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1.
The polymerization of butadiene (Bd) with Co(acac)3 in combination with methylaluminoxane (MAO) was investigated. The polymerization of Bd with Co(acac)3‐MAO catalysts proceeded to give cis‐1,4 polymers (94 – 97%) bearing high molecular weights (40 × 104) with relatively narrow molecular weight distributions (Mw's/Mn's). The molecular weight of the polymers increased linearly with the polymer yield, and the line passed through an original point. The polydispersities of the polymers kept almost constant during reaction time. This indicates that the microstructure and molecular weight of the polymers can be controlled in the polymerization of Bd with the Co(acac)3‐MAO catalyst. The effects of reaction temperature, Bd concentration, and the MAO/Co molar ratio on the cis‐1,4 microstructure and high molecular weight polymer in the polymerization of Bd with Co(acac)3‐MAO catalyst were observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2793–2798, 2001  相似文献   

2.
The effect of an alkyl substituted in the aromatic ring of the salen ligand on the polymerization of butadiene (Bd) with (salen)Co(II) complexes in combination with methylaluminoxane (MAO) was investigated. The activity for the polymerization of Bd was influenced significantly by the introduction of alkyl groups at the 3,3′,5,5′‐positions in the aromatic ring of the salen ligand, and both the polymerization rate and 1,4‐cis contents increased in the following order with respect to the alkyl group: H < CH3 < t‐C4H9. This is in good agreement with the bulkiness of the alkyl groups. The activity for the polymerization of the (salen)Co(II) complex possessing t‐C4H9 at the 3,3′‐positions was higher than that of the (salen)Co(II) bearing t‐C4H9 at the 5,5′‐positions. Thus, the introduction of bulky substituents at the 3,3′‐positions of the salen ligand was an important factor in achieving both high activity and high 1,4‐cis selectivity in the polymerization of Bd with (salen)Co(II) complexes in combination with MAO. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4088–4094, 2006  相似文献   

3.
Copolymerization of styrene (St) and butadiene (Bd) with nickel(II) acetylacetonate [Ni(acac)2]-methylaluminoxane (MAO) catalyst was investigated. Among the metal acetylacetonates [Mt(acac)x] examined, Ni(acac)2 showed a high activity for the copolymerization of St and Bd giving copolymers having high cis-1,4-microstructure in Bd units in the copolymer. The effect of alkylaluminum as a cocatalyst on the copolymerization of St and Bd with the Ni(acac)2-MAO catalyst was observed, and MAO was found to be the most effective cocatalyst for the copolymerization. The monomer reactivity ratios for the copolymerization of St and Bd with the Ni(acac)2-MAO catalyst were determined to be rSt = 0.07 and rBd = 3.6. Based on the obtained results, it was presumed that the random copolymers with high cis-1,4-microstructure in Bd units could be synthesized with the Ni(acac)2-MAO catalyst without formation of each homopolymer. The polymerization mechanism with the Ni(acac)2-MAO catalyst was also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3838–3844, 1999  相似文献   

4.
A new diphosphinoamine ligand [Ph2PN(p‐C6H4OMe)PPh2] was prepared through aminolysis reaction of p‐methoxyaniline with Ph2PCl in the presence of NEt3. Consequently, the corresponding nickel (II) diphosphinoamine complex [(p‐C6H4OMe)N(PPh2)2NiCl2] was synthesized and characterized. The solid‐state structure of the complex was determined by single‐crystal X‐ray diffraction. As combined with methylaluminoxane (MAO), the complex displayed high catalytic activity for vinyl polymerization of norbornene. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

5.
Polymerization of 2‐pentene with [ArN?C(An)C(An)·NAr)NiBr2 (Ar?2,6‐iPr2C6H3)] ( 1‐Ni) /M‐MAO catalyst was investigated. A reactivity between trans‐2‐pentene and cis‐2‐pentene on the polymerization was quite different, and trans‐2‐pentene polymerized with 1‐Ni /M‐MAO catalyst to give a high molecular weight polymer. On the other hand, the polymerization of cis‐2‐butene with 1‐Ni /M‐MAO catalyst did not give any polymeric products. In the polymerization of mixture of trans‐ and cis‐2‐pentene with 1‐Ni /M‐MAO catalyst, the Mn of the polymer increased with an increase of the polymer yields. However, the relationship between polymer yield and the Mn of the polymer did not give a strict straight line, and the Mw/Mn also increased with increasing polymer yield. This suggests that side reactions were induced during the polymerization. The structures of the polymer obtained from the polymerization of 2‐ pentene with 1‐Ni /M‐MAO catalyst consists of ? CH2? CH2? CH(CH2CH3)? , ? CH2? CH2? CH2? CH(CH3)? , ? CH2? CH(CH2CH2CH3)? , and methylene sequence ? (CH2)n? (n ≥ 5) units, which is related to the chain walking mechanism. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2858–2863, 2008  相似文献   

6.
A novel, water‐soluble Rh complex, (nbd)Rh[PPh2(m‐NaOSO2C6H4)] [C(Ph)?CPh2] ( 1 ) was synthesized by the reaction of [(nbd)RhCl]2, Ph2P(m‐NaOSO2C6H4) and Ph2C?C(Ph)Li, whose structure was determined by NMR and IR spectroscopies. The Rh catalyst 1 induced the polymerization of phenylacetylene (PA) in water to give two kinds of polymers; one was soluble in organic solvents such as tetrahydrofuran (THF) and CHCl3, and the other was insoluble in common organic solvents. The polymerization of sodium p‐ethynylbenzoate (p‐NaOCO‐PA) homogeneously proceeded with 1 in water at 60 °C to give the polymer in high yield. Poly(p‐NaOCO‐PA) was treated with 1 N HCl and then reacted with (CH3)3SiCHN2 to obtain poly(p‐MeOCO‐PA). The methyl‐esterified polymer was insoluble in THF and CHCl3, which suggests that the formed poly(p‐MeOCO‐PA) has cis–cisoidal structure. The polymer obtained from the polymerization of [p‐CH3(OCH2CH2)2O2CC6H4]C?CH with 1 in water was soluble in methanol, ethanol, and THF, and partly soluble in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2100–2105, 2004  相似文献   

7.
The copolymerization of styrene (St) with a styrene‐terminated polyisoprene macromonomer (SIPM) by a nickel(II) acetylacetonate [Ni(acac)2] catalyst in combination with methylaluminoxane (MAO) was investigated. A SIPM with a high terminal degree of functionalization and a narrow molecular weight distribution was used for the copolymerization of St. The copolymerization proceeded easily to give a high molecular weight graft copolymer. After fractionation of the resulting copolymer with methyl ethyl ketone, the insoluble part had highly isotactic polystyrene in the main chain and polyisoprene in the side chain. Lowering the MAO/Ni molar ratio and the polymerization temperature were favorable to producing isospecific active sites. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1241–1246, 2000  相似文献   

8.
Supported type cocatalysts using triphenylcarbenium perchlorate (Ph3CClO4) were prepared by impregnation on inorganic carrier, magnesium chloride (MgCl2) and applied to ethylene polymerizations with rac‐Et[Ind]2ZrCl2. Homogeneous polymerizations with Ph3CClO4 were also carried out for comparison. The activity of homogeneous polymerization was much lower than that obtained with methylaluminoxane (MAO). On the other hand, rac‐Et[Ind]2ZrCl2 activated by the supported type Ph3CClO4/MgCl2 system displayed high activity comparable to that obtained with MAO. From the results of fractionation and polymerization of the rac‐Et[Ind]2ZrCl2‐Ph3CClO4/MgCl2 catalyst system, it was found that the increased activity mainly came from the active species in the supernatant part. UV‐vis spectroscopic measurements combined with ICP analysis indicate that the active species in the supernatant fraction are composed of a stoichiometric amount of perchlorate and metallocene catalyst.  相似文献   

9.
Inorganic siliceous porous materials such as MFI type zeolite, mesoporous silica MCM‐41 and silica gel with different average pore diameters were applied to the adsorptive separation of methylaluminoxane (MAO) used as a cocatalyst in α‐olefin polymerizations. The separated MAOs combined with rac‐ethylene‐(bisindenyl)zirconium dichloride (rac‐Et(Ind)2ZrCl2) were introduced to propylene polymerization, and their influences on the polymerization activity and stereoregularity of the resulting polymers were investigated. The polymerization activity and isotactic [mmmm] pentad of the produced propylene were markedly dependent upon the pore size of the porous material used for adsorptive separation. From the results obtained from solvent extraction of the produced polymers, it was suggested that there are at least two kinds of active species with different stereospecificity in the rac‐Et(Ind)2ZrCl2/MAO catalyst system.  相似文献   

10.
Abstract

Methyl methacrylate (MMA) was found to be effectively polymerized with bis(cyclopentadienyl)titanium dichloride (CP2TiCl2) in a water-methanol mixture (1:1, v/v). The polymerization proceeded heterogeneously because the resulting poly(MMA) was insoluble in the system. The rate (R p) of the heterogenous polymerization was apparently expressed by R p = k[Cp2TiCl2]2[MMA]2˙5 (at 40°C). The resulting poly(MMA) was observed to consist of tetrahydrofuran (THF)-soluble and insoluble parts. In contrast with the usual radical poly(MMA), the THF-insoluble part was soluble in benzene, toluene, and chloroform but insoluble in polar solvents such as ethyl acetate, acetone, acetonitrile, dimethylformamide, and dimethylsulfoxide. The polymerization was found to be profoundly accelerated by irradiation with a fluorescent room lamp (15 W). The results of copolymerization of MMA and acrylonitrile indicated that the present polymerization proceeds through a radical mechanism.  相似文献   

11.
Homopolymerization of a styrene‐terminated polyisoprene macromonomer (SIPM) by half‐titanocene catalysts in combination with methylaluminoxane (MAO) was investigated. Polymerization of the SIPM with CpTiCl3‐MAO as the catalyst was found to proceed readily to give a high molecular weight polymer. 1H and 13C NMR spectra of the poly(SIPM) after ozonolysis of the isoprene side chain revealed that poly(SIPM) is a highly syndiotactic polymer. Syndiotactic poly(SIPM) is soluble in usual solvents in spite of having highly syndiotactic sequences on its main chain and a considerable degree of polymerization.  相似文献   

12.
The polymerization of methyl methacrylate (MMA) catalyzed with cyclopentadienylnickel‐methylaluminoxane (Cp2Ni‐MAO) was investigated. Polymerization readily proceeds with this catalyst, and the resulting polymer is rich in syndiotactic content. The effects of the MAO/Ni system on the polymerization activity of MMA were observed, and it was found that only small amounts of MAO are required to reach high polymerization activity.  相似文献   

13.
A novel metallocene catalyst was prepared from the reaction of (η3‐pentamethylcyclopentadienyl)dimethylaluminum (Cp*AlMe2) and titanium(IV) n‐butoxide Ti(OBu)4. The resulting titanocene Cp*Ti(OBu)3 was combined with methylaluminoxane (MAO)/tri‐iso‐butylaluminum (TIBA) to carry out the syndiotactic polymerization of styrene. The resulting syndiotactic polystyrene (sPS) possesses high syndiotacticity according to 13C NMR. Catalytic activity and the molecular weight of the resulting sPSs were discussed in terms of reaction temperature, concentration of MAO, amounts of scavenger TIBA added, and the hydrogen pressure applied during polymerization.  相似文献   

14.
The kinetics of propylene polymerization initiated by ansa‐metallocene diamide compound rac‐Me2Si(CMB)2Zr(NMe2)2 (rac‐1, CMB = 1‐C5H2‐2‐Me‐4‐tBu)/methylaluminoxane (MAO) catalyst were investigated. The formation of cationic active species has been studied by the sequential NMR‐scale reactions of rac‐1 with MAO. The rac‐1 is first transformed to rac‐Me2Si(CMB)2ZrMe2 (rac‐2) through the alkylation mainly by free AlMe3 contained in MAO. The methylzirconium cations are then formed by the reaction of rac‐2 and MAO. Small amount of MAO ([Al]/[Zr] = 40) is enough to completely activate rac‐1 to afford methylzirconium cations that can polymerize propylene. In the lab‐scale polymerizations carried out at 30°C in toluene, the rate of polymerization (Rp) shows maximum at [Al]/[Zr] = 6,250. The Rp increases as the polymerization temperature (Tp) increases in the range of Tp between 10 and 70°C and as the catalyst concentration increases in the range between 21.9 and 109.6 μM. The activation energies evaluated by simple kinetic scheme are 4.7 kcal/mol during the acceleration period of polymerization and 12.2 kcal/mol for an overall reaction. The introduction of additional free AlMe3 before activating rac‐1 with MAO during polymerization deeply influences the polymerization behavior. The iPPs obtained at various conditions are characterized by high melting point (approximately 155°C), high stereoregularity (almost 100% [mmmm] pentad), low molecular weight (MW), and narrow molecular weight distribution (below 2.0). The fractionation results by various solvents show that iPPs produced at Tp below 30°C are compositionally homogeneous, but those obtained at Tp above 40°C are separated into many fractions. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 737–750, 1999  相似文献   

15.
Organo‐modified layered silicates were synthesized and used as inorganic carriers for CoCl2(PtBu2Me)2‐MAO catalyst in the polymerization of 1,3‐butadiene, yielding cis‐1,4‐enriched polybutadiene. The organoclays were prepared by: (i) intercalation of (ar‐vinyl‐benzyl)trimethyl ammonium chloride salt through an ion exchange reaction, and (ii) the edge‐surface grafting by trimethylchlorosilane. The ammonium modifier acts as “spacer” increasing the layer d‐spacing and as “filler” favoring the silylation of the edge‐surface clay hydroxyls. The grafted silane prevents the MAO cocatalyst from reacting with the edge‐OHs, by forcing it to react within the interlayer clay region. MAO lead to methylation of the cobalt complex and carbanion abstraction to give a cobalt‐methyl cation that is stabilized by the MAO anion. The nanoconfined cationic alkylated species insert the butadiene on the Co‐Me bond affording the growth of the polymer chains within the clay layers. The growing of the macromolecular chains fills the interlayer silicate region giving an intercalated polybutadiene rubber nanocomposite. The role of the silicate organo modification on the heterogeneous catalyst structural features, the polymerization behavior and the nanocomposite structures are discussed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

16.
cis‐Selective polymerizations of isoprene with the catalysts composed of η5‐C5H4(R)TiCl3 (1; R?H, 2 ; tert‐Bu) and methylaluminoxane were investigated. Both catalysts showed remarkable catalytic activities for the polymerization of isoprene. The polymerization activities were strongly affected by the substituent introduced on cyclopentadienyl ring. Introduction of bulky tert‐butyl group was found to be effective for enhancement of polymerization activity, but the cis‐content of polyisoprene prepared by the 2 /MAO catalyst was lower than that by 1 /MAO catalyst. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1841–1844, 2004  相似文献   

17.
This article discusses a new borane chain transfer reaction in olefin polymerization that uses trialkylboranes as a chain transfer agent and thus can be realized in conventional single site polymerization processes under mild conditions. Commercially available triethylborane (TEB) and synthesized methyl‐B‐9‐borabicyclononane (Me‐B‐9‐BBN) were engaged in metallocene/MAO [depleted of trimethylaluminum (TMA)]‐catalyzed ethylene (Cp2ZrCl2 and rac‐Me2Si(2‐Me‐4‐Ph)2ZrCl2 as a catalyst) and styrene (Cp*Ti(OMe)3 as catalyst) polymerizations. The two trialkylboranes were found—in most cases—able to initiate an effective chain transfer reaction, which resulted in hydroxyl (OH)‐terminated PE and s‐PS polymers after an oxidative workup process, suggesting the formation of the B‐polymer bond at the polymer chain end. However, chain transfer efficiencies were influenced substantially by the steric hindrances of both the substituent on the trialkylborane and that on the catalyst ligand. TEB was more effective than TMA in ethylene polymerization with Cp2ZrCl2/MAO, whereas it became less effective when the catalyst changed to rac‐Me2Si(2‐Me‐4‐Ph)2ZrCl2. Both TEB and Me‐B‐9‐BBN caused an efficient chain transfer in the Cp2ZrCl2/MAO‐catalyzed ethylene polymerization; nevertheless, Me‐B‐9‐BBN failed in vain with rac‐Me2Si(2‐Me‐4‐Ph)2ZrCl2/MAO. In the case of styrene polymerization with Cp*Ti(OMe)3/MAO, thanks to the large steric openness of the catalyst, TEB exhibited a high efficiency of chain transfer. Overall, trialkylboranes as chain transfer agents perform as well as B? H‐bearing borane derivatives, and are additionally advantaged by a much milder reaction condition, which further boosts their applicability in the preparation of borane‐terminated polyolefins. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3534–3541, 2010  相似文献   

18.
The kinetics of the ethylene‐norbornene copolymerization, catalyzed by rac‐Et(Ind)2ZrCl2/MAO, 90%rac/10%meso‐Et(4,7‐Me2Ind)2ZrCl2/MAO and rac‐H2C(3‐tert‐BuInd)2ZrCl2/MAO was followed by sampling from the reaction mixture at fixed time intervals. Catalyst activity, copolymer composition and molar mass were studied as a function of time. The polymers showed an unusually low polydispersity and a significant increase in their molar mass with time, suggesting a quasi‐living polymerization.  相似文献   

19.
A series of N‐(2‐benzimidazolyquinolin‐8‐yl)benzamidate half‐titanocene chlorides, Cp′TiLCl ( C1 – C8 : Cp′ = C5H5, MeC5H4, or C5Me5; L = N‐(benzimidazolyquinolin‐8‐yl)benzamides)), was synthesized by the KCl elimination reaction of half‐titanocene trichlorides with the correspondent potassium N‐(2‐benzimidazolyquinolin‐8‐yl)benzamide. These half‐titanocene complexes were fully characterized by elemental and NMR analyses, and the molecular structures of complexes C2 and C8 were determined by the single‐crystal X‐ray diffraction. The high stability of the pentamethylcyclopentadienyl complex ( C8 ) was evident by no decomposing nature of its solution in air for one week. The oxo‐bridged dimeric complex ( C9 ) was isolated from the solution of the corresponding cyclopentadienyl complex ( C3 ) solution in air. Complexes C1 – C8 exhibited good to high catalytic activities toward ethylene polymerization and ethylene/α‐olefin copolymerization in the presence of methylaluminoxane (MAO) cocatalyst. In the typical catalytic system of C1/ MAO, the polymerization productivities were enhanced with either elevating reaction temperature or increasing the ratio of MAO to titanium precursor. In general, it was observed that higher the catalytic activity of the catalytic system lower the molecular weight of polyethylene. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3154–3169, 2009  相似文献   

20.
The influence of ligand structure on copolymerization properties of metallocene catalysts was elucidated with three C1‐symmetric methylalumoxane (MAO) activated zirconocene dichlorides, ethylene(1‐(7, 9)‐diphenylcyclopenta‐[a]‐acenaphthadienyl‐2‐phenyl‐2‐cyclopentadienyl)ZrCl2 ( 1 ), ethylene(1‐(7, 9)‐diphenylcyclopenta‐[a]‐acenaphthadienyl‐2‐phenyl‐2‐fluorenyl)ZrCl2 ( 2 ), and ethylene(1‐(9)‐fluorenyl‐(R)1‐phenyl‐2‐(1‐indenyl)ZrCl2 ( 3 ). Polyethenes produced with 1 /MAO had considerable, ca. 10% amount of trans‐vinylene end groups, resulting from the chain end isomerization prior to the chain termination. When ethene was copolymerized with 1‐hexene or 1‐hexadecene using 1 /MAO, molar mass of the copolymers varied from high to moderate (531–116 kg/mol) depending on the comonomer feed. At 50% comonomer feed, ethene/1‐olefin copolymers with high hexene or hexadecene content (around 10%) were achievable. In the series of catalysts, polyethenes with highest molar mass, up to 985 kg/mol, were obtained with sterically most crowded 2 /MAO, but the catalyst was only moderately active to copolymerize higher olefins. Catalyst 3 /MAO produced polyethenes with extremely small amounts of trans‐vinylene end groups and relatively low molar mass 1‐hexene copolymers (from 157 to 38 kg/mol) with similar comonomer content as 1 . These results indicate that the catalyst structure, which favors chain end isomerization, is also capable to produce high molar mass 1‐olefin copolymers with high comonomer content. In addition, an exceptionally strong synergetic effect of the comonomer on the polymerization activity was observed with catalyst 3 /MAO. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 373–382, 2008  相似文献   

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