CA1255443A - Process for producing rubber-like olefin copolymer - Google Patents

Abstract

Abstract of the Disclosure:
A process for producing a rubber-like olefin copolymer, which comprises random-copolymerizing ethylene with an .alpha.-olefin or with an .alpha.-olefin and a non-conjugated diene with a catalyst consisting of (A) a powder obtained by contacting a homogeneous solution of a chlorine-containing magnesium compound containing a phosphorus compound having a P=O bond with a solution of a liquid titanium compound or a homogeneous solution of a titanium compound containing a phosphorus compound having a P=O bond or containing an ether and (B) an organic aluminum compound or an alcohol-modified organic aluminum compound.
Said rubber-like olefin copolymer has a high degree of randomness.

Description

~5~'~3 1 This invention relates to a process for producing a copolymer having a high degree of randomness by random-copolymerizing ethylene with an ~-olefin or with an a-olefin and a non-conjugated diene with a highly active Ziegler catalyst.
Catalysts for polymeriza~ion o~ olefins have been greatly advanced since 7,iegler catalysts were discovered, and the finding of highly active cat~lysts have enabled the indus~rialization of the production processes of polyethylene or polypropylene requiring no catalyst-removal step.
On the other hand, ethylene-~-olefin copolymer rubber, in particular, ethylene-propylene copolymer rubber is produced using a vanadium compound~
organic aluminum compound as a catalyst.
Said catalyst has a high random-polymeriz-ability, but reduces in catalyst activity at high temperatures, resulting in a ~reat reduction in produc-tivity. Therefore, the polymerization should be effected at a relatively low temperature, and a very high energy is necessary ~or removing the polymerization reaction haat. Furthermore, when metallic vanadium remains în the rubber, the rubber becomes liable to be deteriorated, and therefore, sufficient removal of the catalyst is required.

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. ., .-l Under such technical circumstances, a patent has been applied for on copolymerization of ethylene and an ~-olefin at a relatively high temperature under high activity using a ti-tanium compound (Japanese Patent Application Kokai (Laid~Open) No. 104,6~7/78 and U.S.P.
4,302,565. The former patent application aims at modifying a polypropylene resin, and the latter at modifying a polyethylene resin, but none of them aim at obtaining a rubber-like random copolymer.

The production of a copolymer having a high degreee of randomness by copolymerizing ethylene with an ~-olefin under a high activity by use of a titanium compound as a catalyst is very dif~icult, and can by no means be predicted from techniques for the produc-tion of resins such as polyethylene, polypropylene and the like.
The present inventors have conducted extensive research on a process for pxoducing a rubber-like olefin copolymer having a high degree of randomness using a highly active solid catalyst. As a result, it has been ound that by using catalyst comprising a finely divided substance containing Ti, Mg and P and an organic aluminum compound or an alcohol-modified organic aluminum compound, there can be obtained an ethylene-~-olefin copolymer rubber which has a high activity and a very high degree of randomness.
According to this invention, there is provided : a process for producing a rubber-like olefin copolymer ~ . , having a high degree of randomness, whlch comprises copolymerizing ethylene with from 30 to 70% o~ an ~-olefin or with an ~-olefin and a non-conjugated diene us:Lng a cataly~t comprising:
(A) a powder obkalned by con~aini.ny (1) a homogeneous solution containing a chlorlne-containing magnesium compound and a phosphate or a phosphorus compound of the formula O~P(OH)j (OR3)k R4l wherein Rl, R2, R and R are independently hydrocarbon groups having 1 to 20 carbon atoms; ; is 1 or 2, k and l are independently 0, 1 or 2 where j iO k ~ l = 3 with

(2) a titanium compound preferably a powder deposited from a homogeneous solution obtained by con~acting (1) the above-mentioned homogeneous solution with (Z) the above titanium compound, and (B3 an organlc aluminum compound or an alcohol-modified organic aluminum compound.
First of all, the catalyst component ~A) used in ~his invention is explained below.
The chlorine-containing magnesium compound includes specifically MgC12 and Mg(OH)Cl. MgC'12 is preferably anhydrous, and there may also be used those which have been subjected to modifi~ation treatment such as grinding by means o~ the ball mill, grinding by means of a vibration mill, aomplexation treatment or the like. Mg(OH)Cl can be obtained by heating MgCl2.6H20 at a high temperakure.
As the phosphate compound there may be used at least one of the compounds represented by the general ~ormulas, o~P(OR2)3

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~ 25711-375 and o=P(oH)j(oR3)k ~he~ei.n R2 and ~3 are independently hydrocarbon groups having 1 to 20 carbon atoms; and j is 1 or ~ and k is 1 or 2, where j ~ k is 3. Preferred are compounds represented by the formula, o=P(oH)j(oR3)k, and more preferably are those compounds ~hat j is 1, namely monohydroxy compounds.
Specific examples of these compounds include trimekhyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-iso-propyl phosphate, ~ri-n-butyl phosphate, tri-i-bu~yl phosphate, tri-t-butyl phosphate, tri-n-hexyl phosphate, tri-n-octyl phosphate, ~ri-2-ethylhexyl phosphate, trilauryl phosphate, triacetyl phosphate, tristearyl phospha~e, trioleyl phosphate, triphenyl phosphate, tritolyl phosphate, trixylyl phosphate, octyldiphenyl phosphate, tolyldiphenyl phosphate, xylydiphenyl phosphate, monohydroxydiethoxyphosphine oxide, monohydroxydipro-poxyphosphine oxide, monohydroxydi-n-butoxyphosphine oxide, mono-hydroxydi-sec-butoxyphosphine oxide, monohydroxydi-t-butoxy-phosphine oxide, monohydroxydi-n-hexyloxyphosphine oxide, mono-hydroxydi-n-octyloxyphosphine oxide, monohydroxydi-2-ethylhexyl-oxyphosphine oxide, monohydroxydi-n-decyloxyphosphine oxide, mono-hydroxydi-n-dodecylphosphine oxide, monohydroxy(n-butyl)-n-butoxy-phosphine oxide, monohydroxy(n-hexyl)-n-hexyloxyphosphine oxide, monohydroxy(n-octyl)-n-octyloxyphosphine oxide, monohydroxy(2-ethylhexyl)-2-ethylhexyloxyphosphine oxide, monohydroxydib-ltyl phosphine oxide monohydroxydi-2-ethylhexylphosphine oxide and the like.

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The homogeneous solution (1) containing a chlorine containing magnesium compound and the phosphate or phosphorus compound of compound (A) (hereinafter referred to a~ the phosphorus compound) may be prepared either in a large amount of the phosphorus compound or in the presence of a hydrocarbon or halogenated hydrocarbon solvent. When the phosphorus compound is solid or waxy, the preparation should be carried out in the presence of such a solvent.
Specific examples of these solvents include n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-decane, petroleum ether, ligroin, k~rosine, benzene, toluene, xylene, cyclohexane, methylcyclohexane, 4a -$i .. . ...
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~2S~ 3 l methylene chloride, ethyl chloride, ethyl bromide, 1,2-dichloroethane, l,l-dichloroethane, n-butyl chloride, n-octyl chloride, monochlorocyclohexane, monochlorobenzene, o-dichlorobenzene, and the like.
However, any other solvents may be used. These solvents may be used alone or in admixture of two or more.
As to the chlorine-containing magnesium compound, a homogeneous solution of the chlorine-containing magnesium compound can be obtained by add-ing to the chlorine-containing magnesium compound one of the above-mentioned phosphorus compounds in an amount of 1 to 30 moles, preferably 2 to 10 moles, per mole of the chlorine-containing magnesium compound in the presence or absence of the solvent mentioned above, and stirring the resulting mixture at a temperature of ~30C to 120C, preferably 0C to 60C, for 2 minutes to 20 hours, preferably 5 minutes to 5 hours.
In addition, titanium tetrachloride is added to the aforesaid solution containing the chlorine-containing magnesi~m compound and the phosphoruscompound, in such a proportion that the atomic ratio Ti/Mg is prefera~ly from 0.2 to 2.0, more preferably from 0.1 to 1.5.
The solution containing the chlorine-cQntain;ng magnesium compound and the phosphoruscompoun~ may be prepared in a large amount of titanium tetrachloride. That is to say, a homogeneous solution ` can ~e obtained by adding the chlorine-containing _ S_ -,:

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1 magnesium compound and the phosphorus compound to a large excess of titanium tetrachloride. However, in this case, the dissolution becomes difficult if a hydrocarbon or a halogenated hydrocarbon coeY~iStS.
Therefore, it is desirable to prevent these solvents from coexisting.
Although the method of preparing a liquid containing a chlorine~containing magnesium compound, a phosphorus compound, and titanium tetrachloride is not critical, the following processes may be used:
(1) a process comprising adding 1 to 30 moles of the phosphorus compound to 1 mole of the chlorine-containiny magnesium compound in the presence or absence of a hydrocarbon or a halogenated hydrocarbon to obtain a solution, and adding thereto a 0.2 to 2 moles of titanium tetrachloride, (2) a process comprising grinding together 1 mole of the chlorine-containing magnesium compound and 0.2 to 2 moles of titanium tetrachlc ide by means of a vibration mill, a ball mill or the like to obtain a ground mixture, adding thereto 1 to 3Q moles of the phosphorus compound to obtain a solution, and if necessary, diluting the solution with one of the abovve-mentioned solvents, ~3~ a process comprising wet-grinding together 1 mole of the chlorine-containing magnesium compound, Q~2 to 2 moles of titanium tetrachloride, 1 to 3Q moles of the phosphorus compound, and if necessary, one of i'G

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1 the above-mentioned solvents by means of a vibration mill, a ball mill or the like -to obtain a solution, and

(4) a process comprising adding 5 to 1, ooa moles of titanium tetrachloride to 1 mole of the chlorine s containin~ magnesium compound to obtain a suspension, adding thereto 2 to 10 moles of the phosphorus compound to dissolve them in the large amount of titanium tetrachloride.
The titanium compound (2) in this invention is represented by the general formula, Ti(OR)pX3 p or Ti(OR)qX4 q, wherein R is a hydrocarbon group, X is a halogen, p is 0, 1, 2 or 3, q is 0 or an integer of 1 to 4, and includes, for example, TiC14, TiBr4, TiI4, Ti(OC2H5)C13, Ti(OC6H5~C13, Ti(OC2H5~2C12, Ti(OC6H5)C12, Ti (OC2H5)3Cl, Ti(OC2H~)4, Ti(OC6H13)4, TiC13, Ti(oC2H5)3~ Ti(On C4Hg)3, ( 6 5)4 Among them, titanium trichloride (TiC13) and titanium tetrachloride (TiC14~ are particularly preferred.
When titanium trichloride is used as the titanium compound (2~, it is preferable to from a homogeneous solution containing titanium trichloride.
In the preparation of such a solution, titanium trichloride can be dissolved by use o~ an ether such as diethyl ether, di-n-propyl ether, di-n-butyl ether, bis(.l-octenyll ether, anisole, diphenyl ether or the like or the above-mentioned phosphorus compound having a P=o bond~ In this case, the amount of the ether 7 _ , ~ 3 1 or the phosphorus compound used is such that in ~erms of the molar ratio to the titanium compound, the ether or the phosphorus compound/Ti ranges f~om 1.5 to 20, preEera~ly from 2.0 to 10.
As the titanium trichloride, there may be used homogeneous solutions prepared by the processes described in U.S.P. 4,377,671; 4,366,297; and 4,356,160.
The mixing amounts of the homogeneous solution containing the titanium compound and the homogeneous solu-tion containing the chlorine-containing magnesium compound are such that the molar ratio of Mg to Ti is 0.1 - 10,000, preferably 1 - 1,000.
The temperature at which the powder as the catalyst component (A) is deposited is 0 to 200C, preferably 20~ to 150~C.
As a depositing agent, there may be used organic aluminum compounds or halogen-containing compounds of titanium, vanadium, boron, sulfur, tin, germanium and the like, such as TiCl~, TiC13(OC2H5), TiC13(On C4Hg), (C2H5)C12~ A12(C2H5)3C13 and the like.
Preferably used are titanium halides and organic aluminum compounds particularly preferably TiC14, Al(C2H5)C12 and A12(C2H5)3 3 The amount of the depositing agent used is 1.0 to 200 moles, preferably 1.0 to 100 moles, per mole of the ether and/or the phosphorus compound contained in the homogeneous solution containing the titanium compound and the chlorine-containing magnesium compound.

l The ~eposition treatment o~ the powder as the catalyst component (A) may be carried out in the presence of an inorganic solid carrier. The inoryanic solid carrier is an inorganic solid having a surface area o 50 m2/g or more, preferably 60 m2/g or more, an average particle diameter of 200 ~ or less, preferably 150 ~ or less, and an average pore diameter of 50 A or more, preferably 60 A
or more, and examples thereof are silica, alumina, zeolite, magnesia, etc. The amount of said inorganic solid carrier used is 0.5 to 200 g, preferably 1 to 100 g, per gram of the chlorine-containing magnesium used.
The powder as the catalyst component (A) pre-pared in the manner described above is preferably washed sufficiently with pentane, hexane, heptane, benzene, toluene or the like, and then used as a catalyst for polymerization in suspension in such a solvent.
When the infrared absorption spectrum of the aforesaid sufficiently washed powder was measured by the KBr tablet method, the characteristic absorption due to the phosphorus compound was observed.
The amount of the phosphorus compound present in said powder can be determined by pouring a suspension of said powder in any of the above-mentioned solvents into water to decompose the catalyst, and then measuring the gas chromatogram of the solvent layer. The titanium content was determined by a colorimetric method, and the magnesium content by an atomic absorption method.
.. The Mg/Ti ratio of said powder ranges from 0.5 ~ q ~ - ~,0 --1 to 100 (molar ratio), preferably from 0.5 to 50 (molar ratio), and the phosphorus compound/Ti ratio ranges ~rom 0.01 to 2 (molar ratio), preferabl~ from 0.05 to 2 (molar ratio).
Next, the catalyst component (B) is explained below.
The catalyst component (B) is an organic aluminum compound or an alcohol-modified organic aluminum compound.
As the catalyst component (B), preferred are organic aluminum compounds represented by the general ~ormula, AlRrX3 r' wherein R is a hydrocarbon residue having 1 to 12 carbon atoms, X is a halogen atom, and r is a ~7alue of 1 to 3, and alcohol-modified organic aluminum compounds obtained by contacting ~lRrX3 r with an alcohol having 1 to 2 carbon atoms.
The organic aluminum compound includes, for example, trialkylaluminums such as trimethylaluminum, t~iethlaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri~n-octylaluminum, tri-n-dodecyl-aluminum and the like; dialkylaluminum halides such asdiethylaluminum chloride, diethylaluminum bromide, di-n-butylaluminum chloride, di-n-octylaluminum chloride, di-n-octylaluminum bromide and the like; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, isobutylaluminum sesquichloride and the like; and mono-alkylaluminum dihalides such as ethylalurninum dichloride, n-butylaluminum dichloride, ethylaluminum dibromide and `::
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~55~3 1 the like. Among them, trialkylaluminums are ~referred.
The alcohol as a rnodifier used in the alcohol-modified organic aluminum compound as -the ca~alyst component (B) includes alcohols having 1 to 20 carbon atoms such as methyl alcohol, ethyl alcohol, prop~l alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, dodecvl alcohol, nonylphenyl alcohol, stearyl alcohol and the like.
The aleohol-modified organie aluminum eompound as the eatalyst eomponent (B) ean be prepared by contaet-ing an organoaluminum compound represented by the formula, AlRrX3 r' with an aleohol.
In the preparation of the aleohol-modified organie aluminum eompound, the same solvents as those used for preparing the eatalyst eomponent (A) (described above) may be used.
The modifieation of the organie aluminum compound is generally carried out at a temperature of -10C to 50C, preferably 0C to 30C. The modifi-eation time is 0.1 to 2.0 hours, preferably 0.5 to1.0 hour.
The amount of the aleohol used as the modifier is 0.05 to 0.5 mole, preferably 0.1 to a . 3 mole, per mole of the organie aluminum eompound. The ratio between the eatalyst eomponent (A) and the eatalyst eomponent (B) is sueh that the amount of the organie aluminum eompound in the eatalyst eomponent (B) ~`
_ ~ _ ~2S~'k3 1 is 1.5 to 200 moles, preferably 2 to 100 moles, per mole of Ti in the catalyst component (A).
The monomers used in this inven-tion are ethylene, ~-olefins and non-conjuyated dienes. As the ~-olefins, there may be used, for e~ample, propylene butene-l, pentene-l, 4-methylpentene-1, hexene-l, heptene~l, 4-methylhexene-1, octene-l, and the like.
The non-conjugated dienes may be any of the non-conjugated dienes used for renderlng the copolymer vulcanizable in this type of copolymerization, and include, for example, l,4-hexadiene, dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornadiene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, S-isopropenyl-2-norbornene, tetrahydroindene, and the like. These non-conjugated dienes are added to a polymerization reactor in the amount necessary for the iodine value in the copolymer being 2 to 50, preferably 3 to 40. In this case, two or more of the non-conjugated dienes may be used as a mixture.
The polymerization temperature is usually 10 to 150C, preferably 30 to 120C. The polymeriz-ation pressure ranges usually from atmospheric pressure to 100 kg/cm2G.
The copolymerization may be either solution polymerization or suspension polymerization. That is to say, the polymerization can be effected by suspension polymerization using propylene as a medium by suspension polymerization using a solvent in ~hich the resulting C _ ,ac~;~ _

5~3 l polymer is slightly soluble, or b~ solution pol~meriz-ation using a solvent in which the resulting pol~mer is well soluble.
Specific examples of the polymerization solvent are as follows: hydrocarbon sol~ents such as propylene, which is a monomer, hexane, heptane, octane, kerosine, benzene, toluene, xylene, cyclohe~ane and the likej and halogenated ~ydrocarbon solvents such as methylene chloride, monochloroethane, l,l-dichloroethane, 1,2-dichloroethane, 1,2-dichloropropane, monochlorobutane, monochlorobenzene, and the like.
These solvents may be used in admixture of two or more in order to control the solubiliky parameter.
The molecular weight of the copolymer can, if necessary, be controlled by use of hydrogen.
Next, this invention is further explained below in more detail referring to Examples, which are not by way of limitation but by way of illustration.
Among the physical properties of the copoly-mers in the E~amples, Mooney viscosity was determinedby measure.ment under the conditions that the pre~eating time was l minute, the measurement time was 4 minutes and the measurement temperature was 100C; propylene conte~t was determined from lnfrared absorption spectrum; iodine value was determined b~ titration method; and heat of fusion of crystal was determined by means of a differential scanning calorimeter (DSC~.
- lOQ% ~odulus, tensile strength, elonga~ion at break f~ ~

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l and Shore A hardness were determined by measurement methods according to JIS K6301. Ti-tanium content of each catalyst was determined by colorimetry, Mg content is determined by chelatometry, and phosphorus compound content was determined by colorimetry.
The quantity of heat absorbed determined by means of DSC indicates quantity of heat absrobed owing to the melting of crystalline portion in each rubber-like copolymer. Therefore, that the quantity of heat absorbed is small indicates that the crystalline portion content is low. In other words, the degree of randomness of the copolymer is high.

Examples 1-1 to 1-4 (1) Preparation of catalyst component (Al (solid complex) A rotator and 1 g (10.5 mmoles) of anhydrous magnesium chloride were placed in a 100-ml flask which had sufficiently been dried and then purged with nitrogen.
Thereto were added the predetermined amount of the solvent shown in Table 1 whic~ had been dried by use of molecular sieves and the predetermined amount of the phosphorus compound shown in Table 1. The resul~ing mixture was stirred at room temperature for 20 minutes, upon whîch the magnesium chloride was completely dis-solved and a colorless, transparent, homogeneoussolution was obtained.
To the homogeneous solution was added 1.16 ml !

:' 1 (10.5 mmoles) of titanium chloride, and the resulting mixture was allowed to stand for 30 minutes to o~tain a yellow, transparent, homogeneous solu-tion. When 12 ml of titanium tetrachloride was gradually added to this solution with stirring, yellow fine powder was produced.
After the stirring was continued for 2 hours, a yellow finely divided solid complex was deposited from the solution, and the supernatant was removed by iltration.
To the residue was added 80 ml of fresh dried n-hexane, and the resulting mixture was stirred for 30minutes, whereby the residue was washed. This washing procedure was repeated 6 times. A yellowish-white finely divided solid complex was obtained. Normal hexane was added to this complex to obtain a total volume of 50 ml of a slurry.
(2) Copolymerization of ethylene and 5-ethylidene-2-norbornene A 3-liter separable flask was equipped with a stirring blade, a three-way cock, a gas-blowing tube, a thermometer and a dropping funnel for addition of 5-ethylidene-2-norbornene, and then sufficiently purged with nitrogen. In this flask was placed 2 liters of n-~exane which had ~een dried ~y use of molecular sieves and degassed. Into the flask whose tempera-ture was controlled to 35C were in ~ oduced for 10minutes, through the gas-blowing tube, dried ethylene at a rate of 4 liters/min, propylene at a rate of 6 liters/min, and hydrogen at a rate of 0.2 liter/min ;3 1 in the form of a mixed gas, immediately after which 2 ml of a n-hexane solution of triisobutylaluminum having a concentration of 1 mole/liter was added. Thereafter, the slurry in n-hexane of the catalyst component (A) prepared ln above (1~ was added in an amount or 0.05 mmole in terms of titanium atom, and polymerization was initiated.
Simultaneously with the initiation of the polymerization, a mixed solution of 10 ml of 5-ethyl-idene-2-norbornene and 200 ml of n-hexane was added dropwise at a rate of 7 ml/min, and polymerization was effected for 30 minutes. During the polymerization, a mixed gas of the monomers at the respective flow rates described above was introduced into the flask. The polymerization temperature was controlled to 35~C by external cooling.
During the copolymerization, substantially no gel was produced. After 30 minutes, the polymerization was stopped by addition of 20 ml of methanol. A small amount of an antioxidant was added, after which steam stripping was carried out to o~tain solid rubber. The yield, the Mooney viscosity, and the propylene content of the copolymer were determined. The results are shown in Table 1.
The raw rubber physical properties of the copolymer obtained in Example 1 were as follows:

100% Modulus = 7 kg/cm Tensile strength = 17 kg/cm Elongation at break = 4,500 Shore A hardness = 32 1 Comparative Fxample 1-1 An attempt was made to prepare a solid complex by repeating the same procedure as in Example l 1, except that the tri-n-butyl phosphate [OP(OC4H9)3]
used in Example 1-1 was replaced by tri-n-butyl S phosphite [P(OC4Hg)3]. However, no solid complex was deposited. From this Comparative Example, it can be seen that a O = P bond is needed in the form of a phosphorus compound.

Comparative Example l-2 An attempt was made to prepare a solid complex by repeating the same procedure as in Example 1 l, except that the monochlorobenzene solvent used in Example 1 1 was replaced by n-hexane. ~owever, an oily precipitate was formed and no solid complex was deposited. From this Comparative Example, it can be seen that the solvent to be used is important.

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1 Examples 2-1 to 2-5 (1~ Preparation of catalyst component (A) (solid complex) A rotator and 1 g ~10.5 mmoles) of anhydrous magnesium chlo;-ide were placed in a 100-ml flask which had sufficiently been dried and then purged with nitrogen. Thereto were added the predetermined amount of the solvent shown in Table 2 which had been dried by use of molecular sieves and the predetermined amount of the phosphorus compound shown in Table 2. When ~he resulting mixture was stirred at room temperature for 20 minutes, the magnesium chloride was completely dissolved and a colorless, transparent, homogeneous solution was obtained.
To the homogeneous solution was added 1.16 ml (10.5 mmoles) OL titanium tetrachloride, and the result-ing mixture was deteriorated for 30 minutes to obtain a yellow, transparent, homogeneous solution. When a mixture of 40 ml of n-hexane and 12 ml of titanium tetrachloride was gradually added to this solution with stirring, yellow fine powder ~as produced. A yellow, finely divided, solid complex was deposited by continu-ing the stirring for 2 hours, and the supernatant was removed by filtration. To the residue was added 80 ml of fresh dried n-hexane, and the resulting mixture was stirred for 30 minutes, whereby the residue was washed.
This washing procedure was repeated 6 times to obtain ~; a yellowish-white finely divided solid complex.

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1 Normal hexane was added to this complex to o~tain a total volume of 50 ml of a slurry.
(2) Copolymerization of ethylene, propylene and 5-ethylidene~2-norbornene A 3-liter separable flask was equipped with a stirring blade, a three-way cock, a gas blowing tube, a thermometer and a dropping funnel for addition of 5-ethylidene-2-nor~ornene, and then sufficiently purged with nitrogen. In this flask was placed 2 liters of n-hexane which had been dried by use of molecular sieves and degassed. Into the flask whose temperature was controlled to 35C were introduced for lO minutes dried ethylene at a rate of 4 liters/min, propylene at a rate of 6 liters/min, and hydrogene at a rate of 0.2 liter/min in the form of a mixed gas, through the gas blowing tube, immediately after which 2 ml of a triisobutylaluminum solution in n-hexane having a concentration of l mole/liter was added. Therea~ter, the n-hexane slurry of the catalyst component (A~
prepared in above (1~ was added thereto in an amount of O ~ as mmole in terms of titanium atom, and polymeriz-ation was initiated.
Simultaneously with the initiation o~ the polymerization, a mixed solution of lO ml of 5-ethyl-idene-2-norbornene and 200 ml of n-hexane was added dropwise at a rate of 7 ml/min, and the polymerization was effected for 30 minutes. During the polymerization, - a mixed gas of the monomers at the respective flow rates t ~ _ c~/ _ .. . . .
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l described above was introduced int~ the flask. A-t this time, the polymerization temperature was controlled to 35C by external cooliny.
During the polymerization, sugstantiall~ no gel was produced. After 30 minutes, the polymerization was stopped by addition of 20 ml of methanol. A small amount of an antioxidant was added, after which steam stripping was carried out to obtain a solid rubber.
The yield, the Mooney viscosity, and the prospylene content of the copolymer were measured. The results are shown in Table 2.
The raw rubber physical properties of the copolymer obtained in Example 2-1 were as follows:
lO0~ Modulus - 7 kg/cm2 Tensile strength = 16 kg/cm2 Elongation at break = 4,600 Shore A hardness = 31 Example 2-6 (1) Preparation of the catalyst component (A~
A finely divided solid complex was prepared by the process of Example 2-1 and washed with three 80-ml portions of water, after which 50 ml of n-hexane and 12 ml of titanium tetrachloride were freshly added 2Q to the complex, and the resulting mixture was stirred at 6QqC for 2 hours. The supernatant was removed by filtration, after which 80 ml of n-hexane was added to ` the residue, and the resulting mixture was stirred for _ ,;~ _ - ~.

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~Z~4'~3 1 30 minutes, whereby the residue was washed. This wash-ing procedure was repeated 6 times. ~ yellowish-white, finely divided, solid complex was obtained. Mormal hexane was added to this complex to obtain a total volume of SO ml of a slurry.
(2) Copolymerization of ethylene, propylene and 5-ethylidene-2-norbornene The copolymerization was effected by repeating the same procedure as in Example 2-1. The results are shown in Table 2.

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1 Examples 3-1 to 3-5 (1~ Preparation of the catal~sk component (A~
Under a nltrogen steam, 100 g o magnesium chloride hexahydrate was placed in a 300~ml flask, and heated to 300C. It first forrned a homogeneous solu-tion t and further heating resulted in a white solid.
The solid was ground under a nitrogen stream and then heated at 300C for 10 hours under reduced pressure to obtain a powder of Mg(OH)Cl.
A rotator was placed in a 100-ml flask which had sufficiently been dried and then purged with nitrogen, and 1 g (13 ~noles) of the Mg(OH)Cl powder was placed therein. Thereto were added 36 mmoles of the phosphorus compound shown in Table 3 whiah had been dried by use of molecular sieves and then degassed and 30 ml of the solvent shown in Table 3, and the resulting mixture was heated to 130C. In this state r the Mg(OH)Cl powder did not dissolve, but when 13 mmoles of titanium tetra-chloride was placed in the flask, the Mg(OH~Cl powder dissolved to give a brown homogeneous solution. The homogeneous solution was further heated at 130C for 2 hours, thereafter cooled to room temperature, and then made up to a total volume of 130 ml with n-hexane, whereby a solution having a concentration of 0.1 mole/
liter in te~ns of Ti, i .

1 (2) Copolymerization of ethylene, propylene and 5-ethylidene-2-norbornene A 3-liter separable flask was equipped with a stirring blade, a three-way cock, a gas blowing tube, a thermometer and a dropping funnel for addition of 5-ethylidene-2-norbornene, and then sufficiently purged with nitrogen. In this flask was placed 2 liters of n-hexane which had been dried by use of molecular sieves and degassed. Into the flask whose temperature was controlled to 35C were introduced for 10 minutes dried ethylene at a rate of 4 liters/min, propylene at a rate of 6 liters/min and hydrogen at a rate of 0.2 liter/min in the form of a mixed gas through the gas blowing ~ube, immediately after which 2 ml of a tri-isobutylaluminium solution in n-haxane having a concentration of 1 mole/liter was added. Thereafter, the n-hexane solution of the catalyst component ~A) prepared in above (1) was added in an amount of 0.05 mmole in terms of titanium atom, and polymerization was 2Q initiated.
Simultaneously with the initiation of the polymerization, a mixed solution of 10 ml of 5-ethylidene-2-norbornene and 200 ml of n-hexane was added dropwise at a rate of 7 ml/min, and the poly-merization was effected for 3Q minutes. During thepolymerizaticn, a mixed gas of the monomers at the respective flow rates described above was introduced into the flask. At this time, the polymerization .:

.

5~

1 temperature was controlled to 35C by external cooling.
Duriny the copolymerization, substantially no gel was produced. After 30 minutes, the polymerization was stopped by addition of 20 ml of methanol. A small amount of an antioxidant was added, after which steam stripping was carried out to obtain solid rubber. The yield, the Mooney viscosity, and the propylene content of the copolymer were measured. The results are shown in Table 3.
The raw rubber physical properties of the copolymer obtained in Example 3 - 1 were as follows:
100% Modulus = 7 kg/cm2 Tensile strength = 17 kg/cm2 Elongation at break = 3,500%
Shore A hardness + 35 . . ,:
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1 Example ~-1 (1) Preparation of catalyst component (A) Under a nitrogen stream, 100 g of magnesium chloride hexahydrate was placed in a 300-ml flask, and heated to 300C. It formed a homogenenous solution, and further heating resulted in a white solid. The solid was ground in a ni-trogen stream and then heated at 300C for 10 hours under reduced pressure to obtain a powder of Mg(OH)Cl.
A rotator and lg (13 mmoles) of the Mg(OH)Cl powder were placed in a 100-ml flask which had sufficiently been dried and then purged with nitrogen. Thereko was added 36 mmoles of 2-ethylhexyl(di-2-ethylhexyloxy)-phosphine oxide dried by use of molecular sieves, and the resulting mixture was heated to 130C. In this state, the Mg(OH)Cl powder did not dissolve, but when 13 mmoles of titanium tetrachloride was placed in the flask, a brown homogeneous solution was obtained. The homogeneous solu-tion was further heated at 130C continuously for 2 hours.
A rotator was placed in another 100-ml flask which had sufficiently been dried and khen purged with nitrogent and 60 ml of dried n-hexane and 13 mmoles of titanium tetrachloride were placed therein, after whlch the resulting solution was maintained at 60C on a hot water bath. Into this solution was slowly dropped, with vigorous stirring, the above-mentioned homegeneous solution containing magnesium, titanium and phosphorus. A yellow, finely divided, solid complex was immediately produced.

. .
.

''` ' , : "

~2~
1 The stirring was continued at 60C for 2 hours. The stirring was stopped to deposit the yellow, finel~ de~ided solid, and the supernatant was removed by filtration.
To the residue was added 60 ml of fresh, dried n-hexane and the resulting mixture was stirred for 30 minutes, whereby the residue was washed. This washing procedure was repeated 6 times to obtain a yellowish-white, finely divided solid. Normal hexane was added to this solid to make up the total volume to S0 ml. The titanium concentra-tion of the thus obtained finely divided solid complexslurry was 0.024 mole/liter, and Mg/Ti = 10.5 (molar ratio).
(2) Copolymerization of ethylene, propylene and 5-ethylidene-2-norbornene A 3-liter separable flask was equipped with a strring blade, a three-way cock, a gas blowing tube, a thermometer and a dropping funnel for addition of 5-ethylidene-2-norbornene, and then sufficiently purged with nitrogen. In this flask was placed 2 liters of n-hexane which had been dried by use of molecul r sieves and degassed. In~o the flask whose temperature was con-trolled to 35C were introduced for 10 minutes dried ethylene at a rate of 4 liters/min, propylene at a rate .of 6 liters/min, and hydrogen at a rate of 0.2 liter/min in the form of a mixed gas through the gas 10wing tube, immediately after which 2 ml of a n-he~ane solution of triisobutylaluminum having a concentration of 1 mole/liter was added. Thereafter, the n-hexane slurry of the catalyst component (A) prepared in above (1) was added .
, ~z~

1 in an amoun~ of 0.05 mmole in terms of titanium atom, and polymerization was initia~ed.
Simultaneously with the initiation of the poly-merization, a mixed solution of 10 ml of 5-ethylidene-2-norbornene and 200 ml of n hexane was added dropwise ata rate of 7 ml/min, and the polyrnerization was effected for 30 minutes. During the polymerization, a mixed gas of the monomers at the respective ~low rates described above was introduced into the flask. At this time, the polymerization temperature was controlled to 35C by external cooling.
During the copolymerization, substantially no gel was produced. After 30 minutes, the polymerization was stopped by addition of 20 ml of methanol. A small amount of an antioxidant was added, after which steam stripping was carried out to obtain a solid rubber. The yield, the Mooney viscosity, and the propylene content of the copolymer were measured. The results are shown in Table 4.
The raw rubber physical properties of the copolymer obtained in Example 4-1 were as follows:

100% Modulus = 5 kg/cm2 Tensile strength = 15 kg/cm2 Elongation at break = 4,000 %
Shore A hardness = 30 3~

S~

1 Example 4-2 (1) Preparation of catalyst component (A) The same procedure as in Example 4-1 was repeated to obtain a n-hexane slurry of a yellowish-white, finely divided, solid complex. To the slurry ~asadded 10 ml of titanium tetrachloride, and the resulting mixture was stirred at 60C for 2 hours. The stirring was stopped, and the supernatant was removed by ~iltra-tion, after which the same washing procedure as in Example 4-1 was repeated 6 times. Normal hexane was added to the thus washed residue to adjust the total volume to S0 ml. The titanium concentration of the thus obtained finely divided solid complex slurry was 0.025 mole/liter, and Mg/Ti = 9.2 (molar ratio).
lS (2) Copolymerization Copolymerization was effected by repeating the same procedure as in (2) of Example 4-1. The results are shown in Table 4.

Example 4-3 The same procedure as in Example 4-1 was re-peated, except that the phosphorus compound used in Example 4-1 was replaced by 36 mmoles o tri-n-butyl phosphate and 20 ml of monochlorobenzene.
~ light-yellow, finely divided, solid complex was obtained. Normal hexane was added to the complex to adjust the total volume to 50 ml, whereby a slurry was ` obtained. The titanium concentration of the slurry was C - ~ _ ' "~

1 0.01 mole/liter, and Mg/Ti = 26 (mola~ ratio).
The copolymerization results are shown in Table 4.

Example 4-4 The same procedure as in Example 4-1 was re-peated, except that the phosphorus compound used in Example 4-1 was replaced by 36 mmoles of n-butyl(di-n-butoxy)phosphine oxide and 20 ml of monochlorobenzene.
A light-yellow, finely divided, solid complex was obtained. Normal hexane was added ko the complex to adjust the total volume to 50 ml, whereby a slurry was obtained. The titanium concentration of the slurry was 0.027 mole/liter, and Mg/Ti = 8.7 (molar ratio).
The copolymerization results are shown in Table 4.

Example 4-5 The same procedure as in Example 4-1 was re-peated, except that 20 ml of Isoper-E was used as a solvent, to obtain a light-yellow, finely divided, solid complex. Normal hexane was added to the complex to adjust the total volume to 50 ml, whereby a slurry was obtained.
The titanium concentration of the slurry was 0.022 mole/
liter, and Mg/Ti = 10.8 (molar ratio).
The copolymerization results are shown in Table 4.

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" , , ~ ~. ' ' ; , 1 Examples 5-1 to 5-4 (1) Preparation of catalys-t component (A) A 100-ml flask containing a rotator was suf-ficiently purged with nltrogen, after which 1 g (10.5 mmoles) of MgCl2 was placed in the flask. There~o was added 14.5 ml (31.5 mmoles) of dried 2-ethylhexyl(di-2-ethylhexyloxy1phosphine oxide (phosphorus compound (b)), and the resultlng mixture was heated to 70C to dissolve the MgCl2. A homogeneous solution was obtained.
Another 100-ml flask containing a rotator was sufficiently purged with nitrogen, and 20 ml of dried n-hexane, 1.44 ml (13.125 mmoles) of TiC14 and the pre-determined amount of the phosphorus compound (a) shown in Table 5 were placed in this flask, allowed to react at the boiling point of n-hexane (about 70C), and heated and stirred until no more HCl was produced (the reaction time: 3 hours). An orange, homegeneous solution was obtained.
The whole amount of the orange, homogeneous solution was added to the homogeneous MgCl2 solution pre-viously prepared. The resulting mixture was diluted to a total volume of 100 ml by further addition of n-hexane.
When 10 ml of TiCl4 was gradually added to the diluted mixture with stirring while the temperature of the flask was maintained at 50 to 60C, a yeLlow, finely divided solid was deposited. The flask was malntained at S0 to 60"C for 30 minutes after the addition of TiC14.
The stirring was stopped, and the flask was allowed to _,~

,.

1 stand overnlght to precipi~ate the finely divided solid, after which the supernatant was taken out. To the resi~ue was freshly added 80 ml of n-hexane, and after stirring and washing, precipitation was carried out. This washing pro-cedure was repeated 6 times. Normal hexane was added tothe thus washed residue to adjust the total volume to 100 ml. The analytical values for the thus obtained slurry of the finely divided solid complex in n-hexane are shown in Table 5.
(2) Copolymerization of ethylene, propylene and 5-ethylidene-2-norbornene A 3-liter separable flask was equipped with a stirring blade, a three-way cock, a gas blowing tube, a thermometer and a dropping unnel for addition of 5-ethylidene-2-norbornene, and then sufficiently pwrged with nitrogen. In this flask was placed 2 liters of n-hexane which had been dried by use of molecular sieves and then degassed. Into the flask whose temperature was controlled to 35C were introduced for 10 minutes dried ethylene at a rate of 4 liters/min, propylene at a rate of 6 liters/
min, and hydrogen at a rate of 0.2 liter/min in the form of a mixed gas through the gas blowing tube, immediately after which 2 ml of a n-hexane solution of triisobutylalu-minum having a concentration of 1 mole/liter was added.
Thereafter, the n-hexane slurry of the finely divided solid complex (the catalyst component (A)) prepared in above (1) was added in an amount of 0.05 mmole in terms of titanium atom, and polymerization was initiated.

1 Simultaneously with ~he initiation of the poly-.erization, a mixed solutlon of 10 ml of 5-ethyli~ene-2-norbornene and 200 ml of n-hexane was added dropwise at a rate of 7 ml/min, and the polymerization was effected for 30 minutes. During the polymerization, a mixed gas of the monomers at the respective flow ra-tes described above was introduced into the flask.
The polymerization temperature was controlled to 35C by external cooling. During the copolymerization, to substantially no gel was produced. After 30 minutes, the polymerization was stopped by addition of 20 ml of meth-anol. A small amount of an antioxidant was added, after which steam stripping was carried out to obtain a solid rubber. The yield, the Mooney viscosity, and the pro-pylene content of the copolymer were measured. The resultsare shown in Table 5.
The raw rubber physical properties of the copolymer obtained in Example 5-1 were as follows:

100 ~ Modulus = 5 kg/cm2 Tensile strength = 9 kg/cm2 Elongation at break = 4,020 %
Shore A hardness = 29 Example 5-5 The same procedure as in Example 5-1 was re-peated, except that the phosphorus compound (b) used for dissolving MgC12 in Example 5-1 was replaced by .. .
~, .

1 tri-n-butyl phosphate and -th~t 20 ml of monochloro-benzene was used as the solvent for dissolving the MgCl2.
The results are shown in Table 5.

Example 5-6 The same procedure as in Example 5-5 was repeated, except that the tri-n-butyl phosphate used in Example 5-5 was replaced by tri-2-ethylhexyl phosphate. The results are shown in Table 5.

Examples 5-7 to 5-9 (1) Preparation of catalyst component (A) A 100-ml flask containing a rotator was suffi-ciently purged with nitrogen, after which MgCl2 (10.5 mmoles) was placed in the flask. Thereto was added 14.5 ml (31.5 mmoles) of dried 2~ethylhexyl(di-2-ethylhexyloxy)-prosphine oxide (phosphorus compound (b)), and the result-ing mixture was heated to 70C to dissolve the MgC12.
To the thus obtained solution were added 20 ml of dried n-hexane and the predetermined amount of the phosphorus compound (a) shown in Table 5, and the resulting mixture was allowed to react at the boiling point of n-hexane (about 70C), and heated and stirred until no mare HCl was produced (the reaction time: 7 hours). A colorless, transparent, homogeneous solution was obtained. After this solution was adjusted to a total volume of 100 ml with dried n-hexane, 10 ml of TiC14 was gradually added thereto with strring while maintaining the temperature of 0~

~ 3 l the system at 50 to 60C, upon which a yellow, finel~
divided solid was deposite~. The temperature of the system was maintained at 50 to 60C for 30 minutes a~ter the addition of TiC14. The stirring was stopped, and the system was allowed to stand overnight to precipi-tate the finely divided solid, after whlch the supernatant was taken out. The residue was washed by adding thereto 80 ml of n-hexane and stirring the resulting mixture, and then precipitated. This washing procedure was re-peated 6 times. Normal hexane was added to the thuswashed residue to adjust the total volume to 100 ml. The analytical values for the thus obtained slurry of the finely divided solid complex in n-hexane are shown in Table 5.
(2) Copolymerization of ethylene, propylene and 5-ethylidene-2-norbornene The copolymerization was effected by repeating the same procedure as in Example 5-1. The results are summarized in Table 5.

Example 5-10 (1) Preparating of catalyst component (A) A 100-ml flask containing a rotator was suffi-ciently purged with ritrogen, after which 1 g (10.5 mmoles) of MgC12 was placed in the flas~. Thereto was added 14.5 ml (31.5 mmoles) of dried 2-ethylhexyl(di-2-ethylhexyloxy)phosphine o~ide (phosphorus compound (b)), and the resulting mixture was heated to 70C to dissolve ` the MgC12. To the thus obtained solution were added ~ 4~

, .
, . ' ~ .

1 20 ml of dried n-hexane and 10.5 mmoles of dihydroYy-n-butoxyphosphine oxide (phosphorus compound (a)~, an~
they were subjected to reaction at the boiling point of n-hexane and continuously heated and stirred until no more HCl was produced (the reaction time: 6 hours). A
colorless, transparent, homogeneous solution was obtained.
To this solution was added 10.5 mmoles of TiC4, and the resulting mixture was continuously heated and stirred at the boiling point o~ n-hexane until no more HCl was produced (the reaction time: 6 hoùrs). An orange, homo-geneous solution was obtained. The solution was adjusted to a total volume of 100 ml with n-hexane, after which 10 ml of TiC14 was gradually added to the system with stirring while the temperature of said system was main-tained at 50 to 60C. A yellow, finely divided solid wasdeposited. The stirring was continued while the tempera-ture of said system was maintained at 50 to 60C for 30 minutes. The stirring was stopped, and said system was allowed to stand overnight, after which the finely divided solid was precipitated, and the supernatant was taken out. The residue was washed by adding 80 ml of n-hexane freshly and stirring the resulting mixtur2, and then precipitated. This washing procedure was repeated

6 times. Normal hexane was added to the thus washed residue to adjust the total volume to 100 ml. The analyt-ical values or the thus obtained suspension of the finely divided solid complex in n-hexane are shown in Table 5.

lZ~

1 (2) Copolymerizatlon of ethylene, propylene and 5-ethylldene-2-norbornene The copolymeriæation was effected by repeatiny the same procedure as in Example 5-1. ~he results are shown in Table 5.

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1 Example 6-1 ~ombination of the catalyst cornponents (A)(a) and (B) (1) Preparation of catalyst component (A)(a) Into a 300-ml flask purgecl wlth nitrogen were charged 1 g of dried palladium carbon powder r 200 ml of 1,2-dichloroethane and 100 ml of titanium tetrachloride, and 200 mmoles of di-n-butyl ether was added with stirr-ing. Subsequently, hydrogen was fed to the flask for 6 hours at a rate of 0.3 liter/min to obtain a yellowish-black solution.
The soluti.on was filtered to remove the pal-ladium carbon, whereby a yellowish-black, homogeneous solution was obtained. The reduction of the titanium tetrachloride was approximately 100%. Subsequently, the concentration of titanium trichloride was adjusted to 0.4 mole/liter with 1,2-dichloroethane.
On the other hand, 25 g (0.262 mole) of an-hydrous magnesium chloride was placed in a l,000-ml flask purged with nitrogen and was dissolved by addition of 361.5 ml (0.787 mole) of 2-ethylhexyl(di-2-ethylexyloxy)-phosphine oxihe. After the dissolution, the resulting solution was adjusted to a total volu~e of 524 ml with n-hexane.
Subsequently, in a.200-ml flask were placed 20 ml of the above-mentioned magnesium chloride solution, then 20 ml of the above-mentioned titanium trichloride solution, and lastly 145 ml of n-hexane to obtain a green, homegeneous solution.

~i "

1 Into this solution was gradually dropped 10 ml of titanium tetrachloride with stirring. After completion of the dropping, the stirriny was continued for 3 hours, and the thus obtained mixture was then allowed to stand.
As a result, the mixture was separated into a black homo-geneous supernatant and a finely divided solid. The supernatant was removed, after which 200 ml of n-hexane was added to the finely divided solid to wash the finely divided solid. After this washing procedure was repeated 4 times, the total volume of the thus washed finely devided solid slurry was adjust to a total volume of 200 ml. The final state of the product was a n-hexane suspension of a slightly yellow finely divided solid.
The Ti concentration was 0.011 mole/liter, the Mg/Ti molar ratio was 4.5, and the phosphorus compound/Ti molar ratio was 0.23.
(2) Preparation o catalyst component (B) A sufficiently dried 500-ml flask was purged with dried nitrogen, and 200 ml of n-hexane was charged thereinto. S~bsequently, 18.8 ml (0.0747 mole) of tri-isobutylaluminum was added with stirring, and the stirring was continued for 10 minutes after the addition.
On the other hand, a 100-ml flask was purged with dried ni~rogen, after which 50 ml of n-hexane was charged thereinto, and 4.6 ml (0.050 mole) of n-butyl alcohol was added with stirring.
Subsequently, a 200-ml flask was purged with ` nitrogen, after which 100 ml o the above-mentioned _~_ L~L' t3 1 n-hexane solution of triisobutylalurninurn was charyed there~
into, and 3.8 ml of the n-he~ane solution of n-butyl alcohol was gradually dropped thereinto wi-th stirring while nitrogen was blown thereinto (n-butyl alcohol/triisobutyl-aluminum molar ratio = 0.10). During the dropping, thetemperature was maintained at 20C. After completion of the dropping, the stirring and the blowing of nitrogen were continued at 20C for 1 hour.
The thu~ obtained solution was colorless, transparent and homogeneous.
(3) Copolymerization procedure A 3-liter autoclave equipped with a stirrer was purged with nitrogen, after which 800 g of propylene was charged thereinto in a liquid state, and the temperature was raised to 50C. Subsequently, ethylene was fed to the autoclave while the feeding pressure was kept con-stant at 32.0 kg/cm2G. After the pressure in the auto-clave became constant at 32.0 kg/cm G, 15 g of 5-ethylidene-2-norbornene was added.
Subsequently, the catalyst components (A)(a) and (B) were fed to the autoclave in amounts of 0.0388 mmole (in terms of ~i) and 1.552 mmoles (in terms of Al), respectively, over a period of 30 mlnutes. Simultaneously with the initiation of feeding of the catalyst components, the beginning of polymerization was observed.
Durlng the polymerization, the polymerization temperature was maintained at 55~1C by using cooling water. Ethylene was continuously fed to the autoclave 1 so as to keep the pol~merization pressure constant at 32.0 kg/cm G.
The feeding of ethylene was stopped 4~ minutes after the beginning of the polymeriza-tion, and 50 ml of methanol was fed to the au-toclave, after which stirriny was conducted for iO minutes to remove the unreacted gas, whereby a rubber-like copolymer was obtained. The rubber-like copolymer was dried, and thereafter allowed to stand at 150C for 6 hours and then at 20C for 20 hours.
The yield, Mooney viscosity, propylene content, iodine value, and quantity of heat of fusion of crystal of the thus treated rubber-like copolymer were measured.
The results are shown in Table 6.

Example 6-2 Combination of the catalyst components (A)la) and (B) (1) Preparation of catalyst component (A)(a) The catalyst component (A)(a) prepared in Example 6-1 was used.
(2) Preparation of catalyst component (B) A triisobutylaluminium solution in n-hexane and a n-butyl alcohol in n-hexane were prepared by the same procedure as in Example 6-1.
Subsequently, a 200-ml flask was purged with nitrogen, after which 100 ml of the triisobutylaluminum solution in n-hexane was charged thereinto, and 18.9 ml of the n-butyl alcohol solution in n-hexane was gradually dropped thereinto with stirring while nitrogen was bubbled .. ..

1 into the contents of the flask (n-butyl alcohol/tri-isobutylaluminum molar ratio = 0.50).
After completion of the droppiny, the same procedure as ln Example 6-1 was repeated to obtain a colorless, transparent, homogeneous solution.
(3) Copolymerization procedure Copolymerization, heat treatment and measure-ment were carried out under the same conditions as in Example 6-1.
The results are shown in Table 6.

Example 6-3 Combination of the catalyst components (A)(b) and (B) (1) Preparation of catalyst component (A)(b) Into a 200-ml flask purged with nitrogen was charged 1.0 g (10.5 mmoles) of anhydrous magnesium chloride, and 14.5 ml (31.5 mmoles) of dried 2-ethyl-hexyl(di~2-ethylhexyloxy)phosphine oxide was added thereto, after which the resulting mixture was heated to 80C and stirred, whereby the magnesium chloride was dissolved to obtain a homogeneous solution.
On the other hand, a 100-ml flask was purged with nitrogen, and 20 ml of dried n-hexane, 1.44 ml (13.125 mmoles) of titanium tetrachloride and 3.5 ml (10.49 mmoles) of monohydroxydi-2-ethylhexyloxyphosphine oxide were placed therein, subjected to reaction at about 70~C, and continuously heated and stirred for 3 hours until no more hydrogen chloride was produced. The thus ! ~ ~jZ) '', ' '' ~l~S'~ 3 1 o~tained solution was dark-yellow and homogeneous. The whole dark-yellow homogeneous solution was added to the above-mentioned magnesium chloride solution, and n-hexane was ~urther added to adjust the total volume to 100 ml.
When 10 ml of titanium tetrachloride was gradually dropped with stirring in the thus obtalned solution con~aining magnesium chloride and titanium tetrachloride whlle this solution was maintained at about 60C, a yellow, finely divided solid was deposited.
After the addition of titanium tetrachloride, the system was maintained at 60C for 1 hour, and thereafter the stirring was stopped, after which the system was allowed to stand to precipitate the finely divided solid, and the supernatant was removed.
To the residue was freshly added 80 ml of n-hexane to wash the residue, and the resulting mixture was allowed to stand, after which the supernatant was removed. After this washing procedure was repeated 6 times, n-hexane was added to the residue to adjust the total volume to 100 ml.
The thus obtained liquid was a n-hexane sus-pension of a slightly yellow finely divided solid, and the Ti concentration was 0.004 mole/liter, the Mg/Ti molar ratio was 25, and the phosphorus compound/Ti molar ratio was 0.85.
(2) Preparation of catalyst component (B) A n-hexane solution of triethylaluminum and a n-hexane solution of 2-ethylhexyl alcohol were prepared . . .

1 by the same procedure as in Example 6~1.
Subsequently a 200-ml flask was purged with nitrogen, after which 100 ml. of khe triethylaluminum (triethylaluminum: 0.0~ mole) solution in n-hexane was charged thereinto, and 24.3 ml of the 2-ethylhexyl alcohol-(2-ethylhexyl alcohol: 0.012 mole) solution in n-hexane was gradually added with stirring while nitrogen was bu~bled into the contents of the flask (2-ethylhexyl alcohol/triethylaluminum molar ratio = 0.30).
After the addition, the same procedure as in Example 6-1 was repeated to obtain a colorless, trans parent, homogeneous solution.
(3) Copolymerization procedure Copolymerization was effected by using the same 3-liter autoclave as in Example 6-1. The polymerization pressure was 30.5 kg/cm2 and hence the feeding pressure of ethylene was 30.5 kg/cm2, and other conditions were the same as in Example 6-1.
The catalyst components (A)(b) and (B) were fed in amounts of 0O0505 mmole (in terms of Ti) and 2.02 mmole (in terms of Al), respectively, by the same method as in Example 6-1. Polymerization stoppage, heat treat-ment and measurement were carried out by the same, methods as in Example 6~
The results are shown in Table 6.

.

. .
,:
, 1 Comparative Example 6-1 [A case where the arnount of the alcohol used in the catalyst component (B) was increased.]
(1) Preparation of catalyst component (A)(a) The catalyst component (A)(a) prepared in Example 6-1 was used.
(2) Preparation of catalyst component (B) A triisobutylaluminum solution in n-hexane and a n-butyl alcohol solution ln n-hexane were prepared by the same procedure as in Example 6-1, ancl subjected to reaction in a molar ratio of n-butyl alcohol/triisobutyl alcohol of 1.0 to obtain a co',orless, transparent homo-geneous solution.
(3) Copolymerization procedure Copolymerization, heat treatment and measurement were carried out by the same methods as in Example 6-1.
The results are shown in Table 6.

Comparative Example 6-2 [A case where the amount of the alcohol used in the catalyst component (B) was increased]
(1) Preparation o~ catalyst component (A)(b) The catalyst component (A)(b) prepared in Example 6-3 was used.
(2) Preparation o catalyst component (B) A triethylaluminum solution in n-hexane and a 2-ethylhexyl alcohol solution in n-hexane were prepared in the same manner as in Example 6-3 and subjected to reaction in a molar ratio of 2-ethylhexyl alcohol/tri-ethylaluminium o~ 1.0 to obtain a colorless, transparent, l~ ~'3 , .

. . .
:.

~f,>~ 3 l homegeneous solution.
(3) Copolymerization procedure Copolymerization, heat treatment and measure-ment were carried out by the same methocls as in Example 6~3.
The results are shown in Table 6.

Comparative Example 6-3 [A case where an alkylaluminum alkoxide was used as the catalyst component (B)]
(1) Preparation of catalyst component (A)(a) The catalyst component (A)(a) prepared in Example 6-1 was used.
(2) Preparation of alkylaluminum alkoxide A sufficiently dried 200-ml flash was purged with nitrogen, and 100 ml of n-hexane was charged thare-into. In the n-hexane was dissolved 34.5 mmoles of diisobutylaluminum monobutoxide with stirring to obtain a homogeneous solution.
(3) Copolymerization procedure By use of the same 3-liter autoclave as in Example 6~-1, copolymerization was effected under the same conditions as in Example 6-1, except that the polymeriza-tion pressure was 32.0 kg/cm2G and the polymerization temperature was 55C.
The amounts of the catalysts fed were 0.0388 mmoLe (in terms of Ti) for the component (A)(a) and 1.552 mmoles for the diisobutylaluminum monobutoxide, and the '' copolymerization was effected while these catalyst .. ~

'.

~zs~

1 components were fed by the same method as in Example 6-1.
The treatment method and the measurement methods of the thus obtained copolymer were the same as in Example 6-1, The results are shown in Table 6.

Comparative Example 6-4 [A case where an alkylaluminum alkoxide was used as the catalyst component (B)]
(1) Preparation of catalyst component (A)(b) The catalyst component (A)(b) prepared in Example 6-3 was used for polymerization.
(2) Preparation of the alkylaluminum alkoxide A diethylaluminum 2-ethylhexoxide solution in n-hexane was prepared by the same process as in Comparative Example 6-3.
(3) Copolymerization procedure By use of the same 3-liter autoclave as in Example 6-3, copolymerization was effected by the same method as in Example 6-5, except that the pressure was 30.5 kg/cm2G, the temperature was 55C, and the amounts of the catalysts fed were 0.505 mmole (in terms of Ti) for the component (A)(b) and 2.02 mmoles for the diethyl-aluminum 2-ethylhexoxide. The treatment method and the measurement methods of the thus obtained copolymer were the same as in Example 6-3.
The results are shown in Table 6.

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Claims (27)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for producing a rubber-like olefin copolymer, which comprises random-copolymerizing ethylene with from 30 to 70%
of an .alpha.-olefin or an .alpha.-olefin and a non-conjugated diene with a catalyst comprising:
(A) powder obtained by contacting a homogeneous solution (1) containing a chlorine-containing magnesium compound and a phosphate or a phosphorus compound of the formula O=P(OR2)3 or O=P(OH)j (OR3)k R41 wherein R1, R2, R3 and R4 are independently hydrocarbon groups having 1 to 20 carbon atoms; j is 1 or 2, k and 1 are independently 0, 1 or 2 where j + k + 1 = 3 with a titanium compound (2) and (B) an organic aluminum compound or an alcohol-modified organic aluminum compound.

2. A process according to Claim 1, wherein the chlorine-containing magnesium compound for the component (A) is MgCl2 or Mg(OH)Cl.

3. A process according to Claim 1, wherein the compound of component (A) is at least one compound represented by the general formulas, O=P(OR2)3 and O=P(OH)j(OR3)k wherein R2 and R3 are independently hydrocarbon groups having 1 to 20 carbon atoms; and j is 1 or 2 and k is 1 or 2, where j + k = 3.

4. A process according to Claim 1, wherein the compound of component (A) is trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-iso-propyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate, tri-t-butyl phosphate, tri-n-hexyl phosphate, tri-n-octyl phosphate, tri-2-ethylhexyl phosphate, trilauryl phosphate, triacetyl phosphate, tristearyl phosphate, trioleyl phosphate, triphenyl phosphate, tritolyl phosphate, trixylyl phosphate, octyldiphenyl phosphate, mono-hydroxydiethoxyphosphine oxide, monohydroxydipropoxyphosphine oxide, monohydroxydi-n-butoxyphosphine oxide, monohydroxydi-sec-butoxyphosphine oxide, monohydroxydi-t-butoxyphosphine oxide, monohydroxydi-n-hexyloxyphosphine oxide, monohydroxydi-n-octyloxyphosphine oxide, monohydroxydi-2-ethylhexyloxyphosphine oxide, monohydroxydi-n-decyloxyphosphine oxide, monohydroxydi-n-dodecylphosphine oxide, monohydroxy(n-butyl)-n-butoxyphosphine oxide, monohydroxy(n-hexyl)-n-hexyloxyphosphine oxide, mono-hydroxy(n-octyl)-n-octyloxyphosphine oxide, monohydroxy(2-ethyl-hexyl)-2-ethylhexyloxyphosphine oxide, monohydroxydibutyl-phosphine oxide, monohydroxydi-2-ethylhexylphosphine oxide, tolyldiphenyl - 58a -phosphate, or xylyldiphenyl phosphate.

5. A process according to claim 1, wherein in preparing the component (A), the solution containing the chlorine-containing magnesium compound and the phosphate compound is contacted with the titanium compound in one or more solvents of hydrocarbon and halogenated hydrocarbon.

6. A process according to Claim 1, wherein the titanium compound for the component (A) is a compound represented by the general formula, Ti(OR)pX3-p or Ti(OR)qX4-q wherein R is a hydro-carbon group, X is a halogen atom, p is 0, 1,2 or 3, and q is zero or an integer of 1 to 4.

7. A process according to Claim 1, wherein the titanium compound for the component (A) is TiCl3, Ti(OC2H5)3 Ti(On-C4-H9)3, TiCl4, TiBr4, TiI4, Ti(OC2H5)C13, Ti(OC6H5)C13, Ti(OC2H5)2C12, Ti(OC6H5)C12, Ti(OC2H5)3C1, Ti(OC2H5)4 or Ti(OC6H5)4.

8. A process according to Claim 1, wherein the titanium compound for the component (A) is TiC13 or TiC14.

9. A process according to Claim 1, wherein the contact of the homogenous solution (I) with the titanium compound (2) is conducted at a temperature of 0° to 200°C.

10. A process according to Claim 1, wherein the component (A) is a powder deposited by adding a depositing agent to a homogeneous solution obtained by contacting the homogeneous solution with the titanium compound.

11. A process according to Claim 10, wherein the depositing agent is an organic aluminum compound or a halogen-containing compound of titanium, vanadium, boron, sulfur, tin or germanium.

12. A process according to Claim 10, wherein the depositing agent is TiC14, TiC13(OC2H5), TiC13(On-C4H9), Al(C2H5)-C12 or A12(C2H5)3C13.

13. A process according to Claim 10, wherein the depositing agent is TiC14, Al(C2H5)C12 or A12(C2H5)3C13.

14. A process according to Claim 10, wherein the amount of the depositing agent used is 1.0 to 200 moles per mole of the phosphate compound contained in the homogeneous solution.

15. A process according to Claim 1, wherein the powder as the catalyst component (A) has a Mg/Ti molar ratio = 0.5 - 100 and a phosphate compound/Ti molar ratio = 0.01 - 2.

16. A process according to Claim 1, wherein the organic aluminum compound is a compound represented by the general formula AlRrX3-r wherein R is a hydrocarbon residue having 1 to 12 carbon atoms, X is a halogen atom, and r is a number of 1 to 3.

17. A process according to Claim 1, wherein the organic aluminum compound is trimethylaluminum, tri-ethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-dodecyl-aluminum, diethylaluminum chloride, diethylaluminum bromide, di-n-butylaluminum chloride, di-n-octylaluminum chloride, di-n-octylaluminum bromide, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, ethyl-aluminum dichloride, n-butylaluminum dichloride, or ethylaluminum dibromide.

18. A process according to Claim 1, wherein the alcohol of the alcohol-modified organic aluminum compound as the aforesaid component (B) is an alcohol having 1 to 20 carbon atoms, and the used amount thereof is 0.05 to 0.5 mole per mol of the organic aluminum compound.

19. A process according to Claim 18, wherein the alcohol is methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, dodecyl alcohol, nonylphenyl alcohol or stearyl alcohol.

20. A process according to Claim 1, wherein the ratio of the catalyst component (a) to the catalyst component (A) is 1.5 to 200 moles of the organic aluminum compound in (B) per mole of Ti in (A).

21. A process according to Claim 1, wherein the ratio of the catalyst component (B) to the catalyst com-ponent (A) is 2 to 100 moles of the organic aluminum compound in (B) per mole of Ti in (A).

22. A process according to Claim 1, wherein the .alpha.-olefin is propylene, 1-butene, 1-hexene, or 1-octene

23. A process according to Calim 1, wherein the non-conjugated diene is at least one member selected from the group consisting of 1,4-hexadiene, dicyclo-pentadiene, tricyclopentadiene, 5-methyl-2,5-norbor-nadiene, 5-ethylidene-2-norbornene, 5-isopropylidene-2 norbornene, 5-isopropenyl-2-norbornene and tetrahydro-indene.

24. A process according to Claim 1, wherein the non-conjugated diene is used in an amount necessary for the iodine value in the copolymer being 2 to 50.

25. A process according to Claim 1, wherein the polymerization is effected at a temperature of 10° to 150°C at a pressure from atmospheric pressure to 100 kg/cm2G.

26. A process according to Claim 1, wherein the polymerization is effected in the presence of a poly-merization medium.

27. A process according to Claim 26, wherein the polymerization medium is a hydrocarbon or a halogenated hydrocarbon.