CN105669883B - A kind of method that in-situ copolymerization prepares wide/double peak polyethylene - Google Patents
A kind of method that in-situ copolymerization prepares wide/double peak polyethylene Download PDFInfo
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- CN105669883B CN105669883B CN201610114895.0A CN201610114895A CN105669883B CN 105669883 B CN105669883 B CN 105669883B CN 201610114895 A CN201610114895 A CN 201610114895A CN 105669883 B CN105669883 B CN 105669883B
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- 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
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- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/04—Broad molecular weight distribution, i.e. Mw/Mn > 6
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- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/05—Bimodal or multimodal molecular weight distribution
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Abstract
The invention discloses a kind of methods that in-situ copolymerization prepares wide/double peak polyethylene, under ethylene atmosphere, add in major catalyst and co-catalyst containing organic solvent, stirring, generation polymerisation produces polymer, wherein, the major catalyst is N N N tridentate ligand cobalt complex catalysts, and structural formula is as follows：Wherein, R1、R2、R3For halogen atom, hydrogen atom, methyl, ethyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl.This method is easy to operate, easily controllable.
Description
Technical field
The present invention relates to a kind of methods that in-situ copolymerization prepares wide/double peak polyethylene.
Background technology
Alpha-olefin is a kind of important industrial chemicals, C6~C10Alpha-olefin as the most common comonomers of PE, add in
The anti-impact and tear resistance of resin can be significantly improved with ethylene copolymer；C8~C12Alpha-olefin can be used for synthesizing advanced profit
Lubricating oil；C18Lubricant and drilling fluid etc. can be directly used as above.The synthesis of alpha-olefin is mainly made by ethylene oligomerization.Ethylene is neat
Gathering common catalyst mainly has nickel system, chromium system, zirconium system, aluminium system and cobalt system etc..Cobalt series catalyst is due to its high activity, high selection
Property is of increased attention.Brookhart(J.Am.Chem.Soc.,1998,120:7143；United States Patent (USP)
US6103946) and the Gibbson of Britain (Chem.Commun., 1998,849；W0 patents 99/02472) it reports such as lower structure
Cobalt series catalyst：
M=Fe；X=Cl, Br, I
For this kind of cobalt-base catalyst using alkyl aluminum as co-catalyst, catalysis ethylene oligomerization can prepare C6~C20Content>50%
Alpha-olefin.Obtained alpha-olefin generally obeys Schulz-Flory or Poisson (most probable or Poisson) distributions.There is research
Work report such catalyst can catalyzed preparation of poly ethylene, obtained molecular weight of polyethylene distribution is usually unimodal.
The molecular weight and molecular weight distribution of polyethylene have the processing performance of polymer with product mechanical property very bright
Aobvious influence., it is necessary to have the part of high molecular weight to improve the mechanical property of material such as in polyvinyl piping materials, and need low
The part of molecular weight provides itself plasticization, improves the processing performance of product.Recent researches scholars are double to high molecular weight
Peak or polyethylene with wide molecular weight distribution have carried out substantial amounts of research, are concentrated mainly on these three methods：(1) different molecular weight is synthesized
It is kneaded after the polymer of size；(2) multistage reactor stage feeding polymerization is used；(3) bimetallic or more is used in single reactor
Metal active constituent catalyst.Wherein, wide molecular weight distribution is synthesized in single reactor or bimodal polyethylene is most attractive,
It does not transform even, easily implements, resin grade adjustable extent because this method need not carry out existing process units big transformation
Greatly, cost is relatively low, and high low-molecular weight polymer is uniformly mixed, and is the important research direction for producing wide/double peak polyethylene technology
And development trend.Dinuclear metallocene complexes, which have, much to be had been reported for producing wide/double peak polyethylene in single reactor, but
Be metallocene catalyst preparation condition it is harsher, operation difficulty is high in technique, and thermal stability deficiency limits it and widely uses.
The content of the invention
It is an object of the invention to provide a kind of method that in-situ copolymerization prepares wide/double peak polyethylene, this method selection is closed
Suitable N-N-N tridentate ligands cobalt complex catalyst and reaction condition obtain wide/double peak polyethylene.
The method that a kind of in-situ copolymerization of the present invention prepares wide/double peak polyethylene, under ethylene atmosphere, addition contains
Polymerisation production polymer occurs for the major catalyst and co-catalyst of organic solvent, stirring, wherein, the major catalyst is
N-N-N tridentate ligand cobalt complex catalysts, structural formula are as follows：
Wherein, R1、R2、R3For halogen atom, hydrogen atom, methyl, ethyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl.
The cobalt complex catalyst, co-catalyst is methylaluminoxane (MAO), modified methylaluminoxane (MMAO),
Trimethyl aluminium (AlMe3), the green (AlEtnCl of tonsilon3-n), triisobutyl aluminium (AliBu3), three pentafluorophenyl group boron (B (C6F5)3)
Or three pentafluorophenyl group aluminium (Al (C6F5)3), first choice is methylaluminoxane or the methylaluminoxane of modification.
The molar ratio of the major catalyst and co-catalyst is 1:0~8000.The organic solvent may be selected from the C of straight chain5
~C8Alkane etc., as one embodiment of the present of invention, select hexane and heptane or toluene.The temperature of the polymerisation
It spends for -50~150 DEG C, preferable temperature is 20~120 DEG C.The pressure of the polymerisation is 0.1~l0MPa, and preferably pressure is
0.1~5MPa.
The present invention has the following advantages compared with prior art：
The present invention selects suitable N-N-N tridentate ligands cobalt complex catalyst and reaction condition, in single-reactor
It is middle to use ethylene as monomer polymerization reactions acquisition wide/double peak polyethylene, C in alpha-olefin in oligomer6~C12Selectivity be
40%~60%.The present invention is easy to operate without exacting terms, can realize that high added value wide/double peak gather in aq slurry process
The production of ethylene.
The catalyst highest catalytic activity is up to 2.4 × 107G (polymer)/(mol Coh).
Description of the drawings
Fig. 1 is the product molecular weight distribution figure of embodiment 10.
Fig. 2 is the product molecular weight distribution figure of embodiment 11.
Fig. 3 is the product molecular weight distribution figure of embodiment 12.
Fig. 4 is the product molecular weight distribution figure of embodiment 13.
Specific embodiment
The N-N-N tridentate ligands cobalt complex catalyst that the present invention uses is prepared using following methods：
I prepares pyridine diimine ligand：
Pyridine diimine ligand structure formula is as follows：
The ligand is obtained by the reaction by raw material and the aromatic imine with different substituents of 2,6-diacetylpyridine.
The cobalt complex catalyst of II synthetic ligands：
Within the temperature range of -78~60 DEG C, pyridine diimine ligand and cobalt compound prepared by step I are in molar ratio
1:The ratio of (0.1~5) reacts 0.5~100h in organic solvent, obtains ligand cobalt complex catalyst.
Organic solvent may be selected from tetrahydrofuran, ether, dichloromethane, petroleum ether, 1,4- dioxane, toluene and benzene etc.
One kind.
Aromatic imine is 2-aminotoluene, 3- methylanilines, 4- methylanilines, 2- ethyl aniline, 3- ethyl aniline, 4- second
Base aniline, 2- isopropyl anilines, 3- isopropyl anilines, 4- isopropyl anilines, 2,4- diisopropyl anilines, 2,3- diisopropyl benzenes
Amine, 2,6- diisopropyl anilines, 2- fluoroanilines, 2- chloroanilines, 2- bromanilines, 3- fluoroanilines, 3- chloroanilines, 3- bromanilines, 4-
Fluoroaniline, 4- chloroanilines, 4- bromanilines, 2,4- dimethylanilines, the one of 2,6- dimethylanilines and 2,4,6- trimethylanilines
Kind.
Embodiment 1
The catalyst structure formula used in the present embodiment is as follows：
Ethylene oligomerization carries out in 250mL autoclaves.Reaction kettle is heated to 120 DEG C first, then vacuumizes 2h.It
The ethylene of certain pressure is filled with after being replaced by high pure nitrogen more than three times, treats that temperature is down to room temperature.Add in co-catalyst 2mL first
Toluene solution of the toluene solution (10%) and 40mL of base aikyiaiurnirsoxan beta containing 10 μm of ol catalyst, and further add toluene extremely
50mL.After stirring 5min, temperature and ethylene pressure are risen into 70 DEG C and 1MPa respectively, continuously add toluene to 50mL.Reaction
Reaction kettle is cooled to less than 10 DEG C by 30min, is slowly deflated, and reaction solution is gone out with 5% hydrochloric acid-Yi Chun Rong Ye temper.The oligomeric production of gained
Object directly collects organic phase component, using the distribution situation of GC-FID detection oligomer.Catalyst activity is 1.81 × 106G is (low
Polymers)/(mol Coh)
Embodiment 2
As different from Example 1, ethylene pressure rises to 2MPa, obtains product as oligomer, catalyst activity 2.74
×106(oligomer)/(mol Coh).
Embodiment 3
As different from Example 1：The catalyst structure formula used in the present embodiment is as follows：
Product is oligomer, and catalyst activity is 1.63 × 106(oligomer)/(mol Coh).
Embodiment 4
As different from Example 1：The catalyst structure formula used in the present embodiment is as follows：
Product is oligomer, and catalyst activity is 2.09 × 106(oligomer)/(mol Coh).
Embodiment 5
Catalyst structure formula is the same as embodiment 4；
Catalytic reaction experiment obtains product as oligomer, catalyst activity is 3.08 × 10 with embodiment 26(oligomer)/
(mol Co·h)。
Embodiment 6
As different from Example 1：The catalyst structure formula used in the present embodiment is as follows：
Product is oligomer, and catalyst activity is 1.18 × 106(oligomer)/(mol Coh).
Embodiment 7
As different from Example 1：The catalyst structure formula used in the present embodiment is as follows：
Product is oligomer, and catalyst activity is 0.074 × 107(oligomer)/(mol Coh).
Embodiment 8
As different from Example 1：The catalyst structure formula used in the present embodiment is as follows：
Product is oligomer, and catalyst activity is 0.315 × 106(oligomer)/(mol Coh).
Embodiment 9
As different from Example 1：The catalyst structure formula used in the present embodiment is as follows：
Product is oligomer, and catalyst activity is 0.43 × 106(oligomer)/(mol Coh).
Embodiment 10
The catalyst structure formula used in the present embodiment is as follows：
Catalytic reaction is tested：It is carried out in 250mL autoclaves.Reaction kettle is heated to 120 DEG C first, then vacuumizes
2h.After be filled with the ethylene of certain pressure after more than high pure nitrogen displacement three times, treat that temperature is down to room temperature.Add in co-catalyst
Toluene solution of the toluene solution (10%) and 40mL of 2mL methylaluminoxane containing 10 μm of ol catalyst, and further add toluene
To 50mL, the high-purity H of 20mL are added in syringe2.After stirring 5min, logical ethylene gas makes pressure in kettle rise to 1MPa, by temperature
50 DEG C are risen to, 30min is reacted, after reaction cut-off, reaction kettle is cooled to less than 10 DEG C, is slowly deflated, 5% salt of reaction solution
Acid-Yi Chun Rong Ye temper goes out.The product of gained is through precipitating, filtering, washing, and dry 12h is to constant weight in 50 DEG C of baking ovens.Product is height
Polymers, weight 120g, catalyst activity are 2.4 × 107(polymer)/(mol Coh).Resulting polymers molecular weight is Mw=
33476, Mn=1949；Molecular weight distribution is 17.2.
Embodiment 11
As different from Example 10：
Reaction temperature rises to 70 DEG C, H2Addition is 30mL.Product is high polymer, weight 77g, catalyst activity for 1.54 ×
107(polymer)/(mol Coh).Resulting polymers molecular weight is Mw=146594, Mn=1817；Molecular weight distribution is
80.7。
Embodiment 12
As different from Example 10：The catalyst structure formula used in the present embodiment is as follows：
Product is high polymer, and weight 3.5g, catalyst activity is 0.7 × 107(polymer)/(mol Coh).Gained polymerize
Object molecular weight is Mw=86125, Mn=4957；Molecular weight distribution is 17.3.
Embodiment 13
As different from Example 10：The catalyst structure formula used in the present embodiment is as follows：
Product is high polymer, and weight 72g, catalyst activity is 1.44 × 107(polymer)/(mol Coh).Gained polymerize
Object molecular weight is Mw=160539, Mn=2742；Molecular weight distribution is 58.5.
Table 1
Above example is only intended to be illustrated present disclosure rather than limit, therefore with the present invention's
Any change in the comparable meaning and scope of claims is all considered as being included within the scope of the claims.
Claims (9)
1. a kind of method that in-situ copolymerization prepares wide/double peak polyethylene, which is characterized in that under ethylene atmosphere, addition has
Polymerisation production polymer occurs for the major catalyst and co-catalyst of solvent, stirring, wherein, the major catalyst is N-
N-N tridentate ligand cobalt complex catalysts, structural formula are as follows：
Wherein, R1、R2For halogen atom, hydrogen atom, methyl, ethyl, normal-butyl, isobutyl group, tertiary butyl；R3For halogen atom, first
Base, ethyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl；
The molar ratio of the major catalyst and co-catalyst is 1:0~8000.
2. the method that in-situ copolymerization prepares wide/double peak polyethylene according to claim 1, which is characterized in that the co-catalysis
Agent for methylaluminoxane, the methylaluminoxane of modification, trimethyl aluminium, ethylaluminium chloride, triisobutyl aluminium, three pentafluorophenyl group boron or
Three pentafluorophenyl group aluminium.
3. the method that in-situ copolymerization prepares wide/double peak polyethylene according to claim 1, which is characterized in that the co-catalysis
Agent is methylaluminoxane or the methylaluminoxane of modification.
4. the method that wide/double peak polyethylene is prepared according to 1 or 2 or 3 in-situ copolymerization of claim, which is characterized in that described
The temperature of polymerisation is -50~150 DEG C.
5. the method that in-situ copolymerization prepares wide/double peak polyethylene according to claim 4, which is characterized in that the polymerization is anti-
It is 20~120 DEG C to answer temperature.
6. the method that in-situ copolymerization prepares wide/double peak polyethylene according to claim 4, which is characterized in that the polymerization is anti-
The pressure answered is 0.1~l0MPa.
7. the method that in-situ copolymerization prepares wide/double peak polyethylene according to claim 6, which is characterized in that the polymerization is anti-
It is 0.1~5MPa to answer pressure.
8. the method that in-situ copolymerization prepares wide/double peak polyethylene according to claim 6, which is characterized in that described organic molten
Agent is the alkane of C5~C8 of straight chain.
9. the method that in-situ copolymerization prepares wide/double peak polyethylene according to claim 8, which is characterized in that described organic molten
Agent is hexane, heptane or toluene.
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| CN1240455A (en) * | 1996-12-17 | 2000-01-05 | 纳幕尔杜邦公司 | Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis (imines) and novel complexes of pyridinebis (imines) with iron and cobalt |
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| DE69426936T3 (en) * | 1993-10-21 | 2006-07-27 | Exxonmobil Oil Corp. | POLYOLEFIN MIXTURES FROM BIMODAL MOLECULAR WEIGHT DISTRIBUTION |
| EP0989141A1 (en) * | 1998-09-25 | 2000-03-29 | Fina Research S.A. | Production of multimodal polyethelene |
| AU5215899A (en) * | 1999-07-15 | 2001-02-05 | Dow Chemical Company, The | High density ethylene homopolymers and blend compositions |
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| CN1240455A (en) * | 1996-12-17 | 2000-01-05 | 纳幕尔杜邦公司 | Polymerization of ethylene with specific iron or cobalt complexes, novel pyridinebis (imines) and novel complexes of pyridinebis (imines) with iron and cobalt |
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