Monomer-isomerization polymerization. XIX. Monomer-isomerization copolymerizations of methylbutenes and 2-butene with Ziegler-Natta catalyst

The copolymerization of 3-methyl-1-butene (3M1B), 2-methyl-2-butene (2M2B), or 2-methyl-1-butene (2M1B) with trans-2-butene (2B) was attempted in the presence of a Ziegler-Natta catalyst. It was found the 3M1B underwent monomer-isomerization copolymerization with 2B to give a copolymer consisting of both 3M1B and 1-butene (1B) units, with an infrared (IR) spectrum in good agreement with that obtained from the copolymerization of 3M1B with 1B under similar conditions. When the apparent copolymerization parameters obtained by a TiCl₃–(C₂H₅)₃Al catalyst were compared, the apparent reactivity of 3M1B observed in the 3M1B-2B system was much higher than that in the 3M1B-1B system. However, 2M2B and 2M1B did not undergo monomer-isomerization copolymerization with 2B, and only the homopolymer of 1B was obtained under similar conditions.     

Monomer-isomerization polymerization. XVIII. Monomer-isomerization copolymerizations of 4-phenyl-2-butene with 4-methyl-2-pentene and 3-heptene with Ziegler-Natta catalyst

4-Phenyl-2-butene (4Ph2B) undergoes monomer-isomerization copolymerization with 4-methyl-2-pentene (4M2P) and 2-and 3-heptene (2H and 3H) with TiCl₃–(C₂H₅)₃Al catalyst at 80°C to produce copolymer consisting exclusively of 1-olefin units. For comparison the copolymerization of 4-phenyl-1-butene (4Ph1B) with 4-methyl-1-pentene (4M1P) and 1-heptene (1H) was carried out under similar conditions. The composition of the copolymers obtained from these copolymerizations was determined from the ratios of optical densities D₁₃₈₀ and D₁₆₀₀ of infrared (IR) spectra of their thin films. The apparent monomer reactivity ratios for the monomer-isomerization copolymerization of 4Ph2B with 4M2P, 2H, and 3H in which the concentration of olefin monomer in the feed was used as internal olefin and those for the copolymerization of 4Ph1B with 4M1P and 1H were determined as follows: 4Ph2B(M₁)-4M2P(M₂); r₁ = 0.90, r₂ = 0.20, 4Ph1B(M₁)-4M1P (M₂); r₁ = 0.40, r₂ = 0.70, 4Ph2B(M₁)-2H(M₂); r₁, = 0.45, r₂ = 1.85, 4Ph2B(M₁)-3H(M₂); r₁ = 0.50, r₂ = 1.20, 4Ph1B(M₁)-1H(M₂); r₁ = 0.55, r₂ = 0.75. The difference in monomer reactivity ratios seemed to originate from the rate of isomerization from 2- or 3-olefins to 1-oletins in these monomer-isomerization copolymerizations.     

Monomer-isomerization polymerization. XXI.. Monomer-isomerization copolymerization of 3-methyl-1-butene and 2-pentene with ziegler–natta catalyst

3-Methyl-1-butene (3M1B) was found to undergo monomer-isomerization copolymerization with 2-pentene (2P) in the presence of Ziegler–Natta catalyst to give a copolymer exclusively consisting of 3M1B and 1-pentene (1P) units, the same as that obtained from copolymerization of 3M1B and 1P. The apparent copolymerization parameters were determined. The amount of 3M1B unit incorporated in the copolymers was found to increase in the copolymerization system of 3M1B-2P more than in that of 3M1B-1P. The polymers consisting of nearly complete 3M1B units were produced at a rapid rate through monomer-isomerization copolymerization of 3M1B with 2P in the presence of TiCl₃ ? (C₂H₅)₃Al catalyst.     

Monomer-isomerization polymerization. XVII. Monomer-isomerizations copolymerizations of 2-butene with 3-heptenes and 4-methyl-2-pentenes with Ziegler-Natta catalyst

2-Butene(2B) copolymerizes with 3-heptene(3H) and 4-methyl-2-pentene(4M2P) by a monomer-isomerization copolymerization mechanism in the presence of TiCl₃–(C₂H₅)₃Al catalyst at 80°C to yield the copolymers of 1-olefin units. By comparison, the copolymerization of 1-butene(1B) with 4-methyl-1-pentene(4M1P) was also carried out under similar conditions. The composition of the copolymers obtained from these copolymerizations was determined from the ratios of optical densities D₇₂₃/D₁₃₈₀ and D₁₁₇₀/D₁₃₈₀ in their infrared (IR) spectra. The apparent monomer reactivity ratios for the monomer-isomerization copolymerization of 2B with 3H and 4M2P, in which the concentration of olefin monomer in the feed was used as 2-olefin, were determined as follows: cis-2B(M₁)/3H(M₂); r₁ = 4.00, r₂ = 0.20: trans-2B(M₁)/3H; r₁ = 3.50, r₂ = 0.20; 4M2P(M₁)-trans-2B(M₂): r₁ = 0.05, r₂ = 9.0. These results indicate that the isomerization of 2-olefins to 1-olefins was important to monomer-isomerization copolymerization.     

Monomer-isomerization polymerization. XI. Monomer-isomerization copolymerizations of 2-butene with 2-pentene and 2-hexene with Ziegler-Natta catalyst

2-Pentene and 2-hexene were found to undergo monomer-isomerization copolymerizations with 2-butene by Al(C₂H₅)₃–VCl₃ and Al(C₂H₅)₃–TiCl₃ catalysts in the presence of nickel dimethylglyoxime or transition metal acetylacetonates to yield copolymers consisting of the respective 1-olefin units. For comparison, the copolymerizations of 1-pentene with 1-butene and 1-hexene with 1-butene by Al(C₂H₅)₃–VCl₃ catalyst were also attempted. The compositions of the copolymers obtained from these copolymerizations were determined by using the calibration curves between the compositions of the respective homopolymer mixtures and the values of D₇₆₆/D₁₃₈₀ in the infrared spectra. The monomer reactivity ratios for the monomer-isomerization copolymerizations of 2-butene (M₁) with 2-pentene and 2-hexene, in which the concentrations of both 1-olefins calculated from the observed isomer distribution were used as those in the monomer feed mixture, and for the ordinary copolymerizations of 1-butene (M₁) with 1-pentene and 1-hexene by Al(C₂H₅)₃-VCl₃ catalyst were determined as follows: 2-butene (M₁)/2-pentene (M₂): r₁ = 0.14, r₂ = 0.99; 1-butene (M₁)/1-pentene (M₂): r₁ = 0.30, r₂ = 0.74; 2-butene (M₁)/2-hexene (M₂): r₁ = 0.11, r₂ = 0.62; 1-butene (M₁)/1-hexene (M₂): r₁ = 0.13, r₂ = 0.90.     

Monomer-isomerization polymerization. XX. Monomer-isomerization polymerization of 2-, 3-, and 4-octenes with Ziegler–Natta catalyst

A study of the monomer isomerization polymerization of 2-, 3-, and 4-octenes has been made with TiCl₃–(C₂H₅)₃Al catalyst at 80°C in comparison with the ordinary polymerization of 1-octene. It was found that all these octenes underwent monomer-isomerization polymerization to give high-molecular-weight homopolymer consisting exclusively of the 1-octene unit. The addition of an isomerization catalyst such as nickel acetylacetonate accelerated this polymerization. The rates of polymerization were found to decrease in the following order: 1-octene > 2-octene > 3-octene > 4-octene. These results indicate that the isomerization proceeded by a stepwise double-bond migration. It was also found that the monomer-isomerization copolymerization of 2-octene and 2-butene occurred under similar conditions and produced copolymers of both 1-olefin units.     

Monomer-isomerization polymerization. XXVI. Formation of polyallylcyclohexane from propenylcyclohexane through monomer-isomerization polymerization with Ziegler–Natta catalysts

Monomer-isomerization polymerization of propenycyclohexane (PCH) with TiCl₃ and R_3-xAICI_x (R = C₂H₅ or i-C₄H₉, x = 1–3) catalysts was studied. It was found that PCH underwent monomer-isomerization polymerization to give a high molecular weight polymer consisting of an allylcyclohexane (ACH) repeat unit. Among the alkyaluminum cocatalysts examined, (C₂H₅)₃Al was the most effective cocatalyst for the monomer-isomerization polymerization of PCH, and a maximum for the polymerization was observed at a molar ratio of Al/Ti of about 2.0. The addition of isomerization catalysts such as nickel acetylacetonate [Ni(acac)₂] to the TiCl₃–(C₂H₅)₃Al catalyst accelerated the monomer-isomerization polymerization of PCH and gave a maximum for the polymerization at a Ni/Ti molar ratio of 0.5. PCH also undergoes monomer-isomerization copolymerization with 2-butene (2B).     

Monomer-isomerization polymerization. XXIII.. Monomer-isomerization polymerization of 5-phenyl-2-pentene with ziegler–natta catalysts

5-Phenyl-2-pentene (5Ph2P) was found to undergo monomer-isomerization polymerization with TiCl₃–R₃Al (R = C₂H₅ or i-C₄H₉, Al/Ti > 2) catalysts to give a polymer consisting of exclusively 5-phenyl-1-pentene (5Ph1P) unit. The geometric and positional isomerizations of 5Ph2P to its terminal and other internal isomers were observed to occur during polymerization. The catalyst activity of alkylaluminum examined to TiCl₃ was in the following order: (C₂H₅)₃Al > (i-C₄H₉)₃Al > (C₂H₅)₂AlCl. The rate of monomer-isomerization polymerization of 5Ph2P with TiCl₃–(C₂H₅)₃Al catalyst was influenced by both the Al/Ti molar ratio and the addition of nickel acetylacetonate [Ni(acac)₂], and the maximum rate was observed at Al/Ti = 2.0 and Ni/Ti = 0.4 in molar ratios.     

Copolymerization of styrene and isoprene with Ni(acac)2-methylalumoxane catalyst

Copolymerization of styrene (St) and isoprene (IP) with nickel(II) acetylacetonate [Ni(acac)₂] and methylalumoxane (MAO) catalyst was investigated. It was found that the Ni(acac)₂-MAO catalyst is effective for the copolymerization of St and IP. From the copolymerization of St (M₁) and IP (M₂) and IP (M₂) with the Ni(acac)₂-methylalumoxane catalyst, the monomer-reactivity ratios were determined to be r₁ = 1,18 and r₂ = 0,88, i.e., ideal copolymerization was found to proceed to give perfectly random copolymers without formation of any homopolymer. The microstructure of IP units in the copolymers exhibits high cis-1,4 contents.     

Monomer-isomerization polymerization. XVI. Monomer-isomerization polymerization of methylpentenes with Ziegler-Natta catalyst

The polymerizations of 4-methyl-1-pentene(4M1P), 4-methyl-2-pentene (4M2P), 2-methyl-2-pentene (2M2P), and 2-methyl-1-pentene (2M1P) with Ziegler-Natta catalyst have been investigated. Both 4M1P and 4M2P were found to polymerize with TiCl₃–(C₂H₅)Al catalyst to give high molecular weight poly(4M1P), while 2M2P and 2M1P did not give polymers with 4M1P units. However, when the polymerizations of 2M1P and 2M2P were carried out with ternary catalyst systems, TiCl₃–(C₂H₅)AlCl–(PPh₃)₂PdCl₂ and TiCl₃–(C₂H₅)AlCl–Ni(SCN)₂ polymers with 4M1P units were obtained in low yield. It was concluded that these four methylpentenes could polymerize with the monomer-isomerization polymerization mechanism to poly(4M1P). The results of the observed isomer distribution of methylpentenes recovered, and the rate of polymerization of four methylpentenes suggest that the isomerization from 2M1P to 4M1P with the above ternary catalyst systems might proceed via a direct one-step isomerization mechanism.     

Homopolymerization and Copolymerization of Isoprene and Styrene with a Neodymium Catalyst Using an Alkylmagnesium Cocatalyst

The catalyst system Nd(acac)₃·2 H₂O/Bu₂Mg/CHCl₃ shows a fairly high activity in both the homo‐ and copolymerization of isoprene (IP) and styrene (St) in toluene at 60°C. Copolymers obtained from various comonomer feed ratios were characterized by means of NMR spectroscopy and gel‐permeation chromatography. The polyisoprene and poly(IP‐co‐St) obtained predominantly consist of cis‐1,4 IP units. Monomer reactivity ratios were evaluated to be r_IP = 5.4 and r_St = 0.38 in the copolymerization.     

Copolymerization of styrene and butadiene with Ni(acac)2-methylaluminoxane catalyst

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 r_St = 0.07 and r_Bd = 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     

Studies of the polymerization of diallyl compounds. XXVII. Copolymerization of diallyl tartrate with several vinyl monomers

The radical copolymerization of diallyl tartrate (DATa) (M₁) with diallyl succinate (DASu), diallyl phthalate (DAP), allyl benzoate (ABz), vinyl acetate (VAc), or styrene (St) was investigated in order to disclose in more detail the characteristic hydroxyl group's effect observed in the homopolymerization of DATa. In the copolymerization with DASu or DAP as a typical diallyldicarboxylate, the dependence of the rate of copolymerization on monomer composition was different for different copolymerization systems and unusual values larger than unity for the product of monomer reactivity ratios, r₁r₂, were obtained. In the copolymerization with ABz or VAc (M₂), the r₁ and r₂ values were estimated to be 1.50 and 0.64 for the DATa/ABz system and 0.76 and 2.34 for the DATa/VAc system, respectively; the product r₁r₂ for the latter copolymerization system was found again to be larger than unity. In the copolymerization with St, the largest effect due to DATa monomer of high polarity was observed. Solvent effects were tentatively examined to improve the copolymerizability of DATa. These results are discussed in terms of hydrogen-bonding ability of DATa.     

Synthesis of Graft Polymers by Copolymerization of Macromonomers. II. Copolymerization Kinetics of Styrene-and Methacrylate-Terminatedpoly(2-Acetoxyethyl Methacrylate) Macromonomers

Styrene-terminated poly(2-acetoxyethyl methacrylate) macromonomer (EBA), methacrylate-terminated poly(2-acetoxyethyl methacrylate) macromonomer (MPA), and methacrylate-terminated poly(methyl methacrylate) macromonomer (MPM) were synthesized and subjected to polymerization and copolymerization by a free-radical polymerization initiator (AIBN). EBA and MPA were homopolymerized at various concentrations. EBA exhibited higher reactivity than styrene. The reactivity of MPA, however, was almost equal to that of glycidyl methacrylate. Cumulative copolymer compositions were determined by GPC analysis of copolymerization products. The reactivity ratios estimated were r_a = 0.95 and r_b , = 0.90 for EBA macromonomer (a)-methyl methacrylate (b) copolymerization. These values were not consistent with literature values for the styrene-methyl methacrylate and p-methoxy-styrene-methyl methacrylate systems. The reactivity ratios estimated for MPA and 2-bromoethyl methacrylate were r_a - 0.95 and r_b , = 0.98; equal to the glycidyl methacrylate-2-bromoethyl methacrylate system. MPA or MPM was also copolymerized with styrene, and the reactivity ratios were r_a = 0.40, r_a = 0.60 and r_a = 0.39, r_a = 0.58, respectively. These estimates were in good agreement with the reactivity ratios for glycidyl methacrylate and styrene. Thus, no effect of molecular weight was observed for both copolymerization systems.     

Quantitative Determination of the Contribution of Charge‐Transfer Complex in the Microemulsion Copolymerization of N‐Butyl Maleimide and Styrene

By using sodium dodecyl sulfate (SDS) and pentanol (PTL) as emulsifiers, the oil‐in‐water microemulsion containing N‐butyl maleimide (NBMI, M₁) and styrene (St, M₂) was prepared. The microemulsion copolymerization using potassium persulfate (KPS) as an initiator was investigated. On the basis of kinetic model proposed by SHAN Guo‐Rong, the reactivity ratios of free monomers and the charge‐transfer complex (CTC) in the copolymerization were found to be r₁₂ = 0.0420, r₂₁ = 0.0644, r_1C = 0.00576 and r_2C = 0.00785, respectively. A kinetic treatment based on this model was used to quantitatively estimate the contribution of CTC to the total copolymerization rate in the NBMI/St copolymerization. It was about 17.0–20.0% for a wide range of monomer feed ratios.     

Monomer-isomerization polymerization. XIII. Monomer-isomerization polymerization of 1,4-cyclohexadiene with Ziegler-Natta catalyst

1,4-Cyclohexadiene underwent monomer-isomerization polymerization to yield poly(1,3-cyclohexadiene) with a Ziegler-Natta catalyst comprising TiCl₄–Al(C₂H₅)₃ catalyst with Al/Ti molar ratios of 0.5–3.0 at 60°C for 96 hr. Good yields of polymer were obtained (49.5% yield at Al/Ti = 3.0; [η] = 0.04 dl/g). The infrared and NMR spectra of the polymer were identical to those of poly-(1,3-cyclohexadiene), confirming that 1,4-cyclohexadiene first isomerizes to 1,3-cyclohexadiene and then homopolymerizes to give poly-1,3-cyclohexadiene. 1,3-Cyclohexadiene polymerized without isomerization easily in the presence of TiCl₃–Al(C₂H₅)₃ catalyst at Al/Ti molar ratios of 0.5–3.0 at 60°C for 3 hr (76.3% yield at Al/Ti = 3.0; [η] = 0.06 dl/g).     

Radical copolymerization of crotonyl compounds with styrene

The monomer reactivity ratios for the radical copolymerization of crotononitrile (CN), methyl crotonate (MC), and n-propenyl methyl ketone (PMK) with styrene (St) were measured at 60°C. in benzene and little penultimate unit effect was shown for these systems. The values obtained were: St–CN, r₁ = 24.0, r₂ = 0; St–MC, r₁ = 26.0, r₂ = 0.01; St–PMK, r₁ = 13.7, r₂ = 0.01. The rate of copolymerization and the viscosity of the copolymer decreased markedly as the molar fraction of the crotonyl compound in the monomer mixture increased. The Q–e values were also calculated to be as follows: CN, e = 1.13, Q = 0.009; MC, e = 0.36, Q = 0.015; PMK, e = 0.61, Q = 0.024. A linear relationship was obtained between the e values of the crotonyl compounds and their Hammett constants σ_m.     

Copolymerization and Copolymers of 2,4,5-Tribromostyrene with Styrene and Acrylonitrile

Abstract

2,4,5-Tribromostyrene (TBSt) was copolymerized with styrene (St) or acrylonitrile (AN) in toluene solution using 2,2′-azobisisobutyronitrile as free radical initiator. The copolymerization reactivity ratios were found to be for the system TBSt/St r ₁ = 1.035 ± 0.164 (TBSt) and r ₂ = 0.150 ± 0.057 (St), and for the system TBSt/AN r ₁ = 2.445 ± 0.270 (TBSt) and r ₂ = 0.133 ± 0.054 (AN). The e and Q values were also calculated. The initial copolymerization rate, R _p, for both systems linearly increases as the content of TBSt in the monomer mixture increases. However, these values are somewhat higher when AN was used as a comonomer. A similar behavior has also been established for the course of the copolymerization reactions to high conversion. The resulting copolymers and TBSt-homopolymer show similar thermal stabilities of polystyrene. However, the glass transition temperature increases markedly with increasing TBSt content.     

Ferrocene-containing polymers. II. Radiation-induced copolymerizations of ferrocenylmethyl methacrylate with styrene,methyl methacrylate,and ethyl acrylate

Ferrocenylmethyl methacrylate (FMMA) was copolymerized with styrene (St), methyl methacrylate (MMA), and ethyl acrylate (EA) in benzene solution at 25°C by γ radiation. The reactions proceeded by a free radical mechanism, and monomer reactivity ratios were derived by the Tidwell–Mortimer method for St(M₁)–FMMA(M₂), r₁ = 0.35 and r₂ = 0.46; for MMA(M₁–FMMA)(M₂), r₁ = 0.85 and r₂ = 1.36; for EA(M₁)–FMMA(M₂), r₁ = 0.36 and r₂ = 3.03. The Q and e values of FMMA determined from copolymerization with St were 0.97 and 0.55, respectively. Terpolymerization of a MMA–FMMA–EA system based on the Alfrey–Goldfinger equations was studied. This is a typical terpolymerization system in which reactivities of the monomers obey the Q–e scheme. Comparing the results obtained here with those previously reported for other monomers, we concluded that FMMA is one of the most highly reactive monomers among alkyl methacrylates.     

Synthesis of substituted polymethylenes by radical polymerization of N,N,N′,N′-tetraalkylfumaramides and their characterization

Radical polymerization of N,N,N′,N′-tetraalkylfumaramides (TRFAm) bearing methyl, ethyl, n-propyl, isopropyl, and isobutyl groups as N-substituents (TMFAm, TEFAm, TnPFAm, TIPFAm, and TIBFAm, respectively) was investigated. In the polymerization of TEFAm initiated with 1,1′-azobiscyclohexane-1-carbonitrile (ACN) in benzene, the polymerization rate (R_p) was expressed as follows: R_p = k [ACN]^0.28 [TEFAm]^1.26, and the overall activation energy was 102.1 kJ/mol. The introduction of a bulky alkyl group into N-substituent of TRFAm decreased the R_p in the following order: TMFAm > TEFAm > TnPFAm > TIBFAm > TIPFAm ～ 0. The relative reactivities of these monomers were also investigated in radical copolymerization with styrene (St) and methyl methacrylate (MMA). In copolymerization of TRFAm (M₂) with St (M₁), monomer reactivity ratios were determined to be r₁ = 1.07 and r₂ = 0.20 for St–TMFAm, and r₁ = 1.88 and r₂ = 0.11 for St–TEFAm, from which Q₂ and e₂ values were estimated to be 0.35 and 0.44 for TMFAm, and 0.19 and 0.47 for TEFAm, respectively. The other TRFAm were also copolymerized with St, but copolymerization with MMA gave polymers containing a small amount of TRFAm units. The polymer from TRFAm consists of a less-flexible poly(N,N-dialkylaminocarbonylmethylene) structure. The solubility and thermal property of the polymers were also investigated.