Catalyst for polymerization of alpha-olefins

专利摘要:
1502567 Complexes MONTEDISON SpA 24 March 1976 [28 March 1975] 11917/76 Heading CIA [Also in Divisions C2 C3 and B1] Novel complexes of the formula wherein M = Mg, Mn and/or Ca; m = from 0À5 to 2; M<SP>1</SP> = Ti, V or Zr; X = Cl, Br or I; Y=one or more of halogen or halogen and oxygen, in an amount to satisfy the valence of M<SP>1</SP>; and are prepared by reacting a halide MX 2 at from room temperature to 150‹ C. with a compound M'Y in POCl 3 as solvent. The reaction may also be carried out in another solvent E selected from an ester of an organic carboxylic acid, an alcohol, an ether, an amine, an ester of carbonic acid, a nitrile, a phosphoramide or an ester of phosphoric or phosphorous acid to produce the complex and an excess of POQ 3 added to the complex or to a solution thereof in the solvent E to replace the substituent E by POCl 3 . Exemplified is the preparation of MgTiCl 6 .5POCl 3 .
公开号:SU1075949A3
申请号:SU762337707
申请日:1976-03-26
公开日:1984-02-23
发明作者:Джаннини Умберто；Альбидзати Энрико；Пароди Сандро；Пириноли Франко
申请人:Монтэдисон С.П.А. (Фирма)；
IPC主号:

专利说明:

The invention relates to the catalysis of trade for the polymerization and copolymerization of olefins and can be used in the polymerization of 4-olefins. A known catalyst for the polymerization of o-olefins, which is the product of the interaction of anhydrous magnesium or zinc halides with vanadium or titanium halides in combination with an organoaluminum compound with a compound ij. However, this catalyst has a strong corrosive effect due to its increased chlorine content. and causes an increased content of chlorine in the polymer. The closest to the invention in its technical essence and the effect achieved is a catalyst for the polymerization of olefins, containing a halogen-containing compound of a transition metal, a compound of a metal from the group II of the periodic system and an aluminum or organic compound, or Diethyl alkyne chloride, or trihexyl aluminum in the following ratio of catalyst components, wt.%: a transition metal compound on a carrier is a metal compound P group 0.03-0.13; organo-aluminum compound 99.87-99.97. When ets - as a transition metal compound, the catalyst contains a halogen-containing compound of titanium or vanadium, as a compound of the metal of the group N - magnesium dihalide or manganese, or calcium, or zinc, or chromium, or iron, or cobalt, or nickel, which has been pretreated with electro-donor additives. As an organoaluminum compound, besides those mentioned above, the catalyst contains tripropyl aluminum or diethyl aluminum bromide or diethyl aluminum and phenol or t dietilalk mini or ethoxychloride etilalkmini or ethyl sesquichloride (1ini 2. A disadvantage of the known catalyst is its high corrosive effect, which is caused by the high chlorine content in the catalyst (the amount of Ti Fe Mg compound and dialgative component is O, 2-5.9%). Thus, the atomic ratio of the C0 / T1-and MD-Ti complex is at least 50: 1. This, in turn, causes a high chlorine content in the polymer. The aim of the invention is to reduce the corrosive action of the catalyst while maintaining a high polymer yield. This goal is achieved by the fact that the catalyst for the polymerization of Si-olefins contains as a halogen-containing compound of the transition metal and a compound of the metal M of the group of the periodic system a complex of the following formula. vS.t. where M is magnesium or manganese, or calcium; M-titanium / or zirconium, or vanadium; X is chlorine or bromine, or iodine; Y - OCH-) or or N () 2 ,, or (OqHa); , C, H, .OH,, (f) yO, CHjCOOC H -,, Cx% eooc Hf, co (df2) -g / CH ,, (coocjH) ,,, CrHfN, C.HjCN, POCgj, t ( CH.) Nt PO; 1-4, 2-14,. . with the following content of the catalyst components, May.%: Complex of the indicated formula Ml PU 0.05-6.98 Organic alkali 93, 02-99.95 compound Reduction of the corrosive effect of the catalyst (while maintaining a high polymer yield) is due to the fact that the content decreases chlorine in the complex (for example, the maximum atomic ratio of C0 / Ti is 8: 1 instead of 50: 1). For the preparation of the catalyst, titanium trichloride was used, which was prepared by known methods 3j and 4j. Complexes of the MJM composition. nE is obtained by reacting in appropriate ratios X with a compound at a temperature range from room temperature to specific solvent E, acting as electron donors, after which they are separated by crystallization from the same solvent or by evaporation of the solvent, or by precipitation with a solvent, in which the complexes are insoluble. If halogenide MX or compound mu is poorly soluble in solvent E, it is recommended that the reaction be carried out in another suitable solvent, the electron donor (E), to produce a complex that, after isolation, can be processed at a temperature from room temperature to 150 s with an excess of solvent E, which displaces the solvent E. It is also possible to mix an excess solution of the bodies G with a solution of the complex М МХ OEP in the solvent Е. Typically, the molar ratio between the reactants MXj and MU corresponds to the value in the resulting complex. However, it is also possible to use an excess of the halide MXj to obtain very active catalytic components; as compared to the usual ulobrebl4 for the preparation of the target complex (molar ratio MX / MU above 2). In such a case, when the solvent is crystallized or evaporated or precipitated with an appropriate solvent, a mixture consisting of the target complex (or the complex, containing solvent E and the complex obtained from MXg halide and solvent E (or solvent E) is separated.
You can also use a mixture of the proposed pre-prepared complexes with anhydrous magnesium two-halide.
, The X-ray spectrum of such mixtures shows a halo, imendium peak shifted in relation to the interplanar distance of the most intense line, imecys in the spectrum of normal-type dihaloid magnesium. The normal type dichloride and magnesium dibromide spectrum is determined in ASTM-3-p854 for dichloride and in ASTM-15-836 for dibromide.
The dihalide magnesium content is 1-99% by weight (preferably 20-80% by weight).
Such mixtures can be prepared, for example, by co-grinding the components under conditions such that the X-ray spectrum is comminuted. The product shows the dudification described.
In an analogous manner, an excess of MU can be introduced in comparison with what is usually introduced for the preparation of the complex (molar ratio of mu / MX is more than 2). In this case, a mixture of the target complex (or complex, containing solvent E) and complex-g consisting of and solvent E (or solvent E) is isolated.
The catalysts can be used in the polymerization of 06-olefins, in particular ethylene, propylene, by known methods, for example, in the liquid phase, in the presence or absence of an inert solvent or in the gaseous phase. As an inert solvent, an aliphatic or cycloaliphatic hydrocarbon is usually used, for example, hexane, heptane, cyclohexane. The polymerization is carried out at a temperature of from -8 ° to t-200 ° C, preferably from 50 to 10 OOC, under atmospheric pressure or increased. The molecular weight regulation in the polymerization process is carried out by known methods, for example, operation in the presence of alkyl halides, organometallic compounds of zinc or cadmium, or hydrogen.
Example. 1.1 g of TiCPiHR, obtained by reducing titanium tetrachloride with hydrogen (7.1 mmol), was dissolved in nitrogen atmosphere in 100 ml of anhydrous ethyl acetate. Similarly, 0.68 g of anhydrous magnesium chloride (7.1 mmol) was dissolved in 31 ml of anhydrous ethyl acetate. Both solutions are brought into contact for 2 hours at. An extremely soluble product of the reaction is an evaporated solvent. A gray-green powder is obtained, the composition of which, according to the analysis, corresponds to MgTiCv5 2СНjCOOCjН5.
The X-ray diffraction pattern and absorption bands in the infrared region, characteristic of the group, prove that this substance is a compound of a certain line.
For comparison, the complexes T CH, COOC, H MgCe, CH COOC AND their mechanical mixture were analyzed in a molar ratio of 1: 1. Their X-ray and IR spectra are completely different from the spectra of the product described above.
Example 2. A solution of 6.92 g of anhydrous magnesium chloride (72f7 and fiul) in a nitrogen atmosphere in .100 ml of anhydrous ethyl acetate is prepared. Similarly, 7.48 g of Tice, jHR (48, 46 mmol) is dissolved in 72 ml of anhydrous ethyl acetate. Both solutions were reacted by stirring for 4 hours at. The resulting product is very soluble and is isolated by distilling off the solvent. Get a light green powder, which according to the analysis has the formula Mg TijCe, 2 J.
A radiograph of the product reveals a diffraction uncharacteristic of either Tice CHaCOOCj Ify nor iiF2CHjCOOC2Ht. Similarly, the absorption band of the group in the IR region has a different position than that of the complexes of titanium trichloride and magnesium chloride with ethyl acetate.
Example Separately, 0.95 g of TiCCjHR (6.1 mmol) and 0.65 g of anhydrous magnesium chloride (6.1 mmol, respectively, in 80 ml of deaerated anhydrous ethanol and 20 ml of the same alcohol are dissolved under nitrogen atmosphere. Both solutions are obtained in interacting at room temperature for 12 hours. The reaction product is isolated by distilling off the solvent and dried. A sulfuric network is obtained, which according to the analysis data has a composition corresponding to the formula MgTiCEy.
 1 example 4. Under nitrogen atmosphere, 1.4 g (9.05 king) and 0.66 g of anhydrous magnesium chloride (9.05 mmol) are dissolved, respectively, in 100 m of deaerated anhydrous methanol and 50 ml of the same alcohol. Both solutions are reacted for 4 hours at. The reaction product is separated off the solvent and dried. A powder is obtained, which according to the analysis data corresponds to the formula HgTiCBy «lOCH OH.
Example 5. In an inert atmosphere, separately dissolve 2.4 g (10 Mmol) 2 tetrahydrofuran and 3.6 g (10 mmol) TicC G tetrahydrofuran, respectively, in 300 and 200 ml of anhydrous tetrahydrofuran. Both solutions were reacted with stirring for 2 hours at room temperature. The product is isolated by distillation and the solvents are dried. A gray powder is obtained, the analysis of which indicates that it corresponds to the formula MgTiC j5 tetrahydrofuran.
EXAMPLE 6 A solution was prepared of 2.8 g of borated magnesium chloride (29.5 lol) in 59 ml of anhydrous 4.4 g of TiC ASA, obtained by reducing titanium tetrachloride with aluminum and activated by grinding (22, 1 mmol) in 60 ml of anhydrous ethyl acetate. Both solutions were allowed to react for 4 hours at. The resulting dark green solution is evaporated to dryness, a violet (lilac) solid is obtained, which, according to the analysis data, has a composition that corresponds to the formula Mg TijAeceio "12СНЗСООС2Н. This complex also contains aluminum because the reduction of titanium tetrachloride using (metallic) aluminum is in the form of
3Ticey Aesès-
Example. 1.6 g of the C8-VCHeCOOG H complex prepared by the method described in Example 2 is suspended in 30 ml of ethyl benzoate and the suspension obtained is heated at 6 at. The resulting reaction product is filtered off, washed at room temperature with 200 mp of N. heptane, and dried under vacuum. The obtained solid yellow substance corresponds according to the analysis, the formula Kg HLjCtn-2 -.
Primed 8. Prepare a suspension of 1.8 g of the Hg iyC n -lCE COOCyE complex obtained in Example 2 in 30 ml of benzonitrile. Proceed as described in Example 7, and a solid is isolated, corresponding to
According to the analysis data, the formula HgjTi ceij-7CfcH5CN.
Example9. Under nitrogen, a solution of 2.6 g of anhydrous magnesium chloride (27.4 Mmol) and 3 ml of titanium tetrachloride (27.4 mmol), respectively, in 200 and 60 ml of anhydrous ethyl acetate is prepared separately. Both solutions are reacted with stirring for 4 hours at. A yellow crystalline precipitate is formed from the concentrated solution while cooling, the cobalt is isolated, overlaid with ethyl acetate and dried under vacuum at. This product, decomposing at 190 ° C, corresponds according to the analysis to the formula MgTiCf, jH.
The IR and X-ray spectra prove that this is a strictly defined (ie, pure) compound, completely different from the corresponding complexes (-,) 2 and CHjCOOC H ,.
Example 10: To 20 ml and a 0.5 M solution of magnesium chloride in ethyl acetate (10 mmol of magnesium chloride), heated to, 0.22 ml (2 mmol) of titanium tetrachloride are added dropwise. The reaction is carried out for 2 hours at, then the solvent is distilled off under vacuum and the resulting gray residue is dried at.
The X-ray diffraction pattern shows that this substance is a mechanical mixture MdT1Seb-2CH СООСЛНй- and хг СНзСООС, Н.
Example 11. Example 10 is repeated, taken in 0.11 ml of pure titanium chloride, (1 mmol). The obtained precipitate is subjected, after drying, to an x-ray analysis, the data of which indicate that it is a mixture of KgfiC i -2SK SopcUI and MgCBj-CH jCOOCj Hf. The titanium content in this mixture is 1.1%.
Example 12. Example 10 is repeated, but taken in 4.4 ml of pure titanium tetrachloride (40 mmol) The resulting precipitate is subjected to an analysis after drying, which proves that this mixture is MgTlC z CHF, (CH COOCjH),
Example 13. A solution of 2.6 g of magnesium chloride (27.3 Mmol) in 50 ml of anhydrous ethylene carbonate is prepared at. Separately, dissolve 3 MP of ttan tetrachloride (27.3 mmol) in 100 ml of anhydrous ceramics carbonate at. Both solutions are mixed and left to react for 7 hours at. A powdered yellow precipitate is obtained. It is isolated by filtration (in a heated state) and dried under vacuum at. This yellow powder corresponds to the analysis of the formula hOSNMdT1Sv .9COSS2 2 EXAMPLE 14. To a 20 ml solution of 4.6 g of the complex MgTice 2СН “СООС2Н (obtained as described in Example 9) in ethyl acetate is added dropwise 35 ml of pyridine. After a two-hour reaction, a yellow residue is obtained, it is filtered and dried by distilling off the solvent. The yellow solid obtained has a data analysis according to the formula corresponding to the formula, «« eCjHjN, Example 15. 2 g of the MqTlC ir 2CH-eOOCjH j complex (prepared by the method described in Example 9 by the method) are suspended in 30 ml of POCe. The reaction is carried out for 4 hours with stirring and then evaporated to dryness. A yellow powder is obtained which, according to the analysis data, has the composition according to the formula HgTicet BROSbz Example 16. Under nitrogen atmosphere, solutions of 3.15 g (17 mmol) of Cg TiOCH and 1.62 are prepared. g (17 mmol) of anhydrous magnesium chloride, respectively, in 40 to 35 ml of anhydrous ethyl acetate. Both solutions are mixed and heated with stirring for 5 hours while the solvent is distilled off and the material formed is dried under vacuum at. You divide the yellow powder, which according to the data of the analysis, has a composition corresponding to the formula MDT1SY4 (OCH2 zsocos n. Example 17. Prepare a solution of 3.41 g (12.4 mmol) Cf TiOOC-C Hy in 50 ml of anhydrous ethyl acetate and the resulting solution was mixed with 24.8 ml of a 0.5 M solution of anhydrous magnesium chloride in ethyl acetate (12.4 mmol) of magnesium chloride. The reaction was carried out for 4 hours with stirring. After the solvent was distilled off and the resulting substance was dried, a green powder was obtained, according to analysis corresponds to the formula MgTiCCj (OOS-C%) Example 18. Prepare a solution of 26 mmol CC-) TiN () 2 150 m l of anhydrous ethyl acetate and the resulting solution was poured into another solution containing 26 mmol of anhydrous magnesium chloride in 52 m of ethyl acetate. The reaction is carried out for 4 hours at room temperature and stirring, then evaporated and dried,. get brown powder, which according to the analysis corresponds to the following composition: MgTiCe5.tN (C, H5) j ,, PRI me R 19. In nitrogen atmosphere, a solution of 2.12 g (22.4 mmol) of anhydrous chloride is prepared Magnesium in 100 ml of decontaminated anhydrous n. Butylacetate. 7.6 ml (22.4 mmol) of Ti (O-HCi H) are introduced into the resulting solution and the reaction is carried out for 4 hours at. and mixing. After distilling off the solvent under vacuum, a colorless paste is obtained, which, according to data 1, has a composition corresponding to the rmule MgTiCe2. (L-HC4H9) 2CH СООСцН ,. Example 20 To a solution of 3.3 g (18 mmol) of magnesium bromide in 200 ml of anhydrous ether (diethyl ether), 1.98 ml (18 mmol) of titanium tetrachloride are added dropwise and a red precipitate immediately forms. The reaction is carried out at reflux for 4 hours, then the solvent is distilled off and a brown powder is obtained, which, according to the analysis data, has a composition corresponding to the formula mdT1Cvl Br, x L2 (C2H5). . Example 21 "Ex | 1. A solution of 1.7 g (13.5 mmol) of anhydrous manganese chloride in 100 ml of anhydrous ethanol is prepared. Separately, dissolve 2.08 g (13.5 mmol) of titanium trichloride in 100 ml of anhydrous ethanol. Both solutions are mixed and reacted for 4 hours at and 8 hours at. The azure-colored solution formed is evaporated to dryness ii a gray solid is obtained, which according to the analysis corresponds to the formula MnTice5 4С2НуОН. Example 22 A solution of 5.6 g (59 mmol) of anhydrous magnesium chloride in 100 ml of anhydrous zinc is prepared under nitrogen atmosphere. Similarly, a solution of 6.17 g (35.2 mmol) of vanadium trichloride in 150 ml of anhydrous ethyl acetate is obtained. These solutions are mixed and reacted for 4 hours at. and mixing. The resulting green solution is evaporated to dryness, to obtain a brown powder, which according to the analysis corresponds to the formula Md-UC b. . PRI me R 23. Preparing a solution of 0.203 g (2.14 mmol) of anhydrous magnesium chloride in 60 ml of anhydrous tetrahydrofuran. Separately, 0.50 g (2.14 mmol) of zirconium tetrachloride are suspended in 100 ml of anhydrous tetrahydrofuran. The solution is poured into the suspension and the reaction is carried out for 6 hours at. Then evaporated to dryness, get a white solid, which according to the analysis corresponds to the formula KgZrCtf, 4CjHgO. PRI me R 24. In a nitrogen atmosphere prepare a solution of 0.87 g
(7.8 mmol) of anhydrous chloride. calcium in 50 MP of de-aerated anhydrous ethanol and similarly dissolve 1.2 g (7.8 mmol) in 100 ml of de-aerated anhydrous ethanol. Both solutions are mixed and the reaction is carried out for 8 hours at. The solvent is distilled off under vacuum at 40 seconds amdvl 1 of a gray solid, which according to the analysis corresponds to CaTiCgj-4С2Н50Н.
Example 25 2.97 g (10 mmol} of anhydrous iodide, calcium in 100 ml of deaerated anhydrous ethanol and anhydrite dissolve 1.58 g (10 mmol) in 60 ml of deaerated anhydrous ethanol) under nitrogen atmosphere. Both solutions are mixed and carried reaction for 3 h at 40 s. The solvent is distilled off under vacuum while a violet (lilac) substance is separated, which according to the angles of the data corresponds to the formula GaTiCS I 5C, H5OH.
Polymerization of ethylene, in an inert solvent, The corresponding amount of one of the catalytic complexes obtained in the examples, and 1000 ml of deaerated anhydrous desulfurized N. heptane, together with an alkyl 2 aluminum derivative of 2 tan, are added to a stainless steel autoclave equipped with a root stirrer and heated to a predetermined temperature. Hydrogen and ethylene are then fed at a given partial elasticity and the total pressure is kept constant during the whole polymerization process with the aid of a continuous supply of ethylene. After a suitable reaction time, the polymerization is stopped, filtered and the resulting polymer is dried. The viscosity (characteristic) of the polymer is measured in tetrahydronaphthalene at a concentration of 0.25 g of polymer in 100 ml of solvent. The yield is expressed in grams of polymer obtained per gram of titanium, vanadium or zirconium tests 1-XXX1Y).
Polymerization of ethylene in the gas phase. 200 g of powdered completely dry polyethylene, a suitable amount of one of the catalytic complexes prepared as described in the examples, 30 ml of deaerated, anhydrous and desulfurized heptane and 2 mmol of trialkylaluminium are placed in a 2 l stainless steel autoclave equipped with a root-stirrer. After evaporation of the solvent by heating under vacuum, the autoclave is fed under pressure.
2 atm hydrogen and ethylene to a total pressure of 19 atm. During the reaction, a constant pressure is maintained by the continuous addition of ethylene. After a certain period, the polymerisation is cleaved and the polymer formed is isolated (test XXXU).
Polymerization of propylene. In 100 of the catalytic complex obtained in Example 7 and 50 ml of deaerated anhydrous desulfated geltaine are brought together with 2 ml of A.v (IsOg-C | H) f in a dry argon atmosphere into a two-liter stainless steel autoclave equipped with a root a stirrer heated at and containing hydrogen at a partial elasticity of 0.85 atm and 500 ml of anhydrous propylene. The reaction is stopped after 5 hours, the unpolymerized propylene is discharged, the polymer is removed, dried and weighed (test XXXU1).
Example 26: 2.67 g of the MdT1Sb "4CH3COOCdH: complex (prepared as described in Example 9, except that it was not dried at 50, but at) was suspended in 30 ml of diethyl malonate. The reaction is carried out with stirring for 3 hours. Then the suspension is evaporated and a yellow powder is obtained, the composition of which is determined by analysis
accretion
MgTice, ZSNg
Example-p27. 1.9 g of MgTiCgg 4CH CbOC2Hf complex, obtained as in Example 9, except that it is not dried at 50, but is added to 5 ml of anhydrous, and then 20 ml of hexamethylphosphoride is added dropwise. The reaction is carried out at 25 ° C and stirring for 4 hours. Then it is evaporated to dryness and the yellow powder is separated, which, as determined by analysis, has the composition MgTiCP, x 4 C (CH.j).
Example 28. 3.6 g of the complex of iMgTlce 4CH, jCOOC2Hj (obtained as in Example 9, except that heating is not performed at 50, but at) is dissolved in 50 ml of triphenylphosphite. The solution is reacted with stirring for 4 hours. Then the reaction mixture is evaporated to dryness and an orange oil is separated, which, as set forth from the Analysis:., Has the composition MgTice 2Р () 5.,
PRI me R 29. 0,52 g. (5.46 mmol) anhydrous MDS growth
under nitrogen atmosphere in 11 ml of anhydrous ethyl acetate and the resulting solution is added to the suspension. 0.65 g (5.46 mmol) of TlCfj in 100 kn of anhydrous ethyl acetate. All the mixture reacts during the poaching and 6h. The suspension obtained is evaporated to dryness and a black powder of the following composition is obtained: M9T1CI4, H.
PR im ep 30. In a nitrogen atmosphere, dissolve separately 1.9 g
(20 muls) of anhydrous HgCC in 40 ml of anhydrous ethyl acetate; 1,10 ml
(10 mmol) T1Cv4 in 20 MP anhydrous ethyl acetate; 1.15 ml (10 moles of SnCC in 20 MP without beater; | given ethyl acetate. Three solutions are combined and reacted for 4 hours with stirring. A crystalline product precipitates from the peaxiwoH solution after concentration and cooling, and is separated by filtration and dried under vacuum. Anneshis showed that the product has the following sow: AB l4CH- | COOC Hj.
Experiments on the polymerization of ethylene with p {zhmenenie complexes according to measures 1-30 {fivedeia in table 1, after obtaining the resulting catalysts for tests 1-XXXU1 - in table 2.
oh oh oh 00
9t
ABOUT
in
Ltd
oh oh
oh oh oh
about
oo
ABOUT
ABOUT
ABOUT
oh oh
about "about" to g
oi
about
1L
Whitefish
"about
about
91OCH
sch
mh
with
g
ъ
ъ
"H
"about
n m
about
oh oh
about n m
g
about
about "
Ov h
1L. with
h g "
"H
g "
  m
och
(
 I
and n
SP
about
.. about "
tno about
in with
oh oh
1O
Ltd
"about
m
"P m
"P
"P
Ltd
M -1iH

g g
I I o
I
3
"P
one
".Yes
"
sc ”h
about
%
ъ

eo
in
-"her
g
VPCHG
and & 1
n and
nn
about her
about
in
VO
t
MN
go
(H
"
W
8 5
t
V
"H
g
and
"
m

X
and y

"Q
ych "
at
and
V
and
se
 W h tc- --G-,
E
ё. I I I I
Jt
oh
eo
p "g in" about h n -1 -

1-1
S
X x
X
191075949
table 2
20
Continuation of table 2

权利要求:
Claims (1)
[1]
A CATALYST FOR POLYMERIZATION OF Λ-OLEPHINS, containing a halogen-containing compound of a transition metal, a metal compound of group P of the periodic system and an organoaluminum compound, in which the catalyst is ^! contains triethylaluminum or trieobutylaluminum, or diethylaluminium chloride, or trihexlaluminium, characterized in that, in order to reduce the corrosive effect of the catalyst while maintaining a high polymer yield, the catalyst contains a halogen-containing transition metal compound and a metal compound η of a group of the periodic system -complex of the following formula:
M ^ m'h ^ U.pe, where M is magnesium or manganese, or • calcium;
M is titanium and / or zirconium or vanadium;
X is chlorine or bromine or iodine;
Y - OCHj or OSOS ₆ Ng, or, or (OSLH ^) ;
E - CH.OH, CjH _f OH, С ₄ Н _in О, (с'н _у ) _in О, СН4СООС-Н4 ·, chScooc ^ h ,, С, Н _{ч5 СООС g} Н | ·, COiOCHjgb, CH _v ( COOCjHA, C _r H _f N, C ^ HfCN; GROWTH *, [(CH _E ) _X , K], PO;
m = 1-4 ,. η = 2-14, with the following content of catalyst components, wt.%:
The complex of the indicated formula M ^ M ^ X ^ Y · nE 0.05-6.98 Organoaluminium compound 93.02-99.95:

类似技术:

---

公开号 | 公开日 | 专利标题

---

SU1075949A3|1984-02-23|Catalyst for polymerization of alpha-olefins

---

US6818584B2|2004-11-16|Process for preparing a Ziegler-Natta catalyst

---

DE3028759C2|1987-07-16|

---

PL80715B1|1975-08-30|

---

DE2643143A1|1977-06-02|CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS

---

US4814308A|1989-03-21|Preparation of homopolymers and copolymers of ethene by Phillips catalysis

---

DE3212868C2|1987-10-22|

---

SU578008A3|1977-10-25|Method of preparing polyolefins

---

Di Noto et al.1996|New synthesis of a highly active δ‐MgCl2 for MgCl2/TiCl4/AlEt3 catalytic systems

---

US4614727A|1986-09-30|Polymerization catalyst

---

DE2216357A1|1972-10-19|Process for the preparation of polymerization catalysts and their use

---

US4120883A|1978-10-17|Method for producing an organomagnesium complex

---

GB1579725A|1980-11-26|Preparation of violet tici3

---

US4174429A|1979-11-13|Process for polymerizing olefins

---

JPH07650B2|1995-01-11|Method for producing catalyst component for olefin polymerization

---

US4174299A|1979-11-13|Catalysts for the polymerization of olefins

---

SU1071223A3|1984-01-30|Process for preparing chlorine- and phosphorus-containing complex compounds

---

US4208304A|1980-06-17|Catalyst system for producing ethylene polymers

---

US3455974A|1969-07-15|Alkoxy vanadyl fluorides and their preparation

---

US3839313A|1974-10-01|Catalysts for the polymerization of olefins

---

US3707530A|1972-12-26|Method for producing polymers of ethylene

---

US4207205A|1980-06-10|Reduction of TiCl4 with reducing agents modified with Lewis bases

---

KR0145290B1|1998-07-15|Process for prepating a catalyst for the polymerization of olefins

---

Balducci et al.1975|Advances in Catalysts Based on Aluminum Hydride Derivatives for the Synthesis of High-Cis Polyisoprene

---

US3510465A|1970-05-05|Process for polymerizing olefinic hydrocarbons

同族专利:

---

公开号 | 公开日

---

FR2305445A1|1976-10-22|

---

NL7603026A|1976-09-30|

---

SE434159B|1984-07-09|

---

CA1077460A|1980-05-13|

---

NL191261C|1995-04-18|

---

JPS6123201B2|1986-06-04|

---

DK152507C|1988-08-01|

---

IT1037112B|1979-11-10|

---

ZA761816B|1977-03-30|

---

ES446441A1|1977-11-01|

---

BE840058A|1976-09-27|

---

BR7601857A|1976-09-28|

---

DE2612650A1|1976-10-07|

---

DE2612650C2|1990-09-20|

---

ATA219976A|1978-01-15|

---

AU1236576A|1977-09-29|

---

AT345547B|1978-09-25|

---

DK126376A|1976-09-29|

---

US4124532A|1978-11-07|

---

JPS51120992A|1976-10-22|

---

NL191261B|1994-11-16|

---

FR2305445B1|1980-06-20|

---

SE7603541L|1976-09-29|

---

DK152507B|1988-03-07|

---

GB1502567A|1978-03-01|

---

PL106503B1|1979-12-31|

---

AU501075B2|1979-06-07|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3583958A|1967-04-11|1971-06-08|Mitsui Petrochemical Ind|Process and catalyst for manufacture of olefincc polymers|

---

US3850842A|1969-07-08|1974-11-26|Montedison Spa|Polymerization catalysts|

---

JPS4930514B1|1970-08-20|1974-08-13|

---

US3859231A|1972-10-13|1975-01-07|Gulf Research Development Co|Simplified process for manufacture of catalyst component|

---

US3917575A|1972-11-11|1975-11-04|Nippon Oil Co Ltd|Process for production of polyolefins|

---

NL177314C|1974-04-08|1985-09-02|Mitsubishi Chem Ind|METHOD FOR PREPARING A CATALYST COMPLEX, AND METHOD FOR POLYMERIZING AN OLEYLENE WITH THIS CATALYST|DE2721194C2|1977-05-11|1983-09-08|Basf Ag, 6700 Ludwigshafen|Process for the preparation of homo- and copolymers of C? 2? - to C? 6? -? -Monoolefins|

---

DE2721094C2|1977-05-11|1988-09-29|Basf Ag, 6700 Ludwigshafen, De|

---

DE2721058C2|1977-05-11|1983-08-25|Basf Ag, 6700 Ludwigshafen|Process for the preparation of homo- and copolymers of C? 2? - to C? 6? -? -Monoolefins|

---

JPS6119645B2|1977-06-08|1986-05-19|Mitsubishi Chem Ind|

---

IT1092448B|1978-02-09|1985-07-12|Montedison Spa|CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS|

---

US4302566A|1978-03-31|1981-11-24|Union Carbide Corporation|Preparation of ethylene copolymers in fluid bed reactor|

---

US4390677A|1978-03-31|1983-06-28|Karol Frederick J|Article molded from ethylene hydrocarbon copolymer|

---

US4379759A|1979-02-16|1983-04-12|Union Carbide Corporation|Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization|

---

US4302565A|1978-03-31|1981-11-24|Union Carbide Corporation|Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization|

---

JPS54158489A|1978-06-05|1979-12-14|Mitsubishi Petrochem Co Ltd|Polymerization of olefin|

---

FR2436794B1|1978-09-22|1981-07-03|Naphtachimie Sa|

---

JPS6320844B2|1978-10-20|1988-04-30|Nippon Oil Co Ltd|

---

JPS6320845B2|1978-10-26|1988-04-30|Nippon Oil Co Ltd|

---

JPS603323B2|1978-12-11|1985-01-28|Mitsui Petrochemical Ind|

---

CA1118148A|1978-12-14|1982-02-09|Union Carbide Corporation|Preparation of high density ethylenepolymers in fluid bed reactor|

---

US4303771A|1978-12-14|1981-12-01|Union Carbide Corporation|Process for the preparation of high density ethylene polymers in fluid bed reactor|

---

US4233182A|1978-12-26|1980-11-11|Standard Oil Company |High activity catalyst for the polymerization of alpha-olefins|

---

US4293673A|1978-12-28|1981-10-06|Union Carbide Corporation|Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization|

---

US4376062A|1979-11-28|1983-03-08|Union Carbide Corporation|Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization|

---

US4383095A|1979-02-16|1983-05-10|Union Carbide Corporation|Process for the preparation of high density ethylene polymers in fluid bed reactor|

---

US4684703A|1979-02-27|1987-08-04|Union Carbide Corporation|Polymerization catalyst for ethylene homopolymerization|

---

US4395359A|1979-02-27|1983-07-26|Union Carbide Corporation|Polymerization catalyst, process for preparing, and use for ethylene homopolymerization|

---

JPS6354004B2|1979-06-18|1988-10-26|Mitsui Petrochemical Ind|

---

US4363904A|1979-06-18|1982-12-14|Union Carbide Corporation|High tear strength polymers|

---

US4359561A|1979-06-18|1982-11-16|Union Carbide Corporation|High tear strength polymers|

---

ZA802850B|1979-06-18|1981-05-27|Union Carbide Corp|High tear strength polymers|

---

US4246383A|1979-06-25|1981-01-20|The Dow Chemical Company|Process for polymerizing olefins in the presence of a catalyst prepared from an organomagnesium component which does not reduce TiCl4|

---

US4244838A|1979-06-25|1981-01-13|The Dow Chemical Company|High efficiency catalyst for polymerizing olefins|

---

EP0037182B2|1980-03-24|1991-06-12|Imperial Chemical Industries Plc|Preparation of a dried transition metal product|

---

EP0044735A3|1980-07-21|1982-08-25|Imperial Chemical Industries Plc|Transition metal composition, production and use|

---

US6777508B1|1980-08-13|2004-08-17|Basell Poliolefine Italia S.P.A.|Catalysts for the polymerization of olefins|

---

IT1209255B|1980-08-13|1989-07-16|Montedison Spa|CATALYSTS FOR THE POLYMERIZATION OF OLEFINE.|

---

US4311612A|1980-08-25|1982-01-19|Standard Oil Company |Olefin polymerization catalyst|

---

US4496660A|1980-10-01|1985-01-29|The Dow Chemical Company|Catalyst prepared from organo-magnesium compound; oxygen- or nitrogen-containing compound; halide source; transition metal compound and reducing agent|

---

US4380508A|1981-10-22|1983-04-19|The Dow Chemical Company|Ultra high efficiency catalyst for polymerizing olefins|

---

US4381253A|1981-10-22|1983-04-26|The Dow Chemical Company|Ultra high efficiency catalyst for polymerizing olefins|

---

US4544647A|1982-07-29|1985-10-01|The Dow Chemical Company|Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound|

---

US4426316A|1982-09-10|1984-01-17|The Dow Chemical Company|Catalyst prepared from organomagnesium compound, organic hydroxyl-containing compound, reducing halide source and transition metal compound|

---

US4434282A|1982-10-04|1984-02-28|The Dow Chemical Company|Process for polymerizing olefins|

---

US4529715A|1983-10-17|1985-07-16|The Dow Chemical Company|Catalyst prepared from organomagnesium compound, carbon dioxide, reducing aluminum source, transition metal compound and zinc compound|

---

US4496661A|1983-10-24|1985-01-29|The Dow Chemical Company|High efficiency catalyst for polymerizing olefins|

---

IT1178466B|1984-03-20|1987-09-09|Montedison Spa|CATALYSTS FOR THE HOMO AND COPOLYMERISATION OF ETHYLENE AND POLYMERS OBTAINED|

---

US4661465A|1985-10-31|1987-04-28|The Dow Chemical Company|Method for preparing transition metal component of Ziegler-Natta catalysts|

---

US5278118A|1986-10-02|1994-01-11|Ausimont, S.P.A.|Catalysts for the preparation of elastomeric olefinic copolymers|

---

US4918038A|1987-10-29|1990-04-17|Union Carbide Chemicals And Plastics Company Inc.|Process for the production of polyethylene with a broad and/or bimodal molecular weight distribution|

---

EP0380241B1|1989-01-21|1996-03-20|Mitsubishi Chemical Corporation|Process for preparing ethylene copolymers|

---

FI89066C|1989-11-20|1993-08-10|Neste Oy|FOERFARANDE FOER FRAMSTAELLNING AV EN POLYMERISERINGSKATALYTKONPONENT FOER OLEFINER, EN POLYMERISERINGSKATALYTKONPONENT FRAMSTAELLD MED FOERFARANDET OCH DESS BRUK|

---

US5677256A|1990-04-12|1997-10-14|Neste Oy|Method of preparing catalyst composition for polymerizing olefins|

---

US5114897A|1990-04-18|1992-05-19|The Dow Chemical Company|Catalyst and process for polymerizing olefins|

---

US5045612A|1990-04-18|1991-09-03|The Dow Chemical Company|Catalyst and process for polymerizing olefins|

---

KR940000014B1|1990-10-10|1994-01-05|한국과학기술원|Highly active ziegler-natta catalyst for polymerizing hdpe and lldpe and method for preparation thereof|

---

FI86989C|1990-12-19|1992-11-10|Neste Oy|Process for producing a polymerization catalyst component for olefins, a polymerization catalyst component prepared by the process, and its use|

---

US5317036A|1992-10-16|1994-05-31|Union Carbide Chemicals & Plastics Technology Corporation|Gas phase polymerization reactions utilizing soluble unsupported catalysts|

---

US6124412A|1997-12-29|2000-09-26|Saudi Basic Industries Corporation|Alumoxane-enhanced, supported ziegler-natta polymerization catalysts, methods of making same, processes of using same and polymers produced therefrom|

---

US6569964B2|1997-12-29|2003-05-27|Saudi Basic Industries Corporation|Alumoxane-enhanced, supported Ziegler-Natta catalysts, methods of making same, processes of using same and polymers produced therefrom|

---

AU1029701A|1999-11-15|2001-05-30|Basell Technology Company B.V.|Solid catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer|

---

US6281306B1|1999-12-16|2001-08-28|Univation Technologies, Llc|Method of polymerization|

---

US6630544B1|2002-04-18|2003-10-07|Equistar Chemicals, Lp|Propylene polymerization process with enhanced catalyst activity|

---

US6831032B2|2002-08-19|2004-12-14|Novolen Technology Holdings C.V.|Ziegler-Natta catalyst and methods of making and using same|

---

US7223822B2|2002-10-15|2007-05-29|Exxonmobil Chemical Patents Inc.|Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom|

---

KR101113341B1|2002-10-15|2012-09-27|엑손모빌 케미칼 패턴츠 인코포레이티드|Multiple catalyst system for olefin polymerization and polymers produced therefrom|

---

RU2322457C2|2002-12-18|2008-04-20|Базелль Полиолефин Италия С.П.А.|Catalytic components for polymerization of olefins|

---

US6767857B1|2003-05-29|2004-07-27|Fina Technology, Inc.|Process for forming a Ziegler-Natta catalyst system having a controlled morphology|

---

US20050148742A1|2004-01-02|2005-07-07|Hagerty Robert O.|Method for controlling sheeting in gas phase reactors|

---

US7985811B2|2004-01-02|2011-07-26|Univation Technologies, Llc|Method for controlling sheeting in gas phase reactors|

---

US7629422B2|2004-12-21|2009-12-08|Univation Technologies, Llc|Process for transitioning between Ziegler-Natta-based and chromium-based catalysts|

---

EP1731536A1|2005-06-09|2006-12-13|Innovene Manufacturing France SAS|Supported polymerisation catalysts|

---

US20070073012A1|2005-09-28|2007-03-29|Pannell Richard B|Method for seed bed treatment before a polymerization reaction|

---

WO2007065816A2|2005-12-06|2007-06-14|Basell Poliolefine Italia S.R.L.|Catalyst components for the polymerization of olefins|

---

EP1803747A1|2005-12-30|2007-07-04|Borealis Technology Oy|Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films|

---

US8497328B2|2008-08-20|2013-07-30|Basell Poliolefine Italia, s.r.l.|Catalyst components for the polymerization of olefins and catalysts therefrom obtained|

---

WO2010071798A1|2008-12-18|2010-06-24|Univation Technologies, Llc|Method for seed bed treatment for a polymerization reaction|

---

ES2823768T3|2012-12-28|2021-05-10|Univation Tech Llc|Methods to integrate aluminoxane production into catalyst production|

---

CA2943378A1|2014-04-02|2015-10-08|Univation Technologies, Llc|Continuity compositions and methods of making and using the same|

---

WO2016145179A1|2015-03-10|2016-09-15|Univation Technologies, Llc|Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes|

---

CA2983736A1|2015-04-27|2016-11-03|Univation Technologies, Llc|Supported catalyst compositions having improved flow properties and preparation thereof|

---

SG11201907244SA|2017-02-07|2019-09-27|Exxonmobil Chemical Patents Inc|Processes for reducing the loss of catalyst activity of a ziegler-natta catalyst|

---

WO2019182746A2|2018-03-23|2019-09-26|Univation Technologies, Llc|Catalyst formulations|

---

WO2022020025A1|2020-07-22|2022-01-27|Exxonmobil Chemical Patents Inc.|Polyolefin compositions and articles thereof|

法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

---

IT21815/75A|IT1037112B|1975-03-28|1975-03-28|CATALYSTS FOR THE POLYMERIZATION OF OLFINES|

---