POLAR ACTIVATION IN COPOLYMERIZATION OF PROPYLENE AND T-BUTYL-2-(1,1-DIMETHYLHEPT-6-ENYL)-4-METHYLPHENOL OVER A RACEMIC )BIS(ETA-5-4,5,6,7-TETRAHYDRO-1-INDENYL)]ZIRCONIUM DICHLORIDE METHYLALUMOXANE CATALYST SYSTEM
Ce. Wilen et Jh. Nasman, POLAR ACTIVATION IN COPOLYMERIZATION OF PROPYLENE AND T-BUTYL-2-(1,1-DIMETHYLHEPT-6-ENYL)-4-METHYLPHENOL OVER A RACEMIC )BIS(ETA-5-4,5,6,7-TETRAHYDRO-1-INDENYL)]ZIRCONIUM DICHLORIDE METHYLALUMOXANE CATALYST SYSTEM, Macromolecules, 27(15), 1994, pp. 4051-4057
Copolymers of propylene and the polar monomer t-butyl-2-(1,1-dimethylh
ept-6-enyl)-4-methylphenol were obtained with racemic )bis(eta5-4,5,6,
7-tetrahydro-1-indenyl)]-zirconium dichloride and methylalumoxane acti
vator. The copolymers contained from 1.3 to 5.5 wt % of phenolic units
and exhibited high thermooxidative stability even after prolonged ext
raction with a mixture of refluxing (50:50) 2-propanol/cyclohexane. Th
e initial polymerization rate, compared to that of homopolymerization
of propylene, increased up to almost 6 times when the sterically hinde
red phenolic stabilizer monomer was added. A similar increase in activ
ity was recorded when 2,6-di-tert-butylphenol was added during propyle
ne polymerization. The activity enhancement was attributed to the abil
ity of the phenolic stabilizer to function as a large weakly coordinat
ing anion, which stabilizes the cationic polymerization center. The de
gree of microtacticity of the copolymer, isotactic triad mm > 0.96, wa
s similar to that of isotactic polypropylene prepared by the same cata
lyst system. The dominating insertion mechanism was 1,2 addition with
very low amounts of 1,3-addition irregularities. The produced copolyme
rs exhibited lower melting points and crystallinities than polypropyle
ne obtained under similar conditions. According to gel permeation chro
matography, the copolymers had a narrow molecular weight distribution
ranging from 1.9 to 2.1, which is close to those values characteristic
for polymers produced by single-site catalysts.