CN102453157A - Catalyst system for preparing broad-peak/dimodal polyethylene in single reactor - Google Patents
Catalyst system for preparing broad-peak/dimodal polyethylene in single reactor Download PDFInfo
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Abstract
The invention relates to a catalyst system for preparing broad-peak/dimodal polyethylene in a single reactor, wherein the catalyst system belongs to a polymerization catalyst which is used for the macromolecular compound preparation and is obtained only through a carbon-carbon unsaturated bond reaction. The catalyst system is characterized in that the catalyst comprises a main catalyst and an assistant catalyst, wherein the main catalyst comprises a component a or a component b; the component a is a transition metal-containing complex with the molecular formula of R1R2R3MX, R1 is selected from C1-20 alkyl, R2 is selected from C1-20 alkoxy, R3 is selected from C1-20 aryl or arlyoxy, M is Ti or Zr, and X is a halogen atom; the component b is a transition metal compound with the general formula of MXn or MXn(OR)4-n, M is a transition metal Ti or Zr, X is halogen, and n is between 1 and 4; and the assistant catalyst is methyl siloxane (MAO) or triethyl aluminum (TEAL). The catalyst system for preparing broad-peak/dimodal polyethylene in the single reactor provided in the invention has the advantages of easily controlled production technology, realization of the obtaining of broad-peak/dimodal polyethylene resin products with uniform molecular weight distribution, saved investment of equipment for the polyethylene production, and low production cost.
Description
Technical field
The present invention is a kind of being used in single reaction vessel preparation wide/double peak catalyst of polyethylene system.Belong to the macromolecular compound preparation that only obtains and use polymerizing catalyst with the carbon-to-carbon unsaturated bond reaction.
Background technology
The working method of producing wide molecular weight or double peak weight distributing polyethylene resin mainly contains three types: melt blended method, multiple reactor method, single reactor method.Melt blended method is in the reactor drum of parallel connection, to produce the big and less polymkeric substance of relative molecular mass of relative molecular mass respectively, carries out melt blending then in proportion, thus the MWD of controlling polymers.The main drawback of this method is that mixture is difficult to mix, and gel particle content is high, and quality product is difficult to evenly.The multiple reactor method is to adopt two or more placed in-line reactor drums, with different polymerizing conditions, like hydrogen partial pressure difference, polymer temperature and asynchronism(-nization), change comonomer ratio, makes wide molecular weight distribution or bimodal distribution polymkeric substance.This method advantage is that the operation adjustment is flexible, and easy control of reaction system, shortcoming are that the use of staged reactor relates to tangible process efficiency and cost of capital.At present, domestic and international many companies adopt this method all successfully to realize suitability for industrialized production wide molecular weight distribution or bimodal polyethylene product.The Borstar technology of Borealis company with bimodal LLDPE of segmentation reacted and the HDPE that annular-pipe reactor combines with Gas-phase reactor, wherein adopts supercritical propane to make solvent in the annular-pipe reactor.Single reactor method is in single reaction vessel, to adopt monometallic or two or more metal active constituent catalyzer, utilizes active ingredient to have different polymerization behaviors, thereby obtains wide distribution or bimodal polyethylene resins.Compare with dual reactor process; Lower with the investment of single reactor production polyethylene with wide molecular weight distribution Technology, be easy to existing polyethylene device is undergone technological transformation, but catalyst costs is higher; Exploitation has great difficulty; Require catalyst system must control the activity of comonomer, in single reactor, produce the polyethylene with wide molecular weight distribution resin, mainly through adopting the different catalyst system to realize according to the size of molecular weight.U.S. UCC company utilize compound Ti-V and Zr-V catalyzer on vapor phase process Unipol process unit success first synthesize bimodal High molecular weight polyethylene product [US4918038].
In single reaction vessel; The method of early using Titanium series catalyst to produce wide (two) peak MWD polyvinyl resin is that US4264472 adopts titanium tetrachloride/organic magnesium compound catalystsystem; The catalyzer that this method adopts comprises: (1) organic titanic compound, TiCl4 or Ti (OR) aX4-a; (2) organic magnesium compound; (3) mixture of alkyl aluminum compound or organic magnesium compound.This is early to use Ziegler-Natta catalyst to produce the method for wide (two) peak MWD polyvinyl resin.The Vilaterm that this method is produced has the homogeneity and the processing characteristics of wide MWD, excellence, resin density 0.950-0.965g/cm
3, the MFR scope is between 5-105.The weak point of this method is that catalyst activity is low.US4301029 improves on this basis, adopts organic magnesium compound, or with organic aluminide complexing, with halo agent such as silicon halide RbSiX
4-bReact, or react, again with TiCl with etheride RCOX
4Active ingredient is processed in reaction.The density of pe that makes is greater than 0.940g/cm
3, needing improved is that the molecular weight of polyethylene for preparing distributes wide inadequately.
WO9834724 provides the production of a kind of employing Titanium series catalyst to have the poly novel method of bimodal distribution.This Preparation of catalysts technology comprises: (1) provides the slurry of the solid porous silicon-dioxide of non-polar solvent and band-OH group; (2) flood described silicon-dioxide with RMgR`, form midbody (i); (3) handle midbody (i) with tetracol phenixin, form product (ii); (4) handle product (ii) with titanium tetrachloride, form catalyst precursor; (5) this catalyst precursor is mixed this catalyst precursor of activation with the promotor dimethylaluminum chloride.The Vilaterm that makes with this catalyzer has bimodal or three peak shape MWD, and melt flow rate(MFR) is 20-70, and weak point is that MWD is narrower.US4387045 relates to the following catalyzer of employing: titanium tetrachloride, aluminum alkyls, organic magnesium compound, and this catalyzer has higher activity, and the molecular weight distribution of being produced (Mw/Mn) scope is at 4-20.US5258345 discloses a kind of Highh activity polyethylene catalysts system, and this catalystsystem is applicable to production of linear new LDPE (film grade) product.This catalystsystem comprises: organic magnesium compound (RMgR), organic silicide, titanium tetrachloride.The molten stream of polyethylene product that is worth by this method is than greatly between 20-45, weak point be molten stream than on the low side, MWD is narrower.
For there are deficiencies such as catalyst activity is not high, range of molecular weight distributions is narrower in the polyethylene with wide molecular weight distribution that remedies Titanium series catalyst production; Through adding another kind of metallide active ingredient, generally adopt Cr/Ti bimetallic catalytic system to carry out effective improvement.US5032562 provides a kind of catalyst system, and this catalyzer is made up of catalyst precursor and catalyst activator two portions: precursor is to load on the carrier by containing magnesium compound, zirconium thing and titaniferous compound or vanadium, and wherein magnesium compound is Mg (OR)
2, RMgR; Zirconium thing CpZrYnX
2-nTitaniferous compound TiCl
4, TiBr
4Vanadium compounds VOCl
3Or VCL
4Catalyst activator alkylaluminoxane: R
2Al-(Al-O) n-AlR
2, or linear aikyiaiurnirsoxan beta-(Al (R)-O) m-.This catalyzer has unique catalytic performance, the MDPE molecular resin amount wider distribution of production, and the MFR scope is at 50-300, and density is at 0.930-0.940; The HDPE product scope of producing is at 0.940-0.960, and the MFR scope is generally at 100-200.
US5274056, EP0553875 disclose a kind of catalyst system: (1) silicon titanium carrier: silicon components content is 80～100%, and titanium component content is at 1-20%, generally at 5-8%.(2) chromium component: tertiary butyl chromium, two luxuriant chromium etc., content is 0.05～5%, generally 0.5～2%; (3) acvator: diethylaluminum chloride, triethyl-boron, content are at 1～20mg/kg, generally at 3～12mg/kg.The molecular weight of polyethylene of producing distributes (Mw/Mn) scope 12～35, and optimum range is 18～25, and density of pe is at 0.90～0.91g/cc.
Be difficult to that fine silt in accurate control, the polymkeric substance is obvious especially, density, MI and the MWD of restive polymkeric substance yet use two kinds of catalyzer of chromium titanium often to run into reaction conditions simultaneously, substandard products are more, two kinds of catalyzer flow property and homogeneity differs problem such as bigger.To these problems, EP1153943 provides a kind of catalyst system, and chromium content is 0.1～5%, and chromium titanium weight ratio is 95: 5 to 5: 95, optimum range 80: 20 to 20: 80, and the molecular weight of polyethylene of production is distributed in 15～30, and density is 0.940～0.952.The Vilaterm that generates has the wide distribution of wide (two) peak, favorable uniformity.
Obtain in the bimodal polyethylene catalysis technique in the wide distribution of production, the someone uses the monometallic chrome catalysts.CN1050026, CN1050028 have proposed a kind of chromic compound polymerizing catalyst that contains and have produced the wide molecular weight distribution polyolefin method.This catalyzer is to produce catalyst precursor, again with the catalyst precursor thermal activation through deposition monokaryon chromic compound on dry inorganic oxide carrier.The characteristics of this catalyzer are to have higher activity, the thermal activation of the monokaryon chromic compound that need not to carry, and the MWD of polymkeric substance can keep constant higher value maybe possibly broaden basically.MWD (Mw/Mn) scope of the high-density polyethylene resin of producing is 5-20, and generally at 8-18, this series products is suitable for producing application such as blow-molded article, tubing and tough film.
In the chromium-based catalysts system, often use the chromium-based catalysts in alpha-olefine polymerizing to be chromium oxide-based catalyst, this type catalyzer can obtain high-molecular weight homopolymer and multipolymer, but molecular weight is difficult to control.US4918038 relates to the composition catalyst that uses a kind of halide metal compound, and that preparation has is wide/or the method for double peak weight distributing polyethylene.US5330950, US5408015 disclose a kind of Ziegler-Natta catalyst of magnesium oxide carrier and chromium oxide catalyst of adopting and have been mixed with the poly method with wide molecular weight distribution.US5399622 continues polymerization through adding a kind of promotor and metallocene catalyst then through bringing into use chromium oxide catalyst to obtain the new LDPE (film grade) particle.
CN1112371; The CN1209814 current research discloses a kind of have the polyethene method of wide molecular weight distribution and the catalyst system of use thereof; This catalystsystem by two kinds independently catalyzer constitute, comprising: (1) divalence chromated oxide on a kind of inorganic carrier; (2) two luxuriant chromium on the inorganic carrier.Distribution of polymer is greater than 15, and greater than 120, density polymer is between 0.955-0.964 than MFR for molten stream.
The method that US9828348, US9828349 provide a kind of production to have the polyethylene with wide molecular weight distribution resin, the catalyzer of use comprises: first kind of chromium-based catalysts is through reduction and reoxidize, and second kind of chromium-based catalysts through overactivation, restore.Vanadium series catalyst has unique effect in producing wide molecular weight or bimodal distribution Vilaterm technology, when using vanadium series catalyst, use simultaneously with the zirconium metal component.The active site of vanadium is associated with the catalyst performance of the polyethylene product of production wide molecular weight distribution, the zirconium activity be with other wide, generally be bimodal or other multimodal molecular weights distribute and are associated.The relative proportion of vanadium and zirconium influences poly MWD and catalytic activity, and vanadium zirconium ratio increases then active the raising usually, and MWD narrows down.CN1069033 discloses a kind of use vanadium and Zr catalyst system production wide molecular weight distribution or multimodal molecular weight distribution (or bimodal molecular weight distribution) polyolefine technology.This catalyst system is formed and is comprised: (1) zirconium thing, general formula Zr (OR)
2Cl
2(2) vanadium compounds, general formula VCl
4, VOCl
3, or titaniferous compound TiCl
4(3) promotor, three second butyl aluminium; (4) properties-correcting agent, RaCX
4-aWhen this catalystsystem of preparation; Require the zirconium thing at first to contact with solid carrier; And this carrier should not have residual catalytic metal settling maybe can cause the reaction that generates catalyst component or catalyzer before reacting with the zirconium thing, and catalyzer has only the two active sites that do not have magnesium effective constituent.Discover that different vanadium compounds roles is different.VCl
4Compare VOCl
3Wider molecular weight distribution is provided, VOCl
3Has high reaction activity and high.The effect that helps into agent is the reactive behavior that improves or keep vanadium catalyst, influences melting index and molten stream ratio.Catalyzer is responsive to hydrogen, is easy to control molecular weight.The HDPE resin that the wide or multimodal molecular weight that uses the Vilaterm of this Catalyst Production to be applied to high molecular weight film and blown film distributes.
US4935474; US4937299, US4530914 relate to employing zirconocene and two luxuriant titanium hybrid catalyst systems, and the characteristics of this catalyst system are to produce the Vilaterm of wide distribution and/or multimodal distribution; Dispersion index is between 3-8, and the polyvinyl resin of production comprises LLDPE and HDPE product.WO9215619 also adopts zirconocene and two luxuriant titaniums or other metallocene in slurry-phase reactor, to produce bimodal polyethylene.
CN1247875 provides a kind of composite metallocene catalyst vinyl polymerization preparation method, and catalyzer comprises: (1) Me (Ind) is ZrCl (Cp)
2(2) (CH
2CHCH
2CH
2Cp)
2ZrCl.Be characterized in that the Vilaterm of Catalyst Production has short-chain branch branching and wide molecular weight distribution thus, molecular weight distributing index is between 7-10.
CN1053676 relates to the following Primary Catalysts of employing: (1) two (fluorenyl) ethane dichloro and zirconium; (2) two (n-butyl cyclopentadienyl) dichloro closes zirconium.This catalyst system characteristic: first kind of metallocene is the metallocene that contains the bridging of fluorenyl; Second kind of metallocene is the metallocene of bridging not, and when polyreaction, first kind of metallocene produces higher molecular weight; The MWD of the polymeric articles of producing can reach 30 greater than 8 when preferred.
US5539066, US5587501 disclose the aluminum alkyls of a kind of metallocene and different structure and have produced the polyolefinic method of wide molecular weight.US5914289, EP0790259 disclose a kind of novel metallocene catalyst, and the catalyzer general formula is: (IndH
4)
2RMQ
2, Ind is an indenyl, R is C
1-C
4Alkylidene group, Q are alkyl, and M is Ti, Zr, Hf; The constitutional features of catalyzer is the racemize steric isomer.The HDPE product that this method is produced has wide molecular weight distribution, and resin has good physicals and processing characteristics.
US5539076 adopts following catalystsystem: (1) TiCl
4, VCl
4Or VOCl
3Organic magnesium compound; (2) bis cyclopentadienyl zirconium dichloride/MAO.This catalyzer is particularly suitable for fluidized-bed reactor, and the molecular weight of polyethylene dispersion index of production is at 2.5-60, and the per-cent of HMW part is at 50-60 in the resin, and poly density is between 0.930-0.955.CN1087300 also provides a kind of catalyst system (1) two (cyclopentadiene) dichloro to close zirconium; (2) TiCl
4(3) alkylaluminoxane.These catalystsystem characteristics are high molecular weight component and the methods of lower-molecular-weight component relative quantity that can control in bimodal molecular weight distribution or the wide molecular weight distribution resin.
US5747405 is with TiCl
4Close zirconium and load on the magnesium chloride support with two (3-propenyl-cyclopentadiene) dichloro; Be characterized in that the metallocene active constituent loading is on inorganic oxide or muriate; Need not use alkylaluminoxane to make carrier, can prevent metallocene compound under certain conditions (like slurry process) parse from carrier.This method synthetic distribution of polymer broad, dispersion index are suitable for and make goods such as high strength linepipe, blowing between 7-180.It is a kind of from loading type mixed catalyst olefin polymerization catalysis patent that CN1413222 provides; Catalyzer contains Ziegler-Natta component and metallocenes; Wherein metallocenes is attached to the Ziegler-Natta component; In this composite catalyst, Ziegler-Natta includes the solid complex of magnesium, transition metal and alkoxide.This catalyzer is characterised in that and adopts Ziegler-Natta component self to serve as carrier; The performance of catalyzer reaches optimization through the selection of the ratio of selection, metallocene and the Ziegler-Natta component of metallocene; Can prepare HDPE, MDPE and LLDPE resin; The molten stream of polymkeric substance is than between 30-500, and dispersion index is between 5-75.
When adopting Ziegler-Natta and metallocene catalyst system production wide molecular weight distribution or bimodal distribution polyvinyl resin, there is different defects separately.Ziegler-Natta catalyst is the physical properties that is difficult to control synthetic polymer; Specific activity metallocene catalyst active much lower; And the problem that metallocene catalyst system exists is the ratio height of alkylaluminoxane promotor and metallocene; Use the polymkeric substance of metallocene catalysts to be difficult to handle, and lack many ideal physical propertiess owing to single identical polyreaction site makes polymkeric substance.Use Ziegler-Natta catalyst or use metallocene catalyst all can not generate gratifying wide molecular weight distribution or bimodal distribution polyvinyl resin.
In sum, also there is following deficiency in of the prior art being used in single reaction vessel preparation wide/double peak catalyst of polyethylene system:
1. the Titanium series catalyst that adopts must adopt " double-reactor series connection " technology, has increased facility investment, controls complicacy, causes the raising of production cost.
2. have the supported catalyst of two or more active ingredient through preparation, be implemented in the polymerization of polyethylene with wide molecular weight distribution in the single reaction vessel, production technique is wayward, and what obtain is actually MWD polyethylene mixture far from it.Be difficult to obtain the polyethylene product of even molecular weight distribution, and then influence the quality of polyethylene products.
Summary of the invention
The objective of the invention is to avoid above-mentioned weak point of the prior art; And a kind of wide/double peak MWD polyvinyl resin that can in single reaction vessel, prepare is provided; Production technique is easy to control; Can access the wide/double peak MWD polyvinyl resin product of even molecular weight distribution, increase substantially the performance of polyethylene products, and low being used in single reaction vessel preparation wide/double peak catalyst of polyethylene system of polyethylene production low equipment investment, production cost.
The object of the invention can reach through following measure:
Of the present invention being used for comprises main body catalyzer and cocatalyst in single reaction vessel preparation wide/double peak catalyst of polyethylene system, it is characterized in that:
A. the main body catalyzer comprises component a or b, wherein:
A. be a kind of transition metal complex that contains, molecular formula is: R
1R
2R
3MX
In the formula, R
1Be selected from C
1-20Alkyl, R
2Be selected from C
1-20Alkoxyl group, R
3Be selected from C
1-20Aryl or aryloxy, M is Ti or Zr; X is a halogen atom;
B. be that a kind of general formula is MXn or MXn (OR)
4-nTransistion metal compound,
In the formula, M is titanium or zirconium transition metal
X is a halogen, n=1-4
B. cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
The high activated catalyst that can be used for wide (two) peak MWD polyethylene production in the industrial production mainly is that traditional titanium system and chromium is high-effective carrier catalyst.Adopt Titanium series catalyst to produce wide (two) peak MWD Vilaterm and must adopt " double-reactor series connection " technology; The advantage of the wide distribution polyethylene resin of employing reactor drum polyphone explained hereafter is to obtain through the operational condition of regulating and control each reactor drum the rosin products of property; But obvious this method has increased facility investment and running cost; Brought the loss of production efficiency, adopted several reactor drums to produce also simultaneously and can bring difficulty to production control.
Can be employed in the production that realizes polyethylene with wide molecular weight distribution in the single reaction vessel, the supported catalyst that mainly has two or more active ingredient through preparation.The most representative is the composite catalyst of Ziegler-Natta catalyst and metallocene.The shortcoming of this type catalyzer is that what to obtain sometimes is not the polymkeric substance of single a kind of wide distribution; But by the polymerization catalyst of two kinds of catalytic properties obtain distributed pole polymeric blends inequality; The mixture of this heterogencity can bring adverse influence to final material properties; The active site of in fact this catalystsystem does not act synergistically, but works respectively according to characteristic separately.Especially two kinds of catalyzer are difficult to coordinate aspect copolymerization performance, and this brings great difficulty with regard to giving the control of producing.
When catalyst system of the present invention is used for vinyl polymerization,, can realize that through the proportioning of adjustment catalyzer molecular weight of polyethylene distributes easily, in single reactor, realize producing wide/double peak MWD polyvinyl resin.
The object of the invention can also reach through following measure:
The wide/double peak catalyst of polyethylene system that in single reaction vessel, prepares of the present invention is characterized in that:
A. the main body catalyzer comprises said component a and b,
B. said cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
It is optimized technical scheme.
The wide/double peak catalyst of polyethylene system that in single reaction vessel, prepares of the present invention is characterized in that:
A. the main body catalyzer comprises said component a,
B. said cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
Component a loaded on obtains catalyzer on the inert solid carrier,, can also prepare the Vilaterm of wide/double peak MWD.
The wide/double peak catalyst of polyethylene system that in single reaction vessel, prepares of the present invention is characterized in that:
A. the main body catalyzer comprises said components b,
B. said cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
Components b loaded on obtains catalyzer on the inert solid carrier,, can also prepare the Vilaterm of wide/double peak MWD.
The wide/double peak catalyst of polyethylene system that in single reaction vessel, prepares of the present invention is characterized in that the molar ratio of said main body catalyst component and cocatalyst component is: main body catalyzer: cocatalyst=1: 5～50.
The wide/double peak catalyst of polyethylene system that in single reaction vessel, prepares of the present invention is characterized in that the molar ratio of said main body catalyzer a and b is: a: b=1: 5～50.
Disclose a kind of preparation method who is used at the main body catalyst component of single reaction vessel preparation wide/double peak catalyst of polyethylene system of the present invention below, it is characterized in that comprising the steps:
1.. the carrier pre-treatment
With a certain amount of anhydrous MgCl
2Carrier disperses with hexane, adds a small amount of titan-alkoxide and fully disperses, and reacts 30～90 minutes under 70～90 ℃ of temperature, adds the ethanol activation, reacts after 1-5 hour, and is subsequent use;
2.. the preparation of main body catalyst solution
With main body catalyzer a or b or a and b, be dissolved in ethylene dichloride CH
2Cl
2In the solvent,
3.. with the main body catalyst cupport on carrier
The main body catalyst solution that 2. step is prepared adds in the carrier dispersion liquid that 1. step is handled; Behind back flow reaction 2～3h; With hexane wash 3～4 times; Dry under the N2 protection, obtain of the present invention being used in single reaction vessel preparation wide/double peak catalyst of polyethylene polyethylene catalysts main body component.
The method of use that is used in single reaction vessel preparation wide/double peak catalyst of polyethylene system of the present invention is characterized in that comprising the steps:
1.. catalyzer feeds intake
In 1000 milliliters of polymerization reaction kettles that have a whipping appts, drop into the dry hexane of crossing of 250mL, cocatalyst TEAL or MAO5～10 grams; Stir; Then, stir down, main body catalyzer 30mg～100mg is poured in the reaction kettle with hexane; Hexane with 50mL washes down again, drops into the vinyl monomer polymerization fully;
2.. polymerization
1. drop in the reaction kettle of catalyzer to step, feed vinyl monomer, keep ethylene pressure constant, the pressure of ethene is respectively 0.1MPa and 0.8MPa during polymerization, at 70 ℃ of following isothermal reaction 1h; Stopped reaction after logical water coolant is reduced to normal temperature, adds the small amount of hydrochloric acid termination reaction, adds excess ethyl alcohol again and stirs, and filters water, washing with alcohol successively, 60 ℃ of following vacuum-drying 2h, weighing resulting polymers.
Of the present invention being used in single reaction vessel preparation wide/double peak catalyst of polyethylene system, comparing prior art has following positively effect:
1. provide a kind of and can in single reaction vessel, prepare wide/double peak MWD polyvinyl resin; Production technique is easy to control; Can access the wide/double peak MWD polyvinyl resin product of even molecular weight distribution; Increase substantially the performance of polyethylene products, and low being used in single reaction vessel preparation wide/double peak catalyst of polyethylene system of polyethylene production low equipment investment, production cost.
2. a kind of preparation method who is used at the main body catalyst component of single reaction vessel preparation wide/double peak catalyst of polyethylene system of the present invention is provided,
3. a kind of method of use that is used in single reaction vessel preparation wide/double peak catalyst of polyethylene system of the present invention is provided,
4. it is big to have solved in the prior art facility investment, controls complicacy, the problem that production cost is high.
5. obtain the polyethylene product of the wide and even molecular weight distribution of MWD easily, and then high-quality wide/double peak Vilaterm raw material truly is provided for the manufacturing of high-quality polyethylene products.
Description of drawings
Fig. 1 adopts the catalyzer synthetic polymkeric substance GPC of institute spectrogram of the present invention
Embodiment
The present invention below will combine embodiment to make further detailed description:
Prepare the main body catalyst component that is used in single reaction vessel preparation wide/double peak catalyst of polyethylene system of the present invention according to following steps:
1.. the carrier pre-treatment
With the anhydrous MgCl of 100 grams
2Carrier disperses with hexane, adds a small amount of titan-alkoxide and fully disperses, and reacts 30～90 minutes under 70～90 ℃ of temperature, adds the ethanol activation, reacts after 2 hours, and is subsequent use;
2.. the main body Preparation of catalysts
Get component a{2-[1-(2,6-diisopropyl phenyl imines) methyl] pyridine } zirconium chloride is at 30mLCH
2Cl
2Stirring and dissolving under the middle normal temperature splashes into components b TiCl
4(5mmol), solution changes yellow and with the part yellow mercury oxide, be warming up to 50～60 ℃ stir 1h and fully react after, drying under reduced pressure is again with 10mL ether washing drying.Product is the yellow solid powder.
3.. with the main body catalyst cupport on carrier
The main body catalyst solution that 2. step is prepared adds in the carrier dispersion liquid that 1. step is handled, behind back flow reaction 2～3h, with hexane wash 3～4 times, at N
2Protection is dry down, obtains of the present invention being used in single reaction vessel preparation wide/double peak catalyst of polyethylene polyethylene catalysts main body component.
The present invention adopts the polymerisation process of above-mentioned catalyzer following: 1000mL the go into dry hexane of crossing of 250mL and a certain amount of TEAL auxiliary agents such as (or) MAO that has stirring that pack into stirred; Loaded catalyst about 30mg is poured system; Hexane with 50mL washes down again; Feed ethylene gas, keep ethylene pressure constant.The pressure of ethene is respectively 0.1MPa and 0.8MPa during polymerization, at 70 ℃ of following isothermal reaction 1h.Stopped reaction after logical water coolant is reduced to normal temperature, adds the small amount of hydrochloric acid termination reaction, adds excess ethyl alcohol again and stirs, and filters water, washing with alcohol successively, 60 ℃ of following vacuum-drying 2h, weighing resulting polymers.
The result of each embodiment sees table 1.
Adopt components b to make catalyzer, add the vinyl polymerization result that MAO does promotor.
Embodiment 2
Adopt components b to make catalyzer, add the vinyl polymerization result that TEAL does promotor.
Embodiment 3
Adopt component a and b to make catalyzer, add the vinyl polymerization result that MAO does promotor.
Adopt component a and components b to make catalyzer, add the vinyl polymerization result that TEAL does promotor.
Adopt component a and components b to make catalyzer, add the vinyl polymerization result that MAO does promotor.
Adopt component a and components b to make catalyzer, add the vinyl polymerization result that TEAL does promotor.
The different promotors of table 1 are to the polymerization activity influence of titanium complex
Claims (8)
1. one kind is used for comprising main body catalyzer and cocatalyst in single reaction vessel preparation wide/double peak catalyst of polyethylene system, it is characterized in that:
A. the main body catalyzer comprises component a or b, wherein:
A. be a kind of transition metal complex that contains, molecular formula is: R
1R
2R
3MX
In the formula, R
1Be selected from C
1-20Alkyl, R
2Be selected from C
1-20Alkoxyl group, R
3Be selected from C
1-20Aryl or aryloxy, M is Ti or Zr; X is a halogen atom;
B. be that a kind of general formula is MXn or MXn (OR)
4-nTransistion metal compound,
In the formula, M is titanium or zirconium transition metal
X is a halogen, n=1-4
B. cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
2. according to the preparation wide/double peak catalyst of polyethylene system in single reaction vessel of claim 1, it is characterized in that:
A. the main body catalyzer comprises said component a and b,
B. said cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
3. according to the preparation wide/double peak catalyst of polyethylene system in single reaction vessel of claim 1, it is characterized in that:
A. the main body catalyzer comprises said component a,
B. said cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
4. according to the preparation wide/double peak catalyst of polyethylene system in single reaction vessel of claim 1, it is characterized in that:
A. the main body catalyzer comprises said components b,
B. said cocatalyst is methylsiloxane MAO or triethyl aluminum TEAL.
5. according to the preparation wide/double peak catalyst of polyethylene system in single reaction vessel of claim 1, it is characterized in that the molar ratio of said main body catalyst component and cocatalyst component is: main body catalyzer: cocatalyst=1: 5～50.
6. according to the preparation wide/double peak catalyst of polyethylene system in single reaction vessel of claim 1, it is characterized in that the molar ratio of said main body catalyzer a and b is: a: b=1: 5～50.
7. the preparation method who is used for preparing at single reaction vessel the main body catalyst component of wide/double peak catalyst of polyethylene system of a claim 1 is characterized in that comprising the steps:
1.. the carrier pre-treatment
With a certain amount of anhydrous MgCl
2Carrier disperses with hexane, adds a small amount of titan-alkoxide and fully disperses, and reacts 30～90 minutes under 70～90 ℃ of temperature, adds the ethanol activation, reacts after 1-5 hour, and is subsequent use;
2.. the preparation of main body catalyst solution
With main body catalyzer a or b or a and b, be dissolved in ethylene dichloride CH
2Cl
2In the solvent,
3.. with the main body catalyst cupport on carrier
The main body catalyst solution that 2. step is prepared adds in the carrier dispersion liquid that 1. step is handled; Behind back flow reaction 2～3h; With hexane wash 3～4 times; Dry under the N2 protection, obtain of the present invention being used in single reaction vessel preparation wide/double peak catalyst of polyethylene polyethylene catalysts main body component.
8. the method for use that is used for preparing at single reaction vessel wide/double peak catalyst of polyethylene system of claim 1 is characterized in that comprising the steps:
1.. catalyzer feeds intake
In 1000 milliliters of polymerization reaction kettles that have a whipping appts, drop into the dry hexane of crossing of 250mL, cocatalyst TEAL or MAO5～10 grams; Stir; Then, stir down, main body catalyzer 30mg～100mg is poured in the reaction kettle with hexane; Hexane with 50mL washes down again, drops into the vinyl monomer polymerization fully;
2.. polymerization
1. drop in the reaction kettle of catalyzer to step, feed vinyl monomer, keep ethylene pressure constant, the pressure of ethene is respectively 0.1MPa and 0.8MPa during polymerization, at 70 ℃ of following isothermal reaction 1h; Stopped reaction after logical water coolant is reduced to normal temperature, adds the small amount of hydrochloric acid termination reaction, adds excess ethyl alcohol again and stirs, and filters water, washing with alcohol successively, 60 ℃ of following vacuum-drying 2h, weighing resulting polymers.
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| CN113087999A (en) * | 2021-05-13 | 2021-07-09 | 浙江大学 | Method for efficiently preparing high-performance polyolefin blend by single-reactor two-stage process |
| CN113480578A (en) * | 2021-06-23 | 2021-10-08 | 浙江大学 | (alpha-diimine) nickel complex compositions and uses thereof |
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