PROCESS FOR PREPARING POLY ALPHA OLEFINS

Abstract: A compound having the formula Y m X n CC(R¹)=C(R²)R³ where Y is hydrogen, cyano or C₂-C₁₉ carbalkoxy; X is chlorine or bromine; R¹ is hydrogen, chlorine, bromine or -C00R⁴; wherein R⁴ is C₁-C₁₈ alkyl, C₃-C₁₈ alkanyl, C₅-C₆ cycloalkyl, C₇-C₉ aralkyl or C₁-C₁₈ linear or branched alkyl, provided that R¹ ist not chlorine or bromine if R² is chlorine or bromine and if R¹ and R² are hydrogen they must be in the trans configuration; or R¹ and R² together is C₃-C₁₀ alkylene; R³ is an electron withdrawing group; n is 1, 2 or 3 and m is 3-n and the making said compound is disclosed. An intermediate compound, useful in the manufacture of the above compound, having the formula Y m X n CCHR¹-CR²R³X¹ where Y, X, R¹, R², R³, n and m have the meanings given for the compound of this invention and where X¹ is chlorine or bromine with the limitation that when n ist 3, R¹ is hydrogen, X and X¹ are chlorine, if R² is methyl then R³ is not methoxycarbonyl and if R² is hydrogen then R³ is not methylcarbonyl, and a process for making said intermediate is described. A composition incorporating the compound, Y m X n CC(R¹)=C(R²)R³, with a vanadium catalyst, useful as a catalytic agent, i also disclosed. A process for preparing poly(alpha-olefins) employing a compound of the above formula as a catalyst without any of the restrictions relating to the meaning of R¹ and R² is also taught.

Description: CATALYST ACTIVATOR FOR ALPHA OLEFIN POLYMERIZATION BACKGROUND OF THE DISCLOSURE 1. Field of the Invention The instant invention is directed to a compound of the formula YmXnCC(RÚ)=C(Rê)R where Y is hydrogen, cyano or C2-C19 carbalkoxy; X is chlorine or bromine; R1 is hydrogen, chlorine, bromine or -COOR4; wherein R4 is C1-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C1O aryl; R2 is hydrogen, chlorine, bromine or C1-C18 linear or branched alkyl1 provided that R1 is not chlorine or bromine if R2is chlorine or bromine, and if R1 and R2 are hydrogen, they must be in the trans configuration; or R1 and R2 together may be C3-C10 alkylene; R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n; and to the method for making same. The instant invention also deals with the use of said compound as a catalyst activator in the polymerization of alpha-olefins. 2. Background of the Invention In polymerizations of alpha-olefins a transition metal catalyst and an organoaluminum cocatalyst are usually employed. In order to enhance catalyst efficiency and/or regulate polymer molecular weight, a catalyst activator may be used. Among the known activators are those disclosed in U.S. Patent 3,377,325, which uses a sulphur activator; Canadian Patent 833,651 using phosphorous trichloride and 2-nitropropane as activators; U.S. Patent 3,441,564 teaches an organic nitro compound as activator; U. S. Patent 3,444,149 discloses the use of a nitroso compound or a quinone as activator; U.S. Patent 3,462,399 deals with activation by organic nitrates, organic nitrites, azoxy compounds, special organic metallic compound or alkyl disulfides; U.S. Patent 3,507,843 using a phosphorous trichloride as activator; and U. S. Patent 4,347,159 employing a furoate compound as activating agent. None of these activators combine the advantages of catalyst efficiency, control the molecular weight and molecular weight distribution of the polymer produced and are useful in both homogenous and heterogeneous phase systems. Indian J. Pharm. 25, 264-8 (1963) discloses antibacterial compounds having the structure CCl3CH=CHCOOR, R being alkyl, wherein the hydrogen atoms are believed to be in a cis-type configuration. DESCRIPTION OF THE INVENTION The new compounds of this invention are excellent catalyst activators. More specifically, these compounds are especially useful as catalyst activators in the polymerization of alpha-olefins. Uniquely, these compounds activate the catalyst such that the unit weight of catalyst required per unit weight of polymer produced is minimized. These activators also operate to regulate the molecular weight and the molecular weight distribution of the polymerization product. Most surprisingly, they can be employed to polymerize alpha-olefins in combination with homogenous and heterogeneous catalyst systems as well as in solution and polymerizations conducted essentially in the absence of a solvent. In accordance with the instant invention, a compound is provided having the formula YmXnCC(Rl )=C(R2)R3 mn where Y is hydrogen, cyano or C2-C19 carbalkoxy; X is chlorine or bromine; R is hydrogen, chlorine, bromine or -CooR4; wherein R4 is C1-Cl8 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C1O aryl; R is hydrogen, chlorine, bromine or C1-C18 linear or branched alkyl, provided that R1 is not chlorine or bromine if R2 is chlorine or bromine, and if R1 and R2 are hydrogen, they must be in the trans configuration; or R1 and R2 together may be C3-C1o alkylene; R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n; and to the method for making same. The instant invention also deals with the use of said compound as a catalyst activator in the polymerization of alpha-olefins. Preferably, Y is hydrogen; X is chlorine or bromine; R is hydrogen or -COOCH3; R2 is hydrogen, chlorine or C-C4 alkyl; or R and R2 together are propylene or butylene, R is chlorine, bromine, iodine, cyano, nitro, trihalomethyl, halo meaning F, Cl or Br, C2-C19 alkylcarbonyl, C2-C19 alkoxycarbonyl, C1-C18 alkylsulfonyl, C7-Cg aralkylsulfonyl or C7-C18 alkarylsulfonyl. Usually X is chlorine, R1 is hydrogen, R2 is hydrogen or C1-C4 alkyl, R3 is C3- C11 alkoxycarbonyl and n is 3; the proviso being as already stated that if R1 and R2 are hydrogen, they are situated in a trans configuration. Chemicals being representative of the compounds of this invention are enumerated in the Table I below. TABLE I Formula: YmXnCC(RÚ)=C(Rê)R Y X R1 R2 R3 m n H Br C c18H37 H COOCH3 1 2 CN Br COOC6H13 C1 CF3 1 2 COOCH3 - C1 C3H7 CN 3 0 COOC4H9 Br Br CH3 SO2C4H9 2 1 - C1 C1 C12H25 SO2CH2C6H5 5 3 COOC12H25 C1 H c4119 COOC12H25 1 2 - C1 -CH2CH2C(C7H15)H- COOC4H9 0 3 - Cl COOC12H25 H COO cyclo C6H1l 0 3 In further accordance with this invention, there is provided a process for making a compound of the structure YmXnCC(RÚ)=C(Rê)R comprising first reacting a compound having mn the formula CHRÚ-CRêR (A) with a compound of the formula CYmXn (B), wherein R1, R2, R , Y and X are as defined above; n is an integer of 1 to 4; and m is 4-n, in the presence of dichloro trisEtriphenylphosphine]ruthenium, and secondly treating the resultant product with a strong Lewis base such as triethylamine. In the first step of the preparation, the reactants are present at essentially stoichiometric amounts, i . e., the A/B molar ratio being from 1.1/1 to 1/1.1, and the reaction is carried out at temperature of 50-1000C for 0.5-5 hours, usually at reflux temperature. In the second step, dehydrohalogenation is effected by heating the intermediate product of the reaction compounds A and B, YmXn¯1CC(Rl)H-CXR2R3 to 50-1200C in the presence of a strong Lewis base and a solvent inert to the intermediate for 5-100 hours, usually 10-75 hours. A strong Lewis base is understood to mean a basic compound having a PKb of 5 or less, as represented by ammonia, dimethylamine, trimethylamine, di- and triethylamine, dipropylamine and the like. Suitable inert solvents include heptane, octane, isooctane, decane, benzene, toluene, xylene and the like. Another aspect of this invention, is the intermediate compound formed in the preparation of the compound of this invention. That is, the intermediate compound whose formula is Y X CCHRl-CR2R3Xl mn where Y is hydrogen, cyano or C2-C19 carbalkoxy; X is chlorine or bromine; R1 is hydrogen, chlorine, bromine or -CooR4, where R4 is C1-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C10 aryl; R2 is hydrogen, chlorine, bromine or C1-Cl8 linear or branched alkyl; R is an electron withdrawing group; X is chlorine or bromine; n is an integer of 1 to 3; and m is 3-n, except that when n is 3, R1 is hydrogen, X and X1 are chlorine, if R2 is methyl then R3 is not methoxycarbonyl and if R2 is hydrogen then R3is not methylcarbonyl. In yet another aspect of this invention a process for forming the intermediate compound is set forth. In this process a compound of the formula CHR1=CR2R3 is reacted with a compound of the formula CYmXnX1 where R1, R2, R3, X, X1, n and m have the meaning given above for the intermediate compound including the exceptions mentioned therein. This reaction occurs in the presence of dichlorotris (triphenylphosphine )ruthenium. In still another aspect of the present invention a process for the polymerization of alpha-olefins is disclosed. In one embodiment of the process of this invention at least one monomer having the structure CH2=CHQ, where Q is hydrogen or C1-C16 alkyl, is contacted with an anionic polymerization catalyst and a catalyst activating amount of a compound having the formula YmXnCC(R1)=C(R2)R3, wherein Y is hydrogen, cyano or C2-C19 mn 1. carbalkoxy; X is chlorine or bromine; R1 is hydrogen, chlorine, bromine or -COOR4, where R4 is Cl-C18 alkyl C23-C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C10 aryl; R is hydrogen, chlorine, bromine or C1-Cl8 linear or branched alkyl or R1 and R are together C3-C10 alkylene; R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n. In this embodiment the polymerization occurs in the absence of a reaction medium inert to the polymerization. In another embodiment of this process the reaction occurs in the presence of a reaction media inert to the polymerization. In this embodiment the meaning of the function groups in the formula Y,XnCC(Rl)=C(R2)R3 are as given above with the exception that if R is chlorine or bromine than R2 is not chlorine or bromine. In still further accordance with the instant invention a catalyst composition is provided. The composition comprises a vanadium catalyst and a compound of the formula YmXnCC(R)1=C(R2)R3 where Y is hydrogen, cyano or C2-C19 carbalkoxy; X is chlorine or bromine; R1 is hydrogen, chlorine, bromine or -COOR4, wherein R4 is C1-C18 alkyl, C3-C18 alkenyl, C5-C6 cycloalkyl, 7 aralkyl or C6-C10 aryl; R2 is hydrogen1 chlorine, bromine or C1-C18 linear or branched alkyl, provided that R1 is not chlorine or bromine if R2is chlorine or bromine; R1 and R2 together may also be C3-C10 alkylene; R3 is an electron withdrawing; n is an integer of 1 to 3; and m is 3-n. This composition is useful in the catalytic polymerization of alpha-olefins. In a preferred embodiment of the composition of this invention, the meanings of the functional groups of the compound YmXnCC(RÚ)-C(Rê)R are as follows: Y is hydrogen; X is chlorine or bromine; R1 is hydrogen or -COOCH ; R2 is hydrogen, chlorine or C1-C4 alkyl; alternatively R1 and R together are propylene or butylene; R3 is chlorine, bromine, iodine, cyano, nitro, trihalomethyl, halo meaning F, Cl or Br, C2 -C19 alkylcarbonyl, C7-Cg aralkylsulfonyl or C7-C18 alkarylsulfonyl. Still more preferably the functional groups have the meanings: X is chlorine; R1 is hydrogen; R2 is hydrogen or C1-C11 alkoxycarbonyl and n is 3. EXAMPLE 1 Preparation of Butyl 4,4 ,4-trichlorobut-2-transenoate (BTCB). 128 grams (1 mole) of freshly distilled butyl acrylate was reacted with 300 ml of carbon tetrachloride in the presence of 1.92 (2 millimoles) of dichlorotris[triphenylphosphine]ruthenium, under nitrogen, in a three necked (1 liter round bottom) flask, equipped with a condenser, an overhead mechanical stirrer and a thermometer. The reaction mixture was heated to reflux (800C) for about 1 hour, at which time the mixture turned brownish in color. The mixture was cooled to room temperature, and excess CCl4 was removed using a rotary evaporator. The catalyst was precipitated by addition of n-heptane which was separated by decantation from the remaining supernatant brown viscous material. The brown viscous reaction product was isolated by evaporation of the n-heptane (using a rotary evaporator). It weighed 275 grams (9Pm yield). Infrared analysis (IR) of the product did not show an absorption attributable to vinylic type unsaturation indicating the absence of an acrylic double bond. After distillation, at 800C and 26.6 Pa, the reaction product was a clear, colorless oil. The reaction product (289 gm, 1 mole), triethylamine (138 ml, 1 mole) and benzene (500 ml) was placed in a three necked round bottom 2-liter flask equipped with an overhead mechanical stirrer, a condenser and a thermometer. This reaction mixture was heated at reflux (800C) for 50 hours. After adding an additional 30 ml (0.2 mol) of triethylamine reflux was continued for another 20 hours. After this total of 70 hours at reflux, a dark brownish material was obtained. The reaction product was filtered. The solid (C2H5)3NHCl salt was removed leaving a solution from which the benzene solvent was removed by a rotary evaporator. The resultant dark brown viscous material (234 gm, 95% yield) was distilled (72-740C at 40 Pa). The product, butyl 4,4,4-trichlorobut-2transenoate was a colorless, clear viscous oil (90% yield). The IR and nuclear magnetic resonance (NMR) spectral Ú and 13 and nuclear magnetic resonance (NMR) spectral H and 13C) data, which appear in Table II, were consistent with this compound. The elemental analysis for this compound appears in Table III. EXAMPLE 2 Preparation of Methyl 2 -methyl-4,4,4-trichlorobut-2-enoate (MMTB) A carbon tetrachloride addition reaction was carried out in accordance with procedure set out with step 1 of Example 1. However, in this example butyl acrylate was replaced with methyl methacrylate. The addition reaction product was recovered as a colorless, viscous material. The IR spectrum was consistent with that compound. One mole of the above reaction product was dehydrochlorinated in accordance with the procedure enumerated for Step 2 in Example 1. The product of this reaction, methyl 2-methyl-4,4,4-trichlorobut-2-enoate, was recovered as a clear, colorless oil (yield 85%). The IR and NMR data appear in Table II, and its elemental analysis is summarized in Table III. EXAMPLE 3 Preparation of Ethyl 4,4,4-trichlorobut-2-enoate (ETCB) The carbon tetrachloride addition reaction of step 1 of Example 1 was repeated with the exception that butyl acrylate was replaced by ethyl acrylate. The reaction was conducted under the same conditions as were employed in Example 1. The product of this reaction was purified by distillation. The distilled product was obtained in a 93% yield. The IR spectrum was consistent with that compound. Tables II and III provide elemental analysis and 1R and NMR spectral data, respectively, for the ETCB made in accordance with this example. EXAMPLE 4 Preparation of 2-Ethylhexyl 4,4,4-trichlorobut-2-enoate (EHTB) The carbon tetrachloride addition reaction was repeated but for the substitution of 2-ethylhexyl acrylate for butyl acrylate of Example 1. The addition product of this reaction yielded an IR spectrum consistent with that compound. The above reaction product was dehydrochlorinated in accordance with the procedure of Example 1. The resultant product, 2-ethylhexyl 4,4, 4-trichlorobut-2-enoate, was obtained after vacuum distillation in an 80% yield. The IR spectrum was consistent with the title compound. TABLE II Example Calculated % Found 96 No. Compound C H C1 C H C1 1 Butyl 4,4,4-trichloro- 39.13 4.52 43.32 39.10 4.44 43.32 but-2-transenoate 2 Methyl 2-methyl-4,4,4- 33.10 3.22 48.96 32.94 3.12 trichlorobut-2-enoate 3 Ethyl 4,4,4-trichloro- 33.13 3.21 48.3 32.73 3.11 47.83 but-2-enoate TABLE III I.R. AND N.M.R. SPECTROSCOPY DATA Example 1H - NMR (8 PPM) No. Compound 13 C - NMR13c - 1 Butyl 4,4,4-trichlorobut- 0.97 (t,3H), 1.42 (m, 2H), 1.68 (m, 2H) 2-transenoate 4.2 (t, 2H), 6.39 (d, 1H), 7.20 (d, 1H) cIs (J = 9 HZ) TRANS (J = 15 HZ) 13.58, 19.04, 30.53, 65.32, 92.17 121.73, 145.97, 164.63 2 Methyl 4,4,4-trichloro- 1.90 (s, 3H), 4.1 (t, 3K) 6.2 (s, 1H) 2-methylbut-2-enoate 53.42, 62.23, 94.59, 135.25, 143.14, 169.95 3 Ethyl 4,4,4-trichlorobut- 1.30 (t, 3H), 4.25 (q, 2H), 2-enoate 6.36 (d, 1H), 7.2 (d, 1H) 14.01, 61.34, 92.11, 121.69, 145.90 164.43 As mentioned previously, the compounds of this invention are useful as catalyst activators for anionic polymerization of alpha-olefins employing Ziegler-Natta Type catalyst systems. Such catalytic systems are well known in the art and essentially comprise the combination of a transition metal salt catalyst and an organoaluminum or magnesium compound or halide cocatalyst. Such catalytic systems may be homogenous or hetergenous in nature, i.e., they may or may not be soluble in the polymerization medium, and they are capable to polymerizing alpha-olefins. Under alpha-olefins are considered monomers having the formula CH2=CHQ, wherein Q is hydrogen or C1-C16 alkyl such as ethylene, propylene, butene-1, pentene-l, hexane-1, decene-1, dodecene-1, 4-methylpentene-1, 4-ethylhexene-1, and the like which may be homo- or copolymerized to crystalline or essentially amorphous and elastomeric polymers such as polyethylene, polypropylene, polybutene, etc., or ethylene-propylene copolymers or elastomers (EPM). Elastomeric copolymers of ethylene and other alpha-olefins such as propylene may also incorporate copolymerizable non-conjugated dienes such as dicyclopentadiene (DCPD), 5-ethylidenorbornene-2 (ENB) or 1,4-hexadiene (1,4HD). Such terpolymers are known as EPDM's. The cocatalyst-catalyst molar ratio may vary from 2/1 to 500/1, usually 5/1-350/1 and more frequently 10/1-200/1; and when employing the catalyst activators of this invention, the molar activator/catalyst ratio may range from 1/1 to 100/1, more frequently 2/1-80/1 and usually 5/1-50/1. Such polymerizations may be conducted in the presence of an inert medium. Typical media are pentane, hexane, heptane, octane, isooctane, decane, benzene, toluene, methylene chloride, chloroform and the like. In any case, the compounds of this invention exhibit extraordinary activation characteristics when used in such polymerizations as illustrated by the examples below. EXAMPLE 5 Preparation of EPDM To a dry 1500 ml 3-necked round bottom flask equipped with stirrer, thermometer, condenser, gas inlet tube and a 1-liter drop ping funnel was added 1000 ml dry n-heptane solvent. Dry ethylene and propylene monomers were simultaneously introduced until the solvent was saturated, i.e., no further monomer up-take was observed. Then 1.35 ml of a 0.74 M heptane solution of ethylaluminum sesquichloride (EASC) cocatalyst (ca. 1 millimole) was introduced. While maintaining the ethylene-propylene feed, dropwise addition of a solution of 0.05 millimole VOCAL3 catalyst, 0.1 millimole BTCB and 10 millimole ENB, all in 60 ml n-heptane was started causing polymerization to commence. VOCl3, etc., addition took about 50 minutes, but monomer introduction was continued for another 10 minutes, after which time the polymerization was terminated by the addition of 5 mi isopropanol. The polymer in solution was extracted with isoproponal to which. a small amount of antioxidant was added. The stabilized polymer was recovered, weighed and analyzed. The polymer was analyzed as EPDM characterized by an ethylene to propylene weight ratio of 68:32, an intrinsic viscosity of 1.7, as measured in tetralin at 1350C, an iodine number of 8.4 and a glass transition temperature of -520C. The yield of EPDM polymew was 43 grams representing a catalyst efficiency of 860 g polymer per millimole of vanadium. See also summary in Table III. EXAMPLES 6-9 Following essentially the procedure of Example 5, additional polymerizations were conducted. The results are summarized in Table IV. Example 9 is outside this invention. TABLE IV Example No. 5 6 7 8 9 Catalyst activator BTCB MMTB ETCB EHTB none Polymer yield, g 43 26.7 14 37 8.3 g Polymer/millimole V 860 533 280 740 166 V residue in polymer, ppm 59 95 169 70 280 Polymer characteristics Intrinsic viscosity, dl/g* 1.7 3.2 3.35 2.38 2.76 Unsaturation, I2 No. 8.4 10.8 20.9 - Ethylene/propylene, weight 68/32 74/26 75/25 72/28 70/30 * In tetralin at 1350C. The data clearly indicate the extraordinary improvement in catalyst efficiency achieved (i. e., g of polymer per millimole of vanadium catalyst) when using the compounds of this invention as catalyst activators. EXAMPLES 10 and 11 Preparation of EPDM A dry 2-liter Parr [trademark] autoclave, equipped with a pressure gauge, as gas inlet tube, and outlet port and a stirrer was cooled externally with dry ice while flushing with dry nitrogen. Propylene monomer was condensed, and the autoclave temperature was brought to -190C, at which point hydrogen gas was introduced at 138 kPa excess pressure as well as ethylene at the same pressure. Then, while stirring, a solution of catalyst (0.025 millimole), EASC (1.48 millimole), ENB (5.4g) and catalyst activator (0.4 mmole) in 1000 ml heptane was charged to the autoclave which initiated polymerization. The reactor temperature was reduced to -270C using a dry ice-isopropanol bath while ethylene feed was continued at the above pressure for one hour. The polymerization was stooped by adding a sufficient amount of isopropanol (having dissolved therein some antioxidant) to the reactor. The reactor contents, EPDM particles dispersed in monomer, were isolated, dried, weighed and analyzed. The results are summarized in Table V below. TABLE V Example No. 10 11 Ethylene, g 118 114 Propylene, g 490 509 ENB, g 5.4 5.4 EASC, mmol 1.48 1.48 VBDP(1), mmol 0.025 VOCi3, mmol - 0.025 BTCB, mmol 0.4 0.4 A1/V, molar 59.2 59.2 TABLE V (continued) Example No. 10 11 BTCB/V, molar 16 16 Hydrogen, kPa(2) 138 138 Reaction time, minutes 60 60 Polymer yield, g 109.7 89.8 g Polymer/mmol V 4388 3592 Polymer characteristics Ethylene/propylene, weight 62/38 69/31 12 No. 5.9 3.8 I.V. (tetralin at 1350C) 2.54 4.08 V metal in polymer, pmm 11.6 14.2 Remarks (1) VBDP = vanadylbis [diethylphosphate] catalyst (2) Excess pressure The results indicate the excellent catalyst efficiency achieved when using the compounds of this invention as catalyst activators. EXAMPLES 12-16 Preparation of EPDM To a dry 5 gallon stainless steel jacketed reactor provided with a stirrer was added (with cooling medium flowing in the jacketed portion of the reactor) propylene, 1.75 moles hydrogen (3.5g) and ethylene. To this was added EASC in isopentane (120 ml). Stirring was initiated at 175 revolutions per minute. With the temperature in the reactor set at -80C, cooling was discontinued and a solution of 0.2 millimoles of catalyst, 36 milliliters of ENB, catalyst activator (amount provided in Table VI) in 280 ml of isopentane was incrementally added to the reaction mass by means of a positive displacement pump. The addition of the catalyst solutions initiated the reaction. The reaction was terminated by passing the propylene liquid containing suspended polymer into an isopropanol solution containing an antioxidant. The polymer was separated from the liquid phase by filtration and analyzed. A summary of Examples 12-16 appears below in Table VI. TABLE VI Example No. 12 13 14 15 16 Polymerization Ethylene, g 650 750 620 851 809 Propylene, g 7000 7000 7000 7000 7000 ENB, g 17.5 36 36 28.2 33.4 EASC, mmol 16.7 8.3 28 8.3 8.3 VOCi3, mmol 0.097 0.081 0.64 - VBDP(2), mmol - - - 0.123 0.132 BPCC( ), mmol 3.1 2.6 2.9 3.9 4.2 Hydrogen, g 3.5 3.5 3.5 3.5 3.5 A1/V, molar 343 205 87 135 126 BPCC/V, molar 32 32 6 32 32 Reaction time, min. 95 115 123 112 113 Polymer yield, g 493 605 877 1023 1011 g Polymer/mmol V 5082 7470 1370 8320 7660 Polymer characteristics Ethylene/propylene, weight 59/41 59/41 52/48 53/47 52/48 I2 No. 3.2 5.5 2.7 2.7 2.7 I.V., dl/g(3) 2.54 2.0 4.95 3.28 2.82 Remarks: : (1) vanadylbis [diethylphosphate] catalyst (2) butyl perchlorocrotonate catalyst activator (3) in tetraline at 1350C. These experiments demonstrate that the catalyst activator, butyl perchlorocrotonate, known to be suitable for polymerizations of EPDM employing an inert polymerization medium provides unexpectedly improved catalyst efficiency when used essentially in the absence of such an inert medium. EXAMPLE 17 Following essentially the procedure of Example 1, dimethyl 2-trichloromethylbut-2-endioic acid ester (DMBA) was prepared from dimethyl fumarate and bromotrichloromethane and by subsequent dehydrobromination of the intermediate. EXAMPLE 18 Reacting butyl methacrylate with tetrachloromethane and subsequent dehydrohalogenation resulted in the compound n-butyl 2-methyl-4,4,4-trichlorobut-2-enoate (BMTB). EXAMPLE 19 From methyl acrylate and carbon tetrachloride was prepared the intermediate Cl3CCH2CHClCOOCH3, which, upon dehydrohalogenation yielded methyl 4,4,4-trichlorobut-2-enoate (MTCB). EXAMPLES 20-25 Following essentially the procedure of Example 1, additional EPDM preparations were carried out using compounds of this invention as catalyst activators. The results are summarized in Table VII. TABLE VII Example No. 20 21 22 23 24 25 Catalyst Activator MTCB DMBA BMTB/C(1) BMTB/T(2) BTCB/C(1) BTCB/T(2) Polymer yield, g 22 19 46 58 38 58 g polymer/mmol V 440 380 920 1160 760 1160 Remarks: (1) believed to be primarily the cis-isomer (2) believed to be primarily the trans-isomer Improved catalyst activity is clearly demonstrated with transisomers having a more pronounced effect. The foregoing preferred embodiments and examples will make apparent, to those skilled in the art, other embodiments and examples. These embodiments and examples, within the scope and spirit of the instant invention, are within the contemplation of the present invention. Therefore, the scope of the instant invention should be limited only by the appended claims.

Claims: CLAIMS: 1. A compound characterised by the formula YmXnCC(Rl)=C(R2)R3 where Y is hydrogen, cyano or C2-C19 carbalkoxy; X is chlorine or bromine; R1 is hydrogen, 4 4 chlorine, bromine or -COOR; wherein R is C1-C18 alkyl, C3-C18 a2lkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C10 aryl; R is hydrogen, chlorine, bromine or C1-Cl8 linear or branched alkyl, provided that RÚ is not chlorine or bromine of Rê is chlorine or bromine, and if RÚ and Rê are hydrogen, they must be in the trans configuration; or RÚ and Rê together may be C3-C10 alkylene; R is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n. 2. A compound according to claim 1 characterised in that Y is hydrogen, X is chlorine or bromine, R1 is hydrogen or -COOCH3, R2 is hydrogen, chlorine or C1-C4 alkyl or R1 and R2 3 R and R together are propylene or butylene, R is chlorine, bromine, iodine, cyano, nitro, trihalomethyl, halo meaning F, Cl or Br; C2-C10 alkylcarbonyl, C2-C19 alkoxycarbonyl, Cl-Cl8 alkylsulfonyl, C7-Cg aralkylsulfonyl or C7-C18 alkarylsulfonyl. 3. A compound according to claim 1 or claim 2 characterised in that X is chlorine, R1 is hydrogen, R2 is hydrogen of C1-C4 alkyl, R3 is C3-C12 alkoxycarbonyl and n is 3. 4. A compound according to any of the preceding claims characterised in that the compound is methyl 2-methyl4,4,4-trichlorobut-2-enoate, ethyl 4,4,4-trichlorobut-2enoate, butyl 4,4,4-trichlorobut-2-transenoate, 2-ethylhexyl 4,4, 4-trichlorobut-2-enoate, dimethyl 2-trichloromethylbut-2-endioate, butyl 2-methyl-4,4,4 trichlorbut-2enoate or methyl 4,4,4-trichlorbut-2-enoate. 5. A composition characterised in that it comprises a vanadium metal catalyst, and a compound as claimed in any of the preceeding claims. 6. A process for preparing polyalpha-olefins characterised in that the process is conducted essentially in the absence of a reaction medium inert to the poymerisation and the process comprises contacting at least one monomer having the structure CH2-CHQ wherein Q is hydrogen or C1-C16 alkyl with an anionic polymerisation catalyst in the presence of catalyst activating amount of a compound having the formula YmXnCC(RÚ)=C(Rê)R , wherein Y is hydrogen, cyano or C2-C19 carbalkoxy; X is chlorine or bromine; RÚ is hydrogen, chlorine, bromine or -COOR4; wherein R4 is C1-C18 alkyl, -C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C10 aryl; R is hydrogen, chlorine, bromine or C -C linear or branched alkyl, or RÚ and R2 together are C3-C10 alkylene, R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n. 7. A process according to claim 6 characterised in that R3 is chlorine or bromine and R2 is not chlorine or bromine. 8. A process according to claim 6 or claim 7 characterised in that said process is carried out in the presence of a solvent inert to the polymerisation reactants. 9. A process for the preparation of a compound as claimed in any of claims 1 to 4 characterised in that the process comprises: (a) reacting a compound having the formula CHRÚ= C(Rê)R (I) with a compound of the as formula CYmXn(II), where R1, Rê, R3 X and Y are as defined above and n is an integer of 1 to 4 and m is 4-n, in the presence of dichlorotris (triphenylphosphine) ruthenium; and (b) reacting the resultant product with a strong Lewis base. 10. A process according to claim 9 characterised in that said compound II are reacted in step (a) at a molar ratio of 1.1:1.- to 1.0:1.1 respectively. 11. A process according to claim 9 or claim 10 characterised in that said reaction of compounds I and II in step (a) occurs at a temperature of 500 to 1000 over a period of 0.5 to 5 hours. 12. A process in accordance with any of claims 9 to 11 characterised in that step (b) occurs at a temperature in the range of between 500 and 1200C and in the presence of a solvent inert to the product of the reaction of step (a). 13. A process according to claim 12 characterised in that said solvent of step (b) is heptane, octane, isooctane, decane, benzene, toluene or xylene. 14. A process in accordance with any of claims 9 to 13 characterised in that said reaction of step (b) occurs over a period of 5 to 100 hours and said Lewis base has a PKb of 5 or less. 15. A process according to claim 14 characterised in that said reaction of step (b) occurs over a period of 10 to 75 hours and said Lewis base is ammonia, dimethylamine, trimethylamide, diethylamine, triethylamine or dipropylamine. 16. A compound characterised by the formula YmnCCHR1CR231 where Y is hydrogen, cyano or C2-Cl9 carbalkoxy; X is chlorine or bromine; R is hydrogen, chlorine, bromine or -COOR4, where R4 is C1-C18 alkyl, C3 C18 alkenyl, 5 6 cycloalkyl, C7-Cg aralkyl or C6-C10 aryl; R2is hydrogen, chlorine, bromine or Cl-Cl8 linear or branched alkyl; R3 C1 1 is an electron withdrawing group; X is chlorine or bromine; n is an integer of 1 to 3; and m is 3-n, except that when n is 3, R1 is hydrogen, X and X1 are chlorine, if R2 is methyl then R3 is not methoxycarbonyl and if R2 is hydrogen then R3 is not methylcarbonyl. 17. A process for the preparation of a compound as claimed in claim 16 characterised in that the process comprises the reaction of a compound of the formula CHRÚ=CRêR with a compound of the formula CYmXnXÚ, where RÚ, Rê, R , X, XÚ, Y , n and m have the meanings given above, in the presence of dichlorotris(triphenylphosphine) ruthenium.

Inventors: KHAN, J.A., MATTHEWS, D.N., NUDENBURG, W., SMUDIN, D.J.
Applicants: UNIROYAL CHEMICAL COMPANY, INC.
Application year: 1984
Main classification: C07C69
IPC codes: C08F4, C08F10