CA1078806A - Process for preparing polyolefins - Google Patents
Process for preparing polyolefinsInfo
- Publication number
- CA1078806A CA1078806A CA243,161A CA243161A CA1078806A CA 1078806 A CA1078806 A CA 1078806A CA 243161 A CA243161 A CA 243161A CA 1078806 A CA1078806 A CA 1078806A
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- CA
- Canada
- Prior art keywords
- titanium
- halide
- compound
- solid
- catalyst
- Prior art date
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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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Improved catalysts are provided for use in the polymer-ization or copolymerization of olefins. In addition, a process is provided for preparing polyolefins by polymerizing or co-polymerizing olefins using such catalysts. The process for preparing polyolefins by polymerizing or copolymerizing olefins involves using, as a catalyst, a novel titanium-containing solid and an organoaluminum compound and/or an organozinc com-pound. The titanium-containing solid comprises a reaction product obtained by copulverizing (1) a magnesium halide and/or a manganese halide, (2) an aromatic hydrocarbon selected from the group consisting of polycyclic aromatic hydrocarbons, homo-cyclic hydrocarbons, and halogen- and alkyl-substituted prod-ucts thereof, and (3) tetravalent and/or trivalent titanium compounds, wherein the ratio of the halide selected from at least one of the magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5 to 10 weight percent. This process provides a polyolefin with a high bulk density in high yield.
Improved catalysts are provided for use in the polymer-ization or copolymerization of olefins. In addition, a process is provided for preparing polyolefins by polymerizing or co-polymerizing olefins using such catalysts. The process for preparing polyolefins by polymerizing or copolymerizing olefins involves using, as a catalyst, a novel titanium-containing solid and an organoaluminum compound and/or an organozinc com-pound. The titanium-containing solid comprises a reaction product obtained by copulverizing (1) a magnesium halide and/or a manganese halide, (2) an aromatic hydrocarbon selected from the group consisting of polycyclic aromatic hydrocarbons, homo-cyclic hydrocarbons, and halogen- and alkyl-substituted prod-ucts thereof, and (3) tetravalent and/or trivalent titanium compounds, wherein the ratio of the halide selected from at least one of the magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5 to 10 weight percent. This process provides a polyolefin with a high bulk density in high yield.
Description
This invention relates t~ novel catalysts for the polymeriz-ation of olefins. In addi-tion, it is concerned with a process for polymerizing olefins in the presence of -the novel catalyst to give a polyolefin with a high bulk density in high yield and thereby to dispense with the step of removing residual catalyst.
A catalyst consisting of a magnesium halide and a trans-ition metal compound e.g. a titanium compound carried thereon is now known, and Belgian Patent No. 742,112 patented May 25, 1970 by Montecatini Edison provides a disclosure of a catalyst con-sisting of a magnesium halide and ti-tanium tetrachloride co~
pulverized together.
However, when productivity and handling of slurry are taken into consideration, it is desirable in the preparation of poly-olefins that the bulk density of the resulting polymer be as high as possible. From this point of view, a process involving the use of a catalyst consisting of a magnesium halide and a transmiter metal carried therein is disadvantageous in that the bulk density of the resulting polymer is low and the polymeriz-ation activity is not satisfactory, while the process disclosed in Belgian Patent No. 7~2,112 is also disadvantageous in that the bulk density of the resulting polymer is low though the polymerization activity is high. It is desired that an improve-ment be made with respect to both of the above referred to processes This invention in one aspect thereof provides novel poly-merization catalysts which afford polymers with a high bulk den-sity in high yield, as well as processes for preparing such cat-alysts. By another aspect, this invention also provides a process for polymerizing or copolymerizing olefins in the presence of such polymerization catalysts. The use of the catalyst of an aspect of the present invention is a~vantageous in that the poly-merization activity is high enough to reduce partial pressure of ~ 7~6 ~
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`...... . ~ . -~onome~ in polymerization, ehe hi~h bulk density of the resulting polymer .~ .
make~ improvement in productivity possible, the amount of residual catalyst in the resultin~ polymer i9 SO small that the preparation of polyolefin can i-dispense with the step of removing catalyst, which results in a simplified polymer treating step, and consequently there is provided a process for pre-paring polyo3efins which process as a whole is extremely economical.
The present invention in yet another aspect is further advantageous in that the resulting polymer, despite its high bulk density, contains so few fine part~cles below 50 microns in size that it becomes easy to handle poly-.mer particles in the polymer treating stép such as, for example, in centri-fugation and powder transportation.
By one broad aspect of this invention, a process is provided for preparing polyolefins which comprises polymeriæing or copolymeriæing olefins using as catalyst a titanium-containing solid and at least one of an organo-aluminum compound and an organozinc compound, the titanium-containing solid comprising: a reaction product obtained by copulveriæing (1) at least one of a magnesium halide and a manganese halide, (2) an aromatic hydrocarbon selected from the group consisting of polycyclic aromatic hydrocarbonS, mono-cyclic hydrocarbons, and halogen- and alkyl-substituted products thereof, and (3) at least one of a tetravalent and a trivalent titanium compound; wherein the ratio of the halide selected from at least one of magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5 to 10 weight percent.
By a variant of this aspect, the polymerization or copolymerization of olefins is effected at a te~perature ranging from 20 to 120C., under a pressure ranging from ordinary pressure to 70 kg/cm .
By another variant, the polymerization or copolymerization of the olefins is effected at a temperature of 50 - 100C., under a pressure of 2 -60 kg/cm2.
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By stlll another variant of this aspect, the polymerization or co-, polymerization of olefins is effected in t~he presence of hydrogen.
By a further variant, the aromatic hydrocarbon is selected from the group consisting of naphthalene, phenanthrene, triphenylene, chrysene, 3,4-benzophenanthrene, 1,2-benzochrysene, picene, anthracene, tetraphene, 1,2,3,4-dibenzanthracene, pentaphene, 3,4-benzopentaphene, tetracene, 1,2-benzotethra-cene, hexaphene, heptaphene, diphenyl, fluorene, biphenylene, perylene, coro-nene , bisantene, ovalene, pyrene, perinaphthene, benzene, toluene, xylene, and their halogen-substituted and alkyl-substituted derivatives.
By a second broad aspect of this invention, an olefin polymeri~ation catalyst is provided comprising a titanium-containing solid and at least one of an organoaluminum compound and an organozinc compound, the titanium-con-taining solid comprising: a reaction product obtained by copulverizing (1) at least one of a magnesium halide and a manganese halide, ~2) an aromatic hydro-carbon selected from the group consisting of polycyclic aromatic hydrocarbons, monocyclic hydrocarbons and halogen- and alkyl-substituted pro-ducts thereof, and (3) at least one of a tetravelaent and a tri-valent titanium compound; wherein the ratio fo the halide selected from at least one of magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1;0.5 to 1:0.1, and the tianium content of the solid is within the range of 0.5 to 10 weight ~ercent.
By a variant thereof the titanium content is within the range of 1 to 8 weight percent.
By another variant of this aspect, the amount of the organoaluminum compound and/or the organozinc compound is from 0.1 to 1,000 moles per mole of titanium compound.
By another variant, the catalyst includes a vanadium compound in addition to the titanium compound.
By a variation thereof, the mole ratio of the vanadium to titanium is 2:1 to 0.01:1.
By a third broad aspect of this invention, an improvement is pro-~ - 3 - ~'7~
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vided, in a process for the preparation of a catalyst comprising a titanium-containing solid and at least one of an organoaluminum compound and an or-ganozinc compound, the improvement comprising: preparing the titanium-contain-ing solid by copulverizing (1) at least one of a magnesium halide arld a man-ganese halide, (~) an aromatic hydrocarbon selected from the group consisting of polycyclic aromatic hydrocarbon~ monocyclic hydrocarbon~and halogen- and alkyl-substituted products thereof and (3) at least one of a tetravalent and a trivalent tltanium compound; wherein the ratio of the halide selected from at least one of magnesium halide and manganese halide and the aromatic hydro-.
10 carbon is within the range of 1:0.5 to 1:01, and the titaniumsolid is within the range of 0.5 to 10 weight percent.
: By a variant thereof, the titanium content is from 1 to 8 weight percent.
By a third variant of this aspect, the organo compound which is selected from the group consisting of an organoaluminum compound and an organo-zinc compound is used in B
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an amount of from 0.1 to 1,000 moles per mole of titanium compo~lnd.
Examples of magnesium halides used in vario~s aspects of this inven~ion include magnesium chloride, magnesium fluoride, magnesium bromide, magnesium iodide, and mixtures of these,among which magnesium chloride is particularly preferable.
The manganese halide used in various aspects of this in~ention most preferably is manganese chloride, although other halides, for example, manganese fluoride? manganese bromide and manganese iodide are also operative.
The preferable aromatic hydrocarbon used in various aspects of this invention is a polycyclic aromatic compound. Examples include naphthalene, phenanthrene, triphenylene, chrysene, 3,~-ben~ophenanthrene, 1,2~benzochrysene, picene, anthracene, tetraphene, 1,2,3,4-dibenzanthra-cene, pentaphene, 3,4-benzopentaphene, tethracene, 1,2-benzotethracene, hexaphene, heptaphene, diphenyl, fluorene, biphenylene, perylene, ; coronene, bisantene, ovalene, pyrene, perinaphthene, and their halogen-substituted and alkyl-substituted products.
Monocyclic aromatic compounds, e g benzene, toluene and xylene, and their halogen-substituted and alkyl-substituted products are also employable.
Many titanium compounds may be used in various aspects of this invention. Examples of tetravalent titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monoethoxy-trichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydi-chlorotitanium, and a reaction product between silicon tetrachloride and - :
titanium alkoxide. Examples of trivalent titanium compounds include titanium trihalides obtained'by the reduction of titanium tetrahalides with hydrogen, aluminum, titanium or an organometallic compound. Mix-tures of these may, of course,'be'employed. Also, vanadium compounds, such as, for example,'vanadium tetrachloride, vanadium trichloride, ~l0'78~
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vanadyl trichlorlde, and vanadyl triethoxide are o~ten employed together with titanium compounds to render various aspects of this invention more effectlve. In this case, the vanadium to titanium mole ratio is pre-ferably in the range of from 2:1 to 0.01:1.
The manner of the copulverization of the halide selected from a magnesium halide, a manganese halide and mixtures thereof, an aromatic hydrocarbon and a titanium compound in various aspects of the present invention ls not especially critical or restricted. It may be carried out in the simultaneous presence of all these components; or it may be carried Ollt by copulverizing the halide selected from a magnesium halide, a manganese halide, and mixtures thereof, and an aromatic hydrocarbon and thereafter adding a titanium compound followed by further pulveriza-tion; or it may be accomplished by copulverizing a reaction product of an aromatic hydrocarbon and a titanium compound together with a halide selected from a magnesium halide, a manganese halide and mixtures there-of. To support liquid titanium compounds such as, for example 9 titanium tetrachloride, a procedure may be used in which a copulverization pro-duct of a halide selected from a magnesium halide, a manganese halide and mixtures thereof and an aromatic hydrocarbon is contacted with a liquid titanium compound and thereafter unreacted titanium compound is removed by washing. However, the procedure of supporting a required amount of a titanium compound by means of copulverization is simpler in the procedure for catalyst preparation and thus is more desirable.
Moreover, these operations should be conducted in an inert gas atmosphere and moisture should be avoided as far as possible.
The blending ratio of the halide selected from a magnesium halide, a manganese halide and mixtures thereof and an aromatic hydro-carbon is not especially critical or restricted. However, with too great an excess of an aromatic hydrocarbon, the poly~erization activity tends to be decreased, while ~ith too small an amount, the effect of adding the aromatic hydrocarbon cannot be expected. Preferably, the weight ratio of the halide selected from a magnesium halide, a manganese ~7B~
halide~ and miXtures thereo~, to arom~tic hydrocarbon is in the range of from 1:0.5 to 1:0.01.
The amount of a titanium compound to be supported is most preferably adjusted so that the titanium content in the resulting solid is in the range of from 0.5 to 10~ by weight. To obtain a well-balanced activity per titanium and per solid, the range of from 1 to 8% by weight is particularly desirable.
Although the apparatus used for the copulverization is not especially critical or restricted, a ball mill, a vibration mill, a rod mill or an impact mill are usually employed. The conditions used in the pulverization method, such as, for example, the order of mixing, pulverization time and pulverization temperature, can easily be estab-lished by those skilled in the art, in accordance with the manner in which the pulverization is made. In general, the pulverization tempera-ture is in the range between 0C. and 200C., preferably between 20C.
and 100C., and pulverization time is from 0.5 to 50 hours, preferably from 1 to 30 hours.
The polymerization reaction of olefins using the catalyst of aspects of the inv ~ on is conducted in the same manner as in the olefin polymerization reaction by means of a conventlonal Ziegler cata-lyst. Substantially oxygen- and moisture-free conditlons are maintained - -throughout the reaction. The polymerization conditions for olefins include a temperature in the range from 20 to 120C., preferably 50 to 100C., and a pressure in the range from normal to 70 kg/cm , preferably from 2 to 60 kg/cm . Control of molecular weight can be done to a certain degree b~ changing polymerization conditions such as, for example, polymerization temperatures and the molar ratio of catalyst, but can more effectively be done by the addition of hydrogen into the polymerization system. With the catalyst of aspects of the invention, of course, two-or more-stage polymerization reactions having different polymerization conditions such as, for example, hydrogen concentration and polymerization temperatures can also be done ~ithout any trouble.
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The process o~ an aspect of tlle present inventlon can be applied to the polymerization of all the olefins polymerizable with Ziegler catalyst. For example, it is suitabl~ employed for the homo-polymerization of ~-olefins such as, for example, ethylene, propylene, and l-butene, and for the copolymerization of ethylene and propylene, ethylene and l-butene, propylene and l-butene, ethylene and 1,4-hexadiene, ethylene and ethylidenenorbornene, and the like.
Examples of organometallic compounds used in various aspects oE th~ inventlon include organometallic compoun~s Erom metals oE Groups I-IV of the Periodic Table which are generally known as a component of Ziegler catalyst; especially preferable are organoaluminum, and organo-zinc compounds. Examples of suitable organoaluminum compounds are those of the general formulae R3Al, R2AlX, RAlX2, R2AlOR, RAl(OR)X and R3A12X3 wherein R is alkyl or aryl and may be the same or different and X is halogen, and organozinc compounds of the general formula R2Zn wherein R
is alkyl and may be the same or different including triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. The amount of these organometallic compounds used in aspects of the invention is not especially limited or restricted, but usually the compounds can be used at a molar ratio from O.l to 1,000 against titanium compounds (transition metal halides).
The examples which follow are submitted to illustrate various aspects of the invention.
Example 1 (a) Preparation of catalyst 8.3 g. of a commercially available anhydrous magnesium chloride and 1.2 g. of naphthalene were placed in a stainless steel pot with a content volume of 400 ml. containing 25 stainless steel balls each half an inch in diameter. Ball milling was then applied for 16 hours at room temperature under a nitrogen atmosphere. Thereafter, 1.7 g. of titanium tetrachloride was added, and ball milling was further applied for 16 hours at room temperature. The resultln~ solid powder`contained 40 mg. of titanium per g. of the'solid.
(b) Polymerization A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and charged with 1000 ml. of hexane.
To it were added 1 mmol. of trieth~laluminum and 30 mg. of the above-mentioned solid and the temperature was raised to 9aC. with stirring.
The system, which was at a pressure of 2 kg/cm2 G from vapor pressure of the hexane was pressurized with hydrogen to a total pressure of 5.6 kg/cm2 G and then with ethylene to a total pressure of 10 kg/cm2 G
followed by initiation of the polymerization. Ethylene was continuously introduced to maintain the total pressure at 10 kg/cm2 G while conducting the polymerization for 1 hour. After completion of the polymerization, the polymer slurry was transferred to a beaker, from which the hexane was removed under reduced pressure to obtain 160 g. of while polyethylene with a melt index of 5.1. The catalyst activity was 30,3000 g. poly-ethylene/g. Ti hr. C2H4 pressure, 1,210 g. polyethylene/g. solid-hr.-C2H4 pressure. The polymer powder had a bulk density of 0.31. The per-centage of fine particles below 44 microns in size was very small; it was 0.9%.
Comparative Example I
9.5 g. of anhydrous magnesium chloride and 1.7 g. of titanium tetrachloride were placed in a stainless steel pot with a content volume of 400 ml. containing 25 stainless steel balls each half an inch in diameter. Ball milling was then applied for 16 hours at room temperature under a nitrogen atmo~here. The resulting solid powder contained 39 mg.
of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid were used, to yield 145 g. of white polyethylene with a melt index of 5.5. The cata-lyst activity was 28,200 g. polyethylene/g. Ti-hr. C2H4 pressure, 1,100 g. polyethylene/g. solid hr'. C2H4 pressure. The'bulk density of the ~7~
polymer powder was low; it was 0.14.
Example 2 8.3 g. of anhydrous magnesium chloride and 1.2 g. of naphtha-lene were placed in the ball mill pot referred to in Example 1, and ball milling was applied for 16 hours under a nitrogen atmosphere. The rPsulting powder was contacted at 150C. for 2 hours with 50 ml. of titanium tetrachloride. After completion of the reaction, unreacted titanium te~rachloride was removed by washing wi~h hcxane to give a solid containing 19 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure'as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 82 g. of white polyethylene with a melt index of 8.1. The catalyst activity was 32,600 g. polyethylene/g. Ti hr.-C2H4 pressure, 620 g. polyethylene/g. solid-hr.-C2H4 pressure. The bulk density of the polymer powder was 0.24.
Example 3 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 1.2 g. of anthracene and 1.7 g. of titanium tetrachloride. Ball milling was applied for 16 hours under nitrogen atmosphere. The resulting solid powder containing 42 mg. of titanium per g. of the solid.
Polymeri~ation was conducted for 1 hour using the same proced-ure as in Example 1 except that 30 mg. of the solid just mentioned above were used, to yield 174 g. of white polyethylene with a melt index of 5.3. The catalyst activity was 31,500 g. polyethylene/g. Ti hr. C2H4 pressure, 1,320 g. polyethylene/g. solid-hr. C2H4 pressure. The bulk density of the polymer powder was 0.35.
Example 4 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride,'1.2 g. of pyrene and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The'resulting solid powder'contained 39 mg. of ~itanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-: dure as in Example l except that 30 mg. of the solid ~ust mentioned above was used, to yield 131 g. of white polyethylene with a melt index of 4.9. The catalyst activity was 25,400 g. polyethylene/g. Ti hr. C2H4 pressure, 990 g. polyethylene/g. solid-hr. C2H4 pressure. The bulk density of the polymer powder was 0.30.
Example 5 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 1.2 g. o~ pyrene and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 38 mg. of titanium per g. of the solid.
Polymerization was conducted for l hour using the same proce-dure as in Example 1 except that ~30 mg. of the solid just mentioned above was used~ to yield 165 g. of white polyethylene with a melt index of 9.2. The catalyst activity was 32,900 g. polyethylene/g. Ti hr. C2H4 pressure, 1,250 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.33.
Example 6 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 0.5 g. of benzene and 0.9 g~ of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 23 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 141 g. of white polyethylene with a melt index of 6.1. The'caaalyst activity was 46,500 g. polyeth~lene/g. Ti hr. C2H4 pressure, 1,070 g. polyethylene/g. solld hr. C2H4 pressure. The bulk density of the'polymer'powder was 0.28.
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Example 7 In the ball mill pot referred to in Example 1 were placed 8.3 g.
- of anhydrous magnesium c~loride, 1.~ g. of naphthalene, 0.9 g. of titanium tetrachloride and 0.8 g. o~ vanadium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 21 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid ~ust mentioned above was used, to yield 127 g. of white polyethylene with a melt index of 8.1. The catalyst activity was 45,800 g. pol'yethylene/g. Ti hr. C2H4 pressure, 960 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.37.
Example 8 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous manganese chloride, 1.2 g. of naphthalene and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 41 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 46 g. of white polyethylene with a melt index of 7.3. The catalyst activity was 8,550 g. polyethylene/g. Ti-hr. C2H4 pressure, 350 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.32.
- Comparative Example'II
In the ball mill pot referred to in Example 1 were placed 9.S g.
of anhydrous manganese chloride and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 38 mg. of titanium per g. of the solld.
Polymerization was conducted'for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned a~ove was used, to yield 40 g. of white polyethylene with a melt index -of 3.3. The catalyst activity was 7,900 g. polyethylene/g. Ti hr. C2H4 pressure, 300 g. polyethy~lene/g. solid hr.-C2H4 pressure. The bulk density of the polymer powder was 0.13.
Example 9 In the ball mill pot referred to-in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 1.2 g. of anthracene and 1.7 g. of titanium trichloride (TACB TiC13-1/3 AlC13 manufactured by Toho Titanium Co.), and ball milling was applied for 16 hours under a nitrogen atmos-phere. The resulting solid powder contained 35 mg. of titanium per g.
of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 114 g. of white polyethylene with a melt index of 7.2. The catalyst activity was 24,600 g. polyethylene/g. Ti-hr.-C2H4 pressure, 860 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.32.
Comparative Examplé'III
In the ball mill pot referred to in Example 1 were placed 9.5 g.
of anhydrous magnesium chloride and 1.7 g. of the same titanium tri-chloride as that used in Example 9, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 37 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid ~ust mentioned above was used, to yield 104 g. of white polyethylene with a melt index of 5.3. The catalyst activity was 21,400 g. polyethylene/g. Ti hr. C2H4 pressure, 790 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.14.
' Example 10 In the ball mill pot referred to in Example 1 werè placed 5.0 g.
of anh~drous magnesium chloride,'3.3 g. of manganese chloride, 1.2 g. of naphthalene and 1.7'g. of titanium tetrachloride,'and ball milling was applied for 16 hours uncler a ni~rogen atmosphere. The resulting solid powder contained 40 mg. of titanium per g. of the solld.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid ~ust mentioned above was used, to yield 133 g. o~ white polyethylene with a melt index of 4~8. The catalyst actL~ity was 25,200 g. polyethylene/g. Ti hr. C2H4 pressure, 1,010 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.32 ~.pl~ 1}
Uslng 30 mg. of the solld obtained in ExamplP 1 and in the same manncr as in Example 1, hexane, triethylaluminum and the solid were added and the temperature was raised to 90C. The system was then pressurized with hydrogen to a total pressure of 5.6 kg/cm2 G and there-after a mixed ethylene-propylene gas containing 2 mole % of propylene was fed to maintain the pressure of the autoclave at 10 kg/cm G while conducting the polymerization for 1 hour, to yield 182 g. of a white polymer with a melt index of 2.1 containing 5.8 methyl groups per 1,000 carbon atoms. The catalyst aciivlty was 34,500 g. polymer/g. Ti.hr.-C2H4 pressure, 1,380 g. polymer/g. solid-hr. C2H4 pressure. The bulk density of the polymer powder was 0.30.
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A catalyst consisting of a magnesium halide and a trans-ition metal compound e.g. a titanium compound carried thereon is now known, and Belgian Patent No. 742,112 patented May 25, 1970 by Montecatini Edison provides a disclosure of a catalyst con-sisting of a magnesium halide and ti-tanium tetrachloride co~
pulverized together.
However, when productivity and handling of slurry are taken into consideration, it is desirable in the preparation of poly-olefins that the bulk density of the resulting polymer be as high as possible. From this point of view, a process involving the use of a catalyst consisting of a magnesium halide and a transmiter metal carried therein is disadvantageous in that the bulk density of the resulting polymer is low and the polymeriz-ation activity is not satisfactory, while the process disclosed in Belgian Patent No. 7~2,112 is also disadvantageous in that the bulk density of the resulting polymer is low though the polymerization activity is high. It is desired that an improve-ment be made with respect to both of the above referred to processes This invention in one aspect thereof provides novel poly-merization catalysts which afford polymers with a high bulk den-sity in high yield, as well as processes for preparing such cat-alysts. By another aspect, this invention also provides a process for polymerizing or copolymerizing olefins in the presence of such polymerization catalysts. The use of the catalyst of an aspect of the present invention is a~vantageous in that the poly-merization activity is high enough to reduce partial pressure of ~ 7~6 ~
.. . . . . , . :
`...... . ~ . -~onome~ in polymerization, ehe hi~h bulk density of the resulting polymer .~ .
make~ improvement in productivity possible, the amount of residual catalyst in the resultin~ polymer i9 SO small that the preparation of polyolefin can i-dispense with the step of removing catalyst, which results in a simplified polymer treating step, and consequently there is provided a process for pre-paring polyo3efins which process as a whole is extremely economical.
The present invention in yet another aspect is further advantageous in that the resulting polymer, despite its high bulk density, contains so few fine part~cles below 50 microns in size that it becomes easy to handle poly-.mer particles in the polymer treating stép such as, for example, in centri-fugation and powder transportation.
By one broad aspect of this invention, a process is provided for preparing polyolefins which comprises polymeriæing or copolymeriæing olefins using as catalyst a titanium-containing solid and at least one of an organo-aluminum compound and an organozinc compound, the titanium-containing solid comprising: a reaction product obtained by copulveriæing (1) at least one of a magnesium halide and a manganese halide, (2) an aromatic hydrocarbon selected from the group consisting of polycyclic aromatic hydrocarbonS, mono-cyclic hydrocarbons, and halogen- and alkyl-substituted products thereof, and (3) at least one of a tetravalent and a trivalent titanium compound; wherein the ratio of the halide selected from at least one of magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5 to 10 weight percent.
By a variant of this aspect, the polymerization or copolymerization of olefins is effected at a te~perature ranging from 20 to 120C., under a pressure ranging from ordinary pressure to 70 kg/cm .
By another variant, the polymerization or copolymerization of the olefins is effected at a temperature of 50 - 100C., under a pressure of 2 -60 kg/cm2.
~378E~
.
By stlll another variant of this aspect, the polymerization or co-, polymerization of olefins is effected in t~he presence of hydrogen.
By a further variant, the aromatic hydrocarbon is selected from the group consisting of naphthalene, phenanthrene, triphenylene, chrysene, 3,4-benzophenanthrene, 1,2-benzochrysene, picene, anthracene, tetraphene, 1,2,3,4-dibenzanthracene, pentaphene, 3,4-benzopentaphene, tetracene, 1,2-benzotethra-cene, hexaphene, heptaphene, diphenyl, fluorene, biphenylene, perylene, coro-nene , bisantene, ovalene, pyrene, perinaphthene, benzene, toluene, xylene, and their halogen-substituted and alkyl-substituted derivatives.
By a second broad aspect of this invention, an olefin polymeri~ation catalyst is provided comprising a titanium-containing solid and at least one of an organoaluminum compound and an organozinc compound, the titanium-con-taining solid comprising: a reaction product obtained by copulverizing (1) at least one of a magnesium halide and a manganese halide, ~2) an aromatic hydro-carbon selected from the group consisting of polycyclic aromatic hydrocarbons, monocyclic hydrocarbons and halogen- and alkyl-substituted pro-ducts thereof, and (3) at least one of a tetravelaent and a tri-valent titanium compound; wherein the ratio fo the halide selected from at least one of magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1;0.5 to 1:0.1, and the tianium content of the solid is within the range of 0.5 to 10 weight ~ercent.
By a variant thereof the titanium content is within the range of 1 to 8 weight percent.
By another variant of this aspect, the amount of the organoaluminum compound and/or the organozinc compound is from 0.1 to 1,000 moles per mole of titanium compound.
By another variant, the catalyst includes a vanadium compound in addition to the titanium compound.
By a variation thereof, the mole ratio of the vanadium to titanium is 2:1 to 0.01:1.
By a third broad aspect of this invention, an improvement is pro-~ - 3 - ~'7~
- - . . . . . .: . - .
-- -. :.: - . : `. : -: .
.. . .
:
'78~
vided, in a process for the preparation of a catalyst comprising a titanium-containing solid and at least one of an organoaluminum compound and an or-ganozinc compound, the improvement comprising: preparing the titanium-contain-ing solid by copulverizing (1) at least one of a magnesium halide arld a man-ganese halide, (~) an aromatic hydrocarbon selected from the group consisting of polycyclic aromatic hydrocarbon~ monocyclic hydrocarbon~and halogen- and alkyl-substituted products thereof and (3) at least one of a tetravalent and a trivalent tltanium compound; wherein the ratio of the halide selected from at least one of magnesium halide and manganese halide and the aromatic hydro-.
10 carbon is within the range of 1:0.5 to 1:01, and the titaniumsolid is within the range of 0.5 to 10 weight percent.
: By a variant thereof, the titanium content is from 1 to 8 weight percent.
By a third variant of this aspect, the organo compound which is selected from the group consisting of an organoaluminum compound and an organo-zinc compound is used in B
.
. ~ , ..
.. . - ~. ~ .. .
. . . .
an amount of from 0.1 to 1,000 moles per mole of titanium compo~lnd.
Examples of magnesium halides used in vario~s aspects of this inven~ion include magnesium chloride, magnesium fluoride, magnesium bromide, magnesium iodide, and mixtures of these,among which magnesium chloride is particularly preferable.
The manganese halide used in various aspects of this in~ention most preferably is manganese chloride, although other halides, for example, manganese fluoride? manganese bromide and manganese iodide are also operative.
The preferable aromatic hydrocarbon used in various aspects of this invention is a polycyclic aromatic compound. Examples include naphthalene, phenanthrene, triphenylene, chrysene, 3,~-ben~ophenanthrene, 1,2~benzochrysene, picene, anthracene, tetraphene, 1,2,3,4-dibenzanthra-cene, pentaphene, 3,4-benzopentaphene, tethracene, 1,2-benzotethracene, hexaphene, heptaphene, diphenyl, fluorene, biphenylene, perylene, ; coronene, bisantene, ovalene, pyrene, perinaphthene, and their halogen-substituted and alkyl-substituted products.
Monocyclic aromatic compounds, e g benzene, toluene and xylene, and their halogen-substituted and alkyl-substituted products are also employable.
Many titanium compounds may be used in various aspects of this invention. Examples of tetravalent titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monoethoxy-trichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydi-chlorotitanium, and a reaction product between silicon tetrachloride and - :
titanium alkoxide. Examples of trivalent titanium compounds include titanium trihalides obtained'by the reduction of titanium tetrahalides with hydrogen, aluminum, titanium or an organometallic compound. Mix-tures of these may, of course,'be'employed. Also, vanadium compounds, such as, for example,'vanadium tetrachloride, vanadium trichloride, ~l0'78~
~ - 4 -.- . . ,- . - ~ .
..~(3'7~
vanadyl trichlorlde, and vanadyl triethoxide are o~ten employed together with titanium compounds to render various aspects of this invention more effectlve. In this case, the vanadium to titanium mole ratio is pre-ferably in the range of from 2:1 to 0.01:1.
The manner of the copulverization of the halide selected from a magnesium halide, a manganese halide and mixtures thereof, an aromatic hydrocarbon and a titanium compound in various aspects of the present invention ls not especially critical or restricted. It may be carried out in the simultaneous presence of all these components; or it may be carried Ollt by copulverizing the halide selected from a magnesium halide, a manganese halide, and mixtures thereof, and an aromatic hydrocarbon and thereafter adding a titanium compound followed by further pulveriza-tion; or it may be accomplished by copulverizing a reaction product of an aromatic hydrocarbon and a titanium compound together with a halide selected from a magnesium halide, a manganese halide and mixtures there-of. To support liquid titanium compounds such as, for example 9 titanium tetrachloride, a procedure may be used in which a copulverization pro-duct of a halide selected from a magnesium halide, a manganese halide and mixtures thereof and an aromatic hydrocarbon is contacted with a liquid titanium compound and thereafter unreacted titanium compound is removed by washing. However, the procedure of supporting a required amount of a titanium compound by means of copulverization is simpler in the procedure for catalyst preparation and thus is more desirable.
Moreover, these operations should be conducted in an inert gas atmosphere and moisture should be avoided as far as possible.
The blending ratio of the halide selected from a magnesium halide, a manganese halide and mixtures thereof and an aromatic hydro-carbon is not especially critical or restricted. However, with too great an excess of an aromatic hydrocarbon, the poly~erization activity tends to be decreased, while ~ith too small an amount, the effect of adding the aromatic hydrocarbon cannot be expected. Preferably, the weight ratio of the halide selected from a magnesium halide, a manganese ~7B~
halide~ and miXtures thereo~, to arom~tic hydrocarbon is in the range of from 1:0.5 to 1:0.01.
The amount of a titanium compound to be supported is most preferably adjusted so that the titanium content in the resulting solid is in the range of from 0.5 to 10~ by weight. To obtain a well-balanced activity per titanium and per solid, the range of from 1 to 8% by weight is particularly desirable.
Although the apparatus used for the copulverization is not especially critical or restricted, a ball mill, a vibration mill, a rod mill or an impact mill are usually employed. The conditions used in the pulverization method, such as, for example, the order of mixing, pulverization time and pulverization temperature, can easily be estab-lished by those skilled in the art, in accordance with the manner in which the pulverization is made. In general, the pulverization tempera-ture is in the range between 0C. and 200C., preferably between 20C.
and 100C., and pulverization time is from 0.5 to 50 hours, preferably from 1 to 30 hours.
The polymerization reaction of olefins using the catalyst of aspects of the inv ~ on is conducted in the same manner as in the olefin polymerization reaction by means of a conventlonal Ziegler cata-lyst. Substantially oxygen- and moisture-free conditlons are maintained - -throughout the reaction. The polymerization conditions for olefins include a temperature in the range from 20 to 120C., preferably 50 to 100C., and a pressure in the range from normal to 70 kg/cm , preferably from 2 to 60 kg/cm . Control of molecular weight can be done to a certain degree b~ changing polymerization conditions such as, for example, polymerization temperatures and the molar ratio of catalyst, but can more effectively be done by the addition of hydrogen into the polymerization system. With the catalyst of aspects of the invention, of course, two-or more-stage polymerization reactions having different polymerization conditions such as, for example, hydrogen concentration and polymerization temperatures can also be done ~ithout any trouble.
~'7l~
The process o~ an aspect of tlle present inventlon can be applied to the polymerization of all the olefins polymerizable with Ziegler catalyst. For example, it is suitabl~ employed for the homo-polymerization of ~-olefins such as, for example, ethylene, propylene, and l-butene, and for the copolymerization of ethylene and propylene, ethylene and l-butene, propylene and l-butene, ethylene and 1,4-hexadiene, ethylene and ethylidenenorbornene, and the like.
Examples of organometallic compounds used in various aspects oE th~ inventlon include organometallic compoun~s Erom metals oE Groups I-IV of the Periodic Table which are generally known as a component of Ziegler catalyst; especially preferable are organoaluminum, and organo-zinc compounds. Examples of suitable organoaluminum compounds are those of the general formulae R3Al, R2AlX, RAlX2, R2AlOR, RAl(OR)X and R3A12X3 wherein R is alkyl or aryl and may be the same or different and X is halogen, and organozinc compounds of the general formula R2Zn wherein R
is alkyl and may be the same or different including triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. The amount of these organometallic compounds used in aspects of the invention is not especially limited or restricted, but usually the compounds can be used at a molar ratio from O.l to 1,000 against titanium compounds (transition metal halides).
The examples which follow are submitted to illustrate various aspects of the invention.
Example 1 (a) Preparation of catalyst 8.3 g. of a commercially available anhydrous magnesium chloride and 1.2 g. of naphthalene were placed in a stainless steel pot with a content volume of 400 ml. containing 25 stainless steel balls each half an inch in diameter. Ball milling was then applied for 16 hours at room temperature under a nitrogen atmosphere. Thereafter, 1.7 g. of titanium tetrachloride was added, and ball milling was further applied for 16 hours at room temperature. The resultln~ solid powder`contained 40 mg. of titanium per g. of the'solid.
(b) Polymerization A 2 liter stainless steel autoclave equipped with an induction stirrer was purged with nitrogen and charged with 1000 ml. of hexane.
To it were added 1 mmol. of trieth~laluminum and 30 mg. of the above-mentioned solid and the temperature was raised to 9aC. with stirring.
The system, which was at a pressure of 2 kg/cm2 G from vapor pressure of the hexane was pressurized with hydrogen to a total pressure of 5.6 kg/cm2 G and then with ethylene to a total pressure of 10 kg/cm2 G
followed by initiation of the polymerization. Ethylene was continuously introduced to maintain the total pressure at 10 kg/cm2 G while conducting the polymerization for 1 hour. After completion of the polymerization, the polymer slurry was transferred to a beaker, from which the hexane was removed under reduced pressure to obtain 160 g. of while polyethylene with a melt index of 5.1. The catalyst activity was 30,3000 g. poly-ethylene/g. Ti hr. C2H4 pressure, 1,210 g. polyethylene/g. solid-hr.-C2H4 pressure. The polymer powder had a bulk density of 0.31. The per-centage of fine particles below 44 microns in size was very small; it was 0.9%.
Comparative Example I
9.5 g. of anhydrous magnesium chloride and 1.7 g. of titanium tetrachloride were placed in a stainless steel pot with a content volume of 400 ml. containing 25 stainless steel balls each half an inch in diameter. Ball milling was then applied for 16 hours at room temperature under a nitrogen atmo~here. The resulting solid powder contained 39 mg.
of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid were used, to yield 145 g. of white polyethylene with a melt index of 5.5. The cata-lyst activity was 28,200 g. polyethylene/g. Ti-hr. C2H4 pressure, 1,100 g. polyethylene/g. solid hr'. C2H4 pressure. The'bulk density of the ~7~
polymer powder was low; it was 0.14.
Example 2 8.3 g. of anhydrous magnesium chloride and 1.2 g. of naphtha-lene were placed in the ball mill pot referred to in Example 1, and ball milling was applied for 16 hours under a nitrogen atmosphere. The rPsulting powder was contacted at 150C. for 2 hours with 50 ml. of titanium tetrachloride. After completion of the reaction, unreacted titanium te~rachloride was removed by washing wi~h hcxane to give a solid containing 19 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure'as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 82 g. of white polyethylene with a melt index of 8.1. The catalyst activity was 32,600 g. polyethylene/g. Ti hr.-C2H4 pressure, 620 g. polyethylene/g. solid-hr.-C2H4 pressure. The bulk density of the polymer powder was 0.24.
Example 3 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 1.2 g. of anthracene and 1.7 g. of titanium tetrachloride. Ball milling was applied for 16 hours under nitrogen atmosphere. The resulting solid powder containing 42 mg. of titanium per g. of the solid.
Polymeri~ation was conducted for 1 hour using the same proced-ure as in Example 1 except that 30 mg. of the solid just mentioned above were used, to yield 174 g. of white polyethylene with a melt index of 5.3. The catalyst activity was 31,500 g. polyethylene/g. Ti hr. C2H4 pressure, 1,320 g. polyethylene/g. solid-hr. C2H4 pressure. The bulk density of the polymer powder was 0.35.
Example 4 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride,'1.2 g. of pyrene and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The'resulting solid powder'contained 39 mg. of ~itanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-: dure as in Example l except that 30 mg. of the solid ~ust mentioned above was used, to yield 131 g. of white polyethylene with a melt index of 4.9. The catalyst activity was 25,400 g. polyethylene/g. Ti hr. C2H4 pressure, 990 g. polyethylene/g. solid-hr. C2H4 pressure. The bulk density of the polymer powder was 0.30.
Example 5 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 1.2 g. o~ pyrene and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 38 mg. of titanium per g. of the solid.
Polymerization was conducted for l hour using the same proce-dure as in Example 1 except that ~30 mg. of the solid just mentioned above was used~ to yield 165 g. of white polyethylene with a melt index of 9.2. The catalyst activity was 32,900 g. polyethylene/g. Ti hr. C2H4 pressure, 1,250 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.33.
Example 6 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 0.5 g. of benzene and 0.9 g~ of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 23 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 141 g. of white polyethylene with a melt index of 6.1. The'caaalyst activity was 46,500 g. polyeth~lene/g. Ti hr. C2H4 pressure, 1,070 g. polyethylene/g. solld hr. C2H4 pressure. The bulk density of the'polymer'powder was 0.28.
-- 10 -- .
Example 7 In the ball mill pot referred to in Example 1 were placed 8.3 g.
- of anhydrous magnesium c~loride, 1.~ g. of naphthalene, 0.9 g. of titanium tetrachloride and 0.8 g. o~ vanadium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 21 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid ~ust mentioned above was used, to yield 127 g. of white polyethylene with a melt index of 8.1. The catalyst activity was 45,800 g. pol'yethylene/g. Ti hr. C2H4 pressure, 960 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.37.
Example 8 In the ball mill pot referred to in Example 1 were placed 8.3 g.
of anhydrous manganese chloride, 1.2 g. of naphthalene and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 41 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 46 g. of white polyethylene with a melt index of 7.3. The catalyst activity was 8,550 g. polyethylene/g. Ti-hr. C2H4 pressure, 350 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.32.
- Comparative Example'II
In the ball mill pot referred to in Example 1 were placed 9.S g.
of anhydrous manganese chloride and 1.7 g. of titanium tetrachloride, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 38 mg. of titanium per g. of the solld.
Polymerization was conducted'for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned a~ove was used, to yield 40 g. of white polyethylene with a melt index -of 3.3. The catalyst activity was 7,900 g. polyethylene/g. Ti hr. C2H4 pressure, 300 g. polyethy~lene/g. solid hr.-C2H4 pressure. The bulk density of the polymer powder was 0.13.
Example 9 In the ball mill pot referred to-in Example 1 were placed 8.3 g.
of anhydrous magnesium chloride, 1.2 g. of anthracene and 1.7 g. of titanium trichloride (TACB TiC13-1/3 AlC13 manufactured by Toho Titanium Co.), and ball milling was applied for 16 hours under a nitrogen atmos-phere. The resulting solid powder contained 35 mg. of titanium per g.
of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid just mentioned above was used, to yield 114 g. of white polyethylene with a melt index of 7.2. The catalyst activity was 24,600 g. polyethylene/g. Ti-hr.-C2H4 pressure, 860 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.32.
Comparative Examplé'III
In the ball mill pot referred to in Example 1 were placed 9.5 g.
of anhydrous magnesium chloride and 1.7 g. of the same titanium tri-chloride as that used in Example 9, and ball milling was applied for 16 hours under a nitrogen atmosphere. The resulting solid powder contained 37 mg. of titanium per g. of the solid.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid ~ust mentioned above was used, to yield 104 g. of white polyethylene with a melt index of 5.3. The catalyst activity was 21,400 g. polyethylene/g. Ti hr. C2H4 pressure, 790 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.14.
' Example 10 In the ball mill pot referred to in Example 1 werè placed 5.0 g.
of anh~drous magnesium chloride,'3.3 g. of manganese chloride, 1.2 g. of naphthalene and 1.7'g. of titanium tetrachloride,'and ball milling was applied for 16 hours uncler a ni~rogen atmosphere. The resulting solid powder contained 40 mg. of titanium per g. of the solld.
Polymerization was conducted for 1 hour using the same proce-dure as in Example 1 except that 30 mg. of the solid ~ust mentioned above was used, to yield 133 g. o~ white polyethylene with a melt index of 4~8. The catalyst actL~ity was 25,200 g. polyethylene/g. Ti hr. C2H4 pressure, 1,010 g. polyethylene/g. solid hr. C2H4 pressure. The bulk density of the polymer powder was 0.32 ~.pl~ 1}
Uslng 30 mg. of the solld obtained in ExamplP 1 and in the same manncr as in Example 1, hexane, triethylaluminum and the solid were added and the temperature was raised to 90C. The system was then pressurized with hydrogen to a total pressure of 5.6 kg/cm2 G and there-after a mixed ethylene-propylene gas containing 2 mole % of propylene was fed to maintain the pressure of the autoclave at 10 kg/cm G while conducting the polymerization for 1 hour, to yield 182 g. of a white polymer with a melt index of 2.1 containing 5.8 methyl groups per 1,000 carbon atoms. The catalyst aciivlty was 34,500 g. polymer/g. Ti.hr.-C2H4 pressure, 1,380 g. polymer/g. solid-hr. C2H4 pressure. The bulk density of the polymer powder was 0.30.
.
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for preparing polyolefins which comprises polymerizing or copolymerizing olefins using as catalyst a titanium-containing solid and at least one of an organoaluminum compound and an organozinc compound, said titanium-containing solid comprising a reaction product obtained by copulveri-zing: (1) at least one of a magnesium halide and a manganese halide, (2) an aromatic hydrocarbon selected from the group consisting of polycyclic aroma-tic hydrocarbons, monocyclic hydrocarbons and halogen- and alkyl-substituted products thereof and (3) at least one of a tetravalent and a trivalent titanium compound; wherein the ratio of said halide selected from at least one of magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5 to 10 weight percent.
2. Process according to claim 1 wherein said polymerization or co-polymerization of olefins is effected at a temperature ranging from 20° to 120°C., under a pressure ranging from ordinary pressure to 70 kg/cm2.
3. The process according to claim 2 wherein said polymerization or copolymerization of said olefins is effected at a temperature of 50 - 100°C., under a pressure of 2 - 60 kg/cm2.
4. Process according to claims 1, 2 or 3 wherein said polymeriza-tion or copolymerization of olefins is effected in the presence of hydrogen.
5. Process according to claims 1, 2 or 3 wherein said aromatic hy-drocarbon is selected from the group consisting of naphthalene, phenanthrene, triphenylene, chrysene, 3,4-benzophenanthrene, 1,2-benzochrysene, picene, an-thracene, tetraphene, 1,2,3,4-dibenzanthracene, pentaphene, 3,4-benzopenta-phene, tetracene, 1,2-benzotetracene, hexaphene, heptaphene, diphenyl, fluor-ene, biphenylene, perylene, coronene, bisantene, ovalene, pyrene, perinaphth-ene, benzene, toluene, xylene, and their halogen-substituted and alkyl-sub-stituted derivatives.
6. An olefin polymerization catalyst comprising a titanium-contain-ing solid and at least one of an organoaluminum compound and an organozinc compound, said titanium-containing solid comprising a reaction product ob-tained by copulverizing: (1) at least one of a magnesium halide and a mangan-ese halide, (2) an aromatic hydrocarbon selected from the group consisting of polycyclic aromatic hydrocarbons, monocyclic hydrocarbons, and halogen- and alkyl-substituted products thereof, and (3) at least one of a tetravalent and a trivalent titanium compound;
wherein the ratio of said halide selected from at least one of the magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5. to 10 weight percent.
wherein the ratio of said halide selected from at least one of the magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5. to 10 weight percent.
7. The catalyst of claim 6 wherein the titanium content is within the range of 1 to 8 weight percent.
8. The catalyst of claim 6 wherein the amount of said organo com-pound selected from one or both of said organoaluminum compound and said or-ganozinc compound is from 0.1 to 1,000 moles per mole of said titanium com-pound.
9. The catalyst of claim 6 including a vanadium compound in addi-tion to the titanium compound.
10. The catalyst of claim 8 wherein the mole ratio of vanadium to titanium is 2:1 to 0.01:1.
11. In a process for the preparation of a catalyst comprising a ti-tanium-containing solid and at least one of an organoaluminum compound and an organozinc compound, the improvement comprising: preparing said titanium-con-taining solid by copulverizing (1) at least one of magnesium halide and a manganese halide, (2) an aromatic hydrocarbon selected from the group consist-ing of polycyclic aromatic hydrocarbons, monocyclic hydrocarbons and halogent- and alkyl-substituted products thereof and (3) at least one of a tetravalent and a trivalent titanium compound;
wherein the ratio of said halide selected from at least one of magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5 to 10 weight percent. 15
wherein the ratio of said halide selected from at least one of magnesium halide and manganese halide and the aromatic hydrocarbon is within the range of 1:0.5 to 1:0.01, and the titanium content of the solid is within the range of 0.5 to 10 weight percent. 15
12. Process according to claim 11 wherein said titanium content is from 1 to 8 weight percent.
13. Process according to claim 11 wherein said organo compound selec-ted from an organoaluminum compound and an organozinc compound is used in an amount of from 0.1 to 1,000 moles per mole of said titanium compound.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP501475A JPS5180382A (en) | 1975-01-10 | 1975-01-10 | Horiorefuinno seizohoho |
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| CA243,161A Expired CA1078806A (en) | 1975-01-10 | 1976-01-08 | Process for preparing polyolefins |
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| BR (1) | BR7600074A (en) |
| CA (1) | CA1078806A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5465190A (en) * | 1977-11-04 | 1979-05-25 | Toyo Sutoufuaa Kemikaru Yuugen | High active carried catalyst component and monoo or copolymerization of alphaaolefin |
| FR2538396B1 (en) * | 1982-12-24 | 1986-02-21 | Charbonnages Ste Chimique | CATALYTIC SYSTEM FOR USE IN A PROCESS FOR THE POLYMERIZATION OF ETHYLENE |
| FI95580C (en) * | 1991-10-02 | 1996-02-26 | Borealis As | Metal modified olefin polymerization catalyst |
-
1975
- 1975-01-10 JP JP501475A patent/JPS5180382A/en active Granted
- 1975-12-31 IT IT3091875A patent/IT1052077B/en active
-
1976
- 1976-01-08 BR BR7600074A patent/BR7600074A/en unknown
- 1976-01-08 CA CA243,161A patent/CA1078806A/en not_active Expired
- 1976-01-08 FR FR7600362A patent/FR2297217A1/en active Granted
- 1976-01-09 DE DE19762600688 patent/DE2600688A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| FR2297217B1 (en) | 1980-05-30 |
| DE2600688A1 (en) | 1976-07-15 |
| JPS5248915B2 (en) | 1977-12-13 |
| BR7600074A (en) | 1976-08-03 |
| JPS5180382A (en) | 1976-07-13 |
| IT1052077B (en) | 1981-06-20 |
| FR2297217A1 (en) | 1976-08-06 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |