CA1215073A - CATALYST ACTIVATOR FOR .alpha. OLEFIN POLYMERIZATION - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A compound having the formula YmXnCC(R1)=C(R2)R3 where Y
is hydrogen, cyano or C2-C19 carbalkoxy; X is chlorine or bro-mine; R1 is hydrogen, chlorine, bromine or -COOR4; 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 is not chlorine or bromine if R2 is chlorine or bromine and if R1 and R2 are hy-drogen 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 dis-closed.
An intermediate compound, useful in the manufacture of the above compound, having the formula YmXnCCHR1-CR2R3X1 where Y, X, R1, R2, R3, n and m have the meanings given for the com-pound of this invention and where X1 is chlorine or bromine with the limitation 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, and a process for making said intermediate is described.
A composition incorporating the compound, YmXnCC(R1)=C(R2)R3, with a vanadium catalyst, useful as a cata-lytic agent, is also disclosed.
A process for preparing poly(alpha-olefins) employing a com-pound of the above formula as a catalyst without any of the re-strictions relating to the meaning of R1 and R2 is also taught.

Description

~5~173 ss2s 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(Rl)=C(R2)R3 where is hydrogen, cyan or C2-Clg carbalkoxy; X is chlorine or bromide; R is hydrogen, chlorine, bromide or -Coors; wherein R4 is C1-C18 alkyd, C3-C18 alkenyl, C5-C6 cycle y, 7 9 or C6-C10 aureole; R is hydrogen, chlorine, bromide or C1-C18 linear or branched alkyd, provided that R1 is not chlorine or bromide if R2 is chlorine or bromide, and if Al and R2 are hydrogen, they must be in the trays configuration; or R1 and R2 together may be C3-C1o alkaline; R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n; and to the method for malting same. The instant invention also deals with the use of said come pound 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 anti-vapors are those disclosed in U. S. Patent 3,377,325, which uses a Selfware activator; Canadian Patent 833,651 using phosphorous trichloride and 2-nitropropane as activators; U . S . Patent 3,441,564 teaches an organic vitro compound as activator; US. Patent

3,444,149 discloses the use of a nutrias compound or a quinine as activator; US. Patent 3,462,399 deals with activation by organic nitrates, organic nitrites, asks compounds, special organic metallic compound or alkyd disulfides; U . S . Patent 3,507,843 using a pros-porous trichloride as activator, and U . S . Patent 4,347,159 em-plying a fort compound as activating agent.

11 s-- r ) 7 None of these activators combine the advantages of catalyst efficiency, control the molecular weight and molecular weight disk tribution of the polymer produced and are useful in both home-genus and he terogeneous phase systems . Indian J . Harm . 25, 264-8 (1963~ discloses antibacterial compounds having the structure CC13CH=CHCOOR, R being alkyd, wherein the hydrogen atoms are believed to be in a mistype configuration.

DESCRIPTION OF THE INVENTION
The new compounds of this invention are excellent t catalyst t 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 weigh-t and the molecular weight distribution of the polymerization product. Most surprisingly, they can be employed to polymerize alpha-olefins in combination with homogeneous and heterogeneous catalyst systems as well as in solution and polymerizations con-dueled essentially in the absence of a solvent.
In accordance with the instant invention, a compound is pro-voided having the formula YmXnCC(Rl)=C(R2)R3 where Y is hydrogen, cyan or C2-C19 carbalkoxy; X is chlorine or bromide; R1 is hydrogen, chlorine, bromide or -Coors; wherein R4 is C1-C18 alkyd, C3-C18 alkenYl, C5-C6 cycle y, 7 9 or C6-C10 aureole; R2 is hydrogen, chlorine, bromide or C1-C18 linear or branched alkyd, provided that R1 is not chlorine or bromide if R2 is chlorine or bromide, and if R1 and R2 are hydrogen, they must be in the trays configuration; or R1 and R2 together may be C3-C1o alkaline; 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 come pound as a catalyst activator in the polymerization of alpha-olefins.

I to Preferably, Y is hydrogen; X is chlorine or bromide; R is hydrogen or -COUCH; R2 is hydrogen, chorine or C~-C4 alkyd; or R and R together are propylene or battalion, R is chlorine, bromide, iodine, cyan, vitro, trihalomethyl, halo meaning F, Of or Bra C2-C19 alkylcarbonyl, C2-C19 alkoxycarbonyl, C1-C18 alkyd-sulfonyl, C7-Cg aralkylsulfonyl or C7-C18 alkarylsulfonyl. Usually X is chlorine, R is hydrogen, R2 is hydrogen or C1-C~ alkyd, R3 is C3-C11 alkoxycarbonyl and n is 3; the proviso being as already stated that if Al and R are hydrogen, they are situated in a trays 10 configuration.
Chemicals being representative of the compounds of this invent lion are enumerated in the Table I below.

TABLE I

Formula: YmXnCC(R1)=C(R2)R3 Y _ X R1 R2 R3 m n H By C18H37 H COUCH 1 2 ON BrCOOC6H13 Of CF3 1 2 COUCH - Of C3H7 ON 3 0 COOC4Hg By By SHEA SEIKO 2 - Of Of C12H25 O2CH2C6H5 3 CC12H25 Of C4H9 CC12H25 1 2 Of -CH2CH2C(C7H15)H- COOK 0 3 Of CC12H25 H COO cycle C6H11 0 3 In further accordance with this invention, there is provided a 25 process for making a compound of the structure YmXnCC(R1)=C(R2)R3 comprising first reacting a compound having the formula CHRl=CR2R3 (A) with a compound of the formula CYmXn (B), wherein R1, R2, R3, Y and X are as defined above; n `73 is an integer of 1 to 4; and m is 4-n, in the presence of dichloro-tris[triphenylphosphine~ruthenium, and secondly treating the result lent product with a strong Lewis base such as triethyl~mine.
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 them-portray of 50-100C for 0 . 5-5 hours, usually at reflex tempera-lure. In the second step, dehydrohalogenation is effected by heating the in termediate product of the reaction compounds A and B, Yeomen 1CC(R1)H-CXR2R3 to 50 120C 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 Pub of 5 or less, as represented by ammonia, dimethylamine, trimethylamine, dip and triethylamine, dipropylamine and the like. Suitable inert solvents include hop-lane, octane, isooctane, decant, Bunsen, Tulane, zillion 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 where Y is hydrogen, cyan or C2-C19 carbalkoxy; X is chlorine or bromide; R is hydrogen, chlorine, bromide or -COO , where I
1 18 y, 2C3 Cog alkenyl, C5-C6 cycloalkyl, C7-C aralkyl or C6-C10 aureole; R is hydrogen, chlorine, bromide or C1-C18 linear or branched alkyd; R is an electron withdrawing group; X is chlorine or bromide; n is an integer of 1 to 3; and m is 3-n, ox-crept that when n is 3, R1 is hydrogen, X and Al are chlorine, if R2 is methyl then R3 is not methoxycarbonyl and if R2 is hydrogen 3û then R3 is 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 I

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 alkyd, 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, cyan or C2-C19 carbalkoxy; X is chlorine or bromide; R1 is hydrogen, chlorine, bromide or -Coors, where R4 is C1-C18 alkyd C~-C18 alkenyl, C5-C6 cycloalkyl, C7-Cg aralkyl or C6-C10 aureole; R is hydrogen, chlorine, bromide or C1-C18 linear or branched a]kyl or R1 and R2 are together C3-C10 alkaline; 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(R1)=C(R2)R3 are as given above with the exception that if R is chlorine or bromide than R2 is not chlorine or bromide.
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 cyan or C2-C19 carbalkoxy; X is chlorine or bromide; R1 is hydrogen, chlorine, bromide or -Coors, wherein R4 is C1-C18 alkyd, C3-C18 alkenyl, C5-C6 suckle y, 7 9 or C~;-C10 aureole; R is hydrogen, chlorine, bromide or Cluck linear or branched alkyd, provided that R1 is not chlorine or bromide if R2 is chlorine or bromide; R1 and R2 together may also be C3-C10 alkaline; R is an electron withdrawing; n is an integer of 1 to 3;
and m is 3-n. This composition is useful in the catalytic polymer-ization of alpha-olefins.
In a preferred embodiment of the composition of this invention, the meanings of the functional groups of the compound YmXnCC(R1)=C(R2)R3 are as follows: Y is hydrogen; X is chlorine I

or bromide; R1 is hydrogen or -COUCH; R2 is hydrogen, chlorine or C1-C4 alkyd; alternatively R1 and R2 together are propylene or battalion; Eye is chlorine, bromide, iodine, cyan, vitro, truly-methyl, halo meaning F, Of or Bra C2-C19 alkylcarbonyl, C7-Cg S 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 alkoxy-carbonyl and n is 3.

Preparation of_Butyl_4,4,4-trichlorobut-2-transenoate (BTCB).
128 grams (1 mole) of freshly distilled bottle 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 thermos meter. The reaction mixture was heated to reflex (80C) 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 Newton which was separated by recantation from the remaining supernatant brown viscous material. The brown viscous reaction product was isolated by evaporation of the nope-lane (using a rotary evaporator). It weighed 275 grams (97%
yield) .
Infrared analysis (IT) of the product did not show an absorb-lion attributable to vinelike type unsaturation indicating the absence of an acrylic double bond. After distillation, at 80C and 26.6 Pa, the reaction product was a clear, colorless oil.
The reaction product (289 gym, 1 mole), triethylamine (138 ml, 1 mole) and Bunsen (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 reflex (80C) for 50 hours . After adding an additional 30 ml (0. 2 molt of triethylamine reflex was continued for another 20 hours.
After this total of 70 hours at reflex, a dark brownish material was obtained. The reaction product was filtered. The solid (C2H5)3NHCl salt was removed leaving a solution from which the Bunsen solvent was removed by a rotary evaporator. The result lent dark brown viscous material (234 gym, 95% yield) was distilled (72-74C at 40 Pa). The product, bottle 4,4,4-trichlorobut-2-5 transient was a colorless, clear viscous oil (90% yield). The Rand nuclear magnetic resonance (NOR) spectral (OH and 13C) data, which appear in Table II, were consistent with this compound. The elemental analysis for this compound appears in Table III.

10 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 bottle acrylate was replaced with methyl methacrylate . The add lion reaction product was recovered as a colorless, viscous material. The IT 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.
Thea product of this reaction, methyl 2-methyl-4, 4, 4-trichloro-but-2-enoate, was recovered as a clear, colorless oil (yield 85%).
The IT and IMMURE data appear in Table II, and its elemental analysis is summarized in Table III.

proportion of Ethyl 4,4,4-trichlorobut-2-enoate TUB
The carbon tetrachloride addition reaction of step 1 of Example 1 was repeated with the exception that bottle acrylate was replaced by ethyl acrylate . The reaction was conduct ted 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 IT spectrum was consistent with that compound. Tables II and III provide elemental analysis and lo and NOR spectral data, respectively, for the ETCH made in accordance with this example.

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 bottle acrylate of En-5 ample 1. The addition product of this reaction yielded an IT specs trump consistent with that compound.
The above reaction product was dehydrochlorinated in accord dance with the procedure of Example 1. The resultant product, 2-ethylhexyl 4,4,~-trichlorobut-2-enoate, was obtained after vacuum 10 distillation in an 80% yield. The IT spectrum was consistent with the title compound.

TABLE II
Example Calculated % wound %
No. Compound C H Of C H Of 1 Bottle 4,4,4-trichloro- 39.134.52 43.32 39.104.44 43.32 but-2-transenoate 2 Methyl 2-methyl-4,4,4- 33.103.22 ~8.96 32.943.12 trichlorobut-2-enoate 3 Ethyl 4,4,4-trichloro- 33.133.21 48.3 32.733.11 47.83 but- 2 - Genoa lo TABLE III
IRE. AND NOR SPECTROSCOPY DATA
Example llH - NOR (8 PAM) No. Compound 3C - NOR
25 1 Bottle 4,4,4-trichlorobut- 0.97 (t,3H), 1.42 (m, OH), 1.68 (m, OH) transient 4.2 (t, OH), 6.39 (d, lo), 7.20 (d, lo) IS (J = 9 HO) TRAYS (J = 15 HO) 13.58, 19.04, 30.53, 65.32, 92.17 121.73, 145.97, 164.63 30 2 Methyl 4,4,4-trichloro- 1.90 (s, OH), 4.1 (t, OH) 6.2 (s, lo) 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, OH), 4.25 (q, OH), 2-enoate 6.36 (d, lo), 7.2 (d, lo) 14.01, 61.34, 92.11, 121.69, 145.90 164.43 1i7~
g 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 organoalu-minus or magnesium compound or halide cocatalyst.
Such catalytic systems may be homogeneous or heterogeneous 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 alkyd such as ethylene, proxy-tone, button, pontoon, hexane-1, Dyson, dodecene-1,

4-methylpentene-1, 4-ethylhexene-1, and the like which may be home- or copolymerized to crystalline or essentially amorphous and elastomeric polymers such as polyethylene, polypropylene, polyp butane, etc., or ethylene-propylene copolymers or elastomers (EM). Elastomeric copolymers of ethylene and other alpha-olefins such as propylene may also incorporate copolymerizable non-con-jugated dines such as dicyclopentadiene (DCPD), 5-ethylidenor-bornene-2 (EN) 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 pontoon, hexane, Hutton, octane, isooctane, decant, Bunsen, Tulane, ethylene chloride, chloroform and the like.
In any case, the compounds of this invention exhibit extra-ordinary activation characteristics when used in such polymerize-lions as illustrated by the examples below.

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-Lo 73 ~10-ping funnel was added 1000 ml dry Newton solvent. Dry ethyl tone 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 Hutton solution of ethyl-

5 aluminum sesquichloride (EASY) cocatalyst (cay. 1 millimole) was introduced. While maintaining the ethylene-propylene feed, drop-wise addition of a solution of 0 . 05 millimole Vocal catalyst, 0 .1 millimole BTCB and 10 millimole EN, all in 60 ml Newton was started causing polymerization to commence. Vocal, etc., addition 10 took about 50 minutes, but monomer introduction was continued for another 10 minutes, after which time the polymerization was ton-minuted by the addition of 5 ml isopropanol. The polymer in soul-lion was extracted with isoproponal to which a small amount of antioxidant was added. The stabilized polymer was recovered, 15 weighed and analyzed.
The polymer was analyzed as EPDM characterized by an ethyl tone to propylene weight ratio of 68: 32, an intrinsic viscosity of 1.7, as measured in tetralin at 135C, an iodine number of 8.4 and a glass transition temperature of -52C. The yield of EPDM polyp men was 43 grams representing a catalyst efficiency of 860 g polyp men per rnillimole of vanadium.
See also summary in Table III.

-Following essentially the procedure owe Example 5, additional 25 polymerizations were conducted. The results are summarized in Table IV. Example 9 is outside this invention.

~15~1t'73 TABLE IV
Example No. 5 6 7 8 9 Catalyst activator BTCB MMTB ETCH 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, Pam 59 95 169 70 280 Polymer characteristics Intrinsic viscosity, dug 1.7 3.2 3.35 2.38 2.76 Unsaturation, It No . 8.4 10.8 20.9 Ethylene/propylene, weight 68/32 74/26 75/25 72/28 70/30 * In tetralin at 135C.

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 -19C, at which point hydrogen gas was introduced at 138 spa excess pressure as well as ethylene at the same pros-sure. Then, while stirring, a solution of catalyst (0.025 millimole), EASY (1.48 millimole), EBB (5.4g) and catalyst activator (0.4 mole) in 1000 ml Hutton was charged to the autoclave which initiated polymerization. The reactor temperature was reduced -to -27C using a dry ice-isopropanol bath while ethylene feed was continued at the above pressure for one hour . The polymerize lion was stooped by adding a sufficient amount of isopropanol (having dissolved therein some antioxidant) to the reactor. The reactor con tents, EPDM particles dispersed in monomer, were isolated, dried, weighed and analyzed. The results are summarized in Table V below.

SKYE

TABLE V
Example No. 10 11 Ethylene, g 118 114 Propylene, g 490 509 EN, g 5.4 5 4 EASY, Molly 1.48 1.48 VBDP(l) Molly 0.025 Vocal, Molly - 0.025 BTCB, Molly 0.4 0.4 AVOW, molar 59.2 59.2 TABLE V (continued) Example No. 10 11 BTCB/V, molar 16 16 Hydrogen, spa 138 138 Reaction time, minutes 60 60 Polymer yield, g 109.7 89.8 g Polymer/mrnol V 4388 3592 Polymer characteristics Ethylene/propylene, weight 62/38 69/31 It No. 5.9 3.8 IVY. (tetralin at 135C) 2.54 4.08 V metal in polymer, Pam 11.6 14.2 Remarks (1) VBDP = vanadylbis[diethylphosphate] catalyst 25 (2) Excess pressure The results indicate the excellent catalyst efficiency achieved when using the compounds of this invention as catalyst activators.

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 5 portion of the reactor) propylene, 1. 75 moles hydrogen (3 . 5g) and ethylene. To this was added EASY in isopen-tane (120 ml). Stir-ring was initiated at 175 revolutions per minute. With the tempera-lure in the reactor set at -8C, cooling was discontinued and a solution of 0.2 millimoles of catalyst, 36 milliliters of EN, catalyst 10 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 initial ted the reaction. The reaction was terminated by passing the pro-pylon liquid containing suspended polymer into an isopropanol 15 solution containing an antioxidant. The polymer was separated from the liquid phase by filtration and analyzed.
A summary of Examples 12-1~ appears below in Table VI.

TABLE VI
Example No. 12 13 14 15 16 ~merization Ethylene, g 650 750 620 851 809 Propylene, g 7000 7000 7000 7000 7000 EN, g 17.5 36 36 28.2 33.4 EASY, Molly 16.7 8.3 28 8.3 8.3 Vocal, Molly 0.097 0.081 0.64 VB up, Molly - 0.123 0.132 BPCC(2), Molly 3.1 2.6 2.9 3.9 4.2 Hydrogen, g 3.5 3.5 3.5 3.5 3.5 AVOW, 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 or characteristics Ethylene/propylene, weight 59/41 59/41 52/48 53/47 52/48 It No. 3.2 5.5 2.7 2.7 2.7 IVY., dl/g(3) 2.54 2.0 4.95 3.28 2.82 Roman lcs:
(1) vanadylbis[diethylphosphate] catalyst (2) bottle perchlorocrotonate catalyst activator (3) in tetraline at 135C.
These experiments demonstrate that the catalyst activator, bottle perchlorocrotonate, known to be suitable for polymerizations of EPDM employing an inert polymerization medium provides unsex-pectedly improved catalyst efficiency when used essentially in the absence of such an inert medium.

Following essentially the procedure of Example 1, dim ethyl 2-trichloromethylbut-2-endioic acid ester (DMBA) was prepared from dim ethyl fumarate and bromotrichloromethane and by subxequen t dehydrobromination of the intermediate.

5~'73 Reacting bottle me thacrylate with tetrachloromethane and sub -sequent dehydrohalogenation resulted in the compound n-butyl 2-methyl-4, 4 ,4-trichlorobut-2-enoate (BMTB ) .

From methyl acrylate and carbon tetrachloride was prepared the intermediate Cl3CCH2CHClCOOCH3, which, upon dihedral-genation yielded methyl 4,4,4-trichlorobut-2-enoate (MTCB).

hollowing essentially the procedure of Example 1, additional EPD~l preparations were carried out using compounds of this in-mention as catalyst activators. The results are summarized in Table VII .

TABLE VII

Example No. 20 21 22 23 I 25 Catalyst Activator MTCB DMBA BMTB/C(l) BMTB/T(2) BTCB/C(l) BTCB/T( Polymer yield, g 22 19 46 58 38 58 g polymer/mmol V 440 380 920 1160 7601160 Remarks:
(1) believed to be primarily the cis-isomer (2) believed to be primarily the trans-isomer Improved catalyst activity is clearly demonstrated with trays-isomers having a more pronounced effect.
The foregoing preferred embodiments and examples will make 25 apparent, to those skilled in the art, other embodiments and ox-apples . These embodiments and examples, wit thin 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 (15)

What Is Claimed Is:

1. A compound having the formula YmXnCC(R1)=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, C7-C9 aralkyl or C6-C10 aryl; R2 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-C10 alkylene; R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n.

2. The compound of claim 1, wherein 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 together are propylene or butylene, R3 is chlorine, bromine, iodine, cyano, nitro, trihalo-methyl, halo meaning F, Cl or Br; C2-C19 alkylcarbonyl, C2-C19 alkoxycarbonyl, C1-C18 alkylsulfonyl, C7-C9 aralkylsulfonyl or C7-C18 alkarylsulfonyl.

3. The compound of claim 2, wherein X is chlorine, R1 is hydrogen, R2 is hydrogen or C1-C4 alkyl, R3 is C3-C12 alkoxycar-bonyl and n is 3.

4. The compound of claim 2 selected from the group consist-ing of methyl 2-methyl-4,4,4-trichlorobut-2-enoate, ethyl 4,4,4-tri-chlorobut-2-enoate, butyl 4, 4, 4-trichlorobut-2-transenoate, 2-ethyl-hexyl 4,4,4-trichlorobut-2-enoate, dimethyl 2-trichloromethylbut-2-endioate, butyl 2-methyl-4,4,4-trichlorobut-2-enoate and methyl 4, 4, 4-trichlorobut-2-enoate.

5. A composition comprising a vanadium metal catalyst, and a compound of the formula YmXnCC(R1)=C(R2)R3 wherein Y is hydro-gen, 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-C9 aralkyl or C6-C10 aryl; R2 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, or R1 and R2 together may be C3-C10 alky-lene; R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n.

6. An improved process for preparing polyalpha-olefins essentially in the absence of a reaction medium inert to the poly-merization comprising contacting at least one monomer having the structure CH2-CHQ wherein Q is hydrogen or C1-C16 alkyl with an anionic polymerization catalyst; the improvement comprising carrying out said process in the presence of catalyst activating amount of a compound having the formula YmXnCC(R1)=C(R2)R3, wherein 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-C9 aralkyl or C6-C10 aryl; R2 is hydrogen, chlorine, bromine or C1-C18 linear or branched alkyl, or R1 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. The process of claim 6 provided that if R3 is chlorine or bromine R2 is not chlorine or bromine.

8. The process of claim 7 wherein said process is being carried out in the presence of a solvent inert to the polymerization reactants.

9. A process for the preparation of a compound having the formula YmXnCC(R1)=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; C7-C9 aralkyl or C6-C10 aryl; R2 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-C18 alkylene; R3 is an electron withdrawing group; n is an integer of 1 to 3; and m is 3-n comprising:
(a) reacting a compound having the formula CHR1=C(R2)R3 (I) with a compound of the formula CYmXn(II), where R1, R2, R3 X and Y are as defined above and n is an inte-ger of 1 to 4 and m is 4-n, in the presence of dichlorotris(tri-phenylphosphine)ruthenium, at a temperature of 50-100°C; and (b) reacting the resultant product with a strong Lewis base, at 50-120°C in the presence of a solvent insert to the intermediate produced in step (a).

10. A process in accordance with claim 9 wherein said com-pound I and said compound II are reacted in step (a) at a molar ratio of 1.1:1.0 to 1.0:1.1 respectively.

11. A process in accordance with claim 10 wherein said reac-tion of compounds I and II in step (a) occurs at a temperature of 50° to 100°C over a period of 0.5 to 5 hours.

12. A process in accordance with claim 9 wherein step (b) occurs at a temperature in the range of between 50° and 120°C and in the presence of a solvent inert to the product of the reaction of step (a).

13. A process in accordance with claim 12 wherein 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.

14. A process in accordance with claim 13 wherein said reaction of step (b) occurs over a period of 10 to 75 hours and said Lewis base is selected from the group consisting of ammonia, dimethylamine, trimethylamide, diethylamine, triethylamine and dipropylamine.

15. A process in accordance with claim 12 wherein said solvent of step (b) is selected from the group consisting of heptane, octane, isooctane, decane, benzene, toluene and xylene.