CN103193901B - Ethylene polymer preparation method - Google Patents
Ethylene polymer preparation method Download PDFInfo
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- CN103193901B CN103193901B CN201210004684.3A CN201210004684A CN103193901B CN 103193901 B CN103193901 B CN 103193901B CN 201210004684 A CN201210004684 A CN 201210004684A CN 103193901 B CN103193901 B CN 103193901B
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Abstract
The invention relates to an ethylene polymer preparation method. The method is characterized in that a hypergravity reactor is adopted to carry out the preparation; a catalyst selects a late transition metal catalyst; and the preparation method comprises the following steps: adding a mixed solution comprising the catalyst, a diluting agent, a cocatalyst and a copolymerization monomer to the hypergravity reactor, heating the reactor to a required temperature, letting in ethylene, carrying out a polymerization reaction under a hypergravity condition at a reaction temperature of -70-200DEG C under a polymerization pressure of 1-60bar for 1min-6h, removing the diluting agent, washing, drying, and processing to obtain a polymer, wherein the hypergravity level of the reactor in the reaction process is 5-800g, and g is the gravitational acceleration. The method has the advantages of shortening of the average stay time of a material in the hypergravity reactor above 20 times, low energy consumption, high production efficiency, control of the rapid system temperature rising caused by strong heat release in the initial phase of polymerization, no obvious fluctuation of the temperature in the whole polymerization process, high catalyst activity, obviously improved molecular weight of the polymer, and narrow distribution of the molecular weight of the polymer.
Description
Technical field
The present invention relates to a kind of polyvinyl preparation method, specifically a kind of supergravity reactor that adopts prepares polyvinyl method.
Background technology
Polyethylene is a kind of very important synthetic plastics.Current industrial production polyethylene be heterogeneous Zieglar-Natta catalyzer mostly.It is that the people such as Zieglar are at research AlEt
3find during catalysed ethylene oligomerisation, its Primary Catalysts is the early transition metal complex compounds such as titanium, zirconium, chromium and vanadium, AlEt
3, Al (iBu)
3, ZnEt
2deng being promotor, carrier is mostly magnesium compound, such as MgCl
2, Mg (OH)
2, Mg (OH) Cl, MgO etc. are carrier.
The catalyst system of metallocene and MAO composition, the customization that can complete polyolefin structure is the another important breakthrough of field of olefin polymerisation (Kaminsky etc., Adv.Organomet.Chem, 1990,18,99).
The people such as Brookhart (J.Am.Chem.Soc.1995 such as Brookhart M, 117,6414; 1996,118,267) synthesize the α diimine nickel palladium catalyst that steric hindrance is larger, obtain the polyethylene of high molecular for catalyzed ethylene polymerization.
Recently, Gibson etc. and Brookhart etc. find that the pyridine diimine title complex of Fe (II) and Co (II) can catalyzed ethylene polymerization (J.Chem.Commun.1998 such as Gibson V C, 849 efficiently simultaneously; WO 99/12981,1999; The J.Am.Chem Soc.1998 such as BrookhartM, 120,4049; Bennett A M A WO 98/27124,1998).Be mainly metal halide in the rear transition catalyst announced in patent WO 99/02472, the selectivity of this type of catalyzer to alpha-olefin is higher.Patent ZL 200910101039.1 discloses a kind of catalyst system for vinyl polymerization, can obtain a series of products from ethylene oligomer to ultrahigh molecular weight polyethylene(UHMWPE) by change pyridine diimine ligand structure.Patent CN1142142C and patent CN1179982 discloses the late transition metal catalyst based on pyridine diimine ligand structure, and polymerisate is mainly ethylene oligomer, and in polymerization process, product is dissolved in thinner toluene, and system becomes the feature of polymerization in homogeneous phase.But, current based in the polymerization catalyst process of diimide ligand, especially there is strong exothermic phenomenon in the polymerization starting stage, produce a large amount of heat of polymerization (be Ziegler-Natta, the heat release of metallocene catalyst polymerisation starting stage 5-10 doubly), traditional heat-removing way (as water of condensation, cool brine etc.) can not the balance of maintenance system temperature, bring the problem of initial polymerization stage difficult control of temperature, serious on product characteristics impact.
The high-gravity technology of development in recent years changes traditional mass transfer mode, the core of this technology is carried out in supergravity reactor at the mass transfer process of liquid-liquid, liquid-solid phase, gas and liquid phase, can greatly reinforcing mass transfer and micro mixing, improve 1-3 the order of magnitude than the mass transfer coefficient of traditional static state (under gravity field) mass transfer and micro mixing and mixing velocity.Chinese patent 91109255.2,91111028.3, CN200410042631.6,20052010685.3,01268009.5,02114174.6,200510032296 discloses hypergravity swivel arrangements such as comprising rotating packed bed, baffling bed, screw path type, rotating compact disc formula.Patent CN101130585B discloses a kind of method adopting supergravity reactor to prepare isoprene-isobutylene rubber, and device volume is little, and mean residence time shortens 30 times, and the butyl rubber molecules amount of production is high, and reach 30,000, range of molecular weight distributions is narrow, 1.9-3.6.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of polyvinyl preparation method, supergravity reactor technology is used for field of olefin polymerisation, greatly enhance the mass transfer in polymerization process, heat transfer and microcosmic mixing, what improve the polymerization initial stage moves heat energy power, thus proposes a kind of polyvinyl method of preparation that efficiency is high, energy consumption is low.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of polyvinyl preparation method, it is characterized in that adopting supergravity reactor to be prepared, post-transition metal catalyst system selected by catalyzer, by catalyzer, thinner, the mixed solution of promotor and comonomer adds in supergravity reactor, reactor is heated to temperature required after, pass into ethene, polyreaction is carried out under hypergravity condition, temperature of reaction controls between-40-300 DEG C, polymerization pressure 1bar-60bar, polymerization time is 1min-6h, the hypergravity level of reactor is controlled at 5-800g in reaction process, g is universal gravity constant, after reaction terminates, carry out de-thinner, washing, dry aftertreatment, obtain polymkeric substance.In specification sheets be-70-200 DEG C.
As improvement, described supergravity reactor can be high gravity rotating packed bed, baffling bed, helical channel, rotating compact disc or rotor-stator hypergravity swivel arrangement, need before polymerization to use high purity inert gas to purge reaction unit, empty G&W in removing reaction unit, after reaching requirement to outlet moisture content, just start polyreaction.
As preferably, described post-transition metal catalyst system comprises: a) pyridine diimine part; B) methyl ethyl diketone salt compound or halide salt compound; Described promotor can be alkylaluminium cpd, as AlR
3, R is the alkyl of 1 ~ twelve carbon atom, also can be the product of the partial hydrolysis of alkylaluminium cpd, as methylaluminoxane (MAO), ethylaluminoxane (EAO), butyla-luminoxane (BAO); The ratio of the amount of substance of described methyl ethyl diketone salt compound or halide salt compound and pyridine diimine part is 0.01 ~ 100; The ratio of the amount of substance of described promotor and methyl ethyl diketone salt compound is 100 ~ 10000.
Described methyl ethyl diketone salt compound is ferric acetyl acetonade (Fe (acac)
n) or acetylacetone cobalt (Co (acac)
n), n=2,3, halide salt compound is FeX
nor CoX
n, wherein n=2,3, X are F, Cl, Br, I; Described diimide ligand can prepare the ethene polymers of molecular weight 56-10000000g/mol by changing ligand structure, the ethene polymers of preferred 56-7000000g/mol.Typical diimine ligand body structure is as follows, but is not limited only to following described part.
Wherein, R is H or methyl; R1, R2, R3, R4 be methyl, ethyl, sec.-propyl, the tertiary butyl, phenyl one or more, can be the same or different.R5, R6 are H or methyl, can be the same or different.
As improvement, described catalyzer is homogeneous catalyst or heterogeneous catalyst.When adopting heterogeneous catalyst, applicable carrier comprise solid, particle, there is specific surface area be greater than 50m
2g
-1the metal oxide of high-specific surface area, nonmetal oxide, organism or its mixture, example comprises: talcum, silicon-dioxide, aluminum oxide, magnesium oxide, titanium dioxide, zirconium white, pure aluminium silicate, polysiloxane, cyclodextrin and polystyrene etc.
Described comonomer is C
1-C
20alpha-olefin, can add or not add during polymerization, preferably do not add.
Preferred again, described thinner is inertia alkane diluent, comprise the mixture of one or both and the above composition in the alkane of benzene,toluene,xylene, perhydronaphthalene or C6-C12, preferably to the high thinner of boiling point as toluene, dimethylbenzene, perhydronaphthalene, normal heptane or octane etc.
Finally, described polymerization temperature is preferably-40-100 DEG C, and polymerization pressure is preferably 1bar-21bar, and polymerization reaction time is preferably 5min-2h, and hypergravity level is preferably 20-600g.
Compared with prior art, the invention has the advantages that: have employed supergravity reactor, due to the high speed rotating of reactor internal rotor, form a kind of stable Elevated Gravity, its hypergravity level can reach tens to the hundred times of natural gravity acceleration.Under this hypergravity condition, under the polymerization system environment that high dispersive, high turbulence, strong mixing and interface upgrade rapidly in the packing layer rotated, baffling passage or rotating channel, contact in bending duct with great speed of relative movement, enhancement of heat transfer, mass transfer process widely, reaches microcosmic admixture completely fast.Compared with being polymerized with traditional stirring, the mean residence time of material in supergravity reactor at least shortens more than 20 times, and energy consumption is low, production efficiency is high.The phenomenon that the system temperature that polymerization starting stage strong heat release causes raises rapidly is controlled.In whole polymerization process, temperature is without obvious wave phenomenon.Compared with the polyreaction of carrying out under gravity field, catalyst activity is higher, and molecular weight significantly improves, molecular weight distribution sharp.
figure of description
Fig. 1 is vinyl polymerization products distribution figure prepared by the embodiment of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The operation of all air-sensitive materials all adopts standard vacuum double line anhydrous and oxygen-free working method.Agents useful for same uses after all needing refinement treatment.
Molecular weight of polyethylene and molecular weight distribution are measured by gel permeation chromatograph (PL-GPC-220), and 1,2,4-trichlorobenzene, as solvent, measures at 150 DEG C, using the polystyrene compared with narrow molecular weight distribution as standard specimen.
Product liquid part first qualitative test on Gc/ms Analyser Nicolet HPGC6890/MS5973 in oligomerisation experiment.
In oligomerisation experiment, the content of each component of Product liquid part (sample should without suspended solid) measures on gas chromatograph Agilent 68090N.Each component be 1 containing the correction factor measuring Olefin Hydrocarbon Homologous Compound, adopt the calibration curve of 1-hexene and normal heptane to calculate.Pillar flow rate of carrier gas 3.0mlmin-1 during measurement, starting temperature 50 DEG C, constant temperature 5min, then 20 DEG C/min is raised to 270 DEG C.
Above-mentioned implementation process according to the known measure of professional, can adopt the mode of continuous feeding or adopts the mode of batch feed.
Embodiment 1
In 250ml glass reactor, add 100ml toluene, constant temperature to 30 DEG C.Add 2umol2 again, 6-bis-(1-(2,6-dimethyl benzene amido ethyl)) pyridine (L1), 2umol ferric acetyl acetonade and 400umol MAO.Under agitation pass into ethylene gas, ethylene pressure is normal pressure, reacts 30 minutes.Be polymerized in initial 5min, temperature rises to 65 DEG C from 30 DEG C.This reactive behavior is 3.00 × 106g polyethylene/(mol Feh atm).Polymericular weight is Mw=25976, molecular weight distribution 7.72.
Embodiment 2
Carry out in 250ml supergravity reactor.Reaction unit is purged, except the empty G&W in dereaction dress with high pure nitrogen.By 100ml toluene, 2umol2,6-bis-(1-(2,6-dimethyl benzene amido ethyl)) pyridine (L1), after 2umol ferric acetyl acetonade and 400umol MAO mix, constant temperature to 30 DEG C, sends into supergravity reactor, cuts ethene after regulating temperature of reactor to 30 DEG C, reaction pressure is normal pressure, starts polyreaction.Regulate the rotor speed of rotating packed bed reactor, make its hypergravity level be 100g, material mean residence time is less than 30min, material is sent into products pot and adds terminator, subsequently product and thinner is carried out separating treatment.In polymerization process, in temperature fluctuation range ± 0.5 DEG C.This reactive behavior is 7.90 × 106g polyethylene/(mol Feh atm).Polymericular weight is Mw=35976, molecular weight distribution 3.72.
Embodiment 3
In 250ml glass reactor, add 100ml toluene, constant temperature to 30 DEG C.Add 2umol2 again, 6-bis-(1-(2-methyl-6-isopropyl benzene amido ethyl)) pyridine (L2), 10umol acetylacetone cobalt and 3000umol MAO.Under agitation pass into ethylene gas, ethylene pressure is normal pressure, reacts 30 minutes.Temperature rises to 65 DEG C from 30 DEG C.This reactive behavior is 7.10 × 104g polyethylene/(mol Feh atm).Polymericular weight is Mw=25976, molecular weight distribution 7.72.
Embodiment 4
Carry out in 250ml supergravity reactor.Reaction unit is purged, except the empty G&W in dereaction dress with high pure nitrogen.By 100ml toluene, 2umol2,6-bis-(1-(2-methyl-6-isopropyl benzene amido ethyl)) pyridine (L2), after 2umol acetylacetone cobalt and 400umol MAO mix, constant temperature to 30 DEG C, send into supergravity reactor, cut ethene after regulating temperature of reactor to 30 DEG C, reaction pressure is normal pressure, starts polyreaction.Regulate the rotor speed of rotating packed bed reactor, make its hypergravity level be 100g, material mean residence time is less than 30min, material is sent into products pot and adds terminator, subsequently product and thinner is carried out separating treatment.In polymerization process, in temperature fluctuation range ± 0.5 DEG C.This reactive behavior is 5.90 × 105g polyethylene/(mol Feh atm).Polymericular weight is Mw=55976, molecular weight distribution 3.92.
Embodiment 5
In 250ml glass reactor, add 100ml toluene, constant temperature to 0 DEG C.Add 0.2umol2 again, 6-bis-(1-(2,6-DIPA base ethyl)) pyridine (L3), 2umol ferric acetyl acetonade and 3000umol MAO.Under agitation pass into ethylene gas, ethylene pressure is normal pressure, reacts 30 minutes.Temperature rises to 45 DEG C from 0 DEG C.This reactive behavior is 6.11 × 106g polyethylene/(mol Feh atm).Mw=40689, molecular weight distribution 80.
Embodiment 6
Except part select (L3), polymerization temperature is except 0 DEG C, all the other are identical with embodiment 4.This reactive behavior is 8.11 × 106g polyethylene/(mol Feh atm).Mw=40689, molecular weight distribution 20.
Embodiment 7
In 250ml glass reactor, add 100ml toluene, constant temperature to 30 DEG C.Add 2umol2 again, 6-bis-(1-(2-aminotoluene base ethyl)) pyridine, 2umol ferric acetyl acetonade and 3000umol MAO.Under agitation pass into ethylene gas, ethylene pressure is normal pressure, reacts 30 minutes.And the interior mark added when 1ml normal heptane measures as GC (gas-chromatography).Sample centrifugation after-18 DEG C of cold 4h, Product liquid part is preserved in refrigerator, and solid part adds the ethanol solution hydrochloride of 10%, and with after washing with alcohol in vacuum drying oven dry 12h at 50 DEG C.This reactive behavior is 3.967 × 106g polyethylene/(mol Feh atm).Product liquid phase part composition with temperature of reaction result of variations as shown in Figure 1.The selectivity of C8-C24 is 80%.It is 5,0000g/mol that solid product accounts for gross product 10% molecular weight.
Embodiment 8
Except part selects 2,6-bis-(1-(2-aminotoluene base ethyl)) pyridine, all the other adjustments are identical with embodiment 4.This reactive behavior is 9.71 × 106g polyethylene/(mol Feh atm).Product is all ethylene oligomer.C8-C24 selectivity reaches 95.6%.
Embodiment 9
The loaded catalyst of preparation containing part 2,6-bis-(1-(2,6-DIPA base ethyl)) pyridine.Use following silica-gel carrier in the present embodiment:
955 of Grace company production, median size is 40 microns, following activation before using:
150Kg silica gel 955 (Grace company) is added in activation furnace, under gas speed is the nitrogen gas stream of 0.24m/s, activation furnace temperature is risen to 120 DEG C, constant temperature is after 2 hours, be warming up to 600 DEG C by the speed of 50 DEG C/h, constant temperature 4 hours, is then cooled to envrionment temperature at this temperature.The Silica Surface hydroxy radical content processed is between 0.5-0.7mmol/g.Be stored in dry bottle stand-by under nitrogen protection.
The clean Schlenk catalyzer bottle that magnetic stir bar is housed of drying is vacuumized, roasting 20 minutes are taken out with alcohol blast burner, and be filled with high pure nitrogen and repeatedly take a breath, then load 1g through Davison 955 silica gel of thermal activation, add 50ml and be dissolved with a certain amount of catalyzer (Fe (acac)
3/ L
3) toluene solution, at room temperature stir 12.Vacuum takes toluene solvant away after completion of the reaction.Then add a certain amount of MAO (concentration is the MAO toluene solution of 1.5mol/L), stirred at ambient temperature 2h, vacuum-drying, to the pressed powder of good fluidity, obtains loaded catalyst CatA.Keep for subsequent use under nitrogen atmosphere.
By the amount of MAO added during regulating load, load obtains the catalyzer of three kinds of different al/Fe ratio: CatA1, CatA2, CatA3, in table 1.
The loaded catalyst of table 1 different al/Fe ratio
Pressurized slurry is aggregated in the Buchi reactor of 1L and carries out, 300ml heptane is first added during polymerization, add a certain amount of promotor MAO again, then the pressure that ethene reaches setting is passed into, stir 10min, the dissolving of ethene in toluene is reached capacity substantially, then adds rapidly supported catalyst and start reaction, termination reaction after 1h.Polymerization acquired results is as shown in table 2.
Table 2 loaded catalyst vinyl polymerization result a
Embodiment 10
Except the loaded catalyst that used catalyst is in embodiment 9, proportioning raw materials is identical with embodiment 9, and embodiment 4 is shown in operation adjustment.Shown in polymerisate result table 3.
Table 3 loaded catalyst is vinyl polymerization result in supergravity reactor
Embodiment 11
Except adding comonomer 1-hexene 6ml, all the other are identical with embodiment 4.The weight-average molecular weight of product is 106,794, and molecular weight distribution is 3.58.
Embodiment 12
Except hypergravity level is 800g, all the other are identical with embodiment 4, and the weight-average molecular weight of product is 142,781, and molecular weight distribution is 2.95.
Embodiment 13
Except hypergravity level is 5g, all the other are identical with embodiment 1, and the weight-average molecular weight of product is 135,121, and molecular weight distribution is 2.86.
Claims (7)
1. a polyvinyl preparation method, it is characterized in that adopting supergravity reactor to be prepared, post-transition metal catalyst system selected by catalyzer, by catalyzer, thinner, the mixed solution of promotor and comonomer adds in supergravity reactor, reactor is heated to temperature required after, pass into ethene, polyreaction is carried out under hypergravity condition, temperature of reaction controls between-70-200 DEG C, polymerization pressure 1bar-60bar, polymerization time is 1min-6h, the hypergravity level of reactor is controlled at 5-800g in reaction process, g is universal gravity constant, after reaction terminates, carry out de-thinner, washing, dry aftertreatment, obtain polymkeric substance, described supergravity reactor is high gravity rotating packed bed, baffling bed, helical channel, rotating compact disc or rotor-stator hypergravity swivel arrangement, need before polymerization to use high purity inert gas to purge reaction unit, empty G&W in removing reaction unit, after reaching requirement to outlet moisture content, just start polyreaction, described thinner is inertia alkane diluent, comprises the mixture of one or both and the above composition in the alkane of benzene,toluene,xylene, perhydronaphthalene or C6-C12.
2. preparation method according to claim 1, is characterized in that described post-transition metal catalyst system comprises: a) pyridine diimine part; B) methyl ethyl diketone salt compound or halide salt compound; Described promotor is the product of the partial hydrolysis of alkylaluminium cpd or alkylaluminium cpd; The ratio of the amount of substance of methyl ethyl diketone salt compound or halide salt compound and pyridine diimine part is 0.01 ~ 100; The ratio of the amount of substance of promotor and methyl ethyl diketone salt compound is 100 ~ 10000.
3. preparation method according to claim 1, it is characterized in that described catalyzer is homogeneous catalyst or heterogeneous catalyst, wherein the diameter of heterogeneous catalyst is between 100nm-50um, and the carrier be suitable for comprises and has specific surface area and be greater than 50m
2g
-1the metal oxide of high-specific surface area, nonmetal oxide, organism or its mixture.
4. preparation method according to claim 1, is characterized in that described comonomer is C
1-C
20alpha-olefin, can add or not add during polymerization.
5. preparation method according to claim 1, is characterized in that described polymerization temperature is-40-100 DEG C, polymerization pressure 1bar-21bar, and polymerization reaction time is 5min-2h, the horizontal 20-600g of hypergravity.
6. preparation method according to claim 2, it is characterized in that described methyl ethyl diketone salt compound is ferric acetyl acetonade or acetylacetone cobalt, halide salt compound is FeX
nor CoX
n, wherein n=2,3, X are F, Cl, Br, I; Described diimide ligand can prepare the ethene polymers of molecular weight 56-10000000g/mol by changing ligand structure.
7. preparation method according to claim 1, is characterized in that described thinner is toluene, dimethylbenzene, perhydronaphthalene, normal heptane or octane one or more combination.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| CN101130585B (en) * | 2006-08-25 | 2010-11-10 | 北京化工大学 | Method for preparing isobutylene isoprene rubber |
| CN101649012B (en) * | 2009-07-30 | 2011-06-29 | 浙江大学 | Catalyst system for ethylene polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| CN101130585B (en) * | 2006-08-25 | 2010-11-10 | 北京化工大学 | Method for preparing isobutylene isoprene rubber |
| CN101649012B (en) * | 2009-07-30 | 2011-06-29 | 浙江大学 | Catalyst system for ethylene polymerization |
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