CA1120910A - Catalysts components and catalysts for polymerizing olefins prepared from the catalysts - Google Patents
Catalysts components and catalysts for polymerizing olefins prepared from the catalystsInfo
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- CA1120910A CA1120910A CA000303783A CA303783A CA1120910A CA 1120910 A CA1120910 A CA 1120910A CA 000303783 A CA000303783 A CA 000303783A CA 303783 A CA303783 A CA 303783A CA 1120910 A CA1120910 A CA 1120910A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT OF DISCLOSURE
Catalyst components for mixing with organometallic compounds of Groups I, II and III of the Periodic Table, for polymerizing olefins e.g. alpha-olefins of three or more carbon atoms, ethylene and mixtures thereof with alpha-olefins and/or diolefins or multiolefins, consist essentially of the product obtained by successively reacting (A) A Mg compound (halide, alcoholate, haloalcoholate, carboxy late, oxyde, hydroxyde, salt of an inorganic oxygen contain ing acid, Grignard reagent or reaction product of a Grignard reagent with a silicon compound), optionally in the form of a complex with an electron-donor compound, with (B) a compound having general formula [MOx (OR)y-]n, wherein M = Ti, V or Zr, R = an alkyl, an aryl or a cyaloalkyl con-taining 1 to 20 carbon atoms, x may be zero, y is an integer from 1 to 6 (inclusive), and with (C) a compound, other than the aluminum halide , exerting on component (B) a halogenating action and a reducing action, or a mixture of a halogenating compound with a reducing substance.
Catalyst components for mixing with organometallic compounds of Groups I, II and III of the Periodic Table, for polymerizing olefins e.g. alpha-olefins of three or more carbon atoms, ethylene and mixtures thereof with alpha-olefins and/or diolefins or multiolefins, consist essentially of the product obtained by successively reacting (A) A Mg compound (halide, alcoholate, haloalcoholate, carboxy late, oxyde, hydroxyde, salt of an inorganic oxygen contain ing acid, Grignard reagent or reaction product of a Grignard reagent with a silicon compound), optionally in the form of a complex with an electron-donor compound, with (B) a compound having general formula [MOx (OR)y-]n, wherein M = Ti, V or Zr, R = an alkyl, an aryl or a cyaloalkyl con-taining 1 to 20 carbon atoms, x may be zero, y is an integer from 1 to 6 (inclusive), and with (C) a compound, other than the aluminum halide , exerting on component (B) a halogenating action and a reducing action, or a mixture of a halogenating compound with a reducing substance.
Description
This invention relates to polymerization catalysts, and most particularly to catalyst components for the polymerization of olefins.
It is known that ethylene, the alpha-olefins, and mixtures thereof with each other and/or with diolefins can be polymerized with the aid of catalysts prepared from a transition metal halide, such as T~.C14 or TiC13, and ; organometallic compounds of Groups I-III, such as organometallic compounds of Al~ Many modifications of such catalysts have been proposed in the art. However, it is also known, that many of such catalyst systems have drawbacks and disadvantages when used in practice.
This invention provides new catalyst components w~ich result in final catalys-ts that exhibit particularly high activity in the polymerization of olefins while being generally free of various disadvantages when used in actual practice for the production of the olefin polymers on a large commercial scale.
~: According to an aspect of the present invention, there ~ are provided catalyst components obtained by reacting the product of reaction between ~
ZO910 ~`
(A) a magnesium compound selected from the groups:
1) compound having formula XnMg~OR)2_n wherein X`is a halogen atom~ hydroxyl group or an~
. S alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms; R is an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms~ or a -CORI .
radical in which R' has the same meanlng as R;
: 0~ n ~2; or products of reaction of said compound~
with electron-donor compounds;
:
~ 2) compounds ha~ing formula `~ I RMg~
: ¦ wherein X lS a halogen atom, and R is an alkyl~
. aryl or cycloalkyl radical containing 1-20 carbon~
¦ atoms, or pFoducts of reaction of said compounds ¦
; with silicon compounds containing the monomerlc unit -~iO - in which R is the same or different R' ¦ ~ . from Rl~ R being an alkyl, aryl, alkoxy or arylox~
radical~ and R~ being hydrogen?halogen or an alkyl9 aryl or cycloalkyl radlcal containing 1-20 carbon atoms, the polymerization grade of said silicon compound ranging from 2 to lOOO, or ' . I
~-~0910 with silanols of formula R Si ~OH)4 ~ wherein n is 1, 2 or 3 and R is hydrogen, alkylg aryl or cycloalkyl having 1-20 carbon atoms or with con-densation products of said silanols.
3) Mg oxide, Mg hydroxide, Mg hydroxy hali.des~ or Mg salts of inorganic oxygen containing acids;
.' . and (B) a compound of Ti~ V or Zr containing at lea6t two metaloxygen bonds Ti-OR, V-OR and ~r-OR~ wherein R is an a1kyl3 aryl or cycloalkyl radical having l 1-20 carbon atoms, : with . ..
(C) a compound, other than the aluminum halides, cap-: able of exerting a halogenating and a reducing action on compound (B), i.e. capable of substitut-ing in compound tB) at least one group -OR with - ` a halogen atom and of reducing the metal of com-pound (B) to a lower valence, or a mixture of a halogenating compouncl with a reducing substance~
the reaction between compounds (A) and (B) being conducted in the presence of an electron_donor com-- pound when compound (A) is an (A~ 3) compound, and component (C) being a halogenating, but not neces-sarily a reducing compound when (A) is an (A) 2) 25 ~ compound~
compounds ~A) and (B) being reacted in such amounts as to have a transi~ion metal/mg atomic ratio comprised between 0.02 and 20, while com-pound (C) is employed in such an amount as to have 0.5 to 100 gram-a~toms of haloyen per gram-atom of transition metal and 0.1 ~o 100 gram-equivalents of reducing agent per gram-atom of transition metal.
- 3a -' i 1~ 112091V
Examples of (A) 1) compounds are the Mg clihalides~
the ~Ig monO- and dialcoholates~ examples of which are
It is known that ethylene, the alpha-olefins, and mixtures thereof with each other and/or with diolefins can be polymerized with the aid of catalysts prepared from a transition metal halide, such as T~.C14 or TiC13, and ; organometallic compounds of Groups I-III, such as organometallic compounds of Al~ Many modifications of such catalysts have been proposed in the art. However, it is also known, that many of such catalyst systems have drawbacks and disadvantages when used in practice.
This invention provides new catalyst components w~ich result in final catalys-ts that exhibit particularly high activity in the polymerization of olefins while being generally free of various disadvantages when used in actual practice for the production of the olefin polymers on a large commercial scale.
~: According to an aspect of the present invention, there ~ are provided catalyst components obtained by reacting the product of reaction between ~
ZO910 ~`
(A) a magnesium compound selected from the groups:
1) compound having formula XnMg~OR)2_n wherein X`is a halogen atom~ hydroxyl group or an~
. S alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms; R is an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms~ or a -CORI .
radical in which R' has the same meanlng as R;
: 0~ n ~2; or products of reaction of said compound~
with electron-donor compounds;
:
~ 2) compounds ha~ing formula `~ I RMg~
: ¦ wherein X lS a halogen atom, and R is an alkyl~
. aryl or cycloalkyl radical containing 1-20 carbon~
¦ atoms, or pFoducts of reaction of said compounds ¦
; with silicon compounds containing the monomerlc unit -~iO - in which R is the same or different R' ¦ ~ . from Rl~ R being an alkyl, aryl, alkoxy or arylox~
radical~ and R~ being hydrogen?halogen or an alkyl9 aryl or cycloalkyl radlcal containing 1-20 carbon atoms, the polymerization grade of said silicon compound ranging from 2 to lOOO, or ' . I
~-~0910 with silanols of formula R Si ~OH)4 ~ wherein n is 1, 2 or 3 and R is hydrogen, alkylg aryl or cycloalkyl having 1-20 carbon atoms or with con-densation products of said silanols.
3) Mg oxide, Mg hydroxide, Mg hydroxy hali.des~ or Mg salts of inorganic oxygen containing acids;
.' . and (B) a compound of Ti~ V or Zr containing at lea6t two metaloxygen bonds Ti-OR, V-OR and ~r-OR~ wherein R is an a1kyl3 aryl or cycloalkyl radical having l 1-20 carbon atoms, : with . ..
(C) a compound, other than the aluminum halides, cap-: able of exerting a halogenating and a reducing action on compound (B), i.e. capable of substitut-ing in compound tB) at least one group -OR with - ` a halogen atom and of reducing the metal of com-pound (B) to a lower valence, or a mixture of a halogenating compouncl with a reducing substance~
the reaction between compounds (A) and (B) being conducted in the presence of an electron_donor com-- pound when compound (A) is an (A~ 3) compound, and component (C) being a halogenating, but not neces-sarily a reducing compound when (A) is an (A) 2) 25 ~ compound~
compounds ~A) and (B) being reacted in such amounts as to have a transi~ion metal/mg atomic ratio comprised between 0.02 and 20, while com-pound (C) is employed in such an amount as to have 0.5 to 100 gram-a~toms of haloyen per gram-atom of transition metal and 0.1 ~o 100 gram-equivalents of reducing agent per gram-atom of transition metal.
- 3a -' i 1~ 112091V
Examples of (A) 1) compounds are the Mg clihalides~
the ~Ig monO- and dialcoholates~ examples of which are
2 5)2~ gt n C4~9)2~ C21l5 M~C13 n_C H 0 MgCl the Mg carboxylates such as Mg acetate.
As Mg dihalides the following compounds can be em-ployed MgC12y which is tlhe preferred one, MgBr2, ¦ MgI2~ MgCl2.nR0H (R= alkyl group~ n= 1-6)~ for example MgC12o3C2H50H~ or MgC12.n H20 (0' n f 6)~ and adducts of MgCl2 with electron-donor compounds not containing active hydrogen atoms, li~e thc esters of carboxylic acids, the ethers, ketones or amines.
Examples of ~A) 2) compouncls are C~2H5MgC L~ n-C4HgMgCl, n-C H MgBr and products of a reaction of said Grignard 4 9 ~e~y/~ Jr~ ttys,/0~ e reagents with diphenyl disiloxane, ~Lh~ _ 1~
~ co-dimethyl dihydro polysiloxane or diphenyl ¦
- silandiol.
Examples of (A) 3) compounds are ~Ig0 ClMg0H~ Mg carb_ nat e .
The electron-donor compounds used with the (A) 3) com-pounds are preferably selected amongst the esters of organic oxygen containing acids, particularly the esters of aromatic acids, the alcohols such as etha-nol, n-butanol, 2-ethylhexanol, and the silands.
The electron-donor compound is present at least during the haloOenation reaction conducted with component ~ 1~ (C), _4_ ! ! Component (B~ can be represented by the formula / MO ~OR) ~ wherein M is Ti~ V or Zr~ R is an i alkyl, alkenyl9 aryl or cycloalkyl radical having ~ 20 carbon atoms~ x may also be zero~ y being not lower than 2, ~+y = valence of M, and n is an inte-ger from 1 to 6 tinclusiye).
Example of component ~B) are:
2 5)4~ Ti(O-n_C4Hg)4~ Ti~O-i C H ) l ( 6 5)4~ Vt-i-C3H7)4~ Vo(O-i-C3H ) ~
Ti~triacetylacetonate Ti (OCH3)2 ~OC2H5)2.
I
- I Howev0r, haloalcoholates can be also used, as for in~
stance ~n~C4H90)3 TiCl.
I !
Component (C) comprises a halogen-containing, prefe- i rably a chlorine-containing compound, capable of substituting a ¦
l halogen atom for at least one group -OR in component ~B).
Specific examples of such compounds include organic acid halides RCOX ~in which X is halogen, preferably chlorine~ and R is an aliphatic or aromatic radical); hydrogen halides such as ~ HCl, SOCl2, COCl2, TiCl4~ BCl3~ and others-1 Particularly satisfactory results are achieved by ! using halogen-containing silicon compounds or halogen and hydrogen-containing silicon compounds. The latter act as both i reducing agents and halogenating agents. Specific examples ¦ of such silicon compounds include:
.1 ~
~ ', . I
)910 silicon halides having formula SiX4 Y ~ in which X and Y represent halogen atoms~ e.g.g Cl and Br~ and n is a number varying from zero to 3, inclusive, such as SiC14;
chlorosiloxanes;of formula Si n lC12n+2~ in which n is a number varying from 2 to 7 inclusive, e.g., Si20C16;
halogenated polysilanes having for~ula Si X2 ~2' wherein X is halogen and n is a number varying from 2 to 6, inclusive, for instance Si4Cllo;
halogensilanes having formula SiH4 X , in which X is halogen and n is a number varying from 1 to 3~ inclusive~
e.g., SiHC13;
alkyl-halogensilanes having formula R SiH X wherein R is an aliphatic or aromatic radical, X is halogen, n is a number from 1 to 3~ inclusive~ x is a number varying from zero to 2~ inclusive, and y is a number varying from 1 to 3, inclusive~ e-g-, C2H5SiC13; CH3SiC12H; (CH3)2SiC12;
alkoxy-halogensilanes of formula Si(OR)4 X in which X is halogen, R is alkyl or aryl having l to 20 carbon atoms and n is a number from 1 to 3, inclusive, e.g.
SitC2~l5~C13-If the product of the reaction bet~een components (A) and (B) is reacted with a compound which is halogenating agent, and not a halogenating and reducing agent, such halogenatlng compound should be used with a compound which is a reducing agent for the ~A) and (B) reac-tion product~
i.e.~ capable of lo~ering the valen~e of the metal contained ~ \ 1~ 0 in component ~B) to a value below that of its starting valence.
Examples of such useful reducing agents include Na-alkyls, Li-alkyls, Zn-alkyls, Mg-alkyls and corresponding aryl-derivativ-es, Grignard compounds of the type RMgX (R is an aliphatic or aromatic hydrocarbon radical; X is halogen), the Na + alcohol system, and furthermore NaH and LiH.
Particularly effective silicon compounds are the polyhydrosilo-xanes in which the monomer unit has the general formula 1 0 - Si O-R
wherein R is H, halogen~ alkyl with 1 to lQ carbon atoms, aryl~
alkoxyl, aryloxyl or carboxyl, and the polymerization grade ranges from 2 to 1~000~ preferably from 3 to 100. Specific examples of such polyhydrosyloxanes include the compounds:
(CH3)3SiO/ (CH3)}1SiO 7n Si (CH3)3, (CH3HSiO)4g ~CH3HSiO)3, H3Si-O-SiH2-OSiH3~ phenylhydropolysiloxanes in which the hydrogen atoms can be partially replaced by methyl groups.
Other silicon compounds useful are reducing agents in ; 20 the practice of this invention are:
silarles Si M? +2~ in which n is a number equal to or higher than 1~ preferably equal to or higher than 3, e.g., Si3H8;
polysilanes that contain the group (SiH) in which x~ 2;
alkyl- or aryl-silanes R SiH4~ ~in which R is alkyl or aryl and x is a number varying~ from 1 to 3, inclusive, é.g., 6H5)3siH~
alkox~ or aryloxy-silanes ~R0)xSiH4_x ~ in which R
is alkyl or aryl and x is a number varying from 1 to 3~ inclusive~
e.g., (C2H50)3SiH.
The new catalyst-forming components of the invention can be obtained by reac~ing (A), ~B) and (C) in an aliphatic or aromatic hydrocarbon diluent or in the absence of diluent.
Whcn at leas~ one of the reagents is in ths liquicl state at the reaction temperature and pressure~ the use of a solvent oan be omitted.
:
~A) and (B) can be reacted preferably until a homogeneous product is obtained~which is then reacted with component (C).
However, if ~C) consists of a halogenating compound plus a reducing compound, the order of addition makes no diffe-rence: i.e., either the halogenating compound or the reducing ~ compound can be reacted first~ It is also possible to add both - ~compounds simultaneous`ly.
The reactions are conducted at a temperature ranging from -10C to +250C, preferably from 20C to 200C, the selection of the temperature depending also on the type of com-ponent (C)~ because the higher its reducing power, the lower the preferre reaction temperatures.
~ 8 ~
'~ . I
0~11) Sirce (C) is both a halogenating agent and a reducing agent, or it consists of a halogenating compound plus a reducing compound~ the titanium~ Yanadium or zirconium in the final catalyst-forming component is almost entirely in the trivalent state~ provided that a suf~icient quantity of reducing agent is used.
Components tA) and (B) are reacted in such amounts as to have a transition metal/Mg atomic ratio comprised between 0.02 and 20~ preferably between 0.1 and 3, while component ~C) is employed in such amount as to have 0.5 to 100, preferably 1 to 30~ ~ram-atoms of halogen per gram-atom of transition metal and 0.1 to 100, preferably 0~5 to 20, gram-equivalents of reducing agent per gram-atom of transition metal.
The catalytic components of the invention in combina-! tion with organometallic compounds of metals belonging to Groups I, II and III of the Mendelyeev Periodic Table, prefer-ably an hl-alkyl~ provide catalysts particularly effect1ve in the polymerization of ethylene and of alpha-olefins.
The ethylene homopolymers prepared with the aid of these catalysts are characterized by a narrow molecular weight distribution, as resulting from the MI N/MI E ratio between melt index measured according to conditions N of standard ASTM
D 1238 and the melt index measured according to conditions E
of the same standard, such ratio being lower than 10 when the melt index is 5 g/10 min. as determined accordin~ to AS~I D-1238 (condition E).
_9.- 1.
This characteristic renders ths ethylene homopolymers :
obtained with the catalysts o~ the present invention particularly ~i suitable for molding.
The following examples are given to illustrate the ~5 invention in more detail, and are not interld~ to be limiting.
2.4 g of MgC12 ( 0. 025 mole) and 17 g ~0.05~ mole) of Tl(Q-n-C4H9)4 were stirred in a flask in a nitrogen atmosphere at 160C~ after 4 hours MgC12 was throughly di~ssolved.
The resuIting solution~ cooled down to 6 OoC~ was di~luted with 8~ cc of anhydrous n-heptane. Into this solution kept at 600C
and under stirring~ a solution of 5.8 cc (0.05 mole) of SiC14 - ln 20 cc of n-heptane was inbroduced in 1 hour. Once the addltion was completed, the reaction mass was further heated for I h and 30 min. to g80c. The~resulting suspension was again brought to 600C and l9.4 cc (20.6 g) of polymethylhydrosiloxane (PMHS) of formula (CH3)3SlO/~cH3)Hs~o 7 si( CH3)3 ~ wherein n~had a value~of about 35~ was dropped into it at 600C and over ` ~ ~ a time of 2 hours.
At the conclusior. of the addition~ stirring was con-tinued for l hour at a temperature of 980C. After cooling to room temperature~ the resulting precipitate was repeatedly washed with anhydrous n-hexane and finally dried under vacuum at 70C
to constantiweight, thus obtaining 11.2 g of a red-orange power i ¦ containin~ I 95~ of Ti.
~ ~ -10-~ ~ ..
~ llZO910 For the polymerization test~ a stainless steel 2.5-liter autoclave was fed~ in the order stat~d and in a nitrogen atmosphere~ with: 1~000 cc of anhydrous n-hexane~ 1.5 g of Alti-C4H9)3 as co-catalyst and, finally~ 0.014 g oE the cata-lytic powder containing 2.5% of Ti. The autoclave was immediately heated to 85C and 5.2 hydrogen atmospheres as well as 7.8 ethy-lene atmospheres, were introducéd, the ethylene feed being carried on continuously for 4 hours. The suspension was ~ischarged from the autocla~e, filtered, and the polyethylene was dried in an oven to canstant weight. 170 g of polyethylene, corresponcling ; to-a yield of 71,700 g/g of Ti, were thus obtained.
The polymer had a melt index E (MI E) of 3.S g/10 min.~ the MI N/MI E ratio being 8.6.
2.4 g (0.025 mole) of MgCl2 were dissolved in 17 g (0.05 mole) of Ti~0-n-C4Hg)4, as in Example 1. The solution, after cooling to 45C, was diluted with 50 cc of anhydrous ; n-hexane. Into this solution, kept at 45C and under stirring~;~ a solution consisting of 30 cc of anhydrous n-hexane, 8 cc of ;~ 20 PMHS ~of the same type as employed in Example 3) and 17.4 cc (0.15 mole) of SiCl4 was introduced in 3 hours.
At the conclusion of the addition~ the suspension was stirred for a further 1 hour at 45C and then for 1 hour at the hexane reflux temperature. After coo]ing to room temperatur the resulting precipitate was isolated as described in Example 1.
4.4 g of a light brown powder, containing 4.75% of Ti, were obtained.
Il l~LZOglO
Ethylene was polymerized as disclosed in Example 1 except that the autoclave was fed with 0.0146 g of the cataly-tic powder containing 4.75% of Ti. 400 g of polyethylene, corresponding to a yield of 577, 200 g/g of Ti, were obtained.
The polymer had a melt index E of 4 85 g/10 min. and the MI N/MI E ratio was 8.2.
2.4 g of MgC12 ~0.025 mole) were dissolved in 17 g to.o5 mole) of Ti~0-n-C4H9)4 as described in Example 1 The solution~ cooled to 45C~ was diluted with 50 cc of anhydrous n-hexane. Into ths solution5 kept at 45C and under stirring, a solu-tion of 10.65 cc of PMHS ~of the same type as used in ; Example 3)and 20 cc of anhydrous n-hexane was introduced in 1 hour. At the conclusion of the addition, the reaction mass was heated for 1 hour at the hexane reflux temperature. The ; temperature was then brought to 45C, whereupon a solu'ion of 25~5 g (0.15 mole~ of SiC14 and of 20 cc of anhydrous n-hexane was introduced in 90 minutes into the suæpension. At the con-clusion of the addition, the reaction mixture was heated -Eor 90 minutes at the hexane reflux temperature. After cooling to room temperature, the resulting precipitate was isolated as described in Example 1. 6.5 g of a brown powder containing 12.65% of Ti were obtained.
Ethylene was polymerized as in Example 1, with the ~5 exception that 0.0136 g of the catalytic po~der containing 12 . 65% o~ Ti was charged to the autoclave.
l~Og~O
328 g of polyethylene, corresponding to a yield of 190,700 g/g of Ti~ were obtained~ The polymer had a melt index E ~ 4.55 g/10 rnin. t the MI N/MI E ratio was 8.5.
1.35 g of MgC12 ~0.014 mole) were dissol~ed in 8.5 g of Ti(O-n-C4H9)4 (0.025 mole) as described in Example 1. The resulting solution was cooled to room temperature, diluted with 50 cc of n-heptane and introduced, in 2 hours~ into a ~ flask containing 17 cc of a 2.97 molar solution of C2H5MgCl in ; 10 diethyl ether~ kept under stirring and at a temperature of 0C.
Successively the resulting suspension was gradually ; heated to 600C and additioned in 1 hour~ with 34 g (0.2 mole) of SiC14. Once all of the SiC14 was introduced~ the reaction ¦ mixture was stirred for a further 90 minutes~ and the temperature having been raised to 98C. Af-ter cooling to room temperature~
the resulting precipitate was isolated as described in Example 1. 900 g of a grey powder contalning 5.3% of Ti were obtained.
Ethylene wa~ polymeri~ed as in Example 1, except that the autoclave was -fed with 0.016 g of the catalytic powder con-taining 5.3% of Ti.
320 g of polyethylene~ corresponding to a yield of 377~300 g/g of Ti~ were obtained. The polymer had a melt index E of 9.7 g/10 min.; the MI N/MI E ratio was 8.6.
EXA~IPLE 5 204 g of klgCl~ (0.025 mole) were dissolved in 17 g of Ti(O-n-C4Hg)4 (0.05 mole)~ as described in Examp7e 1. The solution was cooled to 40C and diluted with 80 cc of anhydrous -~ ~
n-heptane. In-to th s solution, l~ept under stirring at 40C~
15.7 cc ~0.15 mole) of dichloromethylsilane were introduced in 2 hours~
At the conclusion of said addition~ the suspersion was heated for a further two- hours at a temperature of 98C.
After cooling to room tempërature~ the resultirlg precipitate was isolated as described in Example 1. 4.5 g of a light red powder containing 8005 ~ of Ti were thus obtalned~
Ethylene was polymerized as described in Example 1, with the exception that -the autoclave was fed with 0.0107 g oE
the catalytic powder containing 8.05~ of Ti.
317 g oE polyethylene~ corresponding to a yield of 368~600 g/g of Ti~ were obtained~ The polymer had a melt index E of 3.2 g/10 min.; the MI N/MI E ratio was 8.2.
. I
15 ~ EXAMPLE 6 2.4 g (0~025 mole) of MgCl2 were dissolved in 17 g (0.05 mole) of Ti tO-n C4H9)4, as in Example 1. The resulting solution was cooled to room temperature and diluted with 40 cc of anhydrous n-hexane. Into this solution, successively cooled to 15C and stirred, a solution of 40.9 g (0.3 mole) of SiHC13 in 10 cc of anhydrous n-hexane was introduced in 4 hours. At the conclusion of such addition, the tempera-ture was raised to 600C
and kept at that temperature for 1 hour. Af-ter cooling to room temperature, the resulting precipitate was isolated as described in Example 1. 3.6 g of a grey powder containing 6.4 of Ti were thus obtained.
11~0910 Ethylene was polymerized as in Exampie 1~ with the only exception that the autoclave was fed with 0.0088 g of the catalytic powder containing 6.4% of Ti. 330 g of polyethylene were ob~ned, corresponding to a yield of 586,100 g/g of Ti.
The polymer had a mel-t ind-ex E of 2.3 g/10 min. The MI N/MI E
ratio was 9n 0~
The same procedure of example 2 was followed with the clifference that 4.8 g (0.05 moles~ of Mg C12 were dissolved in a mixture of 17 g ~0.05 moles) of ~i (0-n-C~H9)4 and 4.5 cc (0.05 moles) of n-butanol.
; After dissolution~ 20 cc of anhydrous n-hexane were added and, successively~ 12.7 cc (0.11 moles} of SiCl4 and 24.3 cc of PMHS. Thus~ 8.1 g of catalyst component containing 8 ~ 5~o Of Ti ~ 15 were obtained.
; For the ethylene polymerization test it ~as operated as in example 1~ except that 0.012 g of the catalyst component thus prepa~ed were charged into the autoclave.
170 g of polye-thylene, corresponding to a yield of 167~C00 g/g Ti~ were obtained. The polymer exhibi-ted a melt index E of 4.3 g/10 min. and the MIN/MIE ratio was equal to 8. 8 The same procedure of example 2 was followed with the difference that 4.8 g ~0.05 moles) of MgC12 were dissolved in 34 g (0.1 moles) of Ti(0-n-C4H9)4. After dissolution~ 50 cc of n-hexane wo added and the resulting hexane solution was fel~
15 ~
, ~ 9~
a-t 45C and during 3 hours, into a solution consisting of 20 cc of n-hexane~ 17.3 cc (0.15 molesj of SiCl4 and 16.8 cc of PMHS.
Thus, 11.1 g of catalyst component containing 11.0% Ti were obtain ed.
The ethylene polymerization test o~ example 1 was repeat ed~ except that 0.016 g o-E the catalyst COmpOnerlt thus prepared were employed.
3Z0 g of polyethylene~ corresponding to a yield of 178,000 g/g Ti, were obtained. The melt index E of the polymer was 5.4 g/10 min. and the MIN/MIE ratio was 8Ø
The same procedure of example 2 was followed with -the difference that 2.4 g (0.025 moles) of MgCl2 were dissolved in 31 g to.o5 moles) of Ti (0-n-C9H19~4. After dissolution, 50 cc of n-hexane were added and, successively3 8.6 cc to.o74 moles) of SiC14 and 6.8 cc of PMHS were also added and the whole was reacted at 45C for 3 hours. 4.1 g of a catalyst c~mponent j containing 7.7~ Ti were obtained.
¦ The ethylene polymerization test was carried out as in example 1, with the difference that 0.016 g of the catalyst component thus prepared were charged into the autoclave.
130 g of polyethylene, corresponding to a yield of 102,000 g/g Ti~ were obtained. The melt index E of the polymer was 2.7 g/10 min. and the MIN/MIE ratio was 9.1. -EXA~IPLE 10 Example 5 was repeated employing the same amounts of ~lgCl2, Ti(0- -C4H9~ and n-heptane~ but with the difference that _ 16 -33 cc ~0.3 moles) of tC}13)2 Cl Si H~ in the place of Cl2C~3Si Tls were employed. Thus~ 7.8 g of a catalyst component containing 14.1% Ti were obtained.
The ethylene polymerization test was carried out as in example 1, employing 0.017~ g of the catalyst component thus ¦ prepared.
¦ 265 g of polyethylene~ corresponding to a yield of ¦ of 106,000 g/g Ti~ were obtained. The polymer exhibited a melt index E of 5.9 g/10 min. and the MIN/MIE ratio was 7.9.
Example 8 was repeated with the dif~erellce that the so-lution of SiCl4 and PMHS was added to the other reagents all at once instead of during 3 hours. Thus~ 9.3 g of a catalyst compo-nent containing 5.0 ~0 Ti were obtained.
For the ethylene polymerization test it was operated as in example 1, with the difference that 0.015 g of the catalyst component thus prepa~ed were employed.
l 360 g of polyethylene, corresponding to a yield of : 480~000 g/g Ti~were obtained~ The melt index E of the polymer was 5.3 g/10 min. and the MIN/MIE ratio was 7.9.
EXAMPLE_12 Example 2 was repeated employing 13.g g to.o4 moles) of Ti ~0-n-C4H9~4, 1-8 g t0-019 moles) of MgC12 and 7.1 cc ~0.06 moles) of SiC14; 7-5 g (0-04 moles) of Si (0C2H5~3}1 were used in the place of PMHS. Thus, 3.2 g of a catalyst component con-taining I . 5 ,~ Ti were o~tained.
2'~
Ethylene ~as polymerized as in example 1 by the aid of 0.020 g of the above catalyst component: 195 g of polyethylene, corresponding to a yield of 70,500 g/g Ti~ were obtained. The poly mer exhibited a melt index E of 3.0 g/10 min. and the MIN/MIE
5 ratio was 8.4.
EX~IPLE 13 ~ Example 2 wa5 repeated employing 17 g (0.05 moles) of ¦Ti~0-n-C4Hg)4, 2.2 g ~0.023 moles) of MgCl2, 9.1 cc of PMHS and ¦10 cc (0.1 moles) of SiHCl3 in the place of SiCl4. Thus, 9.1 g of 1 a catalyst component containing 13.0 % Ti were obtained.
By polymerizing ethylene as described in example 1 in the presence of 0.015 g of the catalyst component thus prepared9 129 g of polyethylene corresponding to a yield of 65,ooo g/g Ti were obtained: the polymer exhibited a melt index E of 4.2 g/10 ~min. and the MIN/MIE ratio was 8Ø
~¦ Example 2 was repeated employing 34 g (Ool moles) of Tl(O-n-C~H9)4~ 4.8 g ~0.05 moles) of MgCl2, 17.3 cc ~0.15 moles) of SiC14 and, in the place of PMHSg 28.0 g of a partially methyl~
- 20 ated polymethylhydrosiioxane containing 0.9 by weight of hydrogen (TEGILOXAN PTF 16 produced by Goldschmidt). Thus, 12.2 g of a ca-talyst component containing 9.1% Ti were obtained.
The ethylene polymerization test ~as carried out as in example 1 by the aid of 0.016 g of the above catalyst component and 125 g of polyethylene, corresponding to a yield of ~5,500 g/g Ti, were obtained; the polymer exhibited a melt index E of 1.1 g/10 min. and the ~ IIE ratio was 7.75.
I ~ ~/e J~
~ - 18 -' 11 EXA~IPLE 15 ¦¦ Example 2 was repeated with the difference that 15.9 g (0.052 moles) of Ti ~0-n~C4H9)3 Cl were employed in the place ¦ of Ti~0-n-C4H~)4 and that 5.8 g (0.0176 moles) of MgC12.5C2H50H
¦! were employed in the place of MgC12. Fol]owing the same procedure 5 ¦1 of example 2~ 17.3 cc (0.15 moles) of SiC14 and 20.2 cc of PMHS
il were employed. Thus, 2.9 g of a catalyst component containing 9.4 % Ti were obtained.
The ethylene polymerization test was carried out as in example 1 by the aid of 0.016 g of the above catalyst component I and 296 g of polyethylene~ corresponding to a yield o-E 197,000 ¦ g/g Ti~ were obtained; the melt index E of the polymer was 6.8 ¦ g/10 min. and the MIN/MIE ratio was 9.5.
Into a flask of 250 cc capacity were introduced 0.925 g~
(o.038 moles~ of chips of Mg metal, ~.7 cc of absolute C2H50H
and 25 g ~0.0725 moles) of Ti(0-n-C4H9), the temperature was gradually raised up to 130C and maintained at this ~alue for 2 hours; then the unreacted ethanol was removed by distil-lation. After cooling to 50C, 50 cc of n-hexane were added to 20 - the obtained solution; then 43 cc ~0.375 moles) of SiC14 and 27 cc of PMHS were fed, during 4 hours, into this diluted solution maintained at 50C. After the above addition, the whole was heated at the refluxing temperature of hexane for l hour and~¦
after cooling to room temperature~ the catalytic solid so obtain i 1 ed was washed with hexane un~il disappea~ance of the Cl'ions.
- 1:9-z~9~ l ll ~
After ~rying, 9.4 g of a catalyst component containing 6.3 %
Ti were obtained.
The ethylene polymerization test was carried out as 1 described in example 1, in the presence of 0.0144 g of the above 1 catalyst component, and 411-g of polyethylene, corresponding to a yield of 466,000 g/g T1, were obtained. The polymer exhibited a melt index E of 3.5 g/10 min and the MIN/MIE ratio was 8.7.
2.4 g (0.0167 moles) of anhydrous Mg acetate were reacted with 17 g (0.05 moles) of Ti (O-n-C4H9)4 at 135C for
As Mg dihalides the following compounds can be em-ployed MgC12y which is tlhe preferred one, MgBr2, ¦ MgI2~ MgCl2.nR0H (R= alkyl group~ n= 1-6)~ for example MgC12o3C2H50H~ or MgC12.n H20 (0' n f 6)~ and adducts of MgCl2 with electron-donor compounds not containing active hydrogen atoms, li~e thc esters of carboxylic acids, the ethers, ketones or amines.
Examples of ~A) 2) compouncls are C~2H5MgC L~ n-C4HgMgCl, n-C H MgBr and products of a reaction of said Grignard 4 9 ~e~y/~ Jr~ ttys,/0~ e reagents with diphenyl disiloxane, ~Lh~ _ 1~
~ co-dimethyl dihydro polysiloxane or diphenyl ¦
- silandiol.
Examples of (A) 3) compounds are ~Ig0 ClMg0H~ Mg carb_ nat e .
The electron-donor compounds used with the (A) 3) com-pounds are preferably selected amongst the esters of organic oxygen containing acids, particularly the esters of aromatic acids, the alcohols such as etha-nol, n-butanol, 2-ethylhexanol, and the silands.
The electron-donor compound is present at least during the haloOenation reaction conducted with component ~ 1~ (C), _4_ ! ! Component (B~ can be represented by the formula / MO ~OR) ~ wherein M is Ti~ V or Zr~ R is an i alkyl, alkenyl9 aryl or cycloalkyl radical having ~ 20 carbon atoms~ x may also be zero~ y being not lower than 2, ~+y = valence of M, and n is an inte-ger from 1 to 6 tinclusiye).
Example of component ~B) are:
2 5)4~ Ti(O-n_C4Hg)4~ Ti~O-i C H ) l ( 6 5)4~ Vt-i-C3H7)4~ Vo(O-i-C3H ) ~
Ti~triacetylacetonate Ti (OCH3)2 ~OC2H5)2.
I
- I Howev0r, haloalcoholates can be also used, as for in~
stance ~n~C4H90)3 TiCl.
I !
Component (C) comprises a halogen-containing, prefe- i rably a chlorine-containing compound, capable of substituting a ¦
l halogen atom for at least one group -OR in component ~B).
Specific examples of such compounds include organic acid halides RCOX ~in which X is halogen, preferably chlorine~ and R is an aliphatic or aromatic radical); hydrogen halides such as ~ HCl, SOCl2, COCl2, TiCl4~ BCl3~ and others-1 Particularly satisfactory results are achieved by ! using halogen-containing silicon compounds or halogen and hydrogen-containing silicon compounds. The latter act as both i reducing agents and halogenating agents. Specific examples ¦ of such silicon compounds include:
.1 ~
~ ', . I
)910 silicon halides having formula SiX4 Y ~ in which X and Y represent halogen atoms~ e.g.g Cl and Br~ and n is a number varying from zero to 3, inclusive, such as SiC14;
chlorosiloxanes;of formula Si n lC12n+2~ in which n is a number varying from 2 to 7 inclusive, e.g., Si20C16;
halogenated polysilanes having for~ula Si X2 ~2' wherein X is halogen and n is a number varying from 2 to 6, inclusive, for instance Si4Cllo;
halogensilanes having formula SiH4 X , in which X is halogen and n is a number varying from 1 to 3~ inclusive~
e.g., SiHC13;
alkyl-halogensilanes having formula R SiH X wherein R is an aliphatic or aromatic radical, X is halogen, n is a number from 1 to 3~ inclusive~ x is a number varying from zero to 2~ inclusive, and y is a number varying from 1 to 3, inclusive~ e-g-, C2H5SiC13; CH3SiC12H; (CH3)2SiC12;
alkoxy-halogensilanes of formula Si(OR)4 X in which X is halogen, R is alkyl or aryl having l to 20 carbon atoms and n is a number from 1 to 3, inclusive, e.g.
SitC2~l5~C13-If the product of the reaction bet~een components (A) and (B) is reacted with a compound which is halogenating agent, and not a halogenating and reducing agent, such halogenatlng compound should be used with a compound which is a reducing agent for the ~A) and (B) reac-tion product~
i.e.~ capable of lo~ering the valen~e of the metal contained ~ \ 1~ 0 in component ~B) to a value below that of its starting valence.
Examples of such useful reducing agents include Na-alkyls, Li-alkyls, Zn-alkyls, Mg-alkyls and corresponding aryl-derivativ-es, Grignard compounds of the type RMgX (R is an aliphatic or aromatic hydrocarbon radical; X is halogen), the Na + alcohol system, and furthermore NaH and LiH.
Particularly effective silicon compounds are the polyhydrosilo-xanes in which the monomer unit has the general formula 1 0 - Si O-R
wherein R is H, halogen~ alkyl with 1 to lQ carbon atoms, aryl~
alkoxyl, aryloxyl or carboxyl, and the polymerization grade ranges from 2 to 1~000~ preferably from 3 to 100. Specific examples of such polyhydrosyloxanes include the compounds:
(CH3)3SiO/ (CH3)}1SiO 7n Si (CH3)3, (CH3HSiO)4g ~CH3HSiO)3, H3Si-O-SiH2-OSiH3~ phenylhydropolysiloxanes in which the hydrogen atoms can be partially replaced by methyl groups.
Other silicon compounds useful are reducing agents in ; 20 the practice of this invention are:
silarles Si M? +2~ in which n is a number equal to or higher than 1~ preferably equal to or higher than 3, e.g., Si3H8;
polysilanes that contain the group (SiH) in which x~ 2;
alkyl- or aryl-silanes R SiH4~ ~in which R is alkyl or aryl and x is a number varying~ from 1 to 3, inclusive, é.g., 6H5)3siH~
alkox~ or aryloxy-silanes ~R0)xSiH4_x ~ in which R
is alkyl or aryl and x is a number varying from 1 to 3~ inclusive~
e.g., (C2H50)3SiH.
The new catalyst-forming components of the invention can be obtained by reac~ing (A), ~B) and (C) in an aliphatic or aromatic hydrocarbon diluent or in the absence of diluent.
Whcn at leas~ one of the reagents is in ths liquicl state at the reaction temperature and pressure~ the use of a solvent oan be omitted.
:
~A) and (B) can be reacted preferably until a homogeneous product is obtained~which is then reacted with component (C).
However, if ~C) consists of a halogenating compound plus a reducing compound, the order of addition makes no diffe-rence: i.e., either the halogenating compound or the reducing ~ compound can be reacted first~ It is also possible to add both - ~compounds simultaneous`ly.
The reactions are conducted at a temperature ranging from -10C to +250C, preferably from 20C to 200C, the selection of the temperature depending also on the type of com-ponent (C)~ because the higher its reducing power, the lower the preferre reaction temperatures.
~ 8 ~
'~ . I
0~11) Sirce (C) is both a halogenating agent and a reducing agent, or it consists of a halogenating compound plus a reducing compound~ the titanium~ Yanadium or zirconium in the final catalyst-forming component is almost entirely in the trivalent state~ provided that a suf~icient quantity of reducing agent is used.
Components tA) and (B) are reacted in such amounts as to have a transition metal/Mg atomic ratio comprised between 0.02 and 20~ preferably between 0.1 and 3, while component ~C) is employed in such amount as to have 0.5 to 100, preferably 1 to 30~ ~ram-atoms of halogen per gram-atom of transition metal and 0.1 to 100, preferably 0~5 to 20, gram-equivalents of reducing agent per gram-atom of transition metal.
The catalytic components of the invention in combina-! tion with organometallic compounds of metals belonging to Groups I, II and III of the Mendelyeev Periodic Table, prefer-ably an hl-alkyl~ provide catalysts particularly effect1ve in the polymerization of ethylene and of alpha-olefins.
The ethylene homopolymers prepared with the aid of these catalysts are characterized by a narrow molecular weight distribution, as resulting from the MI N/MI E ratio between melt index measured according to conditions N of standard ASTM
D 1238 and the melt index measured according to conditions E
of the same standard, such ratio being lower than 10 when the melt index is 5 g/10 min. as determined accordin~ to AS~I D-1238 (condition E).
_9.- 1.
This characteristic renders ths ethylene homopolymers :
obtained with the catalysts o~ the present invention particularly ~i suitable for molding.
The following examples are given to illustrate the ~5 invention in more detail, and are not interld~ to be limiting.
2.4 g of MgC12 ( 0. 025 mole) and 17 g ~0.05~ mole) of Tl(Q-n-C4H9)4 were stirred in a flask in a nitrogen atmosphere at 160C~ after 4 hours MgC12 was throughly di~ssolved.
The resuIting solution~ cooled down to 6 OoC~ was di~luted with 8~ cc of anhydrous n-heptane. Into this solution kept at 600C
and under stirring~ a solution of 5.8 cc (0.05 mole) of SiC14 - ln 20 cc of n-heptane was inbroduced in 1 hour. Once the addltion was completed, the reaction mass was further heated for I h and 30 min. to g80c. The~resulting suspension was again brought to 600C and l9.4 cc (20.6 g) of polymethylhydrosiloxane (PMHS) of formula (CH3)3SlO/~cH3)Hs~o 7 si( CH3)3 ~ wherein n~had a value~of about 35~ was dropped into it at 600C and over ` ~ ~ a time of 2 hours.
At the conclusior. of the addition~ stirring was con-tinued for l hour at a temperature of 980C. After cooling to room temperature~ the resulting precipitate was repeatedly washed with anhydrous n-hexane and finally dried under vacuum at 70C
to constantiweight, thus obtaining 11.2 g of a red-orange power i ¦ containin~ I 95~ of Ti.
~ ~ -10-~ ~ ..
~ llZO910 For the polymerization test~ a stainless steel 2.5-liter autoclave was fed~ in the order stat~d and in a nitrogen atmosphere~ with: 1~000 cc of anhydrous n-hexane~ 1.5 g of Alti-C4H9)3 as co-catalyst and, finally~ 0.014 g oE the cata-lytic powder containing 2.5% of Ti. The autoclave was immediately heated to 85C and 5.2 hydrogen atmospheres as well as 7.8 ethy-lene atmospheres, were introducéd, the ethylene feed being carried on continuously for 4 hours. The suspension was ~ischarged from the autocla~e, filtered, and the polyethylene was dried in an oven to canstant weight. 170 g of polyethylene, corresponcling ; to-a yield of 71,700 g/g of Ti, were thus obtained.
The polymer had a melt index E (MI E) of 3.S g/10 min.~ the MI N/MI E ratio being 8.6.
2.4 g (0.025 mole) of MgCl2 were dissolved in 17 g (0.05 mole) of Ti~0-n-C4Hg)4, as in Example 1. The solution, after cooling to 45C, was diluted with 50 cc of anhydrous ; n-hexane. Into this solution, kept at 45C and under stirring~;~ a solution consisting of 30 cc of anhydrous n-hexane, 8 cc of ;~ 20 PMHS ~of the same type as employed in Example 3) and 17.4 cc (0.15 mole) of SiCl4 was introduced in 3 hours.
At the conclusion of the addition~ the suspension was stirred for a further 1 hour at 45C and then for 1 hour at the hexane reflux temperature. After coo]ing to room temperatur the resulting precipitate was isolated as described in Example 1.
4.4 g of a light brown powder, containing 4.75% of Ti, were obtained.
Il l~LZOglO
Ethylene was polymerized as disclosed in Example 1 except that the autoclave was fed with 0.0146 g of the cataly-tic powder containing 4.75% of Ti. 400 g of polyethylene, corresponding to a yield of 577, 200 g/g of Ti, were obtained.
The polymer had a melt index E of 4 85 g/10 min. and the MI N/MI E ratio was 8.2.
2.4 g of MgC12 ~0.025 mole) were dissolved in 17 g to.o5 mole) of Ti~0-n-C4H9)4 as described in Example 1 The solution~ cooled to 45C~ was diluted with 50 cc of anhydrous n-hexane. Into ths solution5 kept at 45C and under stirring, a solu-tion of 10.65 cc of PMHS ~of the same type as used in ; Example 3)and 20 cc of anhydrous n-hexane was introduced in 1 hour. At the conclusion of the addition, the reaction mass was heated for 1 hour at the hexane reflux temperature. The ; temperature was then brought to 45C, whereupon a solu'ion of 25~5 g (0.15 mole~ of SiC14 and of 20 cc of anhydrous n-hexane was introduced in 90 minutes into the suæpension. At the con-clusion of the addition, the reaction mixture was heated -Eor 90 minutes at the hexane reflux temperature. After cooling to room temperature, the resulting precipitate was isolated as described in Example 1. 6.5 g of a brown powder containing 12.65% of Ti were obtained.
Ethylene was polymerized as in Example 1, with the ~5 exception that 0.0136 g of the catalytic po~der containing 12 . 65% o~ Ti was charged to the autoclave.
l~Og~O
328 g of polyethylene, corresponding to a yield of 190,700 g/g of Ti~ were obtained~ The polymer had a melt index E ~ 4.55 g/10 rnin. t the MI N/MI E ratio was 8.5.
1.35 g of MgC12 ~0.014 mole) were dissol~ed in 8.5 g of Ti(O-n-C4H9)4 (0.025 mole) as described in Example 1. The resulting solution was cooled to room temperature, diluted with 50 cc of n-heptane and introduced, in 2 hours~ into a ~ flask containing 17 cc of a 2.97 molar solution of C2H5MgCl in ; 10 diethyl ether~ kept under stirring and at a temperature of 0C.
Successively the resulting suspension was gradually ; heated to 600C and additioned in 1 hour~ with 34 g (0.2 mole) of SiC14. Once all of the SiC14 was introduced~ the reaction ¦ mixture was stirred for a further 90 minutes~ and the temperature having been raised to 98C. Af-ter cooling to room temperature~
the resulting precipitate was isolated as described in Example 1. 900 g of a grey powder contalning 5.3% of Ti were obtained.
Ethylene wa~ polymeri~ed as in Example 1, except that the autoclave was -fed with 0.016 g of the catalytic powder con-taining 5.3% of Ti.
320 g of polyethylene~ corresponding to a yield of 377~300 g/g of Ti~ were obtained. The polymer had a melt index E of 9.7 g/10 min.; the MI N/MI E ratio was 8.6.
EXA~IPLE 5 204 g of klgCl~ (0.025 mole) were dissolved in 17 g of Ti(O-n-C4Hg)4 (0.05 mole)~ as described in Examp7e 1. The solution was cooled to 40C and diluted with 80 cc of anhydrous -~ ~
n-heptane. In-to th s solution, l~ept under stirring at 40C~
15.7 cc ~0.15 mole) of dichloromethylsilane were introduced in 2 hours~
At the conclusion of said addition~ the suspersion was heated for a further two- hours at a temperature of 98C.
After cooling to room tempërature~ the resultirlg precipitate was isolated as described in Example 1. 4.5 g of a light red powder containing 8005 ~ of Ti were thus obtalned~
Ethylene was polymerized as described in Example 1, with the exception that -the autoclave was fed with 0.0107 g oE
the catalytic powder containing 8.05~ of Ti.
317 g oE polyethylene~ corresponding to a yield of 368~600 g/g of Ti~ were obtained~ The polymer had a melt index E of 3.2 g/10 min.; the MI N/MI E ratio was 8.2.
. I
15 ~ EXAMPLE 6 2.4 g (0~025 mole) of MgCl2 were dissolved in 17 g (0.05 mole) of Ti tO-n C4H9)4, as in Example 1. The resulting solution was cooled to room temperature and diluted with 40 cc of anhydrous n-hexane. Into this solution, successively cooled to 15C and stirred, a solution of 40.9 g (0.3 mole) of SiHC13 in 10 cc of anhydrous n-hexane was introduced in 4 hours. At the conclusion of such addition, the tempera-ture was raised to 600C
and kept at that temperature for 1 hour. Af-ter cooling to room temperature, the resulting precipitate was isolated as described in Example 1. 3.6 g of a grey powder containing 6.4 of Ti were thus obtained.
11~0910 Ethylene was polymerized as in Exampie 1~ with the only exception that the autoclave was fed with 0.0088 g of the catalytic powder containing 6.4% of Ti. 330 g of polyethylene were ob~ned, corresponding to a yield of 586,100 g/g of Ti.
The polymer had a mel-t ind-ex E of 2.3 g/10 min. The MI N/MI E
ratio was 9n 0~
The same procedure of example 2 was followed with the clifference that 4.8 g (0.05 moles~ of Mg C12 were dissolved in a mixture of 17 g ~0.05 moles) of ~i (0-n-C~H9)4 and 4.5 cc (0.05 moles) of n-butanol.
; After dissolution~ 20 cc of anhydrous n-hexane were added and, successively~ 12.7 cc (0.11 moles} of SiCl4 and 24.3 cc of PMHS. Thus~ 8.1 g of catalyst component containing 8 ~ 5~o Of Ti ~ 15 were obtained.
; For the ethylene polymerization test it ~as operated as in example 1~ except that 0.012 g of the catalyst component thus prepa~ed were charged into the autoclave.
170 g of polye-thylene, corresponding to a yield of 167~C00 g/g Ti~ were obtained. The polymer exhibi-ted a melt index E of 4.3 g/10 min. and the MIN/MIE ratio was equal to 8. 8 The same procedure of example 2 was followed with the difference that 4.8 g ~0.05 moles) of MgC12 were dissolved in 34 g (0.1 moles) of Ti(0-n-C4H9)4. After dissolution~ 50 cc of n-hexane wo added and the resulting hexane solution was fel~
15 ~
, ~ 9~
a-t 45C and during 3 hours, into a solution consisting of 20 cc of n-hexane~ 17.3 cc (0.15 molesj of SiCl4 and 16.8 cc of PMHS.
Thus, 11.1 g of catalyst component containing 11.0% Ti were obtain ed.
The ethylene polymerization test o~ example 1 was repeat ed~ except that 0.016 g o-E the catalyst COmpOnerlt thus prepared were employed.
3Z0 g of polyethylene~ corresponding to a yield of 178,000 g/g Ti, were obtained. The melt index E of the polymer was 5.4 g/10 min. and the MIN/MIE ratio was 8Ø
The same procedure of example 2 was followed with -the difference that 2.4 g (0.025 moles) of MgCl2 were dissolved in 31 g to.o5 moles) of Ti (0-n-C9H19~4. After dissolution, 50 cc of n-hexane were added and, successively3 8.6 cc to.o74 moles) of SiC14 and 6.8 cc of PMHS were also added and the whole was reacted at 45C for 3 hours. 4.1 g of a catalyst c~mponent j containing 7.7~ Ti were obtained.
¦ The ethylene polymerization test was carried out as in example 1, with the difference that 0.016 g of the catalyst component thus prepared were charged into the autoclave.
130 g of polyethylene, corresponding to a yield of 102,000 g/g Ti~ were obtained. The melt index E of the polymer was 2.7 g/10 min. and the MIN/MIE ratio was 9.1. -EXA~IPLE 10 Example 5 was repeated employing the same amounts of ~lgCl2, Ti(0- -C4H9~ and n-heptane~ but with the difference that _ 16 -33 cc ~0.3 moles) of tC}13)2 Cl Si H~ in the place of Cl2C~3Si Tls were employed. Thus~ 7.8 g of a catalyst component containing 14.1% Ti were obtained.
The ethylene polymerization test was carried out as in example 1, employing 0.017~ g of the catalyst component thus ¦ prepared.
¦ 265 g of polyethylene~ corresponding to a yield of ¦ of 106,000 g/g Ti~ were obtained. The polymer exhibited a melt index E of 5.9 g/10 min. and the MIN/MIE ratio was 7.9.
Example 8 was repeated with the dif~erellce that the so-lution of SiCl4 and PMHS was added to the other reagents all at once instead of during 3 hours. Thus~ 9.3 g of a catalyst compo-nent containing 5.0 ~0 Ti were obtained.
For the ethylene polymerization test it was operated as in example 1, with the difference that 0.015 g of the catalyst component thus prepa~ed were employed.
l 360 g of polyethylene, corresponding to a yield of : 480~000 g/g Ti~were obtained~ The melt index E of the polymer was 5.3 g/10 min. and the MIN/MIE ratio was 7.9.
EXAMPLE_12 Example 2 was repeated employing 13.g g to.o4 moles) of Ti ~0-n-C4H9~4, 1-8 g t0-019 moles) of MgC12 and 7.1 cc ~0.06 moles) of SiC14; 7-5 g (0-04 moles) of Si (0C2H5~3}1 were used in the place of PMHS. Thus, 3.2 g of a catalyst component con-taining I . 5 ,~ Ti were o~tained.
2'~
Ethylene ~as polymerized as in example 1 by the aid of 0.020 g of the above catalyst component: 195 g of polyethylene, corresponding to a yield of 70,500 g/g Ti~ were obtained. The poly mer exhibited a melt index E of 3.0 g/10 min. and the MIN/MIE
5 ratio was 8.4.
EX~IPLE 13 ~ Example 2 wa5 repeated employing 17 g (0.05 moles) of ¦Ti~0-n-C4Hg)4, 2.2 g ~0.023 moles) of MgCl2, 9.1 cc of PMHS and ¦10 cc (0.1 moles) of SiHCl3 in the place of SiCl4. Thus, 9.1 g of 1 a catalyst component containing 13.0 % Ti were obtained.
By polymerizing ethylene as described in example 1 in the presence of 0.015 g of the catalyst component thus prepared9 129 g of polyethylene corresponding to a yield of 65,ooo g/g Ti were obtained: the polymer exhibited a melt index E of 4.2 g/10 ~min. and the MIN/MIE ratio was 8Ø
~¦ Example 2 was repeated employing 34 g (Ool moles) of Tl(O-n-C~H9)4~ 4.8 g ~0.05 moles) of MgCl2, 17.3 cc ~0.15 moles) of SiC14 and, in the place of PMHSg 28.0 g of a partially methyl~
- 20 ated polymethylhydrosiioxane containing 0.9 by weight of hydrogen (TEGILOXAN PTF 16 produced by Goldschmidt). Thus, 12.2 g of a ca-talyst component containing 9.1% Ti were obtained.
The ethylene polymerization test ~as carried out as in example 1 by the aid of 0.016 g of the above catalyst component and 125 g of polyethylene, corresponding to a yield of ~5,500 g/g Ti, were obtained; the polymer exhibited a melt index E of 1.1 g/10 min. and the ~ IIE ratio was 7.75.
I ~ ~/e J~
~ - 18 -' 11 EXA~IPLE 15 ¦¦ Example 2 was repeated with the difference that 15.9 g (0.052 moles) of Ti ~0-n~C4H9)3 Cl were employed in the place ¦ of Ti~0-n-C4H~)4 and that 5.8 g (0.0176 moles) of MgC12.5C2H50H
¦! were employed in the place of MgC12. Fol]owing the same procedure 5 ¦1 of example 2~ 17.3 cc (0.15 moles) of SiC14 and 20.2 cc of PMHS
il were employed. Thus, 2.9 g of a catalyst component containing 9.4 % Ti were obtained.
The ethylene polymerization test was carried out as in example 1 by the aid of 0.016 g of the above catalyst component I and 296 g of polyethylene~ corresponding to a yield o-E 197,000 ¦ g/g Ti~ were obtained; the melt index E of the polymer was 6.8 ¦ g/10 min. and the MIN/MIE ratio was 9.5.
Into a flask of 250 cc capacity were introduced 0.925 g~
(o.038 moles~ of chips of Mg metal, ~.7 cc of absolute C2H50H
and 25 g ~0.0725 moles) of Ti(0-n-C4H9), the temperature was gradually raised up to 130C and maintained at this ~alue for 2 hours; then the unreacted ethanol was removed by distil-lation. After cooling to 50C, 50 cc of n-hexane were added to 20 - the obtained solution; then 43 cc ~0.375 moles) of SiC14 and 27 cc of PMHS were fed, during 4 hours, into this diluted solution maintained at 50C. After the above addition, the whole was heated at the refluxing temperature of hexane for l hour and~¦
after cooling to room temperature~ the catalytic solid so obtain i 1 ed was washed with hexane un~il disappea~ance of the Cl'ions.
- 1:9-z~9~ l ll ~
After ~rying, 9.4 g of a catalyst component containing 6.3 %
Ti were obtained.
The ethylene polymerization test was carried out as 1 described in example 1, in the presence of 0.0144 g of the above 1 catalyst component, and 411-g of polyethylene, corresponding to a yield of 466,000 g/g T1, were obtained. The polymer exhibited a melt index E of 3.5 g/10 min and the MIN/MIE ratio was 8.7.
2.4 g (0.0167 moles) of anhydrous Mg acetate were reacted with 17 g (0.05 moles) of Ti (O-n-C4H9)4 at 135C for
3 hours. Only a partial dissolution ocourred; the reaction ¦mixture was dilu-ted with 35 cc of n-hexane and 31 cc ~31 moles) lof SiHCl3 were dropped into it at 50C during 3 hours.
¦ The solid thus obtained was washed and dried, as illus 'itrated in the preceding examples~ and 1.8 g of a catalyst compo- j nent containing 3.3 % Ti were obtained.
Ethylene was polymerized as described in example 1, with the difference that 0.0123 g of the above catalyst compo-¦ nent were employed, and 160 g of polyethylene corresponding to ayield of 395,000 g/g Ti were obtained. The polymer exhibited a melt index E of 3.2 g/10 min. and the MIN/MIE ratio was 8.4.
The same procedure of example 6 was followed, with the difference that 2.0 g (0~016 moles) of ~fgC12 1.2 H20 and 17 g 1(0.05 molesj of Ti (O-n-C~Hg)~ were employed. The subsequent reaction with Si HC13 was carried out at 50C employing 31 cc ~0~31 moles) of Si H C13 : 2.8 g of a catalyst component contain-li - 20 _ LZ~
ing 10.9 % Ti wcre obtained.
The ethylene polymeri ation test of example 1 was re-peated employing 0.0123 g of the above catalyst component: g 376 of polyethylene, corresponding to a yield of 28t,000 g/g Ti, were obtained. ~~
The polymer had a melt index E of 3.8 g/10 min. and the MIN/MIE ratio was 9Ø
17 g (0.05 moles) of Ti (0-n-C4Hg)4 were introduced into a flask of 250 cc capacity and diluted with 17 cc of die-thyl ether; 17 cc of an ether solution of 0.05 moles of Cl MgC2~1 were dropped, during l hour, into this solution maintained at 0C. After this addition, the temperature was gradually raised ; up to 50C, while at the same time the diethyl ether was removed by distillat1on. The solid residue was suspended in 100 cc of n-hexane and added~ at 50C and during 1 hour~ with 26 cc (0.226 moles) of SiCl4; then the reaction mixture was heated at the refluxîng temperature of n-hexane for one further L
hour. The solid product thus obtained was washed with n-hexane an dried as described in the preceding examples: 10.7 g of a red-brown powder containing 6.95~o Ti wer;e obtained.
Ethylene was polymerized as in example 1, with the dif ference that 0.0122 of the catalytic pol~der thus obtained were employed: 318 g of polyethylene were obtained, corresponding to a yield of 375,000 g/g Ti. The polymer exhibited a melt index E
of 6.6 g /10 min. and the MIN/~SIE ratio was 8.8~
I ~Z~)910 ;I EXAMPLE 20 35 g ~0.1 moles) of Ti (0-n-C4~19)4 were diluted with j 35 cc of toluene in a flask of 500 cc capacity and to this solu-¦l tion were added, at room temperature and during 1 hour~ 66 cc ~ a toluene ~olu-tion containing dissolved a product prepared by reacting~ at 70C in tetrahydrofurane as reaction medium~ 0.75 moles of C4HgMgCl and 0.75 moles (calculated on the silicon) of-PMHS~ removing the tetrahydrofurane by evaporation and replacing it with toluene.
After the addition of the above toluene solution~ the i obtained red-brown solution ~as heated at 70C for 2 hours;
after cooling to room temperature~ 36.3 cc (0.31 moles) of SiCl4 were added during 30 minutes.
~¦ The obtained suspension was then heated for 1 hour a-t 1S i the refluxing temperature of SiC14. The so prepared solid was washed with n-hexane and dried as already described for the catalyst components of the preceding examples: 13.5 g of a catalyst component containing 4.1 % Ti were obtained.
l The ethylene polymerization test of example 1 was repeat ed with the difference that 0.005 g o-f the above catalyst com-ponent were employed: 270 g of polyethylene were obtained~
corresponding to a yield of 1~310,000 g/g Ti. The melt index E
of the polymer was 7.5 g/10 min.~ and the MIN/MIE ratio was 9.1.
EXA~IPLE ~1
¦ The solid thus obtained was washed and dried, as illus 'itrated in the preceding examples~ and 1.8 g of a catalyst compo- j nent containing 3.3 % Ti were obtained.
Ethylene was polymerized as described in example 1, with the difference that 0.0123 g of the above catalyst compo-¦ nent were employed, and 160 g of polyethylene corresponding to ayield of 395,000 g/g Ti were obtained. The polymer exhibited a melt index E of 3.2 g/10 min. and the MIN/MIE ratio was 8.4.
The same procedure of example 6 was followed, with the difference that 2.0 g (0~016 moles) of ~fgC12 1.2 H20 and 17 g 1(0.05 molesj of Ti (O-n-C~Hg)~ were employed. The subsequent reaction with Si HC13 was carried out at 50C employing 31 cc ~0~31 moles) of Si H C13 : 2.8 g of a catalyst component contain-li - 20 _ LZ~
ing 10.9 % Ti wcre obtained.
The ethylene polymeri ation test of example 1 was re-peated employing 0.0123 g of the above catalyst component: g 376 of polyethylene, corresponding to a yield of 28t,000 g/g Ti, were obtained. ~~
The polymer had a melt index E of 3.8 g/10 min. and the MIN/MIE ratio was 9Ø
17 g (0.05 moles) of Ti (0-n-C4Hg)4 were introduced into a flask of 250 cc capacity and diluted with 17 cc of die-thyl ether; 17 cc of an ether solution of 0.05 moles of Cl MgC2~1 were dropped, during l hour, into this solution maintained at 0C. After this addition, the temperature was gradually raised ; up to 50C, while at the same time the diethyl ether was removed by distillat1on. The solid residue was suspended in 100 cc of n-hexane and added~ at 50C and during 1 hour~ with 26 cc (0.226 moles) of SiCl4; then the reaction mixture was heated at the refluxîng temperature of n-hexane for one further L
hour. The solid product thus obtained was washed with n-hexane an dried as described in the preceding examples: 10.7 g of a red-brown powder containing 6.95~o Ti wer;e obtained.
Ethylene was polymerized as in example 1, with the dif ference that 0.0122 of the catalytic pol~der thus obtained were employed: 318 g of polyethylene were obtained, corresponding to a yield of 375,000 g/g Ti. The polymer exhibited a melt index E
of 6.6 g /10 min. and the MIN/~SIE ratio was 8.8~
I ~Z~)910 ;I EXAMPLE 20 35 g ~0.1 moles) of Ti (0-n-C4~19)4 were diluted with j 35 cc of toluene in a flask of 500 cc capacity and to this solu-¦l tion were added, at room temperature and during 1 hour~ 66 cc ~ a toluene ~olu-tion containing dissolved a product prepared by reacting~ at 70C in tetrahydrofurane as reaction medium~ 0.75 moles of C4HgMgCl and 0.75 moles (calculated on the silicon) of-PMHS~ removing the tetrahydrofurane by evaporation and replacing it with toluene.
After the addition of the above toluene solution~ the i obtained red-brown solution ~as heated at 70C for 2 hours;
after cooling to room temperature~ 36.3 cc (0.31 moles) of SiCl4 were added during 30 minutes.
~¦ The obtained suspension was then heated for 1 hour a-t 1S i the refluxing temperature of SiC14. The so prepared solid was washed with n-hexane and dried as already described for the catalyst components of the preceding examples: 13.5 g of a catalyst component containing 4.1 % Ti were obtained.
l The ethylene polymerization test of example 1 was repeat ed with the difference that 0.005 g o-f the above catalyst com-ponent were employed: 270 g of polyethylene were obtained~
corresponding to a yield of 1~310,000 g/g Ti. The melt index E
of the polymer was 7.5 g/10 min.~ and the MIN/MIE ratio was 9.1.
EXA~IPLE ~1
4 g (0.1 moles) of ~IgO, 34 g ~0~1 moles) of Ti(0-n-C4H9~4 and 15 g (0.1 moles) of ethyl benzoate were reacted under stir- I
- j~ ~z~
j.
~ring at 140C for 2 hours.
After cooling of the reaction mixture to 5OQC, 70 cc 1 1!of n-heptane were added and succesively 40 cc of PMHS and 51.7 cc ' ~0.45 moles) of SiC14 were also added during 2 hours and st~
l~lat 50C. After the above additions~ the reaction mixture was heated again at the refluxing temperature of SiC14 for 1 hour.
At -the end the obtained solid was washed with n-hexane ~and dried as described in ihe preceding examples: 7.7 g of a csta llyst component containing 3.6 ~ Ti were obtained.
1~ The ethylene polymerization test was carried out accord ing to the procedure of example 1~ with the exception that 0.016 g of the above catalyst component were employed: 95 g of polyeth~
lene were obtained~ corresponding to a yield o~ 165~000 g/ g Ti.
The melt index E was 2 g/10 min and the MIN/MI~ ratio 9.1.
1 15 ~l EXAMPLE 22 ~jO cc of a suspenslon of 0.125 moles of n-C4H9MgCl in a mixture tetrahydrofurane/toluene (molar ratio 1/4) were dropped, i during 30 minutes and at room temperature~ into a suspension of 13 g (O 06 moles) of diphenyl 6ilandiol in 25 cc of toluene.
40 cc of the so obtained suspension were mixed with 80 cc o~` toluene and 43 cc (0.-126 moles) of TitO-n-C4H9)4. The mixture was heated at 50C, and 25 cc of PMHS and 36 cc (0.3 moles) of SiC14 ~ere fed simultaneously during 2 hours into this heated suspension; at the end, the suspension was heated again at 70C
for 1 hour. The so obtained solid was then washed with n-hexane 11 ~
- 23 ~
i ~
and dried as described in the preceding examples: 17.1 g o~
¦ a catalyst component containing 10. 8~ Ti were obtained.
¦ j The ethylene polymerization test was carried out ac-cording to the procedure of example 1~ with the difference that 0.008 g of the above catalyst component were employed:
144 g of polyethylene were obtained, corresponding to a yield of 167,000 g/~ Ti.
~¦ The polymer exhibited a melt index E of 4~9 g/10 min.
ard the MIN/MIE ratio was 9.2.
- j~ ~z~
j.
~ring at 140C for 2 hours.
After cooling of the reaction mixture to 5OQC, 70 cc 1 1!of n-heptane were added and succesively 40 cc of PMHS and 51.7 cc ' ~0.45 moles) of SiC14 were also added during 2 hours and st~
l~lat 50C. After the above additions~ the reaction mixture was heated again at the refluxing temperature of SiC14 for 1 hour.
At -the end the obtained solid was washed with n-hexane ~and dried as described in ihe preceding examples: 7.7 g of a csta llyst component containing 3.6 ~ Ti were obtained.
1~ The ethylene polymerization test was carried out accord ing to the procedure of example 1~ with the exception that 0.016 g of the above catalyst component were employed: 95 g of polyeth~
lene were obtained~ corresponding to a yield o~ 165~000 g/ g Ti.
The melt index E was 2 g/10 min and the MIN/MI~ ratio 9.1.
1 15 ~l EXAMPLE 22 ~jO cc of a suspenslon of 0.125 moles of n-C4H9MgCl in a mixture tetrahydrofurane/toluene (molar ratio 1/4) were dropped, i during 30 minutes and at room temperature~ into a suspension of 13 g (O 06 moles) of diphenyl 6ilandiol in 25 cc of toluene.
40 cc of the so obtained suspension were mixed with 80 cc o~` toluene and 43 cc (0.-126 moles) of TitO-n-C4H9)4. The mixture was heated at 50C, and 25 cc of PMHS and 36 cc (0.3 moles) of SiC14 ~ere fed simultaneously during 2 hours into this heated suspension; at the end, the suspension was heated again at 70C
for 1 hour. The so obtained solid was then washed with n-hexane 11 ~
- 23 ~
i ~
and dried as described in the preceding examples: 17.1 g o~
¦ a catalyst component containing 10. 8~ Ti were obtained.
¦ j The ethylene polymerization test was carried out ac-cording to the procedure of example 1~ with the difference that 0.008 g of the above catalyst component were employed:
144 g of polyethylene were obtained, corresponding to a yield of 167,000 g/~ Ti.
~¦ The polymer exhibited a melt index E of 4~9 g/10 min.
ard the MIN/MIE ratio was 9.2.
Claims
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
l. Catalyst components for the polymerization of olefins, consisting essentially of the product obtained by reacting the product of reaction between (A) a magnesium compound selected from the groups 1) compounds having formula XnMg(OR)2-n wherein X is a halogen atom, a hydroxyl group or an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms; R is an alkyl, aryl or cyclo-alkyl radical containing 1-20 carbon atoms, or a -COR' radical in which R' has the same meaning as R; O?n?2; or products of reaction of said com-pounds with electron-donor compounds;
2) compounds having formula R Mg X
wherein X is a halogen atom, and R is an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms, or products of reaction of said compounds with silicon compounds containing the monomeric unit in which R is the same or different from R1, R being an alkyl, aryl, alkoxy or aryloxy radical, and R1 being hydrogen, halogen or an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms, the polymerization grade of said sili con compound ranging from 2 to 1000;
3) Mg oxide, Mg hydroxide, Mg hydroxy halides, or Mg salts of inorganic oxygen containing acids and (B) a compound of Ti, V or Zn containing at least two metal-oxygen bonds of the type Ti-OR, V-OR and Zr-OR, wherein R is an alkyl, aryl or cycloalkyl ra-dical having 1-20 carbon atoms, with (C) a compound, other than the aluminum halides, capable of exerting a halogenating and a reducing action on compound (B), i.e. capable of substituting in com-pound (B) at least one group -OR with a halogen atom and of reducing the metal of compound (B) to a lower valence, or a mixture of a halogenating compound with a reducing substance;
the reaction between compounds (A) and (B) being conducted in the presence of an electron-donor com pound when compound (A) is an (A) 3) compound, and component (C) being a halogenating, but not necessa-rily a reducing compound when (A) is an (A) 2) compound;
compounds (A) and (B) being reacted in such amounts as to have a transition metal/mg atomic ratio comprised between 0.02 and 20, while compound (C) is employed in such an amount as to have 0.5 to 100 gram-atoms of halogen per gram-atom of transition metal and 0.1 to 100 gram-equivalents of reducing agent per gram-atom of transition metal.
2, Catalyst components according to claim 1, characte-rized in that anhydrous MgC12 is employed as component (A).
3. Catalyst components according to claim 1, characte-rized in that MgC12.5C2H50H is employed as component (A).
4. Catalyst components according to claim 1, characte-rized in that Mg(OC2H5) is employed as component (A) 5. Catalyst components according to claim 1, characte-rized in that (CH3COO)2 Mg is employed as component (A).
6. Catalyst components according to claim 1, characte-rized in that MgC12.nH20, in which O?n?6, is employed as component (A).
7. Catalyst components according to claim 1, characte-rized in that C2H5MgCl is employed as component (A).
8. Catalyst components according to claim 1, characte-rized in that a reaction product C4H9MgCl/polymethylhydrosiloxane is employed as component (A).
9. Catalyst components according to claim 1, characte-rized in that Mg0 is employed as component (A).
10. Catalyst components according to claim 1, characte-rized in that a reaction product C4H9MgCl/diphenyl silandiol is employed as component (A).
11. Catalyst components according to claim 1, claim 2 or claim 3, characterized in that Ti(O-n-C4H9)4 is employed as component (B).
12. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that Ti(O-n-C4H9)3Cl is employed as component (B).
13. Catalyst components according to claim 1, claim 2, or claim 3 characterized in that a combination of SiCl4 and of a polymethylhydrosiloxane is employed as component (C).
14. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that a combination of SiC14 and of C2H5MgCl is employed as component (C).
15. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that CH3SiCl2H is employed as component (C).
16. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that SiHCl3 is employed as components (C) .
17. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that (CH3)2 SiClH is employed as component (C).
18. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that a combination of SiCl3H and of a polymethylhydrosiloxane is employed as component (C).
20. Process for preparing the catalyst components according to claim 1, claim 2 or claim 3 characterized in that component (A) is reacted with component (B), and that the resulting product is reacted with component (C), such reactions being effected at a temperature ranging from -10°C to +250°C, optionally in the presence of a hydrocarbon diluent.
21. Catalysts for the polymerization of olefins, consisting of a catalyst component according to claim 1 and of a metallorganic compound of a metal of Groups I, II and III of the Periodic Table.
22. Process for polymerizing an olefin monomeric material selected from ethylene, at least one alpha-olefin, mixtures of ethylene and at least one alpha-olefin, mixtures of ethylene and at least one diolefin, mixtures of ethylene and at least one multiolefin, mixtures of ethylene, at least one alpha-olefin and at least one diolefin, and mixtures of ethylene, at least one alpha-olefin and at least one multiolefin, characterized in that the olefin monomeric material is contacted, under polymerization promoting conditions, with a catalyst according to claim 21.
l. Catalyst components for the polymerization of olefins, consisting essentially of the product obtained by reacting the product of reaction between (A) a magnesium compound selected from the groups 1) compounds having formula XnMg(OR)2-n wherein X is a halogen atom, a hydroxyl group or an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms; R is an alkyl, aryl or cyclo-alkyl radical containing 1-20 carbon atoms, or a -COR' radical in which R' has the same meaning as R; O?n?2; or products of reaction of said com-pounds with electron-donor compounds;
2) compounds having formula R Mg X
wherein X is a halogen atom, and R is an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms, or products of reaction of said compounds with silicon compounds containing the monomeric unit in which R is the same or different from R1, R being an alkyl, aryl, alkoxy or aryloxy radical, and R1 being hydrogen, halogen or an alkyl, aryl or cycloalkyl radical containing 1-20 carbon atoms, the polymerization grade of said sili con compound ranging from 2 to 1000;
3) Mg oxide, Mg hydroxide, Mg hydroxy halides, or Mg salts of inorganic oxygen containing acids and (B) a compound of Ti, V or Zn containing at least two metal-oxygen bonds of the type Ti-OR, V-OR and Zr-OR, wherein R is an alkyl, aryl or cycloalkyl ra-dical having 1-20 carbon atoms, with (C) a compound, other than the aluminum halides, capable of exerting a halogenating and a reducing action on compound (B), i.e. capable of substituting in com-pound (B) at least one group -OR with a halogen atom and of reducing the metal of compound (B) to a lower valence, or a mixture of a halogenating compound with a reducing substance;
the reaction between compounds (A) and (B) being conducted in the presence of an electron-donor com pound when compound (A) is an (A) 3) compound, and component (C) being a halogenating, but not necessa-rily a reducing compound when (A) is an (A) 2) compound;
compounds (A) and (B) being reacted in such amounts as to have a transition metal/mg atomic ratio comprised between 0.02 and 20, while compound (C) is employed in such an amount as to have 0.5 to 100 gram-atoms of halogen per gram-atom of transition metal and 0.1 to 100 gram-equivalents of reducing agent per gram-atom of transition metal.
2, Catalyst components according to claim 1, characte-rized in that anhydrous MgC12 is employed as component (A).
3. Catalyst components according to claim 1, characte-rized in that MgC12.5C2H50H is employed as component (A).
4. Catalyst components according to claim 1, characte-rized in that Mg(OC2H5) is employed as component (A) 5. Catalyst components according to claim 1, characte-rized in that (CH3COO)2 Mg is employed as component (A).
6. Catalyst components according to claim 1, characte-rized in that MgC12.nH20, in which O?n?6, is employed as component (A).
7. Catalyst components according to claim 1, characte-rized in that C2H5MgCl is employed as component (A).
8. Catalyst components according to claim 1, characte-rized in that a reaction product C4H9MgCl/polymethylhydrosiloxane is employed as component (A).
9. Catalyst components according to claim 1, characte-rized in that Mg0 is employed as component (A).
10. Catalyst components according to claim 1, characte-rized in that a reaction product C4H9MgCl/diphenyl silandiol is employed as component (A).
11. Catalyst components according to claim 1, claim 2 or claim 3, characterized in that Ti(O-n-C4H9)4 is employed as component (B).
12. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that Ti(O-n-C4H9)3Cl is employed as component (B).
13. Catalyst components according to claim 1, claim 2, or claim 3 characterized in that a combination of SiCl4 and of a polymethylhydrosiloxane is employed as component (C).
14. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that a combination of SiC14 and of C2H5MgCl is employed as component (C).
15. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that CH3SiCl2H is employed as component (C).
16. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that SiHCl3 is employed as components (C) .
17. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that (CH3)2 SiClH is employed as component (C).
18. Catalyst components according to claim 1, claim 2 or claim 3 characterized in that a combination of SiCl3H and of a polymethylhydrosiloxane is employed as component (C).
20. Process for preparing the catalyst components according to claim 1, claim 2 or claim 3 characterized in that component (A) is reacted with component (B), and that the resulting product is reacted with component (C), such reactions being effected at a temperature ranging from -10°C to +250°C, optionally in the presence of a hydrocarbon diluent.
21. Catalysts for the polymerization of olefins, consisting of a catalyst component according to claim 1 and of a metallorganic compound of a metal of Groups I, II and III of the Periodic Table.
22. Process for polymerizing an olefin monomeric material selected from ethylene, at least one alpha-olefin, mixtures of ethylene and at least one alpha-olefin, mixtures of ethylene and at least one diolefin, mixtures of ethylene and at least one multiolefin, mixtures of ethylene, at least one alpha-olefin and at least one diolefin, and mixtures of ethylene, at least one alpha-olefin and at least one multiolefin, characterized in that the olefin monomeric material is contacted, under polymerization promoting conditions, with a catalyst according to claim 21.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23942/77A IT1078995B (en) | 1977-05-24 | 1977-05-24 | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT23942A/77 | 1977-05-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1120910A true CA1120910A (en) | 1982-03-30 |
Family
ID=11211023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000303783A Expired CA1120910A (en) | 1977-05-24 | 1978-05-19 | Catalysts components and catalysts for polymerizing olefins prepared from the catalysts |
Country Status (21)
| Country | Link |
|---|---|
| US (1) | US4218339A (en) |
| JP (1) | JPS5416393A (en) |
| AT (1) | AT362931B (en) |
| AU (1) | AU522013B2 (en) |
| BE (1) | BE867400A (en) |
| BR (1) | BR7803292A (en) |
| CA (1) | CA1120910A (en) |
| DE (1) | DE2822809A1 (en) |
| DK (1) | DK151891C (en) |
| ES (1) | ES470120A1 (en) |
| FR (1) | FR2392037A1 (en) |
| GB (1) | GB1601426A (en) |
| GR (1) | GR72907B (en) |
| IT (1) | IT1078995B (en) |
| MX (1) | MX150091A (en) |
| NL (1) | NL186701C (en) |
| NO (1) | NO153575C (en) |
| PT (1) | PT68068B (en) |
| SE (1) | SE440224B (en) |
| SU (1) | SU812185A3 (en) |
| ZA (1) | ZA782971B (en) |
Families Citing this family (102)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1100285B (en) * | 1978-11-21 | 1985-09-28 | Euteco Spa | CATALYSTS WITH MIXED SUPPORTS FOR CMO- AND CO-POLYMIZATION OF ALFA-OLEFINE |
| JPS55133408A (en) * | 1979-04-05 | 1980-10-17 | Sumitomo Chem Co Ltd | Polymerization of olefin |
| US4363746A (en) | 1979-05-29 | 1982-12-14 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
| US4468477A (en) * | 1980-01-10 | 1984-08-28 | Imperial Chemical Industries Plc | Production of catalyst component, catalyst and use thereof |
| EP0032309A3 (en) * | 1980-01-10 | 1981-08-05 | Imperial Chemical Industries Plc | Production of catalyst component, catalyst and use thereof |
| US4384087A (en) * | 1980-03-24 | 1983-05-17 | Phillips Petroleum Company | Composition of matter and method of preparing same, catalyst, method of producing the catalyst and polymerization process employing the catalyst |
| IT1150031B (en) * | 1980-07-24 | 1986-12-10 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ETHYLENE |
| IT1132230B (en) * | 1980-07-24 | 1986-06-25 | Anic Spa | PROCEDURE FOR THE PRODUCTION OF THE CHOLESTEROL-ESTERASE ENZYME AND FOR HYDROLYSIS OF ESTERS WITH FATTY ACIDS OF CHOLESTEROL BY USING THE ENZYME ITSELF |
| US4429087A (en) | 1980-08-04 | 1984-01-31 | Phillips Petroleum Company | Polymerization catalyst and process |
| IT1209255B (en) | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| US6777508B1 (en) | 1980-08-13 | 2004-08-17 | Basell Poliolefine Italia S.P.A. | Catalysts for the polymerization of olefins |
| US4335016A (en) * | 1981-02-23 | 1982-06-15 | Chemplex Company | Catalyst and method |
| US4394291A (en) * | 1981-03-04 | 1983-07-19 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| JPS57182304A (en) * | 1981-05-07 | 1982-11-10 | Nippon Oil Co Ltd | Production of polyolefin |
| US4617361A (en) * | 1981-05-18 | 1986-10-14 | Phillips Petroleum Company | Process and catalyst for olefin polymerization |
| US4384982A (en) * | 1981-05-18 | 1983-05-24 | Phillips Petroleum Company | Process and catalyst for olefin polymerization |
| US4396747A (en) * | 1981-05-22 | 1983-08-02 | Phillips Petroleum Company | Zirconium-titanium catalyzed olefin polymerization |
| US4472523A (en) * | 1981-05-22 | 1984-09-18 | Phillips Petroleum Company | Zirconium-titanium catalyzed olefin polymerization |
| US4391736A (en) * | 1981-06-05 | 1983-07-05 | Phillips Petroleum Company | Alpha-olefin polymerization |
| FR2510586A1 (en) * | 1981-07-30 | 1983-02-04 | Charbonnages Ste Chimique | HOMOGENEOUS CATALYST COMPRISING A TRANSITION METAL AND MAGNESIUM, PROCESS FOR PREPARING THE SAME AND APPLICATION THEREOF TO THE POLYMERIZATION OF ETHYLENE |
| JPS5834810A (en) * | 1981-08-25 | 1983-03-01 | Nippon Oil Co Ltd | Production of polyolefin |
| IT1169292B (en) * | 1981-12-24 | 1987-05-27 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF ALPHA OLEFINS AND THE CATALYSTS OBTAINED FROM THEM |
| IT1169291B (en) * | 1981-12-24 | 1987-05-27 | Montedison Spa | CATALYST COMPONENTS FOR THE POLYMERIZATION OF ETHYLENE AND ITS MIXTURES WITH OLEFINS AND ITS CATALYSTS OBTAINED FROM THEM |
| US4699961A (en) * | 1982-09-30 | 1987-10-13 | E. I. Du Pont De Nemours & Co. | High efficiency catalysts for varying olefin polymer molecular weight distribution |
| US4511669A (en) * | 1982-09-30 | 1985-04-16 | E. I. Du Pont De Nemours And Company | High efficiency catalysts for varying olefin polymer molecular weight distribution |
| US4518706A (en) * | 1982-09-30 | 1985-05-21 | E. I. Du Pont De Nemours And Company | Hydrocarbon soluble catalyst supports and resultant polymerization catalysts |
| US4440869A (en) * | 1982-09-30 | 1984-04-03 | Conoco Inc. | Olefin polymerization catalyst |
| US4477588A (en) * | 1982-12-15 | 1984-10-16 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4532312A (en) * | 1982-12-15 | 1985-07-30 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| US4472521A (en) * | 1982-12-20 | 1984-09-18 | Stauffer Chemical Company | Supported catalyst for polymerization of olefins |
| JPS59221309A (en) * | 1983-05-31 | 1984-12-12 | Toa Nenryo Kogyo Kk | Catalytic component for polymerizing olefin |
| JPS6049006A (en) * | 1983-08-30 | 1985-03-18 | Toa Nenryo Kogyo Kk | Catalytic component for olefin polymerization |
| JPS6049004A (en) * | 1983-08-30 | 1985-03-18 | Toa Nenryo Kogyo Kk | Catalytic component for olefin polymerization |
| JPS6049007A (en) * | 1983-08-30 | 1985-03-18 | Toa Nenryo Kogyo Kk | Catalyst component for olefin polymerization |
| US4625003A (en) * | 1983-08-30 | 1986-11-25 | Toa Nenryo Kogyo Kabushiki Kaisha | Catalyst component for polymerization of olefins (P-1026) |
| JPS6049005A (en) * | 1983-08-30 | 1985-03-18 | Toa Nenryo Kogyo Kk | Catalytic component for olefin polymerization |
| JPH062772B2 (en) * | 1984-02-28 | 1994-01-12 | 東燃株式会社 | Method for producing catalyst component for olefin polymerization |
| IT1178466B (en) | 1984-03-20 | 1987-09-09 | Montedison Spa | CATALYSTS FOR THE HOMO AND COPOLYMERISATION OF ETHYLENE AND POLYMERS OBTAINED |
| US4866022A (en) * | 1984-03-23 | 1989-09-12 | Amoco Corporation | Olefin polymerization catalyst |
| US4988656A (en) * | 1984-03-23 | 1991-01-29 | Amoco Corporation | Olefin polymerization catalyst |
| US4618662A (en) * | 1984-04-23 | 1986-10-21 | Mobil Oil Corporation | Catalyst composition for polymerizing alpha-olefins |
| US4544716A (en) * | 1984-06-22 | 1985-10-01 | Phillips Petroleum Company | Polyolefin polymerization process and catalyst |
| JPH0665687B2 (en) * | 1984-09-13 | 1994-08-24 | 日産化学工業株式会社 | Improved ethylene polymerization or copolymerization process |
| JPH0730128B2 (en) * | 1984-10-04 | 1995-04-05 | チッソ株式会社 | Method for producing solid catalyst component for olefin polymerization |
| EP0240254A3 (en) * | 1986-03-31 | 1989-07-26 | Exxon Chemical Patents Inc. | Polymerization catalyst, production and use |
| US4829038A (en) * | 1986-06-17 | 1989-05-09 | Amoco Corporation | Alpha-olefin polymerization catalyst system including an advantageous modifier component |
| EP0360297B1 (en) * | 1986-06-17 | 1993-02-10 | Amoco Corporation | Olefin polymerization catalyst |
| CA1293242C (en) * | 1986-06-17 | 1991-12-17 | Gregory Gerasimos Arzoumanidis | Olefin polymerization catalyst |
| US5278118A (en) * | 1986-10-02 | 1994-01-11 | Ausimont, S.P.A. | Catalysts for the preparation of elastomeric olefinic copolymers |
| US5024982A (en) * | 1988-12-14 | 1991-06-18 | Phillips Petroleum Company | Silica-containing olefin polymerization catalysts and process |
| US5238891A (en) * | 1989-06-15 | 1993-08-24 | Phillips Petroleum Company | Olefin polymerization catalyst and process |
| US5237025A (en) * | 1990-10-09 | 1993-08-17 | Phillips Petroleum Company | Process for making bimodal polyolefins using two independent particulate catalysts |
| IT1252041B (en) * | 1990-10-11 | 1995-05-29 | Enimont Anic Srl | SOLID COMPONENT OF CATALYST FOR THE (CO) POLYMERIZATION OF ETHYLENE |
| IT1251796B (en) * | 1991-07-15 | 1995-05-26 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF ETHYLENE |
| JP3311780B2 (en) * | 1991-07-23 | 2002-08-05 | 三菱化学株式会社 | Method for producing olefin polymer |
| IT1262933B (en) * | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | PROCESS FOR THE ALFA-OLEFINE GAS POLYMERIZATION |
| IT1262934B (en) * | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| BE1005982A3 (en) * | 1992-06-09 | 1994-04-12 | Solvay | Process for producing a catalyst solid, solid catalyst and method (co) polymerization of olefins using the solid catalyst. |
| EP0574821B1 (en) * | 1992-06-18 | 1998-03-11 | Montell Technology Company bv | Process and apparatus for the gas-phase polymerization of olefins |
| US5206314A (en) * | 1992-08-31 | 1993-04-27 | Phillips Petroleum Company | Polyolefin polymerization process, process of producing catalyst, and catalyst |
| IT1264679B1 (en) | 1993-07-07 | 1996-10-04 | Spherilene Srl | CATALYSTS FOR THE (CO) POLYMERIZATION OF ETHYLENE |
| IT1269194B (en) * | 1994-01-21 | 1997-03-21 | Spherilene Srl | HIGH PROCESSABILITY POLYMERIC COMPOSITIONS BASED ON LLDPE |
| CN1085219C (en) * | 1994-02-04 | 2002-05-22 | 埃克森美孚化学专利公司 | Dual donor catalyst system for polymerization of olefins |
| US6686433B1 (en) | 1994-02-04 | 2004-02-03 | Exxonmobil Chemical Patents Inc. | Dual donor catalyst system for the polymerization of olefins |
| US5521263A (en) * | 1994-10-18 | 1996-05-28 | Eastman Chemical Company | Catalysts and synthesis of high molecular weight amorphous polyolefins and recovery thereof |
| IT1275573B (en) * | 1995-07-20 | 1997-08-07 | Spherilene Spa | PROCESS AND EQUIPMENT FOR GAS PHASE POMIMERIZATION OF ALPHA-OLEFINS |
| IT1276121B1 (en) * | 1995-11-14 | 1997-10-24 | Montell Technology Company Bv | EXTENSIBLE MULTILAYER FILM |
| IT1276120B1 (en) * | 1995-11-14 | 1997-10-24 | Montell Technology Company Bv | EXTENSIBLE MULTILAYER FILM BASED ON LLDPE |
| IT1281198B1 (en) | 1995-12-18 | 1998-02-17 | Montell Technology Company Bv | SHRINK FILMS BASED ON POLYOLEFIN COMPOSITIONS INCLUDING A LINEAR COPOLYMER OF ETHYLENE WITH ALPHA-OLEFINS |
| IT1292138B1 (en) * | 1997-06-12 | 1999-01-25 | Montell Technology Company Bv | EXTENSIBLE MULTILAYER FILM |
| CN1268962A (en) | 1998-05-06 | 2000-10-04 | 蒙特尔技术有限公司 | Polyolefine compositions and films obtd. therefrom |
| US6087459A (en) * | 1998-05-14 | 2000-07-11 | Exxon Chemical Patents Inc. | Polymeric materials formed using blends of electron donors |
| US6399707B1 (en) | 2000-09-29 | 2002-06-04 | Exxonmobil Chemical Patents Inc. | Impact copolymer and plastomer blend |
| US6566294B2 (en) | 2000-12-21 | 2003-05-20 | Exxonmobil Chemical Patents Inc. | Multi-donor catalyst system for the polymerization of olefins |
| WO2003055921A1 (en) * | 2001-12-24 | 2003-07-10 | Basell Poliolefine Italia S.P.A. | Ziegler natta catalyst for the polymerization of olefins |
| WO2003106511A1 (en) * | 2002-06-13 | 2003-12-24 | Basell Poliolefine Italia S.P.A. | Catalyst components for the polymerization of olefins |
| US7307035B2 (en) * | 2002-07-23 | 2007-12-11 | Basell Poliolefine Italia Spa | Magnesium dichloride-alcohol adducts and catalyst components obtained therefrom |
| US6657024B1 (en) * | 2002-09-03 | 2003-12-02 | Fina Technology, Inc. | Polymerization catalyst system using n-butylmethyldimethoxysilane for preparation of polypropylene film grade resins |
| JP2006502263A (en) * | 2002-10-09 | 2006-01-19 | バセル ポリオレフィン イタリア エス．アール．エス． | Gas phase catalytic polymerization of olefins |
| US20090131593A1 (en) * | 2003-05-21 | 2009-05-21 | Basell Poliolefine Italia S.R.L | Polyethylene films for packaging |
| CA2526574A1 (en) * | 2003-05-21 | 2004-12-02 | Basell Poliolefine Italia S.R.L. | Stretch wrap films |
| US7078468B2 (en) * | 2003-06-27 | 2006-07-18 | Fina Technology, Inc. | Polymerization catalyst system using di-sec-butyldimethoxysilane for preparation of polypropylene |
| CN101573388A (en) * | 2006-12-29 | 2009-11-04 | 弗纳技术股份有限公司 | Succinate-containing polymerization catalyst system using n-butylmethyldimethoxysilane for preparation of polypropylene film grade resins |
| IN2010DN07192A (en) * | 2008-03-14 | 2015-07-24 | Saudi Basic Ind Corp | |
| EA018411B1 (en) * | 2008-04-17 | 2013-07-30 | Сауди Бейсик Индастриз Корпорейшн | Process for the production of ultra high molecular weight polyethylene |
| EP2246368A1 (en) | 2009-04-30 | 2010-11-03 | Borealis AG | Improved ethylene polymerization catalyst composition |
| EP2246369B1 (en) | 2009-04-30 | 2012-09-05 | Borealis AG | Linear low density polyethylene with uniform or reversed comonomer composition distribution |
| EP2284199A1 (en) | 2009-08-14 | 2011-02-16 | Saudi Basic Industries Corporation | A catalyst system and a process for the production of polyethylene |
| WO2011155999A1 (en) | 2010-06-10 | 2011-12-15 | Ineos Usa Llc | Controlling h2 distribution in a horizontal stirred bed reactor |
| WO2013087185A2 (en) * | 2011-12-12 | 2013-06-20 | Saudi Basic Industries Corporation (Sabic) | A catalyst system for the production of ultra-high molecular weight polyethylene |
| US9738761B2 (en) | 2013-01-29 | 2017-08-22 | Ineos Europe Ag | Injection moulded polypropylene articles |
| CN114230931A (en) | 2014-06-25 | 2022-03-25 | 埃克森美孚化学专利公司 | High melt strength polypropylene and extrusion process for maintaining melt strength |
| WO2016094843A2 (en) | 2014-12-12 | 2016-06-16 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system comprising mesoporous organosilica support |
| WO2016195832A1 (en) | 2015-05-29 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizates comprising broad molecular weight distribution polypropylene |
| ES2824925T3 (en) * | 2016-06-30 | 2021-05-13 | Dow Global Technologies Llc | Useful procatalyst compositions for low comonomer incorporation and process for their preparation |
| WO2018022263A1 (en) | 2016-07-29 | 2018-02-01 | Exxonmobil Chemical Patents Inc. | Polymerization processes using high molecular weight polyhydric quenching agents |
| WO2020231526A1 (en) | 2019-05-15 | 2020-11-19 | Exxonmobil Chemical Patents Inc. | Polypropylene-based compositions |
| US11946000B2 (en) | 2019-05-24 | 2024-04-02 | Eastman Chemical Company | Blend small amounts of pyoil into a liquid stream processed into a gas cracker |
| US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
| EP4054997A4 (en) | 2019-11-07 | 2024-02-21 | Eastman Chem Co | Recycle content alpha olefins and fatty alcohols |
| EP4107196A1 (en) | 2020-02-17 | 2022-12-28 | ExxonMobil Chemical Patents Inc. | Propylene-based polymer compositions having a high molecular weight tail |
| WO2024025741A1 (en) | 2022-07-27 | 2024-02-01 | Exxonmobil Chemical Patents Inc. | Polypropylene compositions with enhanced strain hardening and methods of producing same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3094568A (en) * | 1959-12-01 | 1963-06-18 | Gulf Research Development Co | Process for alkylating aromatics in the presence of a heavy metal halide, an organic halide and an organo aluminum halide |
| DE2111455A1 (en) * | 1971-03-10 | 1972-09-28 | Hoechst Ag | Process for the production of polyolefins |
| US4071672A (en) * | 1972-11-10 | 1978-01-31 | Mitsui Petrochemical Industries Ltd. | Process for polymerizing or copolymerizing olefins |
| GB1452314A (en) * | 1972-11-10 | 1976-10-13 | Mitsui Petrochemical Ind Ld | Catalyst compositions for use in the polymerziation of olefins |
| JPS5724361B2 (en) * | 1974-03-27 | 1982-05-24 | ||
| US4105847A (en) * | 1974-11-26 | 1978-08-08 | Mitsui Toatsu Chemicals Inc. | Method for polymerization of ethylene |
| JPS565404B2 (en) * | 1975-02-14 | 1981-02-04 | ||
| IT1038179B (en) * | 1975-05-16 | 1979-11-20 | Montedison Spa | PROCEDURE FOR POLYMERIZATION OF ALPHA OLEFINS WITH AT LEAST THREEATONS OF CARBON |
| IT1042711B (en) * | 1975-09-19 | 1980-01-30 | Montedison Spa | COMPONENTS OF CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
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1977
- 1977-05-24 IT IT23942/77A patent/IT1078995B/en active
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- 1978-05-18 NO NO781728A patent/NO153575C/en unknown
- 1978-05-18 SE SE7805739A patent/SE440224B/en not_active IP Right Cessation
- 1978-05-19 AT AT0364978A patent/AT362931B/en not_active IP Right Cessation
- 1978-05-19 GB GB20685/78A patent/GB1601426A/en not_active Expired
- 1978-05-19 CA CA000303783A patent/CA1120910A/en not_active Expired
- 1978-05-19 AU AU36281/78A patent/AU522013B2/en not_active Expired
- 1978-05-22 PT PT68068A patent/PT68068B/en unknown
- 1978-05-23 US US05/908,670 patent/US4218339A/en not_active Expired - Lifetime
- 1978-05-23 ES ES470120A patent/ES470120A1/en not_active Expired
- 1978-05-23 ZA ZA00782971A patent/ZA782971B/en unknown
- 1978-05-23 BR BR7803292A patent/BR7803292A/en unknown
- 1978-05-23 GR GR56298A patent/GR72907B/el unknown
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- 1978-05-24 JP JP6214478A patent/JPS5416393A/en active Granted
- 1978-05-24 DE DE19782822809 patent/DE2822809A1/en active Granted
- 1978-05-24 BE BE187971A patent/BE867400A/en not_active IP Right Cessation
- 1978-05-24 SU SU782620109A patent/SU812185A3/en active
- 1978-05-29 MX MX173543A patent/MX150091A/en unknown
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| AU522013B2 (en) | 1982-05-13 |
| ATA364978A (en) | 1980-11-15 |
| AT362931B (en) | 1981-06-25 |
| BR7803292A (en) | 1978-12-19 |
| DE2822809A1 (en) | 1978-11-30 |
| FR2392037A1 (en) | 1978-12-22 |
| DE2822809C2 (en) | 1991-07-11 |
| NO153575B (en) | 1986-01-06 |
| NL186701B (en) | 1990-09-03 |
| PT68068B (en) | 1979-10-26 |
| SE7805739L (en) | 1978-11-25 |
| DK219578A (en) | 1978-11-25 |
| JPS5416393A (en) | 1979-02-06 |
| AU3628178A (en) | 1979-11-22 |
| SE440224B (en) | 1985-07-22 |
| IT1078995B (en) | 1985-05-08 |
| GR72907B (en) | 1984-01-04 |
| JPS6366842B2 (en) | 1988-12-22 |
| NO153575C (en) | 1986-04-16 |
| MX150091A (en) | 1984-03-15 |
| GB1601426A (en) | 1981-10-28 |
| NL186701C (en) | 1991-02-01 |
| FR2392037B1 (en) | 1980-04-11 |
| US4218339A (en) | 1980-08-19 |
| BE867400A (en) | 1978-11-24 |
| SU812185A3 (en) | 1981-03-07 |
| ES470120A1 (en) | 1979-01-01 |
| DK151891C (en) | 1988-07-18 |
| ZA782971B (en) | 1979-05-30 |
| DK151891B (en) | 1988-01-11 |
| PT68068A (en) | 1978-06-01 |
| NL7805410A (en) | 1978-11-28 |
| NO781728L (en) | 1978-11-27 |
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