KR20000010908A - Polymerization reaction catalyst accelerator - Google Patents

Abstract

PURPOSE: In a producing method of alpha-olefine copolymer, transition metal catalysts, most commonly V catalyst, and organic-aluminium cocatalysts are added to reactant mixture and act as catalysts. Catalyst activators or accelerators can be selected for the intention of catalyst efficiency and the regulation of polymer molecular weight. CONSTITUTION: The invention relates to the compounds of formula 4, preferably the compounds of formula 5. In formula 1, n is 1, 2, 3, X1 and X2 are independently C or Br, A is O or S, R1 is H or alkyl, aryl, alkylidene, or CH2OR, R3 is H, Cl, Br, or OR6, and R4 is H, alkyl, aralkyl, alkenyl or aryl. And R5 is H, alkyl, aralkyl, alkenyl or aryl, and R6 is H or alkyl, wherein R3 do not exist when R2 is alkylidene.

Description

Polymerization Catalyst Promoter

Field of invention

The present invention relates to novel derivatives of halo-but-3-enoic acid and esters useful as catalyst promoters in ethylene polymerization. The present invention also relates to a process for the preparation of alpha-olefin polymers using the novel derivatives of the halo-but-3-enoic acid and esters, wherein ethylene, at least one polymer alpha-olefin monoma and, optionally, a non-conjugated diene Polymerization together forms an alpha-olefin copolymer.

Background of the Invention

The polymerization of alpha-olefins to prepare alpha-olefin copolymers is well established in the art. In these polymerization reactions, transition metal catalysts, most often vanadium catalysts, and organic-aluminum promoters are added to the reaction mixture to catalyze the polymerization reaction. Catalytic activators or accelerators may also be employed to enhance catalyst efficiency and / or control the polymer molecular weight.

US patent application Ser. No. 08 / 372,689, filed Jan. 12, 1995, which now describes a process for the polymerization of ethylene, in which the process specifically comprises a catalyst promoter compound of the formula

Or in the presence of a catalyst promoter compound of the formula:

In particular, n is 1, 2, 3 or 4; X, X ¹ and X ² are halogen; R ¹ is hydrogen, halogen or alkyl; R ² is hydrogen, halogen, alkyl, alkoxycarbonyl; A is O or S; And R ³ is hydrogen, alkyl, alkenyl or aryl.

EP 0 134 079 discloses a process for the preparation of polyalpha-olefins, in which the process is carried out in particular in the presence of a catalytic activator of the formula

Wherein X is chlorine or bromine, R ¹ and R ² are hydrogen, bromine or chlorine and R ³ is a C ₂ -C ₁₉ alkoxy carbonyl group.

It is an object of the present invention to provide derivatives of novel halo-but-3-enoic acids and esters. Another object of the present invention is to provide novel catalyst promoters useful in the process for preparing alpha-olefin polymers.

Summary of the Invention

The present invention relates to compounds of the formula:

here,

n is 1, 2, 3 or 4;

X ¹ and X ² are each independently chlorine or bromine;

A is O or S;

R ¹ is hydrogen or C ₁ -C ₁₆ alkyl;

R ² is C ₁ -C ₁₆ alkyl; C ₆ -C ₁₆ aryl; C ₁ -C ₄ alkylidene or CH ₂ OR ⁵ ;

R ³ is hydrogen, chlorine, bromine or OR ⁶ ;

R ⁴ is C ₁ -C ₁₆ alkyl; C ₇ -C ₁₆ aralkyl; C ₂ -C ₁₆ alkenyl, or C ₆ -C ₁₈ aryl;

R ⁵ is hydrogen, C ₁ -C ₁₆ alkyl; C ₇ -C ₁₆ aralkyl, C ₂ -C ₁₆ alkenyl, or C ₆ -C ₁₈ aryl; And

R ⁶ is hydrogen or C ₁ -C ₁₆ alkyl,

Wherein if R ² is C ₁ ~C ₄ alkyl Li indenyl, R ³ is not present.

Description of invention

Preferably, the present invention relates to a compound of the following formula.

here,

n is 1 or 2, more preferably 1;

X ¹ and X ² are each independently chlorine or bromine, more preferably chlorine;

A is O or S, more preferably O;

R ¹ is hydrogen or C ₁ -C ₆ alkyl, more preferably hydrogen or C ₁ -C ₄ alkyl;

R ² is C ₁ -C ₆ alkyl; C ₁ -C ₄ alkylidene, or CH ₂ OR ⁵ , more preferably C ₁ -C ₄ alkyl, C ₁ -C ₂ alkylidene or CH ₂ OH;

R ³ is hydrogen, chlorine, bromine or OR ⁶ , more preferably hydrogen or chlorine;

R ⁴ is C ₁ -C ₆ alkyl; C ₂ -C ₆ alkenyl, or C ₆ -C ₁₂ aryl, more preferably C ₂ -C ₄ alkyl, C ₂ -C ₄ alkenyl, phenyl or naphthyl;

R ⁵ is hydrogen, C ₁ -C ₆ alkyl; C ₂ -C ₆ alkenyl, phenyl or naphthyl; And

R ⁶ is hydrogen or C ₁ -C ₆ alkyl,

Wherein if R ² is alkylidene then R ³ is absent.

Especially preferred are the following compounds; here

n is 1;

X ¹ and X ² are each chlorine;

A is O;

R ¹ is hydrogen or methyl;

R ² is methyl, methylene or CH ₂ OH;

R ³ is hydrogen or chlorine;

R ⁴ is C ₂ -C ₄ alkyl.

Wherein if R ² is methylene then R ³ is absent.

The following compounds illustrate the compounds of the present invention:

In general, the compounds of the present invention may be prepared by heating a compound of the following formula at a temperature of at least about 130 ° C. to prepare a compound of formula (I):

Where n, A, X ¹ , X ² , R ¹ , R ² , R ³ and R ⁴ are as defined above.

Alternatively, the compounds of the present invention may be prepared by heating a compound of the formula in the presence of an acid to produce a compound of formula (I):

Where n, A, X ¹ , X ² , R ¹ , R ² , R ³ and R ⁴ are as defined above.

Compound (P) can be prepared as described in US patent application Ser. No. 08 / 372,689, filed Jan. 12, 1995, currently described in U.S. Patent No. or Canadian Patent No. 1,215,073.

The invention also relates to a process for the polymerization of alpha-olefins. Specifically, the process of the present invention relates to the polymerization of ethylene, at least one monoma and optionally non-conjugated diene whose structure is CH ₂ = CHQ, wherein Q is alkyl having from 1 to 8 carbon atoms. Among the monomas (compounds having the structure CH ₂ = CHQ) preferred for use in the process of the invention are propylene, butene-1, pentene-1, hexene-1, 3-methylpentene-1, heptene-1, and octene-1. There is this. Preferred nonconjugated dienes are 5-ethylidene-2-norbornene, dicyclopentadiene and 1,4-hexadiene. In a preferred embodiment, to prepare a ternary interpolymer, an alpha-olefin having the structural formula shown above, wherein Q is an alkyl of 1 to 3 carbon atoms, is chatted. In a more preferred embodiment, the reactants are ethylene, propylene, and 5-ethylidene-2-norbornene or dicyclopentadiene as nonconjugated dienes. The product of this polymerization process is an ethylene-propylene-nonconjugated diene terpolymer (EPDM).

The polymerization reaction of the present invention comprises: (a) a vanadium-containing compound; (b) organo-aluminum compounds; And (c) catalyzed by a catalyst composition comprising a catalyst promoter. Among the vanadium compounds that can be employed as the catalyst of the present invention are U.S. Patent Application Serial No. 08 / 376,689, filed Jan. 12, 1995, vanadium oxytrichloride, vanadium tetrachloride, Vanadium acetyl acetonate, vanadil bis-diethylphosphate, chloro neopentyl vanadate and vanadium containing catalysts.

In addition to the seamium catalyst, the process of the present invention may utilize an organoaluminum compound as a promoter. Preferably, the organo-aluminum compound is alkyl aluminum or alkyl aluminum halide. Of the halides, chloride is the most preferred. Preferred alkyl aluminum chlorides for use in the present invention are ethyl aluminum sesqui chlorides, ethyl aluminum dichloride, diethyl aluminum chloride and diisobutyl aluminum chloride. Ethyl aluminum sesqui chlorides and diethyl aluminum chlorides are most preferred.

Another additive used in the process of the invention is a catalyst promoter. The compounds of formula (I) may be used alone or in combination with other compounds of formula (I) in the polymerization reaction of the invention.

The catalyst promoter is about 10-95% by weight, preferably 30-90% by weight of at least one compound of formula I, wherein n is 1, and about 50-90% by weight, preferably 10-70% by weight Or a composition comprising a compound selected from compounds of the formula:

here:

X, X ¹ , X ² and X ³ are each independently chlorine or bromine;

A is oxygen or sulfur;

R ⁵ is hydrogen or C ₁ -C ₁₆ alkyl, preferably hydrogen or C ₁ -C ₆ alkyl;

R ⁶ is C ₁ -C ₁₆ alkyl, preferably C ₁ -C ₆ alkyl;

R ⁷ is hydrogen, C ₁ -C ₁₆ alkyl; C ₂ -C ₁₆ alkenyl or C ₆ -C ₁₈ aryl, preferably hydrogen or C ₂ -C ₁₂ alkyl; And

R ⁸ is hydrogen, C ₁ -C ₁₆ alkyl or C ₁ -C ₄ alkylidene, preferably hydrogen or C ₁ -C ₆ alkyl.

Wherein R ⁸ is C ₁ ~C ₄ When alkali indenyl X ³ does not exist.

Compounds of formula (IIA) and (IIB) are US patent application Ser. No. 08 / 372,689, filed Jan. 12, 1995, which may be prepared as described in US patent no. Or Canadian patent 1,215,073. have.

As a more preferred embodiment, compositions useful as catalyst promoters in the polymerization process of the present invention comprise from about 30 to 90% by weight of one or more compounds of formula (I):

About 10 to 70% by weight of one or more compounds selected from the group consisting of:

The polymerization method of the present invention can be usually carried out in the following manner. Vanadium-containing compounds (catalysts), organoaluminum compounds (cocatalysts), catalyst promoters, reaction media, and comonoma are introduced into the reaction vessel. The molar ratio of the catalyst promoter to vanadium of the vanadium-containing compound is preferably 3: 1 to 80: 1, more preferably 6: 1 to 64: 1, and most preferably 12: 1 to 48: 1. Range.

The molar ratio of the promoter to the addition of catalyst and catalyst promoter is preferably about 0.5: 1 to about 50: 1, more preferably about 1.5: 1 to 100: 1, and most preferably about 2.5: 1 to 10 The range is: 1. The catalyst concentration is typically about 1 × 10 ⁻⁸ and 3 × 10 ⁻¹ mol of vanadium per liter of total reaction medium.

The reaction medium is an inert medium, optionally used in combination with liquid alphaolefins, such as pentane, hexane, octane, isooctane, decane, benzene, toluene and the like.

The polymerization reaction is usually carried out in the liquid phase in the temperature range of about -25 ℃ to 70 ℃, the reaction time is usually from about 15 minutes to 3 hours in a few minutes or depending on the specific reaction conditions and materials.

The following examples are provided to illustrate the invention.

Example

Example 1

Preparation of Butyl-2-methyl-2,4,4-trichlorobut-3-enoate

Butyl-2-methyl-4,4,4-trichloro-2-enoate (180 g, 0.7 mol, 87%, assayed by GC) was prepared at a pot temperature of 180-200 ° C. and 156-172 ° C. at a pressure of 85 mm Hg. Was distilled to a vapor temperature of 95.5 grams, a light yellow distillate, which was approximately 43% butyl-2-methyl-2,4,4-trichlorobut-3 by GC / mass spectrometry (MS) and NMR. -Enoate (A), and about 2% butyl-2-methylene-4,4-dichlorobut-3-enoate (B) and 45% residual butyl-2-methyl-4,4,4-trichloro It was shown to contain rho-2-enoate starting material. Scale-up at high pot temperatures (140 ° C.) and relatively high distillation pressures (30 mmHg) resulted in distillates containing 85-95% of analysis in (A). It was composed of a monomer.

Example 2

Preparation of Butyl-2-methyl-2,4,4-trichloro-3-enoate and Butyl-2-hydroxymethyl-4,4-dichlorobute-enoate

Butyl-2-methyl-4,4,4-trichlorobut-2-enoate (65.9 grams, 0.25 mol), 20% aqueous hydrochloric acid (78.6 grams) and tetrabutyl ammonium bromide (4 grams, 0.0124 mol, 5 mol) %) Reaction mixture was heated at 105-110 ° C. for 6.5 hours to give 68% butyl-2-methyl-2,4,4-trichlorobut-3-enoate (A), 8% butyl-2-hydroxy Methyl-4,4-dichlorobut-3-enoate (C) and 10% residual butyl-2-methyl-4,4,4-trichlorobut-2-enoate starting material were produced. When the reaction mixture was heated for 37.5 hours, the product contained 60% (A) and 30% (C). The reaction mixture was then cooled and extracted with 3 x 50 ml of diethyl ether, dried over MgSO ₄ and distilled under vacuum to yield a distillate containing 53% (A) and 32% (C). The identity of (C) was confirmed by GC / MS.

Example 3

Preparation of Butyl-2-methyl-2,4,4-trichloro-3-enoate and Butyl-2-hydroxymethyl-4,4-dichlorobute-enoate

Butyl-2-methyl-4,4,4-trichlorobut-2-enoate and butyl-2-methyl-2,4,4-trichlorobut produced by the thermoisomerization method described in Example 1 A 60/40 mixture of -3-enoate (A) (258 grams, 1 mol), with 105% with 20% aqueous hydrochloric acid (300 grams) and tetrabutyl ammonium bromide (9 grams, 0.028 mol, 2.8 mol%) Stir vigorously at 110 ° C. for 13.5 hours, 75% butyl-2-methyl-2,4,4-trichlorobute-enoate (A), 9% butyl-2-hydroxymethyl-4,4-dichlorobut A crude reaction product containing -3-enoate (C) and 5% residual butyl-2-methyl-4,4,4-trichlorobut-2-enoate was prepared. Water was removed by distillation at 73 ° C./0.1 mmHg, distillation containing 83% A, 9% C and 4% residual butyl-2-methyl-4,4,4-trichlorobut-2-enoate The solution was calculated.

Example 4

Preparation of Butyl-2-methyl-2,4,4-trichloro-3-enoate and Butyl-2-hydroxymethyl-4,4-dichlorobute-enoate

Butyl-2-methyl-4,4,4-trichlorobut-2-enoate and butyl-2-methyl-2,4,4-trichlorobut produced by the thermoisomerization method described in Example 1 A 60/40 mixture of -3-enoate (A) (50 grams, 0.2 mol), with 20% aqueous hydrochloric acid (125 grams) and tetrabutyl ammonium bromide (2 grams, 3 mol%) at 105-110 ° C Vigorously stirred for 22 hours, 69% butyl-2-methyl-2,4,4-trichlorobute-enoate (A), 11% butyl-2-hydroxymethyl-4,4-dichlorobut-3- A crude reaction product was prepared containing enoate (C), 5% residual butyl-2-methyl-4,4,4-trichlorobut-2-enoate and about 8% high boiling point material. Water was distilled off from the crude reaction product at 65 ° C./0.1 mm Hg, containing 85% A, 11% C and 2% residual butyl-2-methyl-4,4,4-trichlorobut-3-enoate The solution was produced.

Example 5 and Comparative Example A

Preparation of EPDM in Solution Using Butyl-2-methyl-2,4,4-trichloro-3-enoate and Comparative Active Agent Butyl-2-methyl-2,4,4,4-tetrachlorobutanoate

A 1 gallon glass reactor equipped with a temperature controlling coil was maintained at 30 ° C., charged with 4.2 moles of ethylaluminum sesquichloride dissolved in 1.5 liter of dry hexane and 1.7 ml of hexane and stirring was started. 500 ml of cylinder was pressurized with 1.5 psig of hydrogen, and then hydrogen was charged into the reactor with sufficient propylene such that the red pressure in the reactor was achieved at 15 psig. Ethylidene norbornene (ENB, 6 ml) was then added to the reactor. The reactor was then pressurized to 50 psig with 1.5 / 1 weight ratio of ethylene and propylene. This gaseous ethylene / propylene mixture was continuously fed as required to maintain the pressure in the reactor at 50 psig throughout the polymerization. Next, vanadium oxytrichloride (VOCl ₃ dissolved in 1.5 ml of hexane, 0.075 moles) and butyl-2-methyl-2,4,4-trichloro-3-enoate or comparative active agent butyl-2-methyl- After 2,4,4,4-tetrachlorobutanoate (1.5 mol in 1.5 ml hexane) was added to the reactor, after 5 minutes a certain amount (4 ml) of ENB was added again. The temperature of the reaction mixture produced in the reactor simply rose to about 45 ° C. at the beginning of the polymerization process, but then cooled and maintained at 30 ° C. After 0.5 h, the reaction was terminated by the addition of isopropyl alcohol and the resulting polymer was washed, separated from the reaction mixture and analyzed. Polymers prepared using butyl-2-methyl-2,4,4-trichloro-3-enoate and a comparative active agent butyl-2-methyl-2,4,4,4-tetrachlorobutanoate The analysis results for the prepared polymers are shown in Table 1 below.

Catalyst efficiency is expressed in pounds of polyma / ₃ pounds of VOCl. Propylene composition and Mooney viscosity (ML1 + 4, 125 ° C.) of the polyma product were measured using ASTM D-3900-86, Method D and ASTM D-1646-87, respectively. The ENB composition of the product was measured as described in Rubber Chemistry and Technology 46 (4), 1019 (1973) from Gardner (I, J, Gardner) and Straight (G. Ver Strate).

Compared to butyl-2-methyl-2,4,4,4-tetrachlorobutanoate, butyl-2-methyl-2,4,4-trichloro-3-enoate has good catalytic efficiency and good propylene. Conversion and molecular weight control (as indicated by Mooney viscosity) were provided.

Example Catalyst Promoter ⁴ Catalytic Efficiency ¹ % Propylene % ENB ML 1 + 4 ＠ 100 ℃ A Butyl-2-methyl-2,4,4,4-tetrachlorobutanoate ² 8154 25 8.2 83 One Butyl-2-methyl-2,4,4-trichlorobut-3-enoate ³ 10077 31 6.9 48

¹ polyma pound / ₃ pounds VOCl

98% Butyl-2-methyl-2,4,4,4-tetrachlorobutanoate as measured by ² GC

³ Preparation, as measured in Example 1, measured by GC. 93% Butyl-2-methyl-2,4,4-trichlorobut-3-enoate, 1% Butyl-2-methylene-4,4 -Dichlorobut-3-enoate, 2% butyl-2-methyl-4,4,4-trichlorobut-2-enoate and 3% butyl-2-methyl-2,4,4,4-tetrachloro Butane Oate

⁴ molar ratio accelerator / vanadium = 20/1

In Examples 6, 7, 8 and 9, the catalyst promoter compositions shown in Table 2 below were used.

Accelerator composition Butyl-2-methyl-2,4,4-trichlorobut-3-enoate Butyl-2-methyl-4,4,4-trichlorobut-2-enoate Butyl-2-4,4,4-tetrachlorobutanoate I 12% ¹ 82% 5% II 43% 44% 10% III 94% 2% 2%

Percentage measured by ¹ GC

Example 6

Preparation of Ethylene-Propylene Copolymer (EPM) in Suspension

3-liter stainless steel stirring autoclave (Buchi, Model BEP 280) with jacketed chiller, immersion tube for ethylene supply, thermocouple well, pressure gauge and ports for introduction of hydrogen, propylene and catalyst components Filled with 780 grams of liquid propylene. The temperature was fixed at 15 ° C. by cooling the jacket with water from the circulation conduit. Sufficient ethylene was then added to increase the reactor pressure by 20 psig. 9.25 mol of diethyl aluminum chloride solution dissolved in 16 ml of hexane from the pressurized bomb was then added to the butch with sufficient hydrogen gas to raise the pressure to 280 psig. Next, 11 ml of hexane solution containing 0.08 mol of vanadium oxytrichloride and 1.28 mol of accelerator composition II (from Table 2) were charged from the pressurized bomb all at once. Subsequent exotherm was adjusted by jacket cooling to maintain the temperature at 15 ° C. The pressure was maintained at 280 psig by feeding ethylene to the butch to replace the polymerized ethylene. Inhalation of ethylene began to be detectable slowly after 15 minutes, and the addition of ethylene stopped after 36 minutes.

The contents of the butch are 400 ml of hexane, 0.2 grams of octadecyl 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -propionate as antioxidant and 10 ml for deactivating the catalyst. It was gradually transferred to a two liter stainless steel pressure vessel (Parr reactor) containing isopropanol. After each incremental transfer, propylene was evacuated from the Fahre reactor to lower the pressure and the butch reactor was pressurized again with nitrogen. The transfer continued in this manner until all the contents of the butch were released and all the propylene was vented. The solution remaining in the phage reactor was then removed and filtered through celite. Hexane was then removed by distillation, leaving a low molecular weight ethylene-propylene copolymer. The properties of this copolymer are shown in Table 3 below.

Example 7

EPM preparation in suspension

The same process as in Example 6 was carried out except that accelerator composition I was used instead of accelerator composition II. The properties of the prepared copolymers are listed in Table 3 below.

Example 8

EPM Preparation in Solution

The butch autoclave described in Example 6 was charged with 346 grams of hexane, 518 grams of propylene, 10 psig of ethylene, 15.4 moles of diethyl ammonium chloride and 20 psig of hydrogen. The temperature was maintained at 38 ° C. To produce a catalyst / activator solution, a hexane solution containing 0.01 mol / liter vanadium oxytrichloride and 0.046 mol / liter of accelerator composition III was prepared and 20 ml of this catalyst / activator solution was quickly pumped into the reactor. The exotherm started and was adjusted to maintain the temperature at 38 ° C. by jacket cooling. The catalyst / activator solution was then pumped into the reactor at a rate sufficient to maintain a constant pressure, fed at 2 grams / minute ethylene. After 30 minutes, the pumping of the catalyst / activator solution and the supply of ethylene were stopped.

A solution of 0.15 grams of octadecyl 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate dissolved in 0.15 grams of epoxidized soybean oil and 10 ml of hexane was added, and propylene It was slowly evacuated from the reactor. Another 400 grams of hexane was added to the reactor and the contents heated to 49 ° C. The contents were then transferred to a 3 quart flint glass Chemco reactor containing 350 ml of deoxygenated distilled water. The mixture was stirred rapidly for 30 seconds and then stabilized for 20 minutes. 600 ml of washed hexane solution was then transferred to the second Chemco reactor and washed twice with 160 ml of deoxygenated distilled water. The hexane solution washed twice was then liberated and the hexanes were removed by distillation leaving behind a low molecular weight ethylene-propylene copolymer. The properties of this copolymer are listed in Table 3 below.

Example 9

Preparation of EPM in Solution

The same process as described in Example 8 above was performed except that I was used instead of accelerator composition III. The properties of the prepared copolymers are shown in Table 3 below.

Example Accelerator composition Efficiency ¹ Mv ² % Propylene ³ 6 II ⁴ 13753 4300 52 7 I ⁴ 10260 4295 50 8 III ⁵ 2016 7512 59 9 I ⁵ 1517 7632 56

¹ grammar gram / VOCl ₃ gram

² number average molecular weight

³ weight percentage of the copolymer; Measured using ASTM D-3900-86, Method D.

⁴ molar ratio accelerator composition / vanadium = 16/1

⁵ molar ratio accelerator composition / vanadium = 4.6 / 1

Claims (23)

Compound of the formula here, n is 1, 2, 3 or 4; X ¹ and X ² are each independently chlorine or bromine; A is O or S; R ¹ is hydrogen or C ₁ -C ₁₆ alkyl; R ² is C ₁ -C ₁₆ alkyl; C ₆ -C ₁₆ aryl; C ₁ -C ₄ alkylidene or CH ₂ OR ⁵ ; R ³ is hydrogen, chlorine, bromine or OR ⁶ ; R ⁴ is C ₁ -C ₁₆ alkyl; C ₇ -C ₁₆ aralkyl; C ₂ -C ₁₆ alkenyl, or C ₆ -C ₁₈ aryl; R ⁵ is hydrogen, C ₁ -C ₁₆ alkyl; C ₇ -C ₁₆ aralkyl, C ₂ -C ₁₆ alkenyl, or C ₆ -C ₁₈ aryl; And R ⁶ is hydrogen or C ₁ -C ₁₆ alkyl, Wherein if R ² is C ₁ ~C ₄ alkyl Li indenyl, R ³ is not present. The compound of claim 1, wherein n is 1. The compound of claim 2, wherein A is O. 4. The compound of claim 3, wherein X ¹ and X ² are each chlorine. A compound according to claim 4 wherein: R ¹ is hydrogen or C ₁ -C ₆ alkyl; R ² is C ₁ -C ₆ alkyl; C ₁ -C ₄ alkylidene or CH ₂ OR ⁵ ; R ³ is hydrogen, chlorine, bromine or OR ⁶ ; R ⁴ is C ₁ -C ₆ alkyl; C ₂ -C ₆ alkenyl, or C ₆ -C ₁₂ aryl; R ⁵ is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, phenyl or naphthyl; And R ⁶ is hydrogen or C ₁ -C ₆ alkyl, Wherein R ² is C ₁ ~C ₄ alkylidene if R ³ is not present. A compound according to claim 5 wherein R ¹ is hydrogen or C ₁ -C ₄ alkyl; R ² is C ₁ -C ₄ alkyl; C ₁ -C ₂ alkylidene, or CH ₂ OH; R ³ is hydrogen or chlorine; And R ⁴ is C ₂ -C ₄ alkyl; C ₂ -C ₄ alkenyl, phenyl or naphthyl, Wherein R ² is C ₁ ~C ₂ alkylidene if R ³ is not present. A compound according to claim 6 wherein R ¹ is hydrogen or methyl; R ² is methyl, methylene, or CH ₂ OH; R ³ is hydrogen or chlorine; R ⁴ is C ₂ -C ₄ alkyl, Wherein if R ² is methylene then R ³ is absent. 8. A compound according to claim 7, having the formula A composition useful for the preparation of an ethylene copolymer comprising at least two compounds of claim 1. The composition of claim 9 comprising at least two compounds of claim 8. 10 to 95% by weight of an ethylene copolymer, comprising from 5 to 90% by weight of at least one compound selected from the group consisting of at least one compound of claim 1 wherein n is 1 and a compound of the formula Useful Compositions for Preparation: here: X, X ¹ , X ² and X ³ are each independently chlorine or bromine; A is oxygen or sulfur; R ⁵ is hydrogen or C ₁ -C ₁₆ alkyl; R ⁶ is C ₁ -C ₁₆ alkyl; R ⁷ is hydrogen, C ₁ -C ₁₆ alkyl; C ₂ -C ₁₆ alkenyl or C ₆ -C ₁₈ aryl; And R ⁸ is hydrogen, C ₁ -C ₁₆ alkyl or C ₁ -C ₄ alkylidene, Wherein R ⁸ is C ₁ ~C ₄ When alkali indenyl X ³ does not exist. The composition of claim 11 wherein: R ⁵ is hydrogen or C ₁ -C ₆ alkyl; R ⁶ is C ₁ -C ₆ alkyl; R ⁷ is hydrogen or C ₂ -C ₁₂ alkyl; And R ⁸ is hydrogen or C ₁ -C ₆ alkyl. A composition useful for the preparation of an ethylene copolymer comprising from 30 to 90% by weight of at least one compound of claim 8 and from 10 to 70% by weight of at least one compound selected from the group consisting of compounds of the formula: In the presence of a catalytically effective amount of a catalyst composition, comprising the following (a), (b) and (c), ethylene, wherein CH ₂ = CHQ, wherein Q is an alkyl having from 1 to 8 carbon atoms A process for preparing an alpha-olefin polymer, comprising reacting at least one monoma and, optionally, a nonconjugated diene: (a) vanadium containing compounds; (b) organoaluminum compounds; And (c) at least one compound of claim 1 In the presence of a catalytically effective amount of a catalyst composition, comprising the following (a), (b) and (c), ethylene, wherein CH ₂ = CHQ, wherein Q is an alkyl having from 1 to 8 carbon atoms A process for preparing an alpha-olefin polymer, comprising reacting at least one monoma and, optionally, a nonconjugated diene: (a) vanadium containing compounds; (b) organoaluminum compounds; And (c) at least one compound of claim 2 In the presence of a catalytically effective amount of a catalyst composition, comprising the following (a), (b) and (c), ethylene, wherein CH ₂ = CHQ, wherein Q is an alkyl having from 1 to 8 carbon atoms A process for preparing an alpha-olefin polymer, comprising reacting at least one monoma and, optionally, a nonconjugated diene: (a) vanadium containing compounds; (b) organoaluminum compounds; And (c) at least one compound of claim 8 In the presence of a catalytically effective amount of a catalyst composition, comprising the following (a), (b) and (c), ethylene, wherein CH ₂ = CHQ, wherein Q is an alkyl having from 1 to 8 carbon atoms A process for preparing an alpha-olefin polymer, comprising reacting at least one monoma and, optionally, a nonconjugated diene: (a) vanadium containing compounds; (b) organoaluminum compounds; And (c) The composition of claim 11. In the presence of a catalytically effective amount of a catalyst composition, comprising the following (a), (b) and (c), ethylene, wherein CH ₂ = CHQ, wherein Q is an alkyl having from 1 to 8 carbon atoms A process for preparing an alpha-olefin polymer, comprising reacting at least one monoma and, optionally, a nonconjugated diene: (a) vanadium containing compounds; (b) organoaluminum compounds; And (c) The composition of claim 13. A process for preparing EPDM comprising reacting ethylene, propylene, and nonconjugated diene in the presence of a catalytically effective amount of a catalyst composition comprising (a), (b) and (c): (a) vanadium containing compounds; (b) organoaluminum compounds; And (c) at least one compound of claim 1 EPDM prepared by the method of claim 19. A process for preparing an EPM comprising reacting ethylene and propylene in the presence of a catalytically effective amount of a catalyst composition, comprising (a), (b) and (c): (a) vanadium containing compounds; (b) organoaluminum compounds; And (c) at least one compound of claim 1 EPM prepared by the method of claim 21. From the group consisting of ethylene and copolymerizable mono-alpha olefins and nonconjugated polyenes comprising reacting ethylene with comonoma in the presence of a catalyst composition comprising a vanadium containing compound, an organoaluminum compound, and a catalyst promoter. An improved method of preparing a copolymer of at least one comonoma selected comprising at least one promoter comprising the compound of claim 1.