped in 1～2 hour and finish, then heat to 70～90 DEG C, react 1～3 hour under stirring condition；By product filter pressing to remove solvent, add hydrocarbon solvent stirring, be warming up to 70～90 DEG C, add electron donor III, react 1～2 hour under stirring condition；Add titanium compound, react 1～3 hour under stirring condition；Filter, washing, be dried to obtain；This catalyst ethylene is high with the catalysis activity of long-chain alpha olefin-copolymerization, makes the long-chain alpha alkene insertion rate height of the copolymer prepared, and polymer stacks density is high, and fine powder is few.
Description
Technical field
The present invention relates to a kind of ethylene catalyst with alpha-olefin copolymer and preparation method thereof, particularly relate to a kind of electron donor
Modified Ziegler-Natta catalyst for ethylene and long-chain alpha-olefin copolymerization and preparation method thereof, belongs to olefinic polymerization
Catalyst field.
Background technology
Linear low density polyethylene (LLDPE) is the copolymer of ethylene and alpha-olefin (1-butylene, 4-methyl-1-pentene),
Introducing after 'alpha '-olefin monomers in vinyl polymerization makes the macromole prepared contain a considerable amount of side chain, these short-chain branchs and drawing money on credit
Chain can produce impact to its physical property；By the regulation and control to side chain length, the degree of branching and co-monomer content etc., can make
The product of standby desired properties, gives LLDPE low-temperature flexibility, high-modulus, resistance to bend(ing), puncture resistance, tear resistance,
It is widely used in the field such as thin film, tubing.
Ziegler-Natta catalyst is high due to its catalytic efficiency, the polymer good combination property of production, low cost, therefore
The production of polyethylene occupies an important position.Ziegler-Natta catalyst can not only catalyzed ethylene, propylene homo,
Can also catalyzed ethylene and alpha-olefin (such as 1-butylene, propylene) copolymerizing linear low-density polyethylene (LLDPE).
But the production requirement catalyst system of long-chain branch LLDPE possesses high activity and good copolymerization performance, and traditional
Ziegler-Natta catalyst when catalyzed ethylene is polymerized with long-chain alpha-olefin (such as 1-hexene, 1-octene, 1-decene),
Long-chain alpha-olefin insertion rate is low, and the ethylene copolymer of synthesis has the widest composition distribution；This chain structure feature pair
Many performances of LLDPE have a negative impact, and cause the transparency of thin film, intensity, surface tackiness, heat sealability and heat
Viscous hydraulic performance decline.CN1953809A discloses a kind of catalyst for ethylene copolymer and preparation method thereof, its catalyst
It is by being dissolved with the butyl chloride solution reaction system that the chlorobenzene solution of metal magnesium powder and butyl oxide and activator contain iodine
Standby organo-magnesium compound, the most again with containing PhCCl3Chlorobenzene solution reaction prepare magnesium-containing carrier, then add in carrier
Enter titanium tetrachloride reaction and prepare catalyst.This catalyst has the highest activity for ethylene and 1-hervene copolymer, and gained is polymerized
Composition granule form is preferable, but in copolymer, 1-ahexene content is relatively low, and only 1.2%.In order to solve 1-in ethylene copolymer
Problem that hexene insertion rate is low and obtaining forms narrowly distributing and the wider ethylene hexene copolymer of molecular weight distribution, many specially
Profit adds electron donor and is modified Ziegler-Natta catalyst, possesses high activity and good copolymerizable to preparation
The catalyst system of energy.The method of ethylene copolymerization disclosed in CN1229092A is to be dissolved in organic epoxy by magnesium chloride
Compound, organic phosphorus compound add electron donor formed homogeneous solution, then with at least one precipitation additive and transition
Halogenide and the derivant effect thereof of Titanium and obtain；This catalyst ethylene is high with 1-hervene copolymer activity, copolymerization
In thing, 1-hexene insertion rate is higher, but this catalyst system and catalyzing mother solution in preparation process is more viscous, and catalyst solid separates with mother solution
More difficult, and 1-hexene skewness in copolymer.CN1194993A discloses a kind of catalysis for ethylene slurry polymerization
Agent, it is dissolved in the homogeneous solution of organic epoxy compound thing, organic phosphorus compound and atent solvent by magnesium chloride, then
Adding electron donor, a kind of help diluent and the chloride of transition metals Ti to prepare, this catalyst can be used for second
Alkene closes with alpha-olefin copolymer, but is not carried out the example of ethylene and 1-hervene copolymer formation LLDPE.
Therefore, still a need to develop a kind of catalyst with higher catalytic activity for ethylene Yu alpha-olefin copolymer,
So that the LLDPE prepared has higher alpha-olefin insertion rate and good particle shape, and good physics
Mechanical performance.
Summary of the invention
It is an object of the invention to provide a kind of catalyst for ethylene and alpha-olefin copolymer and preparation thereof and application.This is urged
Agent catalyzed ethylene is high with the catalysis activity of long-chain alpha-olefin copolymerization, makes the long-chain alpha-olefin of the copolymer prepared insert
Rate is high, and particle shape is good, and bulk density is high, and fine polymer powder is few.
The present invention provides a kind of catalyst for ethylene Yu alpha-olefin copolymer, its raw material include magnesium compound, titanium compound,
Electron donor I, electron donor II and electron donor III.
Wherein, described magnesium compound is formula M gR1 nX1 2～nThe combination of one or more in shown compound, in formula,
X1For halogen, n is the integer of 0～2, R1For C1～C15Alkyl or aryl.
Described titanium compound is formula Ti (OR2)mX2 4～mThe combination of one or more in shown compound, in formula, X2
For halogen, m is the integer of 0～4, R2For C1～C6Alkyl or aryl.
Described electron donor I is the esters chemical combination such as diethyl succinate, diisobutyl phthalate and tributyl phosphate
Thing.
Described electron donor II is siloxane compound, and it is general formula R3 xR4 ySi(OR5)zOne in shown compound
Or several combinations, in formula, R3For alkyl, chlorohydrocarbon or halogen, R4For alkyl, chlorohydrocarbon or halogen, R5For hydrocarbon
Base, 0≤x ＜ 2,0≤y ＜ 2,0 ＜ z≤4 and x, y and z are integer.
Electron donor III is methyl ether, ether, butyl ether, oxolane, glycol dimethyl ether, 2,2-dimethylpropane, 1,2-
The ether compounds such as dimethoxy-ethane.
Described magnesium compound is 1 gram of magnesium compound with the ratio of electron donor I, electron donor II and electron donor III:
0.10～0.20 milliliter of electron donor I: 0.20～0.25 milliliter of electron donor II: 0.15～0.35 milliliter of electron donor III.
Described titanium compound adds at twice, and the volume ratio with second time addition is 1:1～2:1 for the first time.
In above-mentioned catalyst, described magnesium compound can be magnesium chloride, magnesium bromide, magnesium iodide and diethoxy magnesium etc.
In the combination of one or more.Preferably, described magnesium compound is magnesium chloride.
In above-mentioned catalyst, described titanium compound can be titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four ethoxies
The combination of one or more in base titanium and a chlorine triethoxy titanium etc..Preferably, described titanium compound is titanium tetrachloride.
In above-mentioned catalyst, described electron donor I can be methyl formate, methyl acetate, ethyl acetate, benzene first
Acid methyl ester, ethyl benzoate, propyl benzoate, diethyl succinate, n-butyl phthalate, phthalic acid
The group of one or more in diisobutyl ester, trimethyl phosphate, triethyl phosphate, tributyl phosphate and triphenyl phosphate etc.
Close.Preferably, described electron donor I is diethyl succinate, ethyl benzoate, diisobutyl phthalate and phosphorus
The combination of one or more in acid tributyl etc..
In above-mentioned catalyst, described electron donor II can be tetramethoxy-silicane, tetraethoxysilane, 4 third oxygen
Base silane, MTES, ethyl triethoxysilane, n-pro-pyl triethoxysilane, a chlorine triethoxy
Silane, 3-chloropropyl triethoxysilane, MTMS, ethyl trimethoxy silane, isobutyl group trimethoxy
Base silane, hexyl trimethoxy silane, dimethyldimethoxysil,ne, diisopropyl dimethoxy silane, dicyclohexyl two
Methoxy silane, Cyclohexyl Methyl Dimethoxysilane, dimethoxydiphenylsilane and phenyl methyl dimethoxysilane
The combination of one or more in Deng.Preferably, described electron donor II is tetraethoxysilane, 3-chloropropyl three ethoxy
The combination of one or more in base silane, hexyl trimethoxy silane, Cyclohexyl Methyl Dimethoxysilane etc..
In above-mentioned catalyst, described electron donor III is ether compound, such as methyl ether, ether, butyl ether, tetrahydrochysene furan
Mutter, the combination of one or more in glycol dimethyl ether, 2,2-dimethylpropane, 1,2-dimethoxy-ethane etc..
The preparation method of the catalyst of ethylene of the present invention and alpha-olefin copolymer, it comprises the following steps:
(1) magnesium compound is dissolved in appropriate hydrocarbon solvent, add alcoholic solvent, under 70～90 DEG C of stirring conditions react 2～
4 hours；
(2) it is subsequently adding electron donor I, reacts 1～2 hour under stirring condition, add electron donor II, stir bar
React 1～2 hour under part；
(3) it is cooled to room temperature, drips titanium compound, dripped in 1～2 hour and finish, then heat to 70～90 DEG C, stirring
Under the conditions of react 1～3 hour；
(4) by above-mentioned reactant filter pressing to remove solvent, adding the stirring of appropriate hydrocarbon solvent, be warming up to 70～90 DEG C, addition is given
Electron III, reacts 1～2 hour under stirring condition；
(5) add titanium compound, react 1～3 hour under stirring condition；Filter, washing, be dried to obtain described for
Ethylene and the catalyst of alpha-olefin copolymer.
Further, the magnesium compound that step is (1) described is magnesium chloride；Described hydrocarbon solvent is hexane, heptane；Described alcohol
Solvent is isobutanol, hexanol.
Further, the electron donor I that step is (2) described be a kind of in diethyl succinate, tributyl phosphate or both
Combination.
Further, the electron donor II that step is (2) described is tetraethoxysilane, 3-chloropropyl triethoxysilane, hexyl
The combination of one or more in trimethoxy silane and Cyclohexyl Methyl Dimethoxysilane.
Further, the (4) described electron donor III of step be oxolane, 2, a kind of in 2-dimethylpropane or both
Combination.
Further, step (3), (5) described titanium compound be titanium tetrachloride.
In above-mentioned preparation method, described hydrocarbon solvent can be in aliphatic hydrocarbon, alicyclic, aromatic hydrocarbon and halogenated hydrocarbons
Kind or several combinations, the addition of hydrocarbon solvent is as the criterion can be smoothed out reaction.Wherein, described aliphatic hydrocarbon can be
The combination of one or more in pentane, hexane, heptane, octane and decane etc.；Described alicyclic can be Pentamethylene.,
The combination of one or more in methyl cyclopentane, hexamethylene and hexahydrotoluene etc.；Described aromatic hydrocarbon can be benzene, first
The combination of one or more in benzene, dimethylbenzene, ethylbenzene and cumene etc.；Described halogenated hydrocarbons can be carbon tetrachloride,
The combination of one or more in dichloroethanes, dichloropropane and chlorobenzene etc..Preferably, described hydrocarbon solvent be hexane and
/ or heptane.
In above-mentioned preparation method, described alcoholic solvent can be aliphatic alcohol and/or alicyclic alcohol.Wherein, described aliphatic alcohol
Can be methanol, ethanol, isopropanol, isobutanol, amylalcohol, hexanol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, capryl alcohol,
The combination of one or more in dodecanol, stearyl alcohol and ethylene glycol etc.；Described alicyclic alcohol can be Hexalin and first
The combination of one or more in cyclohexanol etc..Preferably, described alcoholic solvent is isobutanol and/or hexanol.
The present invention also provides for a kind of carbon monoxide-olefin polymeric for ethylene Yu alpha-olefin copolymer, and it includes following components:
The above-mentioned catalyst for ethylene Yu alpha-olefin copolymer；
A kind of promoter, it is general formula R6 fMX3 3-fThe combination of one or more in shown compound, in formula, R6
For C1-C15Alkyl, X3For halogen, M is metallic element, and f is the integer of 1-3；
Wherein, described catalyst is 1:30～1:150 with the mol ratio of described promoter, respectively with titanium unit in catalyst
The mole of element and the molar amount of M metallic element in promoter.
R in above-mentioned carbon monoxide-olefin polymeric, in promoter formula6It can be methyl, ethyl, n-pro-pyl, different
Butyl, cyclopenta, cyclohexyl and phenyl etc.；Described M can be aluminium element etc..The side of being preferable to carry out according to the present invention
Case, described promoter be trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, chlorodimethylalumiu, diethylaluminum chloride,
Di-isobutyl aluminum chloride, sesquialter methyl chloride aluminum, ethylaluminum sesquichloride, methylaluminium dichloride and ethylaluminium dichloride etc.
In the combination of one or more.It is highly preferred that described promoter is triethyl aluminum and/or triisobutyl aluminium.
Catalyst for ethylene and alpha-olefin copolymer that the present invention provides and preparation method thereof has the advantage that
(1) in catalyst preparation process, Ziegler-Natta is realized by the addition of three kinds of electron donors I, II, III
The purpose of catalyst modification, catalyst preparation process is simple, easy to operate, low cost.
(2) catalyst that the present invention provides can be applicable to ethylene and alpha-olefin copolymer conjunction reaction, especially ethylene and long-chain
Alpha-olefin copolymer closes reaction, such as ethylene and 1-hexene, ethylene and the copolymerization of 1-octene, can prepare alpha-olefin content higher
Ethylene copolymer.Ethylene can reach 500gPE (gcat h) with the catalysis activity of alpha-olefin polymerization under atmospheric pressure-1Above, prepare
In copolymer, the content of alpha-olefin reaches more than 5wt%；And polymer beads is uniform, form is good, and bulk density is high,
Fine polymer powder is few.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described, but protection scope of the present invention is not limited only to following
Embodiment.
Embodiment 1
Present embodiments provide a kind of catalyst for ethylene Yu alpha-olefin copolymer, itself through the following steps that preparation:
(1) different at 1 gram of anhydrous magnesium chloride of addition, 30 ml n-hexanes and 3.75 milliliters in the there-necked flask that argon is replaced
Butanol, is stirred and heated to 70 DEG C, reacts 3 hours, obtains suspension.
(2) in this suspension, add the tributyl phosphate of 0.10 milliliter, stirring reaction 1.5 hours at 70 DEG C, then
Add the tetraethoxysilane of 0.2 milliliter, stirring reaction 1.5 hours at 70 DEG C.
(3) it is cooled to room temperature, the slowly titanium tetrachloride of dropping 20 milliliters, time for adding 90 minutes；Progressively it is warming up to 70 DEG C,
2 hours heating-up times；It is stirred for afterwards reacting 2 hours.
(4) by supernatant filter pressing, add 25 ml n-hexanes, be warmed up to 70 DEG C, add the tetrahydrochysene furan of 0.20 milliliter
Mutter, stirring reaction 1.5 hours.
(5) add the titanium tetrachloride of 20 milliliters, react 2 hours.After reaction terminates, repeatedly wash with normal hexane, directly
To eliminating the titanium tetrachloride that unreacted is complete, then vacuum drying obtains solid catalyst 1.
In catalyst, the mensuration of Ti content uses spectrophotography, and specific experiment step includes: make catalyst molten through concentrated sulphuric acid
Solve, be subsequently adding H2O2React, itself and Ti4+Formed yellow complex, maximum absorption wavelength at 420nm,
The quantitative determination of titanium is carried out with spectrophotography.The Ti content of this catalyst 1 is 4.52wt%.
Embodiment 2
The present embodiment ethylene and alpha-olefin copolymer method for preparing catalyst are with embodiment 1, and difference is:
Isobutanol consumption 4.3 milliliters in step (1).
Step (2) replaces tributyl phosphate, its consumption 0.10 milliliter with diethyl succinate；With hexyl trimethoxy
Silane substitutes tetraethoxysilane, its consumption 0.25 milliliter.
Titanium tetrachloride consumption 30 milliliters in step (3), time for adding is 2 hours, and the response time is 1 hour.
Oxolane consumption 0.35 milliliter in step (4), the response time is 2 hours.
Titanium tetrachloride consumption 22 milliliters in step (5), the response time is 3 hours.
The Ti content of the solid catalyst 2 prepared is 4.04wt%.
Embodiment 3
Present embodiments providing a kind of catalyst for ethylene Yu alpha-olefin copolymer, its preparation method is with embodiment 1, district
It is not:
Isobutanol consumption 2.20 milliliters in step (1).
Tributyl phosphate consumption 0.20 milliliter in step (2)；Tetraethoxy-silicane is substituted with 3-chloropropyl triethoxysilane
Alkane, its consumption 0.22 milliliter.
Titanium tetrachloride consumption 16 milliliters in step (3), time for adding is 2 hours, and the response time is 1 hour.
With 2 in step (4), 2-dimethylpropane substitutes oxolane, its consumption 0.15 milliliter.
Titanium tetrachloride consumption 16 milliliters in step (5).
The Ti content of the solid catalyst 3 prepared is 4.10wt%.
Embodiment 4
Present embodiments providing a kind of catalyst for ethylene Yu alpha-olefin copolymer, its preparation method is with embodiment 1, district
It is not:
Tributyl phosphate consumption 0.15 milliliter in step (2)；Tetraethoxy is substituted with Cyclohexyl Methyl Dimethoxysilane
Silane, its consumption 0.20 milliliter.
Titanium tetrachloride consumption 21 milliliters in step (3), time for adding is 1 hour, and the response time is 3 hours.
With oxolane and 2 in step (4), 2-dimethylpropane mixture replacing oxolane, oxolane consumption is
0.15 milliliter, 2,2-dimethylpropane consumptions 0.15 milliliter.
Titanium tetrachloride consumption 21 milliliters in step (5), 1 hour response time.
The Ti content of the solid catalyst 4 prepared is 3.76wt%.
Embodiment 5
Present embodiments providing a kind of catalyst for ethylene Yu alpha-olefin copolymer, its preparation method is with embodiment 1, district
It is not:
Isobutanol consumption 4.10 milliliters in step (1).
Step (2) replaces tributyl phosphate, its consumption 0.15 milliliter with diisobutyl phthalate；With four ethoxies
Base silane and hexyl trimethoxy silane mixture replacing tetraethoxysilane, tetraethoxysilane consumption 0.10 milliliter,
Hexyl trimethoxy silane consumption 0.10 milliliter.
Titanium tetrachloride consumption 32 milliliters in step (3), time for adding is 2 hours.
With 2 in step (4), 2-dimethylpropane substitutes oxolane, its consumption 0.25 milliliter, and the response time is 2 little
Time.
Titanium tetrachloride consumption 16 milliliters in step (5).
The Ti content of the solid catalyst 5 prepared is 5.12wt%.
Embodiment 6
Present embodiments providing a kind of catalyst for ethylene Yu alpha-olefin copolymer, its preparation method is with embodiment 1, district
It is not:
Isobutanol consumption 2.70 milliliters in step (1).
Step (2) replaces tributyl phosphate, its consumption 0.15 milliliter with diethyl succinate；Tetraethoxysilane is used
Measure 0.25 milliliter.
Titanium tetrachloride consumption 18 milliliters in step (3).
With oxolane and 2 in step (4), 2-dimethylpropane mixture replacing oxolane, its oxolane consumption
0.10 milliliter, 2,2-dimethylpropane consumptions 0.10 milliliter.
Titanium tetrachloride consumption 10 milliliters in step (5), the response time is 3 hours.
The Ti content of the solid catalyst 6 prepared is 3.28wt%.
Embodiment 7
Present embodiments providing a kind of catalyst for ethylene Yu alpha-olefin copolymer, its preparation method is with embodiment 1, district
It is not:
Replacing hexane with normal heptane in step (1), replace isobutanol with hexanol, 90 DEG C are reacted 4 hours.
In step (2), reaction temperature is 90 DEG C, tributyl phosphate consumption 0.25 milliliter；Tetraethoxysilane consumption 0.15
Milliliter.
In step (3), reaction temperature is 90 DEG C.
In step (4), reaction temperature is 90 DEG C, replaces hexane with normal heptane.
The Ti content of the solid catalyst 7 prepared is 4.05wt%.
Comparative example 1
This comparative example provides a kind of comparison catalyst for ethylene Yu alpha-olefin copolymer, its preparation method with embodiment 1,
Difference is:
Step (4) in substitute oxolane with tetraethoxysilane and tributyl phosphate, be initially charged the tetraethoxy of 0.10 milliliter
Silane, stirring reaction 1 hour, it is subsequently adding the tributyl phosphate of 0.12 milliliter, stirring reaction 1 hour.
The Ti content obtaining solid catalyst 8 is 5.68%.
Comparative example 2
This comparative example provides a kind of comparison catalyst for ethylene Yu alpha-olefin copolymer, its preparation method with embodiment 1,
Difference is:
Step (4) in be added without oxolane；Will supernatant filter pressing, add 25 ml n-hexanes, be warmed up to 70 DEG C,
Stirring reaction 1.5 hours.
The Ti content obtaining solid catalyst 9 is 4.15%.
Comparative example 3
This comparative example provides a kind of comparison catalyst for ethylene Yu alpha-olefin copolymer, its preparation method with embodiment 1,
Difference is:
Step (4) middle oxolane consumption is 0.70 milliliter.
The Ti content obtaining solid catalyst 10 is 5.53%.
Comparative example 4
This comparative example provides a kind of comparison catalyst for ethylene Yu alpha-olefin copolymer, its preparation method with embodiment 1,
Difference is:
Step (4) in 2,2-dimethylpropane substitute oxolane, its consumption 0.70 milliliter.
The Ti content obtaining solid catalyst 11 is 3.91%.
Application examples 1～11
Application examples 1～11 provides catalyst that above-described embodiment 1～7 prepares 1～7 and urging of preparing of comparative example 1～4
Agent 8～11 polymerisation process that catalyzed ethylene closes with alpha-olefin copolymer under the conditions of polymerization under atmospheric pressure and result.This polymerization
Reaction makes ethylene and alpha-olefin carry out copolymerization, ethylene pressure 0.1MPa in the there-necked flask of 250 milliliters.It gathers
Conjunction method comprises the following steps: after being sufficiently displaced from there-necked flask with argon, adds normal hexane 100 milli processed through anhydrous and oxygen-free
Rise, add the triethyl aluminium solution (promoter) of a certain amount of 2.0 mol/L (mol/L), add one while stirring
Quantitative catalyst, is warming up to 45 DEG C, adds the comonomer of 1.86～3.8mL, logical vinyl polymerization 0.5 hour.Instead
After Ying, the acidic ethanol adding 10% terminates reaction, and uses washing with alcohol polymer, by polymer after vacuum drying
Weighing, calculate catalysis activity, catalysis activity calculates with every gram of catalyst produced polymer weight (gram) per hour,
Unit: gPE (h gcat)～1。
The polymerizing condition of application examples 1～11 and polymerization result are as shown in table 1, and wherein, alpha-olefin assay uses13C～
NMR method records, and 150 μm following fine polymer powder content uses screen cloth method to record.
As shown in table 1, catalyst 1～6 catalyzed ethylene that embodiment 1～6 prepares is alive with the catalysis of 1-hexene polymerization under atmospheric pressure
Property reaches 600gPE (h gcat)-1Above, in the copolymer prepared, the content of 1-hexene is 5.15～7.15%(mass hundred
Proportion by subtraction)；Catalyst 7 catalyzed ethylene that embodiment 7 prepares is 705gPE (h gcat) with 1-octene polymerization under atmospheric pressure activity～1,
In copolymer, 1-octene content is more than 5.77%(mass percent)；The copolymer 1 50 following fine powder content of μm prepared is equal
Less than 3.40(wt%), polymer stacks density is more than 0.35Kg L-1.And the catalyst 8～11 that comparative example 1～4 prepares
The catalysis activity of catalyzed ethylene and 1-hexene polymerization under atmospheric pressure still can, at 535～731gPE (h gcat)-1Between, but copolymer
Middle 1-ahexene content, the following fine powder content of copolymer 1 50 μm and polymer stacks density can not preferably be balanced.
By table 1 experimental result it follows that the catalyst that the present invention provides can be applicable to ethylene and long-chain alpha-olefin copolymerization
Close reaction, such as ethylene and 1-hexene, the copolymerization of ethylene and 1-octene, can prepare the higher ethylene of alpha-olefin content and α-
Olefin copolymer, and the fine powder content of the polymer prepared is few, and polymer stacks density is high.
Table 1
Claims (11)
1. the preparation method of the catalyst of an ethylene and alpha-olefin copolymer, it is characterised in that:
(1) magnesium compound is dissolved in hydrocarbon solvent, adds alcoholic solvent, under 70～90 DEG C of stirring conditions, react 2～4
Hour；
(2) it is subsequently adding electron donor I, reacts 1～2 hour under stirring condition, add electron donor II, stirring
Under the conditions of react 1～2 hour；
(3) it is cooled to room temperature, drips titanium compound, dripped in 1～2 hour and finish, then heat to 70～90 DEG C, stir
React 1～3 hour under the conditions of mixing；
(4) by product filter pressing to remove solvent, add hydrocarbon solvent stirring, be warming up to 70～90 DEG C, add to electronics
Body III, reacts 1～2 hour under stirring condition；
(5) add titanium compound, react 1～3 hour under stirring condition；
(6) filter, washing, be dried to obtain the catalyst of ethylene and alpha-olefin copolymer；
Described electron donor I is ester type compound；Described electron donor II is siloxane compound；
Described magnesium compound, alcoholic solvent, titanium compound, electron donor I, electron donor II and the ratio of electron donor III
It it is 1 gram of magnesium compound: 2.2～4.3 milliliters of alcoholic solvents: 28～52 milliliters of titanium compounds: 0.10～0.20 milliliter of electron donor
I: 0.20～0.25 milliliter of electron donor II: 0.15～0.35 milliliter of electron donor III；Titanium compound adds at twice, the
Once the volume ratio with second time addition is 1:1～2:1；
Described electron donor III is methyl ether, ether, butyl ether, oxolane, 2,2-dimethylpropane, 1,2-dimethoxy second
The combination of one or more in alkane.
The preparation method of the catalyst of ethylene the most according to claim 1 and alpha-olefin copolymer, it is characterised in that: described magnesium
Compound is the combination of one or more in magnesium chloride, magnesium bromide, magnesium iodide, diethoxy magnesium.
The preparation method of the catalyst of ethylene the most according to claim 1 and alpha-olefin copolymer, it is characterised in that: described titanizing
Compound is one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, purity titanium tetraethoxide and a chlorine triethoxy titanium
Combination.
The preparation method of the catalyst of ethylene the most according to claim 1 and alpha-olefin copolymer, it is characterised in that: described to electricity
Daughter I is methyl formate, methyl acetate, ethyl acetate, essence of Niobe, ethyl benzoate, propyl benzoate, fourth
Diethyl adipate, n-butyl phthalate, diisobutyl phthalate, trimethyl phosphate, triethyl phosphate,
The combination of one or more in tributyl phosphate and triphenyl phosphate.
The preparation method of the catalyst of ethylene the most according to claim 1 and alpha-olefin copolymer, it is characterised in that: described to electricity
Daughter II is tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, MTES, ethyl three second
TMOS, n-pro-pyl triethoxysilane, a chlorine triethoxysilane, 3-chloropropyl triethoxysilane, methyl trimethoxy
TMOS, ethyl trimethoxy silane, trimethoxysilane, hexyl trimethoxy silane, dimethylformamide dimethyl oxygen
Base silane, diisopropyl dimethoxy silane, Dicyclohexyldimethoxysilane, Cyclohexyl Methyl Dimethoxysilane,
The combination of one or more in dimethoxydiphenylsilane and phenyl methyl dimethoxysilane.
The preparation method of the catalyst of ethylene the most according to claim 1 and alpha-olefin copolymer, it is characterised in that: described hydrocarbon is molten
Agent is aliphatic hydrocarbon and/or aromatic hydrocarbon.
The preparation method of the catalyst of ethylene the most according to claim 6 and alpha-olefin copolymer, it is characterised in that: described fat
Hydrocarbon is alicyclic.
The preparation method of the catalyst of ethylene the most according to claim 1 and alpha-olefin copolymer, it is characterised in that: described alcohol is molten
Agent is aliphatic alcohol.
The preparation method of the catalyst of ethylene the most according to claim 8 and alpha-olefin copolymer, it is characterised in that: described aliphatic series
Alcohol is alicyclic alcohol.
10. an ethylene and the catalyst of alpha-olefin copolymer, it is characterised in that: it is ethylene according to claim 1 and α-alkene
Prepared by the preparation method of the catalyst of hydrocarbon copolymerization.
The catalyst application of 11. 1 kinds of ethylene according to claim 10 and alpha-olefin copolymer, it is characterised in that: for ethylene with
The catalyst of alpha-olefin copolymer.
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| US20040102591A1 (en) * | 1995-01-24 | 2004-05-27 | Brookhart Maurice S. | Polymerization of olefins |
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| CN102875704B (en) * | 2012-09-05 | 2015-04-08 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst as well as preparation method and application thereof |
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| US20040102591A1 (en) * | 1995-01-24 | 2004-05-27 | Brookhart Maurice S. | Polymerization of olefins |
| US20060089251A1 (en) * | 2002-12-18 | 2006-04-27 | Basell Poliolefine Italia S.P.A. | Catalyst components for the polymerization of olefins |
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