CA1208400A - Process for preparing polyolefins - Google Patents
Process for preparing polyolefinsInfo
- Publication number
- CA1208400A CA1208400A CA000434306A CA434306A CA1208400A CA 1208400 A CA1208400 A CA 1208400A CA 000434306 A CA000434306 A CA 000434306A CA 434306 A CA434306 A CA 434306A CA 1208400 A CA1208400 A CA 1208400A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- carbon atoms
- general formula
- titanium
- hydrocarbon radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT
An olefin polymerization is carried out by using a catalyst obtained from the following components [I], [II] and [III]:
[I] a solid substance obtained by the reaction of the following (i) through (iv):
(i) a magnesium halide, (ii) a compound represented by the general formula Me(OR)nXz-n wherein Me is an element selected from Groups I through VIII of the Periodic Table, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, z is the valence of Me and n is 0 < n ? z, (iii) a compound represented by the formula R'mSi(OR")nX4-m-n wherein R' and R" are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are 0 ? m < 4 and 0 < n ? 4, provided 0 < m + n ? 4, and (iv) a titanium compound and/or a vanadium compound;
[II] a compound represented by the general formula .
An olefin polymerization is carried out by using a catalyst obtained from the following components [I], [II] and [III]:
[I] a solid substance obtained by the reaction of the following (i) through (iv):
(i) a magnesium halide, (ii) a compound represented by the general formula Me(OR)nXz-n wherein Me is an element selected from Groups I through VIII of the Periodic Table, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, z is the valence of Me and n is 0 < n ? z, (iii) a compound represented by the formula R'mSi(OR")nX4-m-n wherein R' and R" are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are 0 ? m < 4 and 0 < n ? 4, provided 0 < m + n ? 4, and (iv) a titanium compound and/or a vanadium compound;
[II] a compound represented by the general formula .
Description
12~;8~
P~OCE5S FO~ PREPARING POLYOLEFINS
B~CKG~OUND OF Tll~ INV~NTION
The present lnventlon relates to a process for preparing polyolefins us'lng a novel polymerization cata1yst.
Heretoforej in this technical field there has been known from Japanese Patent Publication No.12105/1964 a catalyst whlch compr~ses a magnesium hal~de and a transi tlon metal compound such as a tl-tanium compound supported 1~ thereon, and also known from Belgian Patent No.742,112 a catalyst ob~ained by co-pulverizing a magne8iu~ halide and tltanium tetrachloride.
However, when viewed from the standpoint that as high a catalytlc activity as possible is desired in the production of,polyolefins, the process disclosed in the Japanese Patent Pu~lication 12105/1964 is still ' unsatisfactory ln po~nt of polymerization activi-ty, and the process of the Belgiam Patent. 742,112 gives a fairly lmproved polymerizat~on activity, bu-t s-till leaves room for lmprovement.
I'n West German Patent No.2137872, the amount o a magnes~um halide used is substantially decreased by the co-puIverizat~on of the,magnesium halide with titanium tetrachlor~de'and alumina. But a remarkable lncrease ln act.ivl~y per sol~d which can be regarded as the guidetine for productivity is not recognized, thus leading to a des~re for catalyst of, higher activity.
:~L2~
In the preparation of polyolefins, moreover, it is desirable from the aspects of produc-tivity and slurry handling -that the bulk density oE the resultan-t polymer be as hlgh as posslble. When viewed from this standpoint, the process disclosed in the foregoing Japanese patent publication 12105/1964 affords polymers low in bulk densi-ty and is not satisfactory in point of polymerization activity, and the process of the Belgian patent 742,112 also disadvantageous in that the bulk density of the resuItant polymer is low, although it affords a high polymerization activity. Thus, in both processes, a further improvemen-t is desired.
SUMMARY OF THE INVENTION
It is an object of the present invention to remedy the above-mentioned drawbacks of the prior art.
It is another object of the present invention to provide a process for preparing a novel polymerization catalyst which exhibits a high polymerization activity, which is capable of affording a polymer of high bulk density in high yield and which permits an extremely easy execution of a continuous polymerization, as well as a process ~or homo~ or copolymerizing olefins in the presence of the said polymerization catalyst.
The present invention is concerned with a process for preparlng a polyolefin, characterized by polymerizing at least one olefin in the presence of a catalyst, which catalyst comprises either the following combination ~1) or (2~:
840~
(1) ~I~ a solid substance obtained by the reaction of (i) a magnesium halide, (ii) a compound represented by the general formula Me(OR~nXz n wherein Me is an element of Groups I through VIII of the Periodic T~ble, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, z is the valence of Me and n is O ~ n ~ z, (iii) a compound represen$ed by the general mSi(oR )nX4_m_n wherein R' and R"
are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are O ~ m ~ 4 and O C n c 4, provided O ~ m ~ n ~ 4, and (iv) a titanium compound and/or a vanadium compound;
II a compound represented by the genera1 formula Rl . .
R3-~ S ~ O~qR wherein Rl, R2 and R3 are each R
a hydrocarbon radical having 1 to 24 carbon atoms, alkoxy, hydrogen or halogen, R4 is a hydrocarbon radical having~l to.24 carbon atoms and q is 1 c q ~.30 and ~8~
tIII~ an organometallic compound.
~2~ [I~ a solld substance obtained by -the reac-tion of (i) a magnesium hal.ide, (li) a compound represented by the yeneral Eormula Me(OR)nXz n wherein Me is an element of Groups I through VIII of the Periodic Table, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon . atoms, X is a halogen atom, z is the valence of 10. Me and n is 0.< n c z, liii) a compound represented ky the general ~ormula R'mSi~oR")nX4_m_n wherein R' and R" are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are O ~ m C 4 and 0 < n ~ 4, provided O < m + n c 4, and (iv) a titanium compound and/or a vanadium compound; and rII] a product obtained by the reaction of (v) a compound represented by the general ormula Rl R3 ~ Si - O ~qR4 wherein Rl, R2 and R3 are each a hydrocarbon radical having 1 to 24 carbon atoms, alkoxy, hydrogen or halogen, R4 is a hydrocarbon radlcal having 1 to 24 carbon atoms and q i.s 1-~ q -~ 30~.and Ivi) an organometallic compound.
~2~
The catalyst of the present invention exhihits a very high polymerization activity, resulting in a decreased partial pressure of monomer during polymeriza-tion~ afEords a polymer having a high bulk ~ensity, thus permitting improvement of produc-tivity, remains in -the resultant polymer after polymerization in an extremely small quantity~to the extent that the polyolefin manufac-turing process can dispense with the catalyst removing steps, resulting in a more simplified step for polymer treatment, and thus permits an extremely econQmical production of polyolefins as a whole.
According to the process of the present invention, the amount of polymer produced per unit polymerization reaction vessel is large because of a high buIk density of the poly~er.
Further, when viewed fxom the standpoint of particle size of the resulting polymer, the proportion of coarse particle~ and fine particles below 501u is low despite o a high bulk density of the polymer, thus 20: permitting an sasy execution of a continuous polymeriza-tion reaction and an easy handling of polymer particles, for example, in centrifugal separation in the polymer treating step or in transportation of the powdered polymer.
As a `further advantage of the present invention, mention may be made of an outstanding effect on economy and on productivity. More particuIarly, polyolefins prepared by using the catalyst of the present invention have a high bulk density as previously noted, and lesshydrogen concentration is required -than in -the prior art process Eor obtalnlng a polymer having a desired me:lt lndex, thus resulting in -that -the total pressure can be maintained at a relatively small level throughout the polymerizatlon.
More,over, in the polymerization of olefin using the catalyst of the present invention, the decrease of the olefin absorbing rate is not accelerated with the lapse of time, so the polymerization can be continued for a long time in a small quantity of the catalyst.
Additionally, polymers prepared by using the catalyst of the present invention are extremely narrow in molecular weight distribution and their hexane extraction 15' ,is very small, that is, the by-production of low polymers is mi,nimized. Consequently, it is possible to obtain products of good quality, for example, a product superior in anti-blocking property in film grade.
Thus, the catalyst o the present invention is a novel catàlyst whlch has many such characteristic features and which has remedied the above-mentioned drawbacks of the prior art. And it is quite surprising that the ~oregoing features can easily be attained by using the catalyst of the present invention.
DESCRIPTION OP'PREFERRED'EM~ODIMENTS
As the magnesium ha'ide used in the present invention there is'used a substantially anhydrous one~
8~
examples of which include'magnesium fluoride, magnesium chloride, maynesium bromide and magneslum iodide, with magnesium chloride being par-ticularly preferred.
As examples of the compound represented by the general formula Me(OR)nXz n used in the presen-t invention wherein Me, z, n and R are as previously defined, men-tion may be made of such various compounds as ~aOR, Mg(OR)2, Mg(OR)X, Ca(OR)2, Zn(OR)2,, Zn(OR)X, Cd(OR)2, Al(OR)3, Al(OR)2X, BIOR)3, B(OR)2X, Ga(OR)3, Ge(OR~4, Sn(OR)4, P~OR)3, Cr(OR)2, Mn(OR)2, Fe(OK)2, Fe~OR)3, Co(OR)2 and Ni~OR)2, and as more preferable concrete examples there may be mentioned 'such compounds as NaOC2H5, NaOC4Hg, 3 2 g 2 5)2' Mg50C3H532~ Ca(OC2H5)2' ~n~oC H ) Zn(OC H5)Cl, Al(OCH3)3, Al(OC2H5)3, 2 5 2 Al(OC3H7)3, Al(OC4Hg)4, Al(OC6H5)3, B(OC~H5)3, B~OC2H5)2Cl, ( 2H5)3, P(OC6H5)3 and Fe(OC4Hg)3.
Compounds representedby the general formulae Mg(R)nX2~n' A150R)nX3-n and B(OR)nX3_n are partiCularly preferred'in the present invention. And as the substitu-ent R, alkyl groups having 1 to 4 carbon atoms and phenylgroup are especially preferred.
To exemplify.the compound represented by, the general formula R'mSi(oR")nX4 m n used in the present invention wherein R', R", m and n are as previously defined~ mention may be made of the ollowing:
monomethyltrimethoxysil~ne, ~onomethyltriethoxysilane, monomethyltri-n-~utoxysilane, monomethyltri-sec-butoxysilane, monomethyltriisopropoxysllane, monomethyl-tripentoxysilane, monomethyltrioctoxysilane, ~L2¢;il8~
monomethyltristearoxysilane/ monomethyltriphenoxysilarle, dimethyldime-thoxysilane, dime-thyldie-thoxysilane/ dimethyl-diisopropoxysilane/ dimethyldiphenoxysilane/ trime-thylmono-ethoxysilane, trimethylmonoethoxysilane, trimethylmonoiso-propoxysilane, trimethylmonophenoxysilane, monomethyldi-methoxymonochlorosilane, monomethyldietho~ymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyldiethoxymono-chlorosilane, monomethyldiethoxymonobromosilane, monomethyl-diphenoxymonochlorosilane, aimethylmonoethoxymonochloro-silane, monoethyltrimethoxysilane/ monoethyltriethoxysilanemonoethyltriisopropoxysilane, monoethyltriphenoxysilane/
diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-phenoxysilane, triethylmonomethoxysilane, triethylmono-ethoxysilane, triethylmonophenoxysilane, monoethyldimethoxy-monochlorosilane, monoethyldiethoxymonochlorosilane,monoethyldiphenoxymonochlorosilane, monoisopropyltri-methoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldiethoxysilane, ~0 diphenylmonoethoxymonochlorosilane, monomethoxytrichloro-silane, monoethoxytrichlorosilane, monoisopropoxytrichloro-silane, mono-n-butox~trichlorosilane, monopentoxytrichloro-silane, monooctoxytrichlorosilane, monos-tearoxytrichloro-silane r monophenoxytrichlorosilane, mono p-methylphenoxytrichlorosilane, di~ethoxydichlorosllane,diethoxydichlorosilane,~diisopr~poxydichlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochloxosilane, tri-sec-butoxymonochloro-silane, tetraethoxysilane and tetraisopropbxysilane.
:~Z~8~
As examples of the titanium compound and/or vanadium compound used in the present i.nvention, -there may be mentioned halides, alkoxyhalides, alkoxides and halogenated oxides of titanium and/or vanadium.
Suitable examples of titanium compounds are tetravalent and trivalent titanium compounds. As tetravalent ti-tanium compounds are preferred those represented by the general formula Ti(OR)pX4 p wherein R is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms~ X is a halogen atom and p i.s 0 ~ p ~ 4, such as, ~or example, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxy-trichlorotitanium, dimethoxydichlorotitanium, trimethoxy monochlorotitanium, tetramethoxytitanium, monoethoxytri-chlorotitanium, diethoxydichlorotitanium~ triethoxymono~
chlorotitanium, tetraethoxytitanium, monoisopropoxytri-ch~orotitanium, diisopropoxydichlorotitanium, triisopropoxy-monochlorotitanium~ tetraisopropoxytitanium r monobutoxytrichlorotitanium, dibutoxydichlorotitaniurn, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochloro-titanium and tetraphenoxytitaniu~. To illustrate trivalent titanium compounds, mention may be made of titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium-or an organometallic compound of a metal ~f Gro.ups I through III in the Periodic Table, as well as trivalent titanium compounds obtained by reducing tetravalent alkoxytitanium halides g of the general formula ~i(OR)rX4 r with an organometallic compound of a metal of Groups I through III in -the Periodic Table, in which formula R is an alkyl, aryl or aralkyl group having 1 to 24 caxbon atoms and r is 0 < r ~ 4.
~s examples of vanadium compounds, there are mentioned tetravalent vanadium compounds such as vanadium tetra-chloride~ vanadium tetrabromide, vanadium tetraiodide and tetraethoxyvanadium; pentavalent vanadium compounds such as vanadium oxytrichloride, ethoxydichlorovanadyl, triethoxyvanadyl and tributoxyvanadyl; and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide.
Tetravalent titanium compounds are most preEerred in the present invention.
In order to ma~e the present lnvention more effective, both thè titanium compound and the vanadium compound are often used in combination~ In this case, it is preferable that the V/Ti molar ratio be in the range of 2/1 to 0.01/1.
As examples of the compound of the general R~
formula R3-t-Si - O ~qR4 used in the present invention, R
mention may be made of the compound of the general formula R'mSi(OR")nX4 m n which is used in the catalyst component ~I~, as well as chain-li-ke or cyclic polysiloxanes with ~' 1 a recuxring unit represented by -~ Si - O ~- obtained ~2~ 0~
by condensation of the compounds R'mSi(OR")nX4 m n The method for ob-taining the component LI~ by reacting (i) a magnesium halide, (ii) a compound of the general formula Me(OR)nXz n~ (iii) a compound of the general formula R'mSi(OR")nX4 m n and (iv) a titanium compound and/or a vanadium compound, is not specially limited. For example, these constituents may be contacted together and thereby reacted under heating at a temperature ranging from 20 to 400C, preferably 50 to 300C, usually 10: for 5 minutes to 20 hous in the presence or absence of an inert solvent, or they may be reacted by a co-pulverization treatment, or may be reacted by a combination of these methods. The reaction order of the constituents (i) - (iv) is not specially limited, either.
~s the inert solvent, which is not specially limited, there may be used hydrocarbon compounds and/or derivatives thereof which do not inactivate Ziegler type catalysts. Examples are saturated aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octanel benzene~
toluene, xylene and cyclohexane, as well as alcohols, ethers and esters such as ethanol, diethyl ether,tetra-hydrofuran,~ ethyl acetate and ethyl benzoate.
; In case a co-pulverization treatment is adopted for the reaction, the apparatus for the co-pulverizat.ion ,_ .
is not specially limited, but usually employed is a ball mill, a vibration mill, a rod mill or an impact mill.
Conditions such as the pulverizing temperature and time ` -~2~34(30 can be decided easily by ~hose skilled in -the art according to how to pulverize. Generally, the pulverizing tempera-ture ranges from 0 to 200C, preferably 20 to 100C, and the pulverizing time ranges from'0.5 to 50 hours, preferably 1 to 30 h'ours. Of course, the co-pulverizing operation should be preformed in an inert gas atmosphere, and moisture should be avoided as far as possible.
As to the mixing ra-tio of the magnesium halide and the compound of the general formula Me(OR)nXz n and 10. a too large amount thereof tend to result in lowering of the polymerization act~vity~ A desirable range for the production of a high activity catalyst is from 1/0.001 to 1/2~, preferably 1/0.01.to 1/1 and most preferably 1/0.05 to 1/0.5 in terms of Mg/Me molar ratio.
As to the mixing ratio of the magnesium halide and the compound of the general formula R'mSi(OR")nX4 m n~
both a too large amount of the compound of the general m ~OR )nX4_m_n and a too small amount thereof would not be eEfective. A desirable range is from 1/0.01 to 1/1, preferably l/0~05 to 1/0.5, in terms of Mg/Si molar ratio.
As to the amount of the titanium compound and/or vanadium compound, most preferably it is adjusted so that thè amount of titanium andlox vanad'ium contained in the catalyst component LI~ is in the range of 0.5 to 20 wt.%. The range of-l to 10 wt.% is especially desirable for attaining a well-balanced activity per titanium and/or vanadium and that per solid.
1 ~
~z~v~
As to the amount of the compound represented ~ 1 by the general formula R3-~ Si - O ~qR4 which is used as the catalyst component ~II] in the present invention, both too large and too small amounts thereof would not be effective. Usually, it is used in the -range of 0.1 to 100 moles, preferably 0.3 to 20 moles, per mole of the titanium compound and/or vanadium compound in the catalyst component [I~.
It is also preferable in the present invention that the catalyst component ~I~ thus obtained be supported on an oxide of a metal of Groups II through IV in the Periodic Table. As such oxide, there may be used not only oxides of metals of Groups II through IV in the same Table but also double oxides thereof; of course, mixtures thereof are employable. Examples are MgO, CaO, ZnO BaO, SiO2, SnO2, A12O3, MgO.A12O3, 2 2 3 MgO.SiO2, MgO~CaO.A12O3 and A12O3.CaO, with SiO2, A12O3, SiO2.Al~O3 and MgO.A12O3 being especially preferred.
The method for supporting the catalys-t component ~I~ on the said metal oxide is not specially limi-ted.
As a preferable example, there may be adop-ted a method in which the constituents (i),`~ii), (iii~ and (iv) are allowed to react under heating in an ether compound as solvent in the presence,of the said metal oxide and then the liquid phase portion is removed, or a method in which a product obtained by co-puIverization of the constituents ~ 2~
(i3 and (ii) is allowed t~ react` under heating in an e-ther compound as solvent in the presence of the said metal oxide, then the liquid phase portion is removed and thereafter the constituents (iil~ and (iv) are re~ctcd therewith in an inert solvent under heating.
AS examples of the or~anometallic compound ' used in the present invention, there may be mer~tioned organometallic c'ompourids of metals of Groups I through IV in the Periodic Table which are known as a Ziegler catalyst component. Especial~y preferred are organoaluminum compounds and organozinc compounds. Concrete examples are organoaluminum compounds of the general formulae R3Al, R2AlX, RAlX2, R2AlOR, RAl(oR)x and R3A12X3 wherein Rs, which may be alike or different, are each an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen atom, and organozinc compounds of the general formula R2Zn wherein Rs, which may be alike or different, are each an alkyl grouF having 1 to 20 carbon atoms, such as triethylaluminum, triisopropylaluminum, triisobutyl 20: aluminum, tri~sec-bu~ylaluminum, tri-tert~butylaluminum, t~ihexylaluminum, trloctyla'luminùm, diethylaluminum chloride, diisopropyla'luminùm chloride, ethylaluminum ses~uichloride, diethylæinc, and mixtures thereof.
Together with these organome~allic compounds there may be used-organic carboxylic'acid'esters such as, for example, ethyl benzoate,_..eth~l o- or p-toluylate and ethyl.p-anisate. ~ ""
The amount of the organometallic compound used is not specially limited, but usually ranges from 0.1 _ 14 34~
to 1,000 moles per mole o~ the titanium compound and/or vanadium compound.
In the present lnvention, moreover, the compound of the genera]. formula R3-~ Si - O ~qR4 may be reac-ted R
wi~h the above-exemplified organometallic compound and the product thereby ob~ained may be used. In this case, the reaction ratio is in the range of 1 : 500'to 1 : 1, preferably 1 : lOO'.to 1 : 2, in terms of the compound of,the said general formula : the organometallic compound (molar ratio).
The product obtained by the reaction of the compound of the general formuIa R3-~ Si - O t-qR4 wi-th the organometallic compound is .used in an amount ranging preferably fxom 0.1 : 1 to 100:: 1 and more preferably 0.3': 1 to 20.: 1 in terms of Sl : ~i and/or V ~molar ratio) with respect to the titanium compound and/or vanadium compound in the catalyst component ~
The olefIn polymerization using the catalyst of the present inventlon may be performed in the form of,s'lurry polymerization, solution poiymerization or vapor phase polymerization, with the vapor phase polymeri ~
atlon and s'lurry polymerization being particularly suitable.
The polymerization reaction is carried 'out in the same way as in the conventional olefin polymerization reaction _ 15 841~0 using a Ziegler type cata~yst. That is, the reac-tion is performed in a substantially oxygen- and water-free conditlon and in khe presence or absence of an iner-t hydrocarbon. olefin polymerlzlng condltions lnvolve tempera-tures ranging from 2~ to 120C, preferably 50 to 100C, and pressures ranging from atmospheric pressure to 70 kg/cm2, preferably 2 to 60 kg/cm2. Adjustment of the molecular weight can be done to some extent by changing polymerization conditions such as the polymeriza-tion temperature and the catalyst molar ratio, but the addition of hydrogen into the polymerization system is more effective for this purpose. Of course, using the catalyst of the present invention there can be performed, without any trouble, two- or more-stage polymerization reactions involving different polymerization conditions such as different hydroge~ concentrations and different polymerization temperatures.
The process of the present invention is applic-able to the po~ymerization of all olefins that are polymer-izable with a Ziegler catalyst. Particularly, ~-olefins f C2 to C12 are preferred. For example, the process of the invention is suitabie for the homopolymerization of such ~-olefins as ethylene, propylene, butene-l, hexene-l r 4-methylpentene-1 and octene-l, the copolymeriza-tion of ethylene and propylene, ethylene and butene-l, ethylene and hexene-l, e-thylene and 4-methylpentene-1, ethylene and octene-l, and propylene and bu-tene-l, as well as the copolymerization of ethylene and two or more other ~-olefins.
1~84~
Copolymerization with dienes for the modific-ation of polyolefins is also preferable, for example, w~th bu~adiene, 1,4-hexadierle, ethylidene norbornene and dlcyclopentadiene.
The Eollowing examples serve -to illustrate the invention ln more detail, but shouId not be construed as limiting the invention thereto.
Example 1 (a) Preparation of Solid Catalyst Component [I]
10 g. of a commercially available anhydrous magnesium chloride, 2~3 g. of aluminum triethoxide, 3.2 g. of tetraethoxysilane and 2.5 g. o titanium tetrachloride were placed in a stainless steel pot having a content volume o 400.ml. and containing 25 stainless steel balls each 1/2 inch in diameter, and ball-milled for 16 hours at room temperature in a nitrogen atmosphere to obtain a sQlid catalyst component [I]
containing 35 mg. o titanium per gram thereo.
~b) Polymerization 20. As a vapor phase polymerization apparatus there was used a stainless steel autoclave, and a loop was formed by using a blower, a flow control device and a dry cyjclone. The temperature of the autoclave was adjusted by passing warm water through its jacket.
Into the autoc-l-ave.adjusted to 80~C were fed the above solid;c.atalyst component tI~, monomethyltri-ethoxysilane and triethylaluminum at rates o~ 50 mg/hr r _ 17 o 0.2 mmol/hr and 5 mmol/hr; respectively, and further fed were butene-l, e-thylene and hydrogen gases while adjusting the butene-l/ehtylene ratio (molar ratlo) ln the vapor phase ln the autoclave -to 0.28 and the ilydro~erl concentration to 17~ of the total pressure, and polymeriza-tion was carrled out while maintaining the total pressure at 10 kg/cm .G by circulating the intra-system yases by means of the blower, to afford an ethylene copolymer having a bulk density of 0.35, a melt index (MI) of 1.0 and a density of 0.. 9217. Catalyst activity was 294,000~.
copolymer/g.Ti.
After a continuous operation for 10 hours, the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
F.R. value (F.R. = MIlo/MI2 16) represented in terms of the ratio of a melt index (MIlQ) of the copolymer determined at a load of 10 kg. to a melt index (MI2 16) thereof determined at a load of 2.16 kg. both ~0. at 190C according to the method of ASTM-D1238-73 was 6.7 and thus the molecular welght distribution was extremely narrow.
When a film formed from this copolymer was extracted in boillng hexane for lO hours, its hexane 2S extraction was 0.5 wt % and thus was very small.
Comparative Example 1 A continuous vapor phase polymerlzation of ~2C184~3~
ethylene and butene-l was carried out in the same way as in Example 1 excep-t that the monome-thyl-triethoxysilane was not added, to afford an ethylene copolymer having a bulk density of 0.30, a denslty oE 0.9210 and a melt index of 1.3. Catalytic activity was 310,OOOg.copolymer/g.
Ti.
The F.~R. value of this copolymer was 7.3, and when a film formed from the copolymer was extracted in boiling hexane for lO hours, its hexane extractior- was 1.6 wt.%.
Example 2 10 ml. of ethanol, 20 g. o an anhydrous magnesium chloride and 4.6 g. of triethoxyboron were charged into a three-necked 300 ml. flask equipped with a magnetic induction stirxer and allowed to react for 3 hours under reflux. Thereafter, 150 ml. of n-hexane was added to allow precipitation to take place. Then, after standing, the supernatant liquid was removed, followed by vacuum drying at 200C to obtain a white dry powder.
11 g. of the above white powder, 3~0 g. of dietho~cydiethylsilane and 2.4 g. of titanium tetrachloride were placed in a stainless steel pot having a content volume of 400 ml. and containing 25 stainless steel balls each 1/2 inch in diamete~, and ball milled for 16 hours at room temperature in a nitrogen atmosphere, to give a solid catalyst component ~I~ containing 39 mg. of titanium per gram thereof~
_ 19 :12~8~0 A continuous vapor phase polymerization of ethylene and butene-l was carried 'out in -the same way as in Example 1 excep-t that -the above solid catalyst componen~ CI~ was E~d at a rate oE 5() nlg/llr, to aEEc)r~
an ethylene copolymer having a bulk density of 0.33, a density of 0.9220 and a melt index of 1.2. Catalytic activity was'340,000g.copolymer/g.Ti and thus very high.
After the continuous operation for lO'hours, the autoclave' was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer 6.9, and when a film formed from the copolymer was extracted in boiling hexane for lO hours, its hexane extraction was 0 8 wt.%
and thus very small.
Example 3 10 g. of an anhydrous magnesium chloride, 3~1 g. of diethoxymagnesium and 2.9 g. of titan'ium tetrachloridè were placed in the ball mill pot described in Example 1, and ball-milled for 5 hours at room temperature in a nitrogen atmosphere, then'3.8 g. of . .
methyltriethoxysilane was added, followed by 'further ball milling for ]2 hours, to give a solid catalyst component ~I 3 containing '37 mg. of titanium per gram thereof. ~
A con~in~ous vapor phase polymerization of ethylene and butene-l was carried 'out in the same way as in Example 1 eY.cept that the solid catalyst component _ 20: ~
- ~2~840~
~I~ just prepared above was fed at a rate of 50 mg/hr and a mixture obtained by reacting -triethylaluminum and tetraethoxysilane at a ratio of 1 mole triethylaluminum and 0.1 mole tetraethoxysilane at 85C for 2 hours was fed at a rate of 5 mmol/hr as aluminum, to afford an ethylene copolymer having a buIk'density of 0.34, a density of 0.9215'and a melt index of 0.95. Cataly-tic activity was 258,OOOg.copolymer/g.Ti and thus very high.
After the continuous operation for 10 hours, the 'autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was 6.7, and when a film formed from the copolymer was extracted in boiling hexane for 10 hours, its hexane extraction was 0.4 wt.~ and thus very small.
Example 4 lO'g. of an anhydrous magnesium chloride and
P~OCE5S FO~ PREPARING POLYOLEFINS
B~CKG~OUND OF Tll~ INV~NTION
The present lnventlon relates to a process for preparing polyolefins us'lng a novel polymerization cata1yst.
Heretoforej in this technical field there has been known from Japanese Patent Publication No.12105/1964 a catalyst whlch compr~ses a magnesium hal~de and a transi tlon metal compound such as a tl-tanium compound supported 1~ thereon, and also known from Belgian Patent No.742,112 a catalyst ob~ained by co-pulverizing a magne8iu~ halide and tltanium tetrachloride.
However, when viewed from the standpoint that as high a catalytlc activity as possible is desired in the production of,polyolefins, the process disclosed in the Japanese Patent Pu~lication 12105/1964 is still ' unsatisfactory ln po~nt of polymerization activi-ty, and the process of the Belgiam Patent. 742,112 gives a fairly lmproved polymerizat~on activity, bu-t s-till leaves room for lmprovement.
I'n West German Patent No.2137872, the amount o a magnes~um halide used is substantially decreased by the co-puIverizat~on of the,magnesium halide with titanium tetrachlor~de'and alumina. But a remarkable lncrease ln act.ivl~y per sol~d which can be regarded as the guidetine for productivity is not recognized, thus leading to a des~re for catalyst of, higher activity.
:~L2~
In the preparation of polyolefins, moreover, it is desirable from the aspects of produc-tivity and slurry handling -that the bulk density oE the resultan-t polymer be as hlgh as posslble. When viewed from this standpoint, the process disclosed in the foregoing Japanese patent publication 12105/1964 affords polymers low in bulk densi-ty and is not satisfactory in point of polymerization activity, and the process of the Belgian patent 742,112 also disadvantageous in that the bulk density of the resuItant polymer is low, although it affords a high polymerization activity. Thus, in both processes, a further improvemen-t is desired.
SUMMARY OF THE INVENTION
It is an object of the present invention to remedy the above-mentioned drawbacks of the prior art.
It is another object of the present invention to provide a process for preparing a novel polymerization catalyst which exhibits a high polymerization activity, which is capable of affording a polymer of high bulk density in high yield and which permits an extremely easy execution of a continuous polymerization, as well as a process ~or homo~ or copolymerizing olefins in the presence of the said polymerization catalyst.
The present invention is concerned with a process for preparlng a polyolefin, characterized by polymerizing at least one olefin in the presence of a catalyst, which catalyst comprises either the following combination ~1) or (2~:
840~
(1) ~I~ a solid substance obtained by the reaction of (i) a magnesium halide, (ii) a compound represented by the general formula Me(OR~nXz n wherein Me is an element of Groups I through VIII of the Periodic T~ble, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, z is the valence of Me and n is O ~ n ~ z, (iii) a compound represen$ed by the general mSi(oR )nX4_m_n wherein R' and R"
are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are O ~ m ~ 4 and O C n c 4, provided O ~ m ~ n ~ 4, and (iv) a titanium compound and/or a vanadium compound;
II a compound represented by the genera1 formula Rl . .
R3-~ S ~ O~qR wherein Rl, R2 and R3 are each R
a hydrocarbon radical having 1 to 24 carbon atoms, alkoxy, hydrogen or halogen, R4 is a hydrocarbon radical having~l to.24 carbon atoms and q is 1 c q ~.30 and ~8~
tIII~ an organometallic compound.
~2~ [I~ a solld substance obtained by -the reac-tion of (i) a magnesium hal.ide, (li) a compound represented by the yeneral Eormula Me(OR)nXz n wherein Me is an element of Groups I through VIII of the Periodic Table, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon . atoms, X is a halogen atom, z is the valence of 10. Me and n is 0.< n c z, liii) a compound represented ky the general ~ormula R'mSi~oR")nX4_m_n wherein R' and R" are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are O ~ m C 4 and 0 < n ~ 4, provided O < m + n c 4, and (iv) a titanium compound and/or a vanadium compound; and rII] a product obtained by the reaction of (v) a compound represented by the general ormula Rl R3 ~ Si - O ~qR4 wherein Rl, R2 and R3 are each a hydrocarbon radical having 1 to 24 carbon atoms, alkoxy, hydrogen or halogen, R4 is a hydrocarbon radlcal having 1 to 24 carbon atoms and q i.s 1-~ q -~ 30~.and Ivi) an organometallic compound.
~2~
The catalyst of the present invention exhihits a very high polymerization activity, resulting in a decreased partial pressure of monomer during polymeriza-tion~ afEords a polymer having a high bulk ~ensity, thus permitting improvement of produc-tivity, remains in -the resultant polymer after polymerization in an extremely small quantity~to the extent that the polyolefin manufac-turing process can dispense with the catalyst removing steps, resulting in a more simplified step for polymer treatment, and thus permits an extremely econQmical production of polyolefins as a whole.
According to the process of the present invention, the amount of polymer produced per unit polymerization reaction vessel is large because of a high buIk density of the poly~er.
Further, when viewed fxom the standpoint of particle size of the resulting polymer, the proportion of coarse particle~ and fine particles below 501u is low despite o a high bulk density of the polymer, thus 20: permitting an sasy execution of a continuous polymeriza-tion reaction and an easy handling of polymer particles, for example, in centrifugal separation in the polymer treating step or in transportation of the powdered polymer.
As a `further advantage of the present invention, mention may be made of an outstanding effect on economy and on productivity. More particuIarly, polyolefins prepared by using the catalyst of the present invention have a high bulk density as previously noted, and lesshydrogen concentration is required -than in -the prior art process Eor obtalnlng a polymer having a desired me:lt lndex, thus resulting in -that -the total pressure can be maintained at a relatively small level throughout the polymerizatlon.
More,over, in the polymerization of olefin using the catalyst of the present invention, the decrease of the olefin absorbing rate is not accelerated with the lapse of time, so the polymerization can be continued for a long time in a small quantity of the catalyst.
Additionally, polymers prepared by using the catalyst of the present invention are extremely narrow in molecular weight distribution and their hexane extraction 15' ,is very small, that is, the by-production of low polymers is mi,nimized. Consequently, it is possible to obtain products of good quality, for example, a product superior in anti-blocking property in film grade.
Thus, the catalyst o the present invention is a novel catàlyst whlch has many such characteristic features and which has remedied the above-mentioned drawbacks of the prior art. And it is quite surprising that the ~oregoing features can easily be attained by using the catalyst of the present invention.
DESCRIPTION OP'PREFERRED'EM~ODIMENTS
As the magnesium ha'ide used in the present invention there is'used a substantially anhydrous one~
8~
examples of which include'magnesium fluoride, magnesium chloride, maynesium bromide and magneslum iodide, with magnesium chloride being par-ticularly preferred.
As examples of the compound represented by the general formula Me(OR)nXz n used in the presen-t invention wherein Me, z, n and R are as previously defined, men-tion may be made of such various compounds as ~aOR, Mg(OR)2, Mg(OR)X, Ca(OR)2, Zn(OR)2,, Zn(OR)X, Cd(OR)2, Al(OR)3, Al(OR)2X, BIOR)3, B(OR)2X, Ga(OR)3, Ge(OR~4, Sn(OR)4, P~OR)3, Cr(OR)2, Mn(OR)2, Fe(OK)2, Fe~OR)3, Co(OR)2 and Ni~OR)2, and as more preferable concrete examples there may be mentioned 'such compounds as NaOC2H5, NaOC4Hg, 3 2 g 2 5)2' Mg50C3H532~ Ca(OC2H5)2' ~n~oC H ) Zn(OC H5)Cl, Al(OCH3)3, Al(OC2H5)3, 2 5 2 Al(OC3H7)3, Al(OC4Hg)4, Al(OC6H5)3, B(OC~H5)3, B~OC2H5)2Cl, ( 2H5)3, P(OC6H5)3 and Fe(OC4Hg)3.
Compounds representedby the general formulae Mg(R)nX2~n' A150R)nX3-n and B(OR)nX3_n are partiCularly preferred'in the present invention. And as the substitu-ent R, alkyl groups having 1 to 4 carbon atoms and phenylgroup are especially preferred.
To exemplify.the compound represented by, the general formula R'mSi(oR")nX4 m n used in the present invention wherein R', R", m and n are as previously defined~ mention may be made of the ollowing:
monomethyltrimethoxysil~ne, ~onomethyltriethoxysilane, monomethyltri-n-~utoxysilane, monomethyltri-sec-butoxysilane, monomethyltriisopropoxysllane, monomethyl-tripentoxysilane, monomethyltrioctoxysilane, ~L2¢;il8~
monomethyltristearoxysilane/ monomethyltriphenoxysilarle, dimethyldime-thoxysilane, dime-thyldie-thoxysilane/ dimethyl-diisopropoxysilane/ dimethyldiphenoxysilane/ trime-thylmono-ethoxysilane, trimethylmonoethoxysilane, trimethylmonoiso-propoxysilane, trimethylmonophenoxysilane, monomethyldi-methoxymonochlorosilane, monomethyldietho~ymonochlorosilane, monomethylmonoethoxydichlorosilane, monomethyldiethoxymono-chlorosilane, monomethyldiethoxymonobromosilane, monomethyl-diphenoxymonochlorosilane, aimethylmonoethoxymonochloro-silane, monoethyltrimethoxysilane/ monoethyltriethoxysilanemonoethyltriisopropoxysilane, monoethyltriphenoxysilane/
diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-phenoxysilane, triethylmonomethoxysilane, triethylmono-ethoxysilane, triethylmonophenoxysilane, monoethyldimethoxy-monochlorosilane, monoethyldiethoxymonochlorosilane,monoethyldiphenoxymonochlorosilane, monoisopropyltri-methoxysilane, mono-n-butyltrimethoxysilane, mono-n-butyltriethoxysilane, mono-sec-butyltriethoxysilane, monophenyltriethoxysilane, diphenyldiethoxysilane, ~0 diphenylmonoethoxymonochlorosilane, monomethoxytrichloro-silane, monoethoxytrichlorosilane, monoisopropoxytrichloro-silane, mono-n-butox~trichlorosilane, monopentoxytrichloro-silane, monooctoxytrichlorosilane, monos-tearoxytrichloro-silane r monophenoxytrichlorosilane, mono p-methylphenoxytrichlorosilane, di~ethoxydichlorosllane,diethoxydichlorosilane,~diisopr~poxydichlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochloxosilane, tri-sec-butoxymonochloro-silane, tetraethoxysilane and tetraisopropbxysilane.
:~Z~8~
As examples of the titanium compound and/or vanadium compound used in the present i.nvention, -there may be mentioned halides, alkoxyhalides, alkoxides and halogenated oxides of titanium and/or vanadium.
Suitable examples of titanium compounds are tetravalent and trivalent titanium compounds. As tetravalent ti-tanium compounds are preferred those represented by the general formula Ti(OR)pX4 p wherein R is an alkyl, aryl or aralkyl group having 1 to 24 carbon atoms~ X is a halogen atom and p i.s 0 ~ p ~ 4, such as, ~or example, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxy-trichlorotitanium, dimethoxydichlorotitanium, trimethoxy monochlorotitanium, tetramethoxytitanium, monoethoxytri-chlorotitanium, diethoxydichlorotitanium~ triethoxymono~
chlorotitanium, tetraethoxytitanium, monoisopropoxytri-ch~orotitanium, diisopropoxydichlorotitanium, triisopropoxy-monochlorotitanium~ tetraisopropoxytitanium r monobutoxytrichlorotitanium, dibutoxydichlorotitaniurn, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochloro-titanium and tetraphenoxytitaniu~. To illustrate trivalent titanium compounds, mention may be made of titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium-or an organometallic compound of a metal ~f Gro.ups I through III in the Periodic Table, as well as trivalent titanium compounds obtained by reducing tetravalent alkoxytitanium halides g of the general formula ~i(OR)rX4 r with an organometallic compound of a metal of Groups I through III in -the Periodic Table, in which formula R is an alkyl, aryl or aralkyl group having 1 to 24 caxbon atoms and r is 0 < r ~ 4.
~s examples of vanadium compounds, there are mentioned tetravalent vanadium compounds such as vanadium tetra-chloride~ vanadium tetrabromide, vanadium tetraiodide and tetraethoxyvanadium; pentavalent vanadium compounds such as vanadium oxytrichloride, ethoxydichlorovanadyl, triethoxyvanadyl and tributoxyvanadyl; and trivalent vanadium compounds such as vanadium trichloride and vanadium triethoxide.
Tetravalent titanium compounds are most preEerred in the present invention.
In order to ma~e the present lnvention more effective, both thè titanium compound and the vanadium compound are often used in combination~ In this case, it is preferable that the V/Ti molar ratio be in the range of 2/1 to 0.01/1.
As examples of the compound of the general R~
formula R3-t-Si - O ~qR4 used in the present invention, R
mention may be made of the compound of the general formula R'mSi(OR")nX4 m n which is used in the catalyst component ~I~, as well as chain-li-ke or cyclic polysiloxanes with ~' 1 a recuxring unit represented by -~ Si - O ~- obtained ~2~ 0~
by condensation of the compounds R'mSi(OR")nX4 m n The method for ob-taining the component LI~ by reacting (i) a magnesium halide, (ii) a compound of the general formula Me(OR)nXz n~ (iii) a compound of the general formula R'mSi(OR")nX4 m n and (iv) a titanium compound and/or a vanadium compound, is not specially limited. For example, these constituents may be contacted together and thereby reacted under heating at a temperature ranging from 20 to 400C, preferably 50 to 300C, usually 10: for 5 minutes to 20 hous in the presence or absence of an inert solvent, or they may be reacted by a co-pulverization treatment, or may be reacted by a combination of these methods. The reaction order of the constituents (i) - (iv) is not specially limited, either.
~s the inert solvent, which is not specially limited, there may be used hydrocarbon compounds and/or derivatives thereof which do not inactivate Ziegler type catalysts. Examples are saturated aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, such as propane, butane, pentane, hexane, heptane, octanel benzene~
toluene, xylene and cyclohexane, as well as alcohols, ethers and esters such as ethanol, diethyl ether,tetra-hydrofuran,~ ethyl acetate and ethyl benzoate.
; In case a co-pulverization treatment is adopted for the reaction, the apparatus for the co-pulverizat.ion ,_ .
is not specially limited, but usually employed is a ball mill, a vibration mill, a rod mill or an impact mill.
Conditions such as the pulverizing temperature and time ` -~2~34(30 can be decided easily by ~hose skilled in -the art according to how to pulverize. Generally, the pulverizing tempera-ture ranges from 0 to 200C, preferably 20 to 100C, and the pulverizing time ranges from'0.5 to 50 hours, preferably 1 to 30 h'ours. Of course, the co-pulverizing operation should be preformed in an inert gas atmosphere, and moisture should be avoided as far as possible.
As to the mixing ra-tio of the magnesium halide and the compound of the general formula Me(OR)nXz n and 10. a too large amount thereof tend to result in lowering of the polymerization act~vity~ A desirable range for the production of a high activity catalyst is from 1/0.001 to 1/2~, preferably 1/0.01.to 1/1 and most preferably 1/0.05 to 1/0.5 in terms of Mg/Me molar ratio.
As to the mixing ratio of the magnesium halide and the compound of the general formula R'mSi(OR")nX4 m n~
both a too large amount of the compound of the general m ~OR )nX4_m_n and a too small amount thereof would not be eEfective. A desirable range is from 1/0.01 to 1/1, preferably l/0~05 to 1/0.5, in terms of Mg/Si molar ratio.
As to the amount of the titanium compound and/or vanadium compound, most preferably it is adjusted so that thè amount of titanium andlox vanad'ium contained in the catalyst component LI~ is in the range of 0.5 to 20 wt.%. The range of-l to 10 wt.% is especially desirable for attaining a well-balanced activity per titanium and/or vanadium and that per solid.
1 ~
~z~v~
As to the amount of the compound represented ~ 1 by the general formula R3-~ Si - O ~qR4 which is used as the catalyst component ~II] in the present invention, both too large and too small amounts thereof would not be effective. Usually, it is used in the -range of 0.1 to 100 moles, preferably 0.3 to 20 moles, per mole of the titanium compound and/or vanadium compound in the catalyst component [I~.
It is also preferable in the present invention that the catalyst component ~I~ thus obtained be supported on an oxide of a metal of Groups II through IV in the Periodic Table. As such oxide, there may be used not only oxides of metals of Groups II through IV in the same Table but also double oxides thereof; of course, mixtures thereof are employable. Examples are MgO, CaO, ZnO BaO, SiO2, SnO2, A12O3, MgO.A12O3, 2 2 3 MgO.SiO2, MgO~CaO.A12O3 and A12O3.CaO, with SiO2, A12O3, SiO2.Al~O3 and MgO.A12O3 being especially preferred.
The method for supporting the catalys-t component ~I~ on the said metal oxide is not specially limi-ted.
As a preferable example, there may be adop-ted a method in which the constituents (i),`~ii), (iii~ and (iv) are allowed to react under heating in an ether compound as solvent in the presence,of the said metal oxide and then the liquid phase portion is removed, or a method in which a product obtained by co-puIverization of the constituents ~ 2~
(i3 and (ii) is allowed t~ react` under heating in an e-ther compound as solvent in the presence of the said metal oxide, then the liquid phase portion is removed and thereafter the constituents (iil~ and (iv) are re~ctcd therewith in an inert solvent under heating.
AS examples of the or~anometallic compound ' used in the present invention, there may be mer~tioned organometallic c'ompourids of metals of Groups I through IV in the Periodic Table which are known as a Ziegler catalyst component. Especial~y preferred are organoaluminum compounds and organozinc compounds. Concrete examples are organoaluminum compounds of the general formulae R3Al, R2AlX, RAlX2, R2AlOR, RAl(oR)x and R3A12X3 wherein Rs, which may be alike or different, are each an alkyl or aryl group having 1 to 20 carbon atoms and X is a halogen atom, and organozinc compounds of the general formula R2Zn wherein Rs, which may be alike or different, are each an alkyl grouF having 1 to 20 carbon atoms, such as triethylaluminum, triisopropylaluminum, triisobutyl 20: aluminum, tri~sec-bu~ylaluminum, tri-tert~butylaluminum, t~ihexylaluminum, trloctyla'luminùm, diethylaluminum chloride, diisopropyla'luminùm chloride, ethylaluminum ses~uichloride, diethylæinc, and mixtures thereof.
Together with these organome~allic compounds there may be used-organic carboxylic'acid'esters such as, for example, ethyl benzoate,_..eth~l o- or p-toluylate and ethyl.p-anisate. ~ ""
The amount of the organometallic compound used is not specially limited, but usually ranges from 0.1 _ 14 34~
to 1,000 moles per mole o~ the titanium compound and/or vanadium compound.
In the present lnvention, moreover, the compound of the genera]. formula R3-~ Si - O ~qR4 may be reac-ted R
wi~h the above-exemplified organometallic compound and the product thereby ob~ained may be used. In this case, the reaction ratio is in the range of 1 : 500'to 1 : 1, preferably 1 : lOO'.to 1 : 2, in terms of the compound of,the said general formula : the organometallic compound (molar ratio).
The product obtained by the reaction of the compound of the general formuIa R3-~ Si - O t-qR4 wi-th the organometallic compound is .used in an amount ranging preferably fxom 0.1 : 1 to 100:: 1 and more preferably 0.3': 1 to 20.: 1 in terms of Sl : ~i and/or V ~molar ratio) with respect to the titanium compound and/or vanadium compound in the catalyst component ~
The olefIn polymerization using the catalyst of the present inventlon may be performed in the form of,s'lurry polymerization, solution poiymerization or vapor phase polymerization, with the vapor phase polymeri ~
atlon and s'lurry polymerization being particularly suitable.
The polymerization reaction is carried 'out in the same way as in the conventional olefin polymerization reaction _ 15 841~0 using a Ziegler type cata~yst. That is, the reac-tion is performed in a substantially oxygen- and water-free conditlon and in khe presence or absence of an iner-t hydrocarbon. olefin polymerlzlng condltions lnvolve tempera-tures ranging from 2~ to 120C, preferably 50 to 100C, and pressures ranging from atmospheric pressure to 70 kg/cm2, preferably 2 to 60 kg/cm2. Adjustment of the molecular weight can be done to some extent by changing polymerization conditions such as the polymeriza-tion temperature and the catalyst molar ratio, but the addition of hydrogen into the polymerization system is more effective for this purpose. Of course, using the catalyst of the present invention there can be performed, without any trouble, two- or more-stage polymerization reactions involving different polymerization conditions such as different hydroge~ concentrations and different polymerization temperatures.
The process of the present invention is applic-able to the po~ymerization of all olefins that are polymer-izable with a Ziegler catalyst. Particularly, ~-olefins f C2 to C12 are preferred. For example, the process of the invention is suitabie for the homopolymerization of such ~-olefins as ethylene, propylene, butene-l, hexene-l r 4-methylpentene-1 and octene-l, the copolymeriza-tion of ethylene and propylene, ethylene and butene-l, ethylene and hexene-l, e-thylene and 4-methylpentene-1, ethylene and octene-l, and propylene and bu-tene-l, as well as the copolymerization of ethylene and two or more other ~-olefins.
1~84~
Copolymerization with dienes for the modific-ation of polyolefins is also preferable, for example, w~th bu~adiene, 1,4-hexadierle, ethylidene norbornene and dlcyclopentadiene.
The Eollowing examples serve -to illustrate the invention ln more detail, but shouId not be construed as limiting the invention thereto.
Example 1 (a) Preparation of Solid Catalyst Component [I]
10 g. of a commercially available anhydrous magnesium chloride, 2~3 g. of aluminum triethoxide, 3.2 g. of tetraethoxysilane and 2.5 g. o titanium tetrachloride were placed in a stainless steel pot having a content volume o 400.ml. and containing 25 stainless steel balls each 1/2 inch in diameter, and ball-milled for 16 hours at room temperature in a nitrogen atmosphere to obtain a sQlid catalyst component [I]
containing 35 mg. o titanium per gram thereo.
~b) Polymerization 20. As a vapor phase polymerization apparatus there was used a stainless steel autoclave, and a loop was formed by using a blower, a flow control device and a dry cyjclone. The temperature of the autoclave was adjusted by passing warm water through its jacket.
Into the autoc-l-ave.adjusted to 80~C were fed the above solid;c.atalyst component tI~, monomethyltri-ethoxysilane and triethylaluminum at rates o~ 50 mg/hr r _ 17 o 0.2 mmol/hr and 5 mmol/hr; respectively, and further fed were butene-l, e-thylene and hydrogen gases while adjusting the butene-l/ehtylene ratio (molar ratlo) ln the vapor phase ln the autoclave -to 0.28 and the ilydro~erl concentration to 17~ of the total pressure, and polymeriza-tion was carrled out while maintaining the total pressure at 10 kg/cm .G by circulating the intra-system yases by means of the blower, to afford an ethylene copolymer having a bulk density of 0.35, a melt index (MI) of 1.0 and a density of 0.. 9217. Catalyst activity was 294,000~.
copolymer/g.Ti.
After a continuous operation for 10 hours, the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
F.R. value (F.R. = MIlo/MI2 16) represented in terms of the ratio of a melt index (MIlQ) of the copolymer determined at a load of 10 kg. to a melt index (MI2 16) thereof determined at a load of 2.16 kg. both ~0. at 190C according to the method of ASTM-D1238-73 was 6.7 and thus the molecular welght distribution was extremely narrow.
When a film formed from this copolymer was extracted in boillng hexane for lO hours, its hexane 2S extraction was 0.5 wt % and thus was very small.
Comparative Example 1 A continuous vapor phase polymerlzation of ~2C184~3~
ethylene and butene-l was carried out in the same way as in Example 1 excep-t that the monome-thyl-triethoxysilane was not added, to afford an ethylene copolymer having a bulk density of 0.30, a denslty oE 0.9210 and a melt index of 1.3. Catalytic activity was 310,OOOg.copolymer/g.
Ti.
The F.~R. value of this copolymer was 7.3, and when a film formed from the copolymer was extracted in boiling hexane for lO hours, its hexane extractior- was 1.6 wt.%.
Example 2 10 ml. of ethanol, 20 g. o an anhydrous magnesium chloride and 4.6 g. of triethoxyboron were charged into a three-necked 300 ml. flask equipped with a magnetic induction stirxer and allowed to react for 3 hours under reflux. Thereafter, 150 ml. of n-hexane was added to allow precipitation to take place. Then, after standing, the supernatant liquid was removed, followed by vacuum drying at 200C to obtain a white dry powder.
11 g. of the above white powder, 3~0 g. of dietho~cydiethylsilane and 2.4 g. of titanium tetrachloride were placed in a stainless steel pot having a content volume of 400 ml. and containing 25 stainless steel balls each 1/2 inch in diamete~, and ball milled for 16 hours at room temperature in a nitrogen atmosphere, to give a solid catalyst component ~I~ containing 39 mg. of titanium per gram thereof~
_ 19 :12~8~0 A continuous vapor phase polymerization of ethylene and butene-l was carried 'out in -the same way as in Example 1 excep-t that -the above solid catalyst componen~ CI~ was E~d at a rate oE 5() nlg/llr, to aEEc)r~
an ethylene copolymer having a bulk density of 0.33, a density of 0.9220 and a melt index of 1.2. Catalytic activity was'340,000g.copolymer/g.Ti and thus very high.
After the continuous operation for lO'hours, the autoclave' was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer 6.9, and when a film formed from the copolymer was extracted in boiling hexane for lO hours, its hexane extraction was 0 8 wt.%
and thus very small.
Example 3 10 g. of an anhydrous magnesium chloride, 3~1 g. of diethoxymagnesium and 2.9 g. of titan'ium tetrachloridè were placed in the ball mill pot described in Example 1, and ball-milled for 5 hours at room temperature in a nitrogen atmosphere, then'3.8 g. of . .
methyltriethoxysilane was added, followed by 'further ball milling for ]2 hours, to give a solid catalyst component ~I 3 containing '37 mg. of titanium per gram thereof. ~
A con~in~ous vapor phase polymerization of ethylene and butene-l was carried 'out in the same way as in Example 1 eY.cept that the solid catalyst component _ 20: ~
- ~2~840~
~I~ just prepared above was fed at a rate of 50 mg/hr and a mixture obtained by reacting -triethylaluminum and tetraethoxysilane at a ratio of 1 mole triethylaluminum and 0.1 mole tetraethoxysilane at 85C for 2 hours was fed at a rate of 5 mmol/hr as aluminum, to afford an ethylene copolymer having a buIk'density of 0.34, a density of 0.9215'and a melt index of 0.95. Cataly-tic activity was 258,OOOg.copolymer/g.Ti and thus very high.
After the continuous operation for 10 hours, the 'autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was 6.7, and when a film formed from the copolymer was extracted in boiling hexane for 10 hours, its hexane extraction was 0.4 wt.~ and thus very small.
Example 4 lO'g. of an anhydrous magnesium chloride and
2.1 g. o trie-thoxyphosphorus (P(OEt)3~ were placed in the ball mill pot described in Example l and ball-milled for 3 hours at room temperature in a,nitrogen atmosphere, . .
then 4.5 g. of tetraisopropoxysilane and 3.0 g. of titanium tetrachloride were added, followed by further ~all milling for 16 hours, to obtain a solid catalyst component [I~
25' containing 37 mg. of titanium per gram thereof.
A continuous vapor phase polymerization of -` ~L2~ 0 ethylene and butene-l was carried out in -the same way as in Example 1 except that the solid catalys-t component [I~ just prepared above was fed at a ra-te of 50 mg/hr and monophenyltriethyoxysilane was fed at a rate of 0.25 mmolJhr in place of the monomethyltriethoxysilane, to afford an ethylene copolymer having a bulk density of 0.35, a density of 0.9218 and a melt index of 1.1.
Catalytic activity was 270,000g.copolymer/g.Ti and thus very high.
After the continuous operation for 10 hours, the autoclave was opened and its interior was checked.
As a resuIt, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was 7.0 r and 15' when a film formed from the copolymer was extracted in boiling hexane, its hexane extraction was 0.9 wt.% and thus very small.
Example 5 lO g. of,an anhydrous magnesium chloride, 3.5 2~ g. of diethoxyzinc and'2.8 g. of diisopropoxydichloro-titanium were placed in the ball mill pot described in Example 1, and ball-m,illed ~or 16 hours at room tempe;rature ih a nitrogen atmosphere, then 3.8 g. of triethoxymonochlorosilane was added, followed by urther ball milling for 7 hour~ to obtain a solid catalyst component ~I~ containing 28 mg. of titanium per gram thereof.
~z~
A continuous vapor phase polymerization was carried out in the same way as in Example 1 except that the solid catalyst component [IJ jus-t prepared above was fed at a rate of 50 mg/hr and tetraethoxysilane was fed at a rate of 0.25 mmol/hr in place of the monomethyl-ethoxysilane, to afford an ethylene copolymer having a bulk density of 0.39, a density of 0.9224 and a melt index of 1.2. Catalytic activity was 330,000g.copolymer/g.
Ti and thus very high.
After the continuous operation for 10 hours, the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto~
The F.R. value of this copolymer was 7.0, and when a film formed from the copolymer was extracted in boiling hexane for 10 hours, its hexane extraction was 0.7 wt.% and thus very small.
Example 6 A stainless steel 2 liter autoclave equipped with an induction stirrer was purged with nitrogen and charged with l,OOO ml. of hexane, then 1 mmol of triethylaluminum, 0.1 mmol of tetraethoxysilane and 10 mg.
o the solid catalyst component [I~ obtained in Example 1 were added and the temperature was raised to 85C with stirring. The pressur~-of the system was adjusted to 2 kg/cm2.G by introducing nitrogen, then hydrogen was introduced up to a total pressure of 5 kg/cm2.G and then _ 23 40~
ethylene introduced up to a total pressure of 10 kg/cm2.G
under which condition a polymerization was star-ted, which was continued for 1 hour while maintaining the internal pressure of the autoclave at 10 kglcm2.G. Thereafter, the polymer slurry was transferred into a beaker and hexane was removed under reduced pressure to yield 116 g.
of a white polyethylene having a melt index of 1.0, a density of 0.9631 and a bulk density of 0~38. Ca-talytic activity was 66,300g.polyethylene/g.Ti.hr-C2H4 pressure, 2,320g.polyethylene/g~solid.hr-C2H4 pressure.
The F.R. value of the polyethylene was 7.5 and the molecular weight distribution thereof was very narrow as compared with that in Comparative Example 2.
Its hexane extraction was 0.2 wt.%.
Comparative Example 2 Polymerization was carried out for 1 hour in the same way as in Example 6 except that the tetraethoxy-silane was not added, to yield 134 g. of a white polyethylene having a melt index of 1.4, a density o~
0.9637 and a bulk density of 0.35. Catalytic activity was 76,500g.polyethylene/g.Ti.hr C2H4 pressure, 2,680g.polyethylenetg~solid.hr C2H4 pressure.
; The F.R. value of the polyethylene was 8.3 and its hexane extraction was 0.6 wt.~.
Example 7 The solid catalyst component tI~ obtained in _ 24 lZ~
Example 1 was fed at a rate o~ 5a mg/hr and a product obtained by reacting triethylaluminum and monome-thyl-tri-ethoxysilane at a composition ratio of 5 : 0.22'(molar ratio) for 2 hours at room temperature was fed a-t a ra-te of 5 n~lol/hr as aluminum,' under which condi-tion a continuous vapor phase polymerization of ethylene and butene-l was carried out in the same manner as in Example 1 to afford an ethylene copolymer having a bulk density of 0.34, a density of 0.9214 and a melt index o~ 0.93.
Catalytic activity,was 301,000gOcopolymer/g.Ti and thus very high.
After the continuous operation for 10 hous, ~ the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was ~.8, and w~en a film formed from the copolymer was extracted in boiling hexane for lO hours, its hexane extraction was 0.6 wt.~ and thus very small.
Example 8 10 g. of a commercially available anhydrous magnesium chloride and 4~2 g. of aluminum triethoxide were placed in, a stainless steel p~t having a content volume of 400 ml. and containing 25 stainless steel balls each 1/2 inch in diameter, and ball-milled for 16 hours at room tempera'ture in a nitrogen atmosphere to obtain a reaction product. Then r a three-necked flask equipped ~-- i2~84~
with a s-tirrer and a reflux condenser was purged wi-th nitrogen and then charged with 2.5 g. of the above reaction product and 5 g. of SiO2 (~952, a produc-t of Fuji-Davison) which had been calcined at 600C, then 100 ml. of tetrahydrofuran was added and reaction was allowed to take place at 60C for 2 hours, followed by drying at 12~DC under reduced pressure to remove tetrahydrofuran. Then, 50.ml~ of hexane was added, and after stirring, 1.1 ml. of ti.tanium tetrachloride was added and reaction was allowed to take place for 2 hours under reflux of hexane to obtain a solid powder ~A) containing 37 mg. of titaniu~i per gram thereof.
The solid powder ~A) thus obtained was added into 50 ml. of hexane, then 2 ml.. of tetraethoxysilane was added and reaction was allowed to take place for 2 hours under reflux of hexane to obtain a solid catalyst component.
A continuous vapor phase polymerization was carried out in the same way as in Example 1 except that the solid catalyst component just prepared above was fed at a rate of 150 mgjhr and a product obtained by reacting triethylaluminum and tetraethoxysilane at an Al/Si molar ratio of 20/1 for 1.5 hours at 85C was fed at a rate of 5:mmol/hr as aluminum, to afford an ethylene copolymer having a buIk density of 0.38, a density of 0.9?13 and a melt index o 0.9. Catalytic activity was 543,000g.copolymer./g.Ti and thus.very high.
After the continuous operation for lO.hours, - 26 ~
~Z~840C3 the autoclave was opened and its interior was checked.
As a result, the inner wall and the s-tirrer were clean wlth no polymer adhered thereto.
The F.R~ value oE thls copolymer wa8 6.9, alld when a film formed Erom the copolymer was extracted in boiling hexane for 10 hours, its hexane extraction was 0.8 wt.~ and thus very small.
Example 9 lO g~ of an anhydrous magnesium chloride and 4.2 g. of diethoxymagnesium were placed in the ball mill pot described in Example 8, and ball-milled for 16 hours at room temperature in a nitrogen atmosphere to obtain a reaction product. Then, 2.5 g, of the reaction product and 5 g. of SiO2 which had been calcined at 600C were pu~ in the three-necked flask described in Example 8, then 100 ml. of ~etrahydrofuran was added and reaction was allowed to takè place at 60C for 2 hours, followed by drylng at 120C under re`duced pressure to remove tetrahydrofuran. Then, 50 ml. of hexane was added, and after stirring, 1.1 ml. of titanium tetrachloride was added and reaction was allowed to take place for 2 hours under re1ux of hexane to obtain a solid powder tB) con-taining 36 mg. of titanium per gram thereof.
The solid powder tB) thus obtained was added into 50 ml. of hexane, then 2 ml. oE tetraethoxysilane was added and reaction was allowed to take place for 2 hours under reflux of hexane to obtain a solid catalyst component.
_ 27 ~z~
A continuous vapor phase polymerization was carrled out in the same manner as in Example 8 excep-t that the solid catalyst component just prepared above was fed at a rate of 150 mg~hr, to aEord an ethylene copolymer having a bulk density of 0.41, a density of 0.9203 and a melt index of 0.8. Catalytic activity was 497,000g.copolymer/g.Ti and thus very high.
After the continuous operation for 10 haurs, the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was 6.9, and when a film formed therefrom was extracted in boiling hexane for lO hours, its hexane extraction was 1.0 wt.%
and thus very small.
then 4.5 g. of tetraisopropoxysilane and 3.0 g. of titanium tetrachloride were added, followed by further ~all milling for 16 hours, to obtain a solid catalyst component [I~
25' containing 37 mg. of titanium per gram thereof.
A continuous vapor phase polymerization of -` ~L2~ 0 ethylene and butene-l was carried out in -the same way as in Example 1 except that the solid catalys-t component [I~ just prepared above was fed at a ra-te of 50 mg/hr and monophenyltriethyoxysilane was fed at a rate of 0.25 mmolJhr in place of the monomethyltriethoxysilane, to afford an ethylene copolymer having a bulk density of 0.35, a density of 0.9218 and a melt index of 1.1.
Catalytic activity was 270,000g.copolymer/g.Ti and thus very high.
After the continuous operation for 10 hours, the autoclave was opened and its interior was checked.
As a resuIt, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was 7.0 r and 15' when a film formed from the copolymer was extracted in boiling hexane, its hexane extraction was 0.9 wt.% and thus very small.
Example 5 lO g. of,an anhydrous magnesium chloride, 3.5 2~ g. of diethoxyzinc and'2.8 g. of diisopropoxydichloro-titanium were placed in the ball mill pot described in Example 1, and ball-m,illed ~or 16 hours at room tempe;rature ih a nitrogen atmosphere, then 3.8 g. of triethoxymonochlorosilane was added, followed by urther ball milling for 7 hour~ to obtain a solid catalyst component ~I~ containing 28 mg. of titanium per gram thereof.
~z~
A continuous vapor phase polymerization was carried out in the same way as in Example 1 except that the solid catalyst component [IJ jus-t prepared above was fed at a rate of 50 mg/hr and tetraethoxysilane was fed at a rate of 0.25 mmol/hr in place of the monomethyl-ethoxysilane, to afford an ethylene copolymer having a bulk density of 0.39, a density of 0.9224 and a melt index of 1.2. Catalytic activity was 330,000g.copolymer/g.
Ti and thus very high.
After the continuous operation for 10 hours, the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto~
The F.R. value of this copolymer was 7.0, and when a film formed from the copolymer was extracted in boiling hexane for 10 hours, its hexane extraction was 0.7 wt.% and thus very small.
Example 6 A stainless steel 2 liter autoclave equipped with an induction stirrer was purged with nitrogen and charged with l,OOO ml. of hexane, then 1 mmol of triethylaluminum, 0.1 mmol of tetraethoxysilane and 10 mg.
o the solid catalyst component [I~ obtained in Example 1 were added and the temperature was raised to 85C with stirring. The pressur~-of the system was adjusted to 2 kg/cm2.G by introducing nitrogen, then hydrogen was introduced up to a total pressure of 5 kg/cm2.G and then _ 23 40~
ethylene introduced up to a total pressure of 10 kg/cm2.G
under which condition a polymerization was star-ted, which was continued for 1 hour while maintaining the internal pressure of the autoclave at 10 kglcm2.G. Thereafter, the polymer slurry was transferred into a beaker and hexane was removed under reduced pressure to yield 116 g.
of a white polyethylene having a melt index of 1.0, a density of 0.9631 and a bulk density of 0~38. Ca-talytic activity was 66,300g.polyethylene/g.Ti.hr-C2H4 pressure, 2,320g.polyethylene/g~solid.hr-C2H4 pressure.
The F.R. value of the polyethylene was 7.5 and the molecular weight distribution thereof was very narrow as compared with that in Comparative Example 2.
Its hexane extraction was 0.2 wt.%.
Comparative Example 2 Polymerization was carried out for 1 hour in the same way as in Example 6 except that the tetraethoxy-silane was not added, to yield 134 g. of a white polyethylene having a melt index of 1.4, a density o~
0.9637 and a bulk density of 0.35. Catalytic activity was 76,500g.polyethylene/g.Ti.hr C2H4 pressure, 2,680g.polyethylenetg~solid.hr C2H4 pressure.
; The F.R. value of the polyethylene was 8.3 and its hexane extraction was 0.6 wt.~.
Example 7 The solid catalyst component tI~ obtained in _ 24 lZ~
Example 1 was fed at a rate o~ 5a mg/hr and a product obtained by reacting triethylaluminum and monome-thyl-tri-ethoxysilane at a composition ratio of 5 : 0.22'(molar ratio) for 2 hours at room temperature was fed a-t a ra-te of 5 n~lol/hr as aluminum,' under which condi-tion a continuous vapor phase polymerization of ethylene and butene-l was carried out in the same manner as in Example 1 to afford an ethylene copolymer having a bulk density of 0.34, a density of 0.9214 and a melt index o~ 0.93.
Catalytic activity,was 301,000gOcopolymer/g.Ti and thus very high.
After the continuous operation for 10 hous, ~ the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was ~.8, and w~en a film formed from the copolymer was extracted in boiling hexane for lO hours, its hexane extraction was 0.6 wt.~ and thus very small.
Example 8 10 g. of a commercially available anhydrous magnesium chloride and 4~2 g. of aluminum triethoxide were placed in, a stainless steel p~t having a content volume of 400 ml. and containing 25 stainless steel balls each 1/2 inch in diameter, and ball-milled for 16 hours at room tempera'ture in a nitrogen atmosphere to obtain a reaction product. Then r a three-necked flask equipped ~-- i2~84~
with a s-tirrer and a reflux condenser was purged wi-th nitrogen and then charged with 2.5 g. of the above reaction product and 5 g. of SiO2 (~952, a produc-t of Fuji-Davison) which had been calcined at 600C, then 100 ml. of tetrahydrofuran was added and reaction was allowed to take place at 60C for 2 hours, followed by drying at 12~DC under reduced pressure to remove tetrahydrofuran. Then, 50.ml~ of hexane was added, and after stirring, 1.1 ml. of ti.tanium tetrachloride was added and reaction was allowed to take place for 2 hours under reflux of hexane to obtain a solid powder ~A) containing 37 mg. of titaniu~i per gram thereof.
The solid powder ~A) thus obtained was added into 50 ml. of hexane, then 2 ml.. of tetraethoxysilane was added and reaction was allowed to take place for 2 hours under reflux of hexane to obtain a solid catalyst component.
A continuous vapor phase polymerization was carried out in the same way as in Example 1 except that the solid catalyst component just prepared above was fed at a rate of 150 mgjhr and a product obtained by reacting triethylaluminum and tetraethoxysilane at an Al/Si molar ratio of 20/1 for 1.5 hours at 85C was fed at a rate of 5:mmol/hr as aluminum, to afford an ethylene copolymer having a buIk density of 0.38, a density of 0.9?13 and a melt index o 0.9. Catalytic activity was 543,000g.copolymer./g.Ti and thus.very high.
After the continuous operation for lO.hours, - 26 ~
~Z~840C3 the autoclave was opened and its interior was checked.
As a result, the inner wall and the s-tirrer were clean wlth no polymer adhered thereto.
The F.R~ value oE thls copolymer wa8 6.9, alld when a film formed Erom the copolymer was extracted in boiling hexane for 10 hours, its hexane extraction was 0.8 wt.~ and thus very small.
Example 9 lO g~ of an anhydrous magnesium chloride and 4.2 g. of diethoxymagnesium were placed in the ball mill pot described in Example 8, and ball-milled for 16 hours at room temperature in a nitrogen atmosphere to obtain a reaction product. Then, 2.5 g, of the reaction product and 5 g. of SiO2 which had been calcined at 600C were pu~ in the three-necked flask described in Example 8, then 100 ml. of ~etrahydrofuran was added and reaction was allowed to takè place at 60C for 2 hours, followed by drylng at 120C under re`duced pressure to remove tetrahydrofuran. Then, 50 ml. of hexane was added, and after stirring, 1.1 ml. of titanium tetrachloride was added and reaction was allowed to take place for 2 hours under re1ux of hexane to obtain a solid powder tB) con-taining 36 mg. of titanium per gram thereof.
The solid powder tB) thus obtained was added into 50 ml. of hexane, then 2 ml. oE tetraethoxysilane was added and reaction was allowed to take place for 2 hours under reflux of hexane to obtain a solid catalyst component.
_ 27 ~z~
A continuous vapor phase polymerization was carrled out in the same manner as in Example 8 excep-t that the solid catalyst component just prepared above was fed at a rate of 150 mg~hr, to aEord an ethylene copolymer having a bulk density of 0.41, a density of 0.9203 and a melt index of 0.8. Catalytic activity was 497,000g.copolymer/g.Ti and thus very high.
After the continuous operation for 10 haurs, the autoclave was opened and its interior was checked.
As a result, the inner wall and the stirrer were clean with no polymer adhered thereto.
The F.R. value of this copolymer was 6.9, and when a film formed therefrom was extracted in boiling hexane for lO hours, its hexane extraction was 1.0 wt.%
and thus very small.
Claims (9)
1. A process for preparing a polyolefin, which process comprises polymerizing at least one olefin by using a catalyst, said catalyst having been obtained from the following components [I], [II] and [III]
[I] a solid substance obtained by the reaction of the following (i) through (iv):
(i) a magnesium halide, (ii) a compound represented by the general formula Me(OR)nXz-n wherein Me is an element selected from Groups I through VIII of the Periodic Table, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon atoms, X
is a halogen atom, z is the valence of Me and n is 0 < n ? z, (iii) a compound represented by the formula R'mSi(OR")nX4-m-n wherein R' and R" are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are 0 ? m < 4 and 0 < n ? 4, provided 0 < m + n ? 4, and (iv) a titanium compound and/or a vanadium compound;
[II] a compound reprsented by the general formula wherein R1, R2 and R3 are each a hydrocarbon radical having 1 to 24 carbon atoms, alkoxy, hydrogen or halogen, R4 is a hydrocarbon radical having 1 to 24 carbon atoms and q is 1 ? g ? 30, and [III] an organometallic compound.
[I] a solid substance obtained by the reaction of the following (i) through (iv):
(i) a magnesium halide, (ii) a compound represented by the general formula Me(OR)nXz-n wherein Me is an element selected from Groups I through VIII of the Periodic Table, provided silicon, titanium and vanadium are excluded, R is a hydrocarbon radical having 1 to 24 carbon atoms, X
is a halogen atom, z is the valence of Me and n is 0 < n ? z, (iii) a compound represented by the formula R'mSi(OR")nX4-m-n wherein R' and R" are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m and n are 0 ? m < 4 and 0 < n ? 4, provided 0 < m + n ? 4, and (iv) a titanium compound and/or a vanadium compound;
[II] a compound reprsented by the general formula wherein R1, R2 and R3 are each a hydrocarbon radical having 1 to 24 carbon atoms, alkoxy, hydrogen or halogen, R4 is a hydrocarbon radical having 1 to 24 carbon atoms and q is 1 ? g ? 30, and [III] an organometallic compound.
2. The process of claim 1 wherein said catalyst comprises the combination of a reaction product and the component [I], said reaction product having been obtained by the reaction of the components [I] and [III].
3. The process of claim 1 wherein said Me is magnesium, aluminum, or boron.
4. The process of claim 1 wherein the mixing ratio of said magnesium halide to said compound of the general formula Me(OR)nXz-n is in the range of 1/0.001 to 1/20 in terms of Mg/Me molar ratio.
5. The process of claim 1 wherein the mixing ratio of said magnesium halide to said compound of the general formula R'mSi(OR")nX4-m-n is in the range of 1/0.01 to 1/1 in terms of Mg/Si molar ratio.
6. The process of claim 1 wherein said compound of the general formula is used in an amount ranging from 0.1 to 100 moles per mole of said titanium compound and/or said vanadium compound in the component [I].
7. The process of claim 1 wherein said compound of the general formula is used in an amount ranging from 1/500 to 1/1 in terms of its molar ratio to said organometallic compound.
8. The process of claim 1 wherein said olefin is an .alpha.-olefin having 2 to 12 carbon atoms.
9. The process of claim 1 wherein the polymerization reaction is carried out at a temperature ranging from 20°
to 120°C and at a pressure ranging from atmospheric pressure to 70 kg/cm2.
to 120°C and at a pressure ranging from atmospheric pressure to 70 kg/cm2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP138455/1982 | 1982-08-11 | ||
| JP13845582A JPS5930803A (en) | 1982-08-11 | 1982-08-11 | Preparation of polyolefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1208400A true CA1208400A (en) | 1986-07-22 |
Family
ID=15222408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000434306A Expired CA1208400A (en) | 1982-08-11 | 1983-08-10 | Process for preparing polyolefins |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5930803A (en) |
| CA (1) | CA1208400A (en) |
| DE (1) | DE3328883A1 (en) |
| FR (1) | FR2531717B1 (en) |
| GB (1) | GB2126593B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1219996A (en) * | 1982-11-10 | 1987-03-31 | Kazuo Matsuura | Process for preparing polyolefins |
| US4525555A (en) * | 1983-01-14 | 1985-06-25 | Nippon Oil Company, Limited | Process for preparing polyolefins |
| JPH0735410B2 (en) * | 1986-01-31 | 1995-04-19 | 三菱油化株式会社 | Catalyst for stereoregular polymerization of olefins |
| JPH0762284B2 (en) * | 1986-10-20 | 1995-07-05 | 日本エクスラン工業株式会社 | Method for producing flame-retardant acrylic fiber |
| EP0376145B1 (en) * | 1988-12-26 | 1994-03-23 | Tosoh Corporation | Method for producing a stereoregular polyolefin |
| CA2049373A1 (en) * | 1990-09-07 | 1992-03-08 | Brian J. Pellon | Process for the production of amorphous elastomeric propylene homopolymers |
| KR100334167B1 (en) * | 1997-05-08 | 2002-11-22 | 삼성종합화학주식회사 | Process for polymerizing alpha-olefin |
| KR100334163B1 (en) * | 1998-12-04 | 2002-10-25 | 삼성종합화학주식회사 | Olefin Polymerization or Copolymerization Method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5161589A (en) * | 1974-11-26 | 1976-05-28 | Mitsui Toatsu Chemicals | Echirenno jugohoho |
| JPS5695909A (en) * | 1979-12-28 | 1981-08-03 | Nippon Oil Co Ltd | Preparation of polyolefin |
| IT1209255B (en) * | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| AU546911B2 (en) * | 1981-03-25 | 1985-09-26 | Nippon Oil Company Limited | Olefin polymerizing catalyst |
| JPS57182304A (en) * | 1981-05-07 | 1982-11-10 | Nippon Oil Co Ltd | Production of polyolefin |
| JPS5811509A (en) * | 1981-07-11 | 1983-01-22 | Nippon Oil Co Ltd | Preparation of polyolefin |
| FR2512033B1 (en) * | 1981-08-25 | 1986-02-21 | Nippon Oil Co Ltd | PROCESS FOR THE MANUFACTURE OF POLY-OLEFINS |
-
1982
- 1982-08-11 JP JP13845582A patent/JPS5930803A/en active Granted
-
1983
- 1983-08-10 DE DE19833328883 patent/DE3328883A1/en not_active Withdrawn
- 1983-08-10 CA CA000434306A patent/CA1208400A/en not_active Expired
- 1983-08-10 FR FR8313174A patent/FR2531717B1/en not_active Expired
- 1983-08-11 GB GB08321669A patent/GB2126593B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB8321669D0 (en) | 1983-09-14 |
| GB2126593B (en) | 1986-01-08 |
| FR2531717A1 (en) | 1984-02-17 |
| FR2531717B1 (en) | 1987-01-09 |
| DE3328883A1 (en) | 1984-02-16 |
| JPH0134447B2 (en) | 1989-07-19 |
| GB2126593A (en) | 1984-03-28 |
| JPS5930803A (en) | 1984-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0159150B1 (en) | Magnesium hydrocarbyl carbonate supports | |
| CA1185748A (en) | Process for preparing polyolefins | |
| CA1139498A (en) | Process for the production of polyolefins | |
| CA1208400A (en) | Process for preparing polyolefins | |
| EP0413469B1 (en) | Process for preparing polyolefins | |
| CA1219996A (en) | Process for preparing polyolefins | |
| EP0500392A2 (en) | Process for preparing polyolefins | |
| CA1172623A (en) | Olefin polymerizing catalyst | |
| EP0447079B1 (en) | Process for preparing polyolefins | |
| CA1168400A (en) | Process for polyolefins production | |
| GB2103631A (en) | A process for polyolefins production catalyst components therefor | |
| EP0493118B1 (en) | Process for preparing polyolefins | |
| EP0428375B1 (en) | Process for preparing polyolefins | |
| CA2021311C (en) | Process for preparing polyolefins | |
| CA1222096A (en) | Process for preparing polyolefins | |
| CA1193048A (en) | Process for preparing polyolefins | |
| US4525552A (en) | Process for producing polyolefins | |
| GB2099004A (en) | Process for preparing polyolefins | |
| CA1198724A (en) | Retreating comminuted olefin polymerization catalyst with a titanium (iv) compound and an ester | |
| EP0407143B1 (en) | Process for preparing polyolefins | |
| EP0507574A2 (en) | Process for preparing polyolefins | |
| GB2134911A (en) | Process of producing polyolefins and catalysts therefor | |
| GB2147304A (en) | Process for preparing polyolefins | |
| KR800000341B1 (en) | The manufacturing method of polyoleffine | |
| JPS6412288B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |