Method for scouring of blast furnace, two-component immobilized catalyst for ethylene polymerization, method for production the same (variants), and method for production of polyethylene using this catalyst
FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.
SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.
EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.
7 cl, 5 tbl, 27 ex
The invention relates to the field of chemical industry, in particular to the creation of more efficient new two-component (binary) heterogeneous supported catalysts for the polymerization of ethylene.
It is known that modern highly active catalytic systems based on metallocene catalysts produce polymers, in particular polyethylene with narrow molecular mass distribution (MMD), which creates significant problems during their processing.
To improve processing AIDS polyolefins have resorted to the method of expansion of the mold by mixing melts of polymers with different molecular mass (MM), which leads to significant energy cost.
A more convenient method is the so-called “reactor blend”, which allows on-stage polymerization be used to obtain polymers with good rheological properties of the mixture one-catalysts, or a combination of one-and conventional catalyst of Ziegler-Natta [Cho H.S., Choi Y.H., Lee W.Y. Characteristics of ethylene polymerization over Ziegler-Natta/metallocene catalysts comparison between hybrid and mixed catalysts. Catal. Today 2000, v.63, p.523-530; Margues M.F.W., Pombo C.C., R.A. Silva, A. Conte Binary metallocene supported catalyst propylene polymerization. Eur.Polymer J., 2003, v.39, p.561-567; Application WO 03/029303, C 08 F 4/64, 10.04.2003].
Known catalysts for polymerization of ethylene and copolymerization with α -olefins, comp is Jamie from supported on a carrier, for example SiO2, catalyst of Ziegler-Natta (“early” metal), and then added to it based complex methylalumoxane (MAO) and tridentate connection FeCl2(later metal). As a result of mixing, under certain conditions, the obtained powder caused the catalyst used for the polymerization and copolymerization. The resulting polymer has a MMD (Mw/Mn)=28,5 [Application WO 99/12981, C 08 F 4/70, C 07 D 213/53, C 07 F 15/02, 18.03.1999].
Also known catalyst consisting of a mixture deposited on SiO2or Al2O3or MgCl2or other media tridentate nitrogen-containing bis(imino)pyridinium Fe or Co complex and catalyst of the Ziegler-Natta or metallocene, or deposited CR-oxide catalysts for polymerization and copolymerization α -olefins. [Application WO 00/69869, C 07 F 15/00, 15/02, 15/06; C 08 F 10/00, 4/64, 4/68, 12.04.2000].
The closest in technical essence is a catalytic system consisting of compounds of the earlier metal (Ti, Zr, Hf) with the appropriate ligand and connections “late” metal (Ni, Fe, Pd) with the corresponding ligand with nitrogen skeleton, which is applied on the pre-optimally prepared media, such as SiO2with the subsequent addition of the activator, preferably in the presence of monomer [Application WO 98/38228, C 08 F 4/44, 17.07.2001].
2(3.2· 10-6mole) and dicyclopentadienyl zirconium chloride (0.17· 10-6mole), i.e. the percentage of Ni (χNimixed with Zr is 0.95; methylalumoxane (MAO)/Σcat=4450:1, mol/mol; activity = 39640 kg/molcat·MPa· hour; number of CH3/1000C=21. Example # 2: Tn=40° S; MAO/Σcat=3220:1; χNi=0,87; activity - 5000 kg/molcat·MPa· h; CH3/1000C=12.
The main disadvantages of the prototype are no claimed in the claims of the examples on the polymerization of ethylene in the composition of the catalysts, annenih to the media, that would give the opportunity to evaluate the economic value of a patent (the course of polymerization at elevated temperatures >50° With; no data on the molar ratio of MAO to the mixture of catalyst when applied, as in the above examples of homogeneous mixtures it is too high and is equal to ~4000:1), and confirm the purpose of the invention: receiving branched polymers in the absence of co monomer in real industrial conditions.
In the published literature, we were unable to identify articles and patents describing the applied catalytic system based on binary mixtures of complexes “late” metals with ligands with nitrogen skeleton.
The invention solves the problem of synthesis deposited on the silicon dioxide catalysts based on binary mixtures of complexes “late” metals with ligands with nitrogen skeleton, allowing real conditions using only ethylene to obtain a wide grade range of polyethylenes (PE) with different MM and MMD, including short-chain branches.
The task is solved in that as complexes “late” metals using bis(imino)peredelnyj complex of ferric chloride (I) and bis(imino)acenaphtylene complex of Nickel bromide (II) the following structures:
where (I) R1=qi is logical, R2=R3=CH3; (II) R1=cyclopentyl, R2=R3=CH3and methylalumoxane.
As a substrate (carrier) use silicon dioxide SiO2brand Davison 952W".
The ratio of the molar fractions of iron molar fractions of Nickel is 1:1-1:9.
If the mixture of complexes the iron content is greater than the Nickel content, the activity of the catalyst increases, but at the same time short-chain branching of the resulting polyethylene is reduced. With a ratio higher than 1:9, short-chain branching of the obtained polyethylene increases, but it decreases the activity of the catalyst.
The catalyst according to the invention is prepared by three variants of the method.
In the first embodiment, it is prepared by applying to a substrate a homogeneous mixture of complexes of late transition metals, such as bis(imino)peredelnyj complex of ferric chloride and bis(imino)acenaphtylene complex of Nickel bromide.
The second option on the substrate alternately put bis(imino)peredelnyj complex of ferric chloride, and then bis(imino)acenaphtylene complex of Nickel bromide, or Vice versa.
By the third variant it is prepared by displacement of the individually deposited on a substrate complexes.
As solvents during the application of the catalyst using toluene and n-hexane.
As socata is isatori when applying use MAO.
Suspension polymerization of ethylene is carried out at a pressure of 0.3-1.0 MPa and a temperature of 50-80° C.
As solvents in the polymerization using n-hexane, n-heptane, gasoline and other
Polymerization of ethylene depending on the method of preparation of binary deposited catalyst is carried out in the presence of socializaton - aluminiumresistant (Al[i-C4H9]3or without it.
Below are examples illustrating the invention.
Preparation of the substrate is silicon dioxide.
Preparation of SiO2for applying conducted according to the standard technique: annealed SiO2at 650° C for 4 h in an atmosphere of inert gas argon. The thus prepared carrier material is stored in sealed vials in a desiccator.
Preparation of a mixture of silicon dioxide with methylalumoxane.
Prior to application of the SiO2Tegaserod from the remnants of the air (oxygen) for 1 h at room temperature (troomsby degassing. In all methods of application of the catalyst used SiO2with pre-applied to its surface MAO based 10-18 wt.% Al. For example, in the case of application of MAO (10 wt.% Al) to 1.0 g of SiO2added 0.27 g of a 10%solution of MAO in toluene (F. Witco), which corresponds to 3.1 ml or 4,65· 100-3they say the, then add 7 ml of toluene; when applied at 1.0 g SiO215-18 wt.% Al type of 0.47 g of a 10%solution of MAO in toluene (5.4 ml or 8.1· 10-3mole) and 5 ml of toluene.
Applying the calculated amount of MAO carried out in an inert atmosphere at troomsin a two-neck glass flask with a magnetic stirrer for 3 hours and Then a mixture of SiO2+MAO (SMAO) freed from toluene by vacuum at troomsand washed twice with toluene excess (nenalezena) MAO. The number of MAO in the washing solution of toluene determined by the method of Fourier spectroscopy characteristic absorption band at ~1200 cm-1. After the first washing of the carrier is washed with a small amount of MAO. After a second washing step, the amount of applied MAO saved. Next, perform a final drying SMAO vacuum with stirring. Preparation SMAO carried out before each synthesis deposited catalyst.
Synthesis of deposited catalyst Unit based on 2,6-bis-[1-(2,4-dimethyl-6-cyclohexylaniline)ethyl] pyridine iron chloride (I).
In dvuhgolosy flask containing 0,57 g SMAO in an inert atmosphere at troomsadd 3.2 mg I and 5 ml of toluene. The application I spend for 1 h with constant stirring (trooms). When the molar ratio of MAO: I was 640:1. Drying spend vakuumirovat the receiving (t rooms) to constant weight. Get 0,573 g of dry deposited catalyst In containing 4,9· 10-6mole of catalyst I.
Example 4. (control).
Polymerization of ethylene in the deposited catalyst Unit.
The polymerization of ethylene is carried out in a steel autoclave equipped with a stirrer, a capacity of 150 ml, in which load 44 ml of n-hexane, to 0.73 ml (1,1· 10-4mole) of a solution of [Al(i-C4H9)3] and 0,1328 g In 5 ml n-hexane. Al(i-C4H9)3/Fe(In)=100:1, mol/mol.
The polymerization is carried out at 70° at a pressure of ethylene of 0.3 MPa. The interrupt process by adding to the reaction mixture ethyl alcohol. The resulting suspension of polymer is filtered and dried in vacuum at 60° C. the Yield of polyethylene (PE) 18,1 g; activity 54850 kg PE/molcat·MPa· h; [η ]=3,98 DL/g; Mv=419· 103; ρ =966,5 kg/m3; TPL=139,5°; Δ NPL=186,69 j/g; CH3/1000C=0,3.
Synthesis of deposited catalyst N on the basis of [1,2-bis-(2-cyclopentyl-4,6-dimethylphenylimino)acenaphthen]bromide Nickel II.
In dvuhgolosy flask containing 0.8 g SMAO in an inert atmosphere, add 7 ml of toluene at 0° and 5.3 mg II. Drawing II is carried out at constant stirring for 1 h at 0° C. and Then vacuum to remove toluene (trooms), the residue is again cooled to 0° With, dobavlaut 5 ml n-hexane and 0.3 ml (0,0263 g) of a 10%solution of MAO in toluene and at 0° C and stirring is applied MAO for 1 h Σ MAO/II=620:1. Drying N hold up to constant weight by vacuum from the solvent. 1 g of deposited catalyst N contains 8,5· 10-6mole of catalyst II.
Example 6. (control).
Polymerization of ethylene at N.
The polymerization is conducted according to example 4, but at 50°; hitch N equal 0,1357 g; socialization (Al(i-C4H9)3- no. The output of the PH of the remaining 9.08 g, activity - 25500 kg PE/molcat·MPa· h; [η ]=to 4.0 DL/g; Mv=280· 10-3; ρ =933 kg/m3; TPL=123,6°; Δ NPL=118,4 j/g; CH3/1000C=16,9.
Synthesis of deposited catalyst N on binary mixtures I and II (the first method).
To 1.8 g SMAO in an inert atmosphere at 0° add to 6.3 mg (9,56· 10-6mole) of I and 7.4 mg (becomes 9.97· 10-6mole) II catalyst and 10 ml of toluene, with stirring and in the course of 1 h at 0° To carry out the application of binary mixtures I and II. Then the resulting mixture is freed from toluene by vacuum at trooms, cooled again to 0° C. Σ MAO/Σ cat=525:1, mol/mol. Final drying of the obtained catalyst N conduct the evacuation of n-hexane under stirring at trooms1 g of deposited catalyst N contains 7.5 mg of a mixture of I and II or 3.4 mg (5,19· 10-6mole) of I and 4.1 mg (5,42·10 -6mole) II.
The percentage of iron χFe=[Fe]/([Fe]+[Ni])=0,49; (χNi=0.51).
Polymerization of ethylene at N.
The polymerization catalyst N conducted according to example 6, but under the conditions shown in table 1. The table shows also the results obtained.
|No. Ave||Solvent||The number N, g||Tfloorthat °||Output PE, g||Activity, kg/ molcat·MPa· h||The properties of the polymer|
|[η ], DL/g||Mv, 10-3||MP., °||CH3|
|11**||N gasoline||0,1763||80||6,2||11051||the 3.8||394,0||140,0||4,5|
|*Socialization - Al(i-C4H9)3; Al/Fe(N)=100:1. **pe=0.1 MPa.|
Synthesis of deposited catalyst IV on binary mixtures of I and II catalysts (first option).
The synthesis is carried out in conditions of synthesis catalyst N, but put on SMAO (1.0 g) 0.2 mg I and 2.2 mg II.
1 g of deposited catalyst contains 3· 10-7mole and I 2,85· 10-6mole II, ie χFe=0,10; χNi=0,90.
Polymerization of ethylene on the catalyst IV.
The polymerization is conducted on the catalyst IV in example 6, but in the conditions shown in table 2. The results obtained are also shown in table 2.
|No. Ave||The number IV, g||Tfloor.that °||Output, g||The properties of the polymer|
|[η ], DL/g||Mv·10-3||MP., °||Δ H, j/g|
|13||0,2000||50||3,5||18518||4,8||560, 0m||to 130.6||137,4||12,2|
|14||0,1542||70||4,3||29861||6,0||773,0||110; 130, 8mm||120,0||19,5|
Synthesis of deposited catalyst vHfor binary mixtures I and II catalysts (the second option).
To 1,38 g SMAO add 5.2 mg I in 8 ml of toluene and within 1 h in an inert atmosphere at troomswith constant stirring is applied to the substrate. Then at troomsvaccum toluene, the mixture is cooled to 0° add 5.6 mg II 8.0 ml of toluene and continue drawing II at 0° C for 1 h after the time of deposition of newly vacuum at troomsremove the toluene, and then at 0° add 0.3 ml of 10%solution of MAO in toluene (0,026 g) and 8 ml of n-hexane. The mixture was stirred at 0° C for 1 h Drying of the catalyst vHcarried out in vacuum at troomsunder stirring to constant weight.
1 g of deposited catalyst contains 1,08· 10-5mole of the mixture of I and II catalysts. Σ MAO/Σ cat=520:1, mol/mol, where χFeor =0.51; χNi=0,49.
Polymerization catalyst v H.
The polymerization is conducted according to example 4, but in the conditions shown in table 3. The results obtained are also shown in table 3.
|No. Ave||The number of the VH, g||Tfloor.,°||PeMPa||Output, g||The properties of the polymer|
|[η ], DL/g||Mv·10-3||MP., °||Δ H, j/g|
|*The solvent is n-heptane.|
Synthesis of deposited catalyst VI on binary mixtures of I and II catalysts (the second option).
Synthesis is carried out under the conditions of preparation of the catalyst of the VH, but the first to SMAO (1,23 g) put rolled the ATOR II (5.0 mg), and only then I (conditions of application II and I described in the synthesis of the VH catalyst).
1 g of deposited catalyst contains 1,06· 10-5mole binary catalyst I and II. MAO/Σ cat=534:1; χFe=0,50; χNi=0,50.
Polymerization of ethylene on the catalyst VI.
The polymerization is conducted according to example 4, but in the conditions shown in table 4, which also shows the results.
Synthesis of deposited catalyst vII in binary mixtures and In N catalysts (third option).
Synthesis is carried out by mixing the individual supported catalysts In and N based catalysts I and II (examples 3 and 5). The mixing is carried out before each polymerization in an ampoule.
Polymerization of ethylene on the catalyst VII.
The polymerization is conducted according to example 4, but in the conditions shown in table 5. This table also shows the results.
When comparing results obtained by polymerization of ethylene in two-deposited catalysts synthesized three variants of the method, we can note the following points:
1. The highest activity was observed for catalysts obtained by the first and third variant of the method of application (N and VII catalysts). PR is than for systems obtained using the third variant of the method of application (VII), the polymer yield is higher than the total (additive) output obtained at the individual components of the mixture of catalysts In and N. This result indicates that in a binary mixture of one catalytic component reinforces the other.
2. Regardless of the method of applying catalysts are able to regulate the short-chain branched polyethylenes obtained. The largest branching from the experiments, where the specific content of complex II on the surface of the carrier χNi=0,8-0,9, and IV and VII the catalyst is a high activity, despite a small fraction of the more active component of the catalyst.
3. When the temperature of polymerization up to 80° With activity and catalysts MM and the resulting polymers are retained at a high level.
1. Two-deposited catalyst for polymerization of ethylene, consisting of a mixture of transition metal complexes, alumoxane and the substrate, characterized in that the catalyst comprises a transition metal complexes of bis(imino)peredelnyj complex of ferric chloride and bis(imino)acenaphtylene complex of Nickel bromide.
2. Two-deposited catalyst according to claim 1, characterized in that the ratio of the molar fractions of iron mole is m fractions of Nickel is 1:1-1:9.
3. Two-deposited catalyst according to claims 1 and 2, characterized in that the substrate it contains silicon dioxide.
4. Method of preparation of two-component deposited catalyst for polymerization of ethylene, characterized in that it is prepared by applying to the silicon dioxide of a homogeneous mixture of transition metal complexes, such as bis(imino)peredelnyj complex of ferric chloride and bis(imino)acenaphtylene complex of Nickel bromide.
5. Method of preparation of two-component deposited catalyst for polymerization of ethylene, characterized in that silicon dioxide alternately put bis(imino)peredelnyj complex of ferric chloride, then bis(imino)acenaphtylene complex of Nickel bromide, or Vice versa.
6. Method of preparation of two-component deposited catalyst for polymerization of ethylene, characterized in that it is prepared by mixing the individually deposited on the silicon dioxide complexes, namely bis-(imino)peredelnogo complex of ferric chloride and bis(imino)acenaphtylene complex of Nickel bromide.
7. A method of producing polyethylene, characterized in that the polymerization process is carried out in the presence of a catalyst according to any one of claims 1 to 3.
in which R are, independently of one another, identical and denote C1-C40alkyl; X is, independently from each other, equal or different and denote C1-C40alkyl; M is, independently of one another, identical or different and denote an element of IIIa, IVa, Va group of the Periodic system of elements, provided that one M is boron, a is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl - cation or compound Quaternary ammonium, and a is an integer from 0 to 10, b is an integer from 0 to 10, C is an integer from 0 to 10 and a = C; d is 1; j is an integer from 1 to 3