CA2091303A1 - Polymerization process to prepare a polyolefin from sterically hindered, methyl branched, alpha-olefins - Google Patents

Abstract

ABSTRACT OF THE INVENTION
A process comprising contacting under polymerization conditions: at least one trialkylaluminum cocatalyst; at least one alpha-olefin which has a methyl branch at the 3-position and which has at least five carbon atoms and at least one comonomer; with a catalyst prepared by the process comprising comminuting, at least one aluminum halide, at least one electron donor, at least one metal compound wherein the metal is selected from the group consisting of chromium, hafnium, molybdenum, niobium, tantalum, titanlum, tungsten, vanadium, zirconium, and mixtures thereof, a salt compound wherein at least one component of said salt compound is selected from the group consisting of barium, beryllium, calcium, magnesium, strontium, zinc, and mixtures thereof, to produce a comminuted solid then subjecting said comminuted solid to a double activation-extraction step; to produce a copolymer at a productivity level of at least 700 grams of copolymer per gram of catalyst utilized.

Description

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POLYMERIZATION PROCESS TO PREPARE A POLYOLEFIN FROM

STERICALLY HINDERED, METHYL BRANcHED~ ALPHA-oLEFINS
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BACKGROUND OF THE INVENTION
~ This invention relates to polymeri2ing alpha-olefins which have a ?` methyl branch at the 3-position.
Thousands of processes are known for polymeriæing linear and branched alpha-olefins. Branched alpha-olefins tend to be harder to polymerize than linear alpha-oleEins. This is due, in part, to the steric hindrances to the polymerization process. It is generally accepted -that as the branching substituent is positloned nearer to the double bond, tha ability ,~ to polymerize the branched alpha-olefin correspondingly decreases. However, these branched alpha-olefins upon polymeri~ation yield polymers which tand to have higher melting points and be-tter chemical resistance than their linear cousln3 while retaining good elsctrical propertieS.
;~ An example of a polymerizable branched alpha-olefln~ ls ~ 3-methyl-1-butene. Various processes in the art have produce~
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~ poly(3-methyl-1-butane) in characteristically low yialds. This ~s due to the ,. . .
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2 ~ 3 steric hindrance imposed by the branched methyl group of the monomer which inhibits polymerization. It has long been recognized that long residence times and high polymerization temperatu]res were necessary in order to overcome this steric hiDdranca effect. Typically, polymerlza-tion of 3-methyl-1-butene has been reported as anywhere from about 2 grams of polymer produced pex gram of catalyst, to about 400 grams of polymer produced per gram of catalys-t.
Therefore, a process which produced poly(3-methyl-1-butene) in better yields would make the commercial production of poly(3-methyl-1-butene) more economical. Furthermore, a process which polymerized thesa sterically hindered~ methyl branched at the 3-position, alpha-olefins would be of great scientific and economic value. Additionally, it would be of great value if a sterically hindered, methyl branched at the 3-position, alpha-olefin could be produced at a high productivity rate and wi-th as high of a molcular weight as possible.

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SUMMARY OF THE INVENTION
It is an object of this invention to provide a high productlvity process to produce a high molecular weight copolymer of an alpha olefin having a methyl branch at the 3 position.
It is an object of this invention to provide an improved copolymerization process for preparing a polyolefin from a sterically hindered, methyl branched a-t the 3-position, alpha-olefin and at least one comonomer.
It is another object of this invention to provide an improved copolymerization process for 3-methyl-1-butene and at least one comonomer.
It is still another object of this invention to provide an improved copolymerization process for 3-methyl-pentene and at least one comonomer.
In accordance with this invention a process is provided comprising .

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contacting under polymeriæation conditions: at least one trialkylaluminum cocatalyst; at least one alpha-olafin which has a methyl branch at the 3-position and which has at least five carbon atoms, and at leas-t one comonomer;
with a catalyst prepared by the process comprising comminuting at least one aluminum halide; at least one electron donor; at least one metal compound wherein the metal is selected from the group consisting of chromium, hafnium, molybdenum, niobium, tantalum, titanium, tungsten, vanadium, zirconium, and mixtures thereof; and a salt compound wherein at least one component of said salt compound is selected from the group COnSiStiDg o~
barium, beryllium, calcium, magnesium, strontium, zinc, and mixtures ther~of, to produce a comminuted solid then subjecting said comminuted solid to a double activation-extraction step;
to produce a copolymer at a productivity level of at least 700 grams of copolymer per gram of catalyst utllized.

DETAILED DESCRIPTION OF T~IE INVENTION
CATALYST SYSTEM
` :' Aluminum Halide Component The term aluminum halide is used to refer to aluminum compounds~
having at least one halogen bonded directly to the aluminum. Included are aluminum halids compounds of the formula:
R AlX
y z wherein R is an alkyl, aryl, or cycloalkyl group; X is fluorine, chlorine, bromine, or iodine; z is 1, 2, or 3 and z ~ y = 3.

Examples include~

AlCl3;

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~l-dichloro-phenoxy;
Al-mono-chloro-diphenoxy;
Al-dichloro-xylenoxy;
Al-mono-chloro-dixylenoxy;
Al-dichloro-2,6-t-butyl-p-cresoxy;
Al-dichloro-octoxy; and Al-monoethyl-dichloride.
Presently the most preferred is ~lCl3.

Electron Donor Component Examples of electron donors include organic compounds having a-t least one atom of oxygen, sulfur, nitrog~n, or phosphorus which can function as the electron donor. More specifically, the term electron donor is used to include ethars, esters, ketones, aldehydes, alcohols, carboxyllc acids, phenols, thioethers, thioesters, thioketones, amines, amides, nitriles, isocyanates, phosphites, phosphoryl compounds, and phosphines. Typically it is preferred to ~Ise compounds having no more than 16 carbon atoms per molecula. It is currently believed that aromatic ethers and the esters of aromatic acids ar~ the most useful electron donors.
In an especially preferred embodiment both an aromatic ester and an aromatic ether are employed. The more common esters are those derived from carboxylic acids having 1 to 12 carbon atoms and alcohols having 1 to 12 carbon atoms. The more common ethers are those containing 2 to 12 carbon atoms and 1 to 10 ether oxygen atoms. Typical examples of the aromatic esters include the alkyl and aryl esters of aromatic carboxylic acids such as ben7oic, toluic, p-methoxybenzoic, and phthalic acid. Some specific examples include ethyl benzoate, methyl benzoate, methyl p-tolua-te, ethyl p-toluate, and methyl anisate. The term aromatic ethers is intended to include those ethers having two aromatic groups as well as those having one aromatic group .~

~ ~ ~.L ~ ~ 3 and one alkyl group. Some specific examples include methoxybenzene, phenetole, diphenyl ethar, phenylallyl ether, and benzofuran. The currently most preferred combination is ethyl benzoate and methoxybenzene.

M~tal Compound Component The metal compound component includes tri, tetra, and pentavalent metal compounds. Examples include compounds of the formula MOp(OR)m-X(n 2p m wherein M is a metal selected from the group consisting of chromium, hafnium, molybdenum, niobium, tantalum, titanium, tungsten, vanadium and zirconium, with a valency of n=3, 4, or 5, 0 is oxygen, p is O or 1, R is an alkyl, aryl, cycloalkyl group or substituted derivative thereof, X is a halid~ and n~m>O.
In practice the metal is generally selected from the group consisting of chromium, titanium, vanadium, and 7-irconium. In a preferred embodiment, tha metal is titanium. The choice of a particular metal compound within the above formula will depend upon the reactlon conditions and other constituents present in the catalyst. Some examples of metal compounds having polymerization actlvity are TiCl~, Ti(OCH3)Cl3, Ti(OCHzC~13)Cll, VCl3, VOCl2, VOCl3 and VO(OCH3)C12- In a preferred embodiment liquid titanium tetrachloride is used as the metal compo~nd.

Salt Component Included within the scope of salts referred to above are the halogen containing compounds of barium, beryllium, calcium, magnesium, strontium, and zinc. Specific examples of such compounds include magnesium chloride, magnesium bromide, calcium chloride, ~inc chloride and magnesium hydroxychloride. It is currently believed that the best salt components are the salts of magnesium. Typical examples of such salts includa magnesium dihalides, alkyloxides, aryloxides, and combinations thereof. The pre~erred salt components are M(OR)nX(2 n) where M is magnesium, R is an ~lkyl or aryl . ~
, : : .: : , radical, X i3 a halide and n is 0, 1, or 2. Some typical examples of salts having such a formula are MgC12, MgBr2, MgF2, Mg(OCH3)2, Mg(OCH2CH3)2, Mg(OC6Hs)2. It is within the scope of the invention to employ mixtures of such salts. The currently most preferred embodiment employs magnesium halides, especially magnesium chloride. The molar proportions of the components are illustrated by the table below.

Table of the molar proportlons of the catalyst components based on one mole of metal compound component Component Broad Range Preferred Range Most Preferred Salt Compound 82S.C.280 102S.C.280 142S.C.216 Aluminum Halide Compound 12AHC25 1.25>AHC23.0 1.52AHC22.5 Electron Donor Compound l>EDC>lO 1.52EDC28 22EDC_7 _ An example of a preferred catalyst and the molar propor-tions of its components is:
tl) l mole of TiCl4 (metal compound component) (2~ 15 moles of MgCl2 (salt compound component)

(3) 2 moles of AlCl3 ~aluminum halide component)

(4) 3 moles of C6HsCO~C2Hs and 2 moles of C6HsOCH3; for a total of 5 moles of (electron donor compound components) Preparation of the Catalyst The term comminuting is used herein to refer to grinding or pulverization of the components. This term ls used to distinguish over simple mixing which does not result in any substantial alteration of the particle size of the components of the catalyst. One method to attain such comminuting is by using a ball~ pebble, or rod mill. Basically, these mills are used for 7 ~ 3 ~ ~
tha size reduction of materials prior to processing. They are generslly made up ~f a ro-t~ting drum which operates on a horizontal axis and which is filled partially with a free-moving grinding medium which is harder and tou~her than the material to be ground. The tumblin~ act:ion of the grinding medium (balls~
pebbles, or rods) crushes and grinds the material by a combination of attrition and impact. Grinding generally requires several hours to assure the necessary fineness within particle size limits.
A method of producing the above catalyst system comprises the comminution of the components preferably under an inert atmosphere in a ball or vibration type mill. The salt component is initially charged in-to the mill. If the salt component contains water which must be removed, a sufficient quantity of dehydrating agent ls initially added to the salt component and the resulting mixture is comminuted at temperatures between about 0C and about 90C for about 15 minutes to about 48 hours. Preferably this comminuting is from about 6 hours to about 24 hours, optimally for about 15 hours, at temperatures between 35C and about 50C so that the salt component becomcs substan-tially anhydrous. It is preferred that the catalyst components be substantially anhydrous because the catalyst system is susceptible to water and air degradation. It is important that -the wa-ter content of the catalyst be sufficiently low so as not to substantially interfere with the catalytic activity. Usually it is only the salt component which carries a possibility of a significant amount of water within its composition. Therefore, drying the salt component prior -to use is generally preferred. Further examples of various methods to dehydrate the components of the catalyst are disclosed in U.S. patent 4,680,351 which is hereby incorporated by reference.
Although comminution may take place at temperatures between about 0C and 90C the preferred comminuting temperature is from about 20C to about 40C with a range of 30C to 34C being most preferred. Comminution time . :
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varies but may range from about 15 minutes to abou-t 48 hours. Prsferred commlnution times are from about 12 hours to about 20 hours and most prefsrably are from about 14 hours to about 18 hours. Insufflcisnt comminution will no-t yield a homogeneous composition, while over comminuting may cause agglomerization or may significantly decrease particle size of the catalyst composition causing a possible reduction in the particle size of the polymers produced from the catalyst system. The comminution of the components can be carried out in any order. Ths componsnts can be added one at a time with additional comminution with each newly added component or several of the components can be combined first and comminuted simultaneously. It is also possible to combine some of the components before combining with a comminuted product. Currsntly -the most preferred technique involves co~minuting the salt component and the aluminum halide component, then comminu-ting -that product - with one or more ~lectron donors and then comminuting that product with ths metal compound component. Further examplss of various msthods to comminute ths components are disclosed in U.S. Patent 4,680,351.
The solid obtained as describsd above is then contacted with a liquid undsr conditions sufficient -to extract aluminum from ths solid and to Eurthsr increase ths activity of the catalyst. The amount of ths extrac-tion/activation liquid employed can vary but, typically, it would be ~mployed in such an amount that the resulting slurry would contain about 10 to about 40 weight percent solids based on the total weight of the liquid and solids, more prsferably about 20 to about 30 weight percent solids. The actual temperature and time for the extraction/activation can vary depending on the results dssired. Typically the extraction/ac-tivation would be conducted at a temperature in the range of about 40C to about 120C.
Gsnerally, however) the temperature should be kept below the boiling point of ths liquid having the lowest boiling point. It is currently prsfsrred -to use a temperature in ths range of about 60C to about 110C, ~ore prsf~rably 85C

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to about 105C. It is currently preferred to contact the cstalyst w:Lth the llquid for about 0.5 to about 5 hours, most preferably from about 1 to abou-t 3 hours.
Any suitable organic compounds in combination with t:ttanium tetrachloride can be employed as the extraction/activation liquid. The currently preferred organic compounds are hydrocarbons. Some typical examples include heptane, pentane, 2,3-dimethylpentane, hexane, ben7ene, toluene, xylene, and ethyl benzene. It is currently preferred to use a combination of aromatic and paraffinic hydrocarbons, for example, heptane and toluene. The results obtained will vary depending on the specific extraction/activation liquid employed. For the preferred heptane/toluene/titanium tetrachloride ~- mixture, the heptane would generally account for about 50 to 70 weight percent :! of the liquid, more preferably, the heptane would account for about 54 -to about 62 weight percent of the liquid, ths toluene would generally account for about 30 to 50 weight percent of the liquid, more preferably -the toluene would account for about 3~ to 42 weight percent of the llquid, and the titanium tetrachloride would account for about 1 to about 20 weight percent of the liquid, more preferably about 1 to 10 weight percen-t.
It is currently preferred that after the ex-traction/activation is conducted that the solid component be separated from the liquid component.
This subsequently a-ttained solid componen-t should then again be subjected to an extraction/activation step similar to the previous extraction/activation step. Further examples of various methods to extract/activate the components are disclosed in U.S. patent 4,680,351. A preferred method of preparing the catalyst is disclosed in Example I of this specification.

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~' COCATAL~STS
The catalyst system produced by the foregoing methods disclosed above and in the references cited, and as illustrated in Example I, are ~, " '~

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preferably used in conjunction with a cocatalyst of an organometallic compound. The organometallic compound cocatalys-t is selected from the gro~lp consisting of trialkylaluminums. For example, preferred cocatalysts are triethylaluminum, trimethylaluminum, and triisobutylaluminum. The molar ratio of organometallic cocatalyst to titanium-con-taining catalyst component employed can vary but may range up to about 400 to 1. However, close attention should be paid to the aluminum/titanium mole ratios, in the final total catalyst/cocatalyst package~ because certain mole ratios of these components are preferred over other mole ratios when considering productivity and the weight percent of solubles in the reactor. The term "solubles" is defined in this specification as the amount of soluble polymer left in the monomer, comonomer and/or diluent. The weight percent of solubles is based on the total polymer weigh-t both soluble and insoluble ~See Example VIII).

POLYMERIZATION CONDITIONS
The olefins which can be polymeriæed using this procass are those olefins which ha~e a methyl branch at the 3-position. Fur-thermore, these alpha-olefins should have between about 5 and 21 carbon atoms in the molecule inclusive. Examples of such olefins are 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-heptene, 3-methyl-1-octene, 3-methyl-1-nonene and 3-methyl-1-decene. Additionally, it is within the scope of this invention that these monomars can be copolymerized with other slpha-olefins (fllso called comonomers) such as, for example, etnylene, -- propylene, l-hexene, 4-methyl-1-pentene, 3-ethyl-l-hexene3 l-octene, l-decene, and l-hexadecene. When adding the comonomer to reaction it is preferred that the comonomer be added incrementally or continuously through the polymerization reaction. Incremental or continuous addition of the comonomer is pre~erred because a higher molecular weight copolymer resin is obtained and less reaction solubles are produced. Incremental addition means that the ' :

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11 S~ 3~3 amount of comonomer to be added to the reactor, is divided up into discre-te individual releases in the reactor. For example, if ten mole percent of co-monomer (based on total moles oE monomer and comonomer) is to be added to a reac-tor during the next hour, one mole percen-t of comonomer could be added every 6 minutes, instead of dumping all o the comonomer in at the start of the copolymerization. Continuous addition means that monomer is added through all, or essentially all, of the polymer:Læation period. This addition can be uniform through the addition or its rate can be increased or decreased during the polymerization.
The preferred reactor temperature for polymerizing these monomers i9 in the range of 60C to lZ0C. Preferably it is in the range of 85C to 115C
and most preferably from about 90C to 110C. Temp~ratures high~r than 120C
usually result in catalyst degradation to the point that polymerization results in significantly reduced yield and temperatures below 60~C tend to result in productivlties which are not commercially viabla for these types of monomers. The reactor residence time of the catalyst varies. ~sually, however, lt is in the range of abou-t 0.1 hours to about 4 hours. Nost preferably it i9 In the range of about 0.25 hours to about 2 hours and most preferably it is in the range of about 0.5 hours to about 1.5 hours.
Additionally, hydrogen can be charged to -the reactor in order to facili-tate the polymeriæation. However, it should be noted that higher levels of hydrogen after a certain point tend not to significantly effect the productivity oE the polymeriæation reaction. I-t should also be noted, however, that this hydrogen effect seems related to the particular type of monomer used in the polymerization. Therefore, some leeway ~nd experimenta-tion should be done in order to determine the optimum hydrogen concentration when considering the various production variables (see Example YI). The production of poly(3-methyl-1-butene) sugges-ts that the aluminum/titanium mole ratio should also be regulatcd. The data indicate that an aluminum/titanium mole ratio .

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between about 10 to abou-t 60 is best. Preferably, however, this ratio is between about 15 to about 55 and most preferably it is between 25 to 50, for the polymeriza-tion of 3-methyl-1-butene.

Examples These examples are provided to further flSSiSt a person skilled in the art with understanding this inven-tion. The particular reactants, conditions, and the like, are intended to be ~enerally illustrative of this invention and are not meant to be construed as unduly limiting the reasonabla scope of this invention. Examples I-IX illustrate the polymerization process and the variety of different settings. Example X describes the b~nefit of copolymerization in a variety of ways.

Example I: Preparation of a Tvpical Catalyst Used in This Invention This example illustrates a preferred method of making the catalyst.
This method is similar to those methods disclosed in U.S. Patents 4,555,496 and 4,680,351 which are hereby incorporated by reference.
The components of the catalys-t were comminuted in a nitrogen purged 250 liter ball mill. To this ball mill was added:
[1] 130.0 pounds of anhydrous magnesium chloride (MgCl2);
[2] 24.5 pounds of aluminum chloride (AlCl3).
The temperature of the ball mill was then brought to a temperature in the range of 30C to 34C. The contents of the ball mill were -then ball milled for 16 hours. During this ball milling and in all subsequent ball millings the temperature was maintained between 30C and 34C. To the ball mill was then added:
[3] 41.4 pounds of ethyl benæoate (C6HsC02C2Hs).

The ethyl benæoate was slowly added over a period of 1 hour while the ball mill was milling. After the addition of ethyl benzoate was completed : . , ' ' -: . ~ '; . . ~ `

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13 ~J~3~3 the ball mill was allowed -to mill an addi-tional 2 hours. To the ball mill was then added:
[4] 24.8 pounds of methoxybenæene (C6HsOCH3).
The methoxybenzene was slowly added over a period of 0.5 hours while the ball mill was milling. ~fter the addition of the me-thoxybenzene was completed the ball mill was allowed to mill an additional 2.5 hours. To the ball mill was then added:

[5] 17.7 pounds of titanium tetrachloride (TiCl~).
The titanium tetrachloride was slowly added over a period of 0.5 hours while the ball mill was milling. After the addition of the titanium tstrachloride was completed the ball mill was allowed to mill an additional 16 hours. The resulting solid was then recovered from the ball mlll and screened to remove ~20 mesh course material. A portion of the finer resulting matarial obtained af-tex the screening was subjected to -the following double activation/extraction process. To a 20 gallon glass ~acketed stainlass steel reactor equipped with a 200 rpm agitator the following was added:
[1] 26.0 pounds of the screened material;
[2] 46.8 pounds of hep-tane (C~13(CH7)sCH3);
[3] 31.2 pounds of toluane (C6H5CH3);
[4] 4.2 pounds of tltanium tetrachloride.
The reactor was then heated to a temperature between 95C and lOO~C.
This temperature was maintained for 2 hours. During these heating steps the reac-tor was constantly agitated. The resulting mixture was then immediately filtered to recover the solid material. To the reactor was then added:
[5] the filtered solid material;

[6] 46.8 pounds of heptane;

[7] 31.2 pounds of toluene;

[8] 4.2 pounds of titanium tetrachloride.

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14 ~ 3 The reactor was then heated to a tempera-ture between 95C and 100C.
This temperature was maintained for 2 hours. During these heating steps -the reactor was cons-tantly agitated. The rasulting mixture was then immediately filtered to recover the solid material. To the reactor was then added:

[9] the solid material;
~ 10] 26.0 pounds of heptane.
The reactor was then agitated for 0.25 hours. After thc agitation was complete the resulting mixture was filtered to recover the solid material.
To this solid material was added:
[11] 26.0 pounds of heptane.
The resulting slurry was then collected as the catalyst used in th~
following inventive examples.

Example II: Initial Catalyst Survey In this example a variety of transition metal catalysts were evaluated at reac-tion temperatures between 60C and 120C in a series of 4 hour runs. A total of 8 different catalysts were used in this initial survey.
These catalysts are described in Table IIA.

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Table IIA

Welght Percent of Metal Components ! b Catalyst Ti Mg Al Comments _ _ _ _ _ _ _ _, _ 2.2~0.9 .68 Catalyst used in this invention B 1.718.3 .
C 15.5 - - Titanium trichloride with 50 wt%
polypropylene prepolymer D 21.8 - - Ti-tanium Chloride with 30 w-t%
stereoregulator E 31.1 - - Titanium trichlorido F 0.4 3.9 - Catalyst with 80 wt% polypropylene prepolymer G 2.019.5 - Same catalyst as F without -the prepolymer H 24.1 - 4.5 .. _ . ... ~
- b"-" indicates zero or a trace amount.
Catalysts B through H are catalysts known for their polymerization ability with propylene.
CThe weight percents were determined by Plasma analysis.

A reactor residence time oE 4 hours was used in all runs. This time was selected on the basis of early work which suggested tha-t longer residsnce times are necessary in order to optimize polymer yield. It has since been discovered that shorter rosidence times are adequate for some of the ca-talysts surveyed. Triethylaluminum was used as the cocatalyst for this study.
Regardless of catalyst charge, the samo amount of triethylaluminum (TEA) (4.63mmol, 5.0 mL of a 15 wt% solution in heptane) was used in each run. This -lead to the broad disparity in the aluminum/titanium ratios shown in Table IIB
below.
All of the polymerizations were performed in a one gallon, stainl~ss ~` steel Autoclave Eng:Lneers reactor. Under a purge of nitrogen, the reac-tor was `:

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charged with the selected catalystJ 5.0 m:illiliters of trie-thylflluminum solution, and then sealed. 3-Nethyl-l~butene was drained into the reactor from a 2.0 liter reservoir followad by a press~lre drop of 25 psig from a 300 milliliter cylinder of hydrogen. The reactor was then heated -to the desired temperature and held there for 4 hours. After this time, a mixture of acetylacetone and propylene oxide were added to deactivate the catalyst.
Unreacted monomer was then drained from the bo-ttom of the reactor into fl grounded aluminum pan. The polymer was -then washed with 2 liters of n-heptane at 80C for 30 minutes, then removed from the reactor, and dried in an aluminum pan at 75C for 2 hours.

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It is apparent from Table IIB that inventive catalys-t ~ is by far the best catalyst of those screened for this type of polymerization. Although this productivity is much less than the cata]yst productivity reported for such commercial production operations as polyethylene and polypropylene, it is still at least 2 to 4 times higher than what has previously been reportsd in the llterature for the polymerization of 3-methyl-1-butene~ Furthermore, the yield of poly(3-methyl-1-butene) with catalyst A is high enough to produce this specialty polymer in a commercially viable process.

xample III: Polymerization of 3-methyl-1-butene~ 3-methYl-l-Pentene and 3-ethYl-l-hexene A further study was done to compare the productivity of various catalysts for polymerizing the above-mentioned monomers. All of the runs were performed using a procedure similar to the procedure in Example II.

.

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Table III

Catalyst Catalyst Yield Reactor-Solubl~s Prod~lctivity Run Type ~onomer (g) (g) (g) (wt.%) (g/g) 3 A 3MB1 0.1593201.70 17.39 7.9 1375

11 Cl 3MB1 0.625866.04 5.74 8.0 229 19 E 3NB1 0.5092175.97 8.68 4.7 363 33 Al 3NB1 0.149326.70 30.47 53.3 383 . _ _ _ _ 34 Al 3MP1 0.164115.09 45.46 75.0 369 A2 3MP1 0.1712114.06 23.65 17.1 804 36 A 3MP1 0.1763375.23 23.34 5.6 2261 37 C' 3MP1 0.994763.17 31.39 33.1 190 38 D2 3MP1 0.508189.88 23.10 20.4 31 39 A 3EH1 0.30494.53 12.04 72.6 5 lSee footnota 1 in Table IIB.
- 2See footnote 2 in Table IIB
3Catalyst Al is made the same way as Catalyst A except no electron donors are added and Catalyst Al was not subjected to a double activation/extraction.
Catalyst A2 is mada the same way as Catalyst A except Catalyst A2 was not -~ subjected to a double activation/extraction. Runs 3, 11, 19, and 33polymerized 3-methyl-1-butsne (3MBl) a-t 100C and 4 hour reactor residence - time with 25 psig of hydrogen. Runs 34-38 polymerized 3-methyl-1-pentene (3MPl) at 100C for 2 hour reactor residence time and 50 psig of hydrogen.
Runs 39 polymerized 3-ethyl-1-hexene (3EHl) at lOO~C for a 2 hour reactor residence time with 50 psig of hydrogen.
The data clearly show that catalys-t A performed better than any of the other catalysts in ~he series. However, it is interesting -to note that the polymerization of 3-ethyl-1-hexene did not perform as well. For example, comparing runs 36 with 39, it is apparent that 3-methyl-1-pentene polymerized to yield about 4200 percent more polymer than 3-ethyl-1-hexene. Upon closer inspection it is also apparent that -the polymerization of 3-ethyl-1-hexene generated about 1200 percent more solubles than did the 3-methyl-1-pentene.
Therefore, it can clearly be seen that while catalyst A is not particularly effective in the polymerization of 3-ethyl-1-hexene it is the catalyst of choice for polymerizing alpha-olefins which havs a methyl branch at the - 3-position.

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21 ~ 3~3 Example IV: Reactor Temperature EfEect on the Polymerization of 3MBl and 3MPl with Catalyst A
~ serles of runs was conducted to determine the optimum temperature at which maximum productivity i5 obtained. The procedure utilized to attain .
the data below was similar to the procedure used in Example II. The specified temperature was used for 2 houls with 50 psig of hydrogen and 5.0 milliliters of TEA solution. The data are summarized below.

Table IV

Amo~mt of Reactor Catalyst Polymer Reactor-Solubles Productivity Run Monomer Temp (C) (g) Yield (g) (wt%) (g/g) 3MBl 50 0.262992.46 13.3212.6 402 41 3MB1 60 0.2792162.92 17.319.6 646 42 3MB1 70 0.2844199.11 20.379.3 772 43 3MB1 80 0.3506279.43 27.909.1 877 44 3MB1 90 0.3531310.29 25.797.7 952 3MB1 100 0.3388338.61 28.907.9 1085 46 3MB1 110 0.2920257.75 28.029.8 979 47 3MB1 120 0.3031228.57 25.139.9 837 48 3MP1 60 0.2312241.80 32.7311.9 1187 49 3MP1 80 0.1856286.71 27.258.7 1692 3MP1 90 0.1536297.07 22.457.0 2080 51 3MP1 95 0.1766377.40 19.494.9 2247 52 3MP1 100 0.1763375.23 23.345.9 2261 53 3MP1 110 0.1818296.62 25.207.8 1770 54 3MP1 120 0.1562204.00 26.6511.6 1477 ____ The data in Table IV show the effect of the reactor temperature on 3MBl and 3MPl polymerization. To maximize productivity, the data indicate that the reactor temperature range between 60C and 120C is preferred.

Operating within this temperature range also minimizes the total level of solubles generated. Consequently, it it preferred to operate within these - : . : :

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temperature ranges listed in Table IV in order to generate maximum productivity whil~ minimizing the amoun-t of reactor solubles.

.

Example V: Reactor Residence Time Effect on th~ Polymerization of 3MBl and 3MPl with Catal~lst A
~ series of runs was conducted to show -the effect of reactor residence time on the polymerization of 3MBl and 3MPl. The procedure utilized in this run was slmilar to the procedure utilized in Exampl~ II. A reactor temperature of 100C for the specified residence time was used along with 50 pslg of hydrogen for runs 63-68 and 25 psig o~ hydrogen ~or runs 55-62. The data are summarizsd below.

Table V

Amount of Residence Catalyst Polymer Reactor-Solubles Productivity Run Monomer Time thr) (g) Yield (g) (wt%) (g/g 3MB1 0.25 0.144772.15 9.09 11.2 561 56 3MB1 0.50 0.1636126.73 13.80 9.8 859 57 3MB1 0.75 0.1445122.80 12.81 9.5 938 58 3MBl 1.00 0.1558148.63 15.77 9.6 1055 59 3MB1 2.00 0.1512148.28 14.84 9.1 1079 3MB1 3.00 0.1683176.98 16.22 8.4 1148 61 3MBl 4.00 0.1593201.70 17.39 7.9 1375 62 3MB1 5.00 0.1703204.53 14.90 6.8 1288 63 3MP1 0.25 0.2398215.88 24.02 10.0 1000 64 3MP1 0.50 0.1597259.63 27.65 9.6 1799 3MPl 1.00 0.1784316.15 21.85 6.5 1895 66 3MP1 1.50 0.1654282.78 20.62 6.8 1834 67 3MP1 2.00 0.1838335.26 21.80 6.1 1943 68 3MP1 3.00 0.1811380.57 21.43 5.3 2220 :

The data in Table V above illustrate that the productivity increases from a residence -time of 0 hours (time a-t which the reactor reaches the -~ desired operating temperature) to about 1 hour, after which little gain in .,,~

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~ 23 ~ 3 ~ 3 productivity is reallzed. While not wanting to be bound by theory, it is believed that after about 1 hour the catalyst begins to decay which leads to only modest gains in productivity at longer residence timss. Additionally, it ~hould be noted that the amount of react:or solubles generatsd in thiæ reaction tends to decrease with residence time. Therefore, it is apparent that there are competing considerations between lowering the amoun-t of reactor solubles by increasing the reactor residence time and generating maximum economical productivity with a lower reactor residence time.

Example VI: Hydro~en Concentration Effect on the Polymerization of 3MBl and 3MPl with Catalvst A
A series of runs was done to illustrate the effect of the hydrogen concentration on the polymerization of 3MBl and 3MPl. These runs were conducted using procedures similar -to the procedures used in Example II. A
reactor temperature of 100C was used for a 2 hour residence time with the specified amount of hydrogen. The data are summarized below.

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Table VI

~-~ Amount of , Hydrogen Catalys-t Polymer Re.actor-Solublas Productivity Run Monom~r (psig) (g)Yi~ld (g) (wt%) (g/g ; 69 3MB1 0 0.3828113.52 6.40 5.3 313 3MB1 25 0.4119309.98 14.92 4.6 789 71 3MB1 50 0.4278397.64 18.30 4.4 972 72 3MB1 75 0.4399471.65 20.32 4.1 111~
73 3MB1 100 0.4217491.10 21.77 4.2 1216 74 3MB1 150 0.4244526.05 17.44 3.2 1281 3MB1 200 0.4214539.97 17.54 3.2 1323 76 3MB1 300 0.3996513.23 24.01 4.5 1344 77 3MBl 400 0.3938509.27 31.02 5.7 1372 78 3MP1 0 0.16496.40 12.36 65.9 114 79 3MP1 25 0.2077203.50 12.33 5.7 1039 3MP1 50 0.1833307.82 24.94 7.5 1815 81 3MP1 100 0.1694336.91 26.50 7.3 2145 82 3MP1 150 0.2048413.88 25.64 5.8 2146 83 3MP1 200 O.lR09449.58 26.96 5.7 2634 84 3MP1 400 0.1805497.79 28.74 5.5 2917 .
.~

The data above illustrates that the productivity starts to level off aftor a charge of 100 psig of hydrogen. Since, in general, increased hydrogen levels resul-t tn hlgher flow rates, it is usually desirable to keap the hydrogen level at an amount lower -than what would optimlze productivity. That 1SJ productivity is sacrificed at the expense of processing characteris-tics and properties.

,:
Example VII: Cocatalyst Survey with Catalyst A
In the previous catalyst screening study (see Example II}, triethylaluminum was used exclusively as the cocatalyst for polymerizing 3MBl.

To determine if some other cocatalyst provided a better result with the catalyst used in this invention, a series of runs was performed varying the cocatalyst from run to run. To insure the comparisons would be meaningful, :

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the aluminum to titanium mole ratio (Al/Tl) and all of the reactor conditions were held constant. The procedure u-tili~ed in this example was similar to the procedure utilized in Example II. A reactor temperature of 100C and a reactor residence tlme oE 2 hours was used. Additionally, 50 psig of hydrogen was used and -the Al/Ti mole ratio was equal to about 40. The data are summarized below.

Table VII

ProductivitySolubles (wt%) RunCocatalyst(g/g) Reactor Flow Rate ... .
TMA 940 7.5 95 86 TEA 1199 8.4 48 87 TIBA 983 5.8 35 88 DEAC 521 10.9 255 89 EASC 40 38.8 > 1000 90 EADC 10 100.0 (1) TMA = Trimethylaluminum (2) TEA = Triethylalumlnum (3) TIBA = Triisobutylaluminum (4) DEAC = Diethylaluminum chloride (5) EASC = Ethylaluminum sesquichloride (6) EADC = Ethylalumlnum dichloride (7) The flow rate was measured using the procedure similar to ASTM
D1238-82. This flow rate was measured a-t 320C under a 5 kilogram load after a 5 minute hold period. During the hold the resin was weighted with a 360 gram load.

None of the other cocatalysts screened were any more effective than TEA for optimizing the productivity of 3MBl. All of the trialkylaluminums (runs 85-87) were effective cocatalysts. Substituting alkyl groups with chlorides (as in runs 88-90~, however, resulted in progressively lower productivities and higher reactor solubles.

:

26 ~ 3 ~ 3 Example VIII._ The Aluminum/Titanium Mole Ratio Effect on the Polymerization of 3MBl A series of runs with increasing amount of TEA was used to determine the effect of the Al/Ti mole ratio on the polymerization of 3MBl. The procedure utilized was similar to the procedure utilized in E~ample II. A
reactor temperature of 100C for 2 hours was used. Additionally, a 50 psig hydrogen charge was utilized along with TEA as a cocatalyst.

.

Table VIII

Al/Ti ProductivitySolubles (wt%) RunNole Ratio (g/g) Reactor Flow Rate -, 91 1 0 ` 92 2.5 10 50.0 ---933.75 25 31.7 ---94 5 199 17.6 959 564 8.8 97 96 15 945 6.8 71 97 20 963 5.7 59 98 30 1022 4.9 47 99 40 1061 6.2 48 100 50 1076 6.9 83 101 60 1124 6.6 80 The data above show that a Al/Ti mole ratio of 15 results in near optimum results. Increasing levels of TEA do not afford significant increases ln productivity, but increasing the Al/Ti mole ratio to almost 50 tended to minimize the polymer flow rate. Furthermore, an Al/Ti mole ratio of 30 - appears to be optimum for minimizing the amount of reactor solubles.
~ Consequently, it is clear to see that tha Al/Ti mole ratio should preferably ;~ be between about 10 to about 60.

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Example IX: The Effect of a TEA/DEAC_Cocatalys Mixture _n the Polymerization oE 3MBl In the polymerization of propylene with certain Ziegler type catalysts, a mixture of TEA and DEAC as a cocatalyst system has been shown to result in enhanced productivity at a specific compositioll of the cocatalyst mixture. To determine if such an effect might occur in the polymerization of 3MBl with the catalyst used in this invention, a series of runs was performed in which the composition of the TEA/DEAC cocatalyst mixture was constantly changed. The procedure utilized in this example was similar to the procedure utilized in Example II. A reactor temperature of 100C for 2 hours was utilized. Additionally, 50 psig of hydrogen was included and the Al/Ti mole ratio was held constant at about 40. Tha data are summarized below.

Table IX

Productivity Solubles (wt70) Run% DEAC ~g/g) Reactor Flow Rate 102 0 1199 8.4 73 103 10 1175 8.7 74 104 20 1076 7.8 109 105 30 1054 8.4 137 106 40 1036 8.3 133 107 50 973 8.3 182 108 60 9~4 7.4 13~
109 70 884 7.5 1~6 110 80 751 9.O 177 111 90 536 7.4 233 112 100 521 10.9 300 :

As shown in the data above, enhanced produc-tivity was not observed.

Productivity dropped as the percent composition of DEAC in the cocatalyst mixture was increased. An opposite effect was observed in the flow rate.

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28 ~ 3 Therefore, the effect observed in propylene type polymerizations was not observed in the polymerization of 3-methyl-1-butene.

Example X: Gopolymerization with 3-methyl-1-butene A series of runs were conducted to determine the productivity of this catalyst with 3-methyl-1-butene and a comonomer. The procedure utilized, in this example, was similar to the procedure utilized in Example II. A
reactor tempera-ture of 100C for two hours was used. Additionally~ a 50 psig hydrogen charge was utilized along with 5.0 milliliters of TEA as a cocatalyst. The data are summarized helow.

Table X

Mol % Comonomer Productivity Run Comonomer~ Char&ed Found2 ~g/g) ... _ ............ .... _ _ ... _ . . ...
113 None 0.00 0.00 969 114 l-Hexene 0.25 0.46 1064 115 l-llexene 0.50 0.96 990 116 l-Hexene 1.00 2.06 1020 117 l-Hcxene 2.50 4.36 1097 118 l-Hexene 5.00 7.82 1170 119 l-Decene 0.25 0.44 1007 120 l-Decene 0.50 0.46 1011 121 l~Decene 1.00 1.23 989 122 l-Decene 2.50 3.09 1026 123 l-Decene 5.00 4.17 1251 _ _ _ 124 l-Hexadecene 0.25 0.22 1085 125 l-Hexadecene 0.50 0.45 1036 126 l-Hexadecene 1.00 0.79 967 127 l-Hexadecene 2.50 1.37 1314 128 l-Hexadecene 5.00 3.19 1560 lComonomer added in quarter additions at T= 0,30,60, and 90 minutes.
2Determined by infrared analysis.
As can be seen from the above data, various comonomers can be : .;
- copolymerlzed with 3-methyl-1-butene at high productivities, (i.e., ~ 700 ~:

.

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29 ~ 3~3 g/g). The above data was analyzed to determine if there was a correlation between -the amo~nt of comonomer charged to the reactor and the amount of comonomers incorporated in the resulting resln. The results are presented below.

Table X-A: Analys:is of l-Hexene Data RunComonomer Charge Comonomer Incorporation (Mole Percent) Number(Mole Percent) Actual Calculated 113 o.oo o.oo 0 0O
114 0.25 0.46 0.51 115 0.50 0.96 1.01 116 1.00 2.06 2.02 _ Tha calculated mole percents come from the linear equation indicated by the data. Using the mole percent charge as the x-coordinate and using the actual mole percent as the y-coordinate, a linaar equation in the form of y=mx+b was deduced. (m ts equal to the slope of the line and b is equal to the y-intercept, which in all cases is ~ero because wi-thout a comonomer charge no comonomer can be incorporated). This linear equation was y=2.02x. The correlation of thls line was 0.9988, where a correlation of plus or minus 1.00 is considered a perfect correlation. Consequently, the amount of comonomer charged -to the reactor is a good predictor of the amount of comonomer incorporated for l-hexene.
A similar analysis was done on l-decene. The results are presented below.

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~ 3 Table X-B: Analysis of l-Decene Data Run Comonomer Charge Comonomer Incorporation ~Mole Percent) Number (Mole Percent) Actual Calculated 113 o.oo 0 0O 0 0O
119 0.25 0.44 0.30 120 0.50 0.46 0.61 121 1.00 1.23 1.20 The eq~lation of the line that generated the calculated data was y=1.20x. The correlation of this line was O.Y747. Consequently, the amount of comonomer charged to the reactor is a good predictor of -tha amount of comonGmer incorporated, for l-decene.
A similar analysis was done on l-hexadecene. The results are presented below.
:
Table X-C: Analysis of l-Hexadecene Data . . _ . . _ .
Run Comonomer Charge Comonomer Incorporation (Nole Percent) Number(Nole Percent) Actual Calculated -. --. -- _ . . . .. _ . _ 113 o.oo o.oo 0 0O
124 0.25 0.22 0.20 125 0.50 0.45 0.41 126 1.00 0.79 0.82 The equation of the line that generated the calcula-ted data was y=0.82x. The correlation of this line uas 0.9960. Consequently, the amount of comonomer charged to the reactor is a good predictor of the amount of comonomer incorporated, for l-hexadecene.
Using procedures simllar to those used to calculate the data in Tables X-A through X-C, diflerent methods of comonomer addition were comp-red.

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31 ~ 3 . The polymerizations were conducted in a manner similar to the polymeriza-tion - proceduro in Exanlple II. A reactor temperature of 100C Eor two hours WflS
used. Additionally, a 50 psig hydrogen charge was utilized along with 5.0 milliliters of TEA as a cocatalyst. The results are summarized below.
., Run Comonomer Amount Method Amount Weight of Flow Activity Number Added Added Addedl incorporated2 Solubles Rate3 (g/g) . . .
129 l-decene 0.40 A 0.88 9.1 114 817 130 l-decene 0.60 A 1.3212.0 90 831 131 l-decene 0.60 C 0.77 9.5 68 1026 132 l-decene 1.00 C 1.28 8.3 65 1019 133l-hexadecene 0.20 A 0.30 - 91 1191 134l-hexadecene 0.40 A 0.60 - 330 1168 135l-hexadecene 0.20 B 0.23 9.4 43 1089 136l-hexadecene 0.60 C 0.5210.8 39 992 _ _ __ . . .
lMethod A was adding all of the comonomer to the reactor before heat was added to the system. Nethod B was quarter additions of the comonomcr at Time=0,15,30, and 45 minutes. Method C was quarter additions at Time=0,30,60, and 90 minu-tes.
Amount incorporated was calcul~tcd usin~ linear analysis -techniqucs similar to those in Table X-A through X-C.
3See Note 7, Table VII

It is apparent that changing the method of comonomer addition from a ba-tch method (method A) to a incremental method (methods B~C) lowers the flow rate indicating an increased molecular weight. (Compare runs 131 vs. 129, 132 vs. 130~ 135 vs. 133, 136 vs. 134.) It is further suggested that as the comonomer addition becomes more continuous a further lowering of the flow rate , ~ can be expected. Furthermore, another benefit is the lowering of -the amount i of solubles wbich can significantly affect the economics of a polymerization . process.

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Claims (24)

THAT WHICH IS CLAIMED IS:

1. A process comprising contacting under polymerization conditions:
(A) at least one trialkylaluminum cocatalyst;
(B) at least one alpha-olefin which has a methyl branch at the 3-position and which has at least five carbon atoms, and at least one comonomer; with (C) a catalyst prepared by the process comprising comminuting (a) at least one aluminum halide (b) at least one electron donor (c) at least one metal compound wherein the metal is selected from the group consisting of chromium, hafnium, molybdenum, niobium, tantalum, titanium, tungsten, vanadium, zirconium, and mixtures thereof, and (d) a salt compound wherein at least one component of said salt compound is selected from the group consisting of barium, beryllium, calcium, magnesium, strontium, zinc, and mixtures thereof to produce a comminuted solid then subjecting said comminuted solid to a double activation-extraction step;
to produce a copolymer at a productivity level of at least 700 grams of copolymer per gram of catalyst utilized.

2. A process according to claim 1 wherein said polymerization conditions comprise a polymerization temperature between about 60°C and 120°C, a reactor residence time between about 0.1 hours and 4 hours, and an amount of hydrogen.

3. A process according to claim 2 wherein said comonomer is added incrementally during said reactor residence time.

4. A process according to claim 2 wherein said comonomer is added continuously during said rector residence time.

5. A process according to claim 1 wherein said aluminum halide is aluminum trichloride.

6. A process according to claim 1 wherein said electron donor is selected from the group consisting of ethylbenzoate, methoxybenzene and mixtures thereof.

7. A process according to claim 1 wherein said metal in said metal compound is titanium.

8. A process according to claim 1 wherein said metal compound is titanium tetrachloride.

9. A process according to claim 1 wherein said component of said salt compound is magnesium.

10. A process according to claim 1 wherein said salt compound is magnesium chloride.

11. A process according to claim 1 wherein said trialkylaluminum cocatalyst is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum and mixtures thereof.

12. A process according to claim 1 wherein said alpha-olefin is selected from the group consisting of 3-methyl-1-butene, 3-methyl-1-pentene and mixtures thereof.

13. A process comprising contacting under polymerization conditions:
(A) a trialkylaluminum cocatalyst selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and mixtures thereof;
(B) 3-methyl-1-butene and at least one comonomer; with (C) a catalyst prepared by the process comprising comminuting (a) aluminum chloride (b) an electron donor selected from the group consisting of ethylbenzoate, methoxybenzene, and mixtures thereof (c) titanium tetrachloride (d) magnesium chloride to produce a comminuted solid then subjecting said comminuted solid to a double activation-extraction step;
to produce a copolymer at a productivity level of at least 700 grams of copolymer per gram of catalyst utilized.

14. A process according to claim 13 wherein said polymerization conditions comprise a polymerization temperature between about 90°C and 110°C, a reactor residence time between about 0.25 hours and 3 hours, an amount of hydrogen, and an aluminum/titanium mole ratio between about 10 and 60.

15. A process according to claim 14 wherein said comonomer is added incrementally during said reactor residence time.

16. A process according to claim 14 wherein said comonomer is added continuously during said rector residence time.

17. A process comprising contacting under polymerization conditions:
(A) a trialkylaluminum cocatalyst selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and mixtures thereof;
(B) 3-methyl-1-pentene and at least one comonomer; with (C) a catalyst prepared by the process comprising comminuting (a) aluminum chloride (b) an electron donor selected from the group consisting of ethylbenzoate, methoxybenzene, and mixtures thereof (c) titanium tetrachloride (d) magnesium chloride to produce a comminuted solid then subjecting said comminuted solid to a double activation-extraction step;
to produce a copolymer at a productivity level of at least 700 grams of copolymer per gram of catalyst utilized.

18. A process according to claim 17 wherein said polymerization conditions comprise a polymerization temperature between about 60°C and 120°C, a reactor residence time between about 0.25 hours and 3 hours, and an amount of hydrogen.

19. A process according to claim 17 wherein said comonomr is added incrementally during said reactor residence time.

20. A process according to claim 17 wherein said comonomer is added continuously during said rector residence time.

21. A composition of matter made by the process according to claim 1, which prior to subjecting said composition of matter to any catalyst removal process, contains less than 27 parts per million by weight of titanium.

22. A composition of matter made by the process according to claim 13, which prior to subjecting said composition of matter to any catalyst removal process, contains less than 27 parts per million by weight of titanium.

23. A composition of matter made by the process according to claim 17, which prior to subjecting said composition of matter to any catalyst removal process, contains less than 27 parts per million by weight of titanium.

24. A composition of matter, which prior to subjecting said composition of matter to any catalyst removal process, contains less than 27 parts per million by weight of titanium, and where said composition of matter is made from an alpha-olefin which has a methyl branch at the 3-position and a comonomer.