Synthesis and copolymerization of 2,2-dimethyl-4-methylene glutaric anhydride

Trumbo, David L.; Abbey, Kirk J.; Carlson, G. M.

doi:10.1002/pol.1987.140250507

Cited by 6 publications

(7 citation statements)

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“…Methyl methacrylate macromonomers of general structure ( 4 ) have recently become of importance as precursors to block − and graft copolymers − and as chain transfer agents. ,, …”

Section: Introductionmentioning

confidence: 99%

“…Methyl methacrylate macromonomers of general structure (4) have recently become of importance as precursors to block [1][2][3] and graft copolymers [4][5][6][7][8][9][10] and as chain transfer agents. 2,11,12 However, there are currently few quantitative data available on the chain transfer constants of macromonomers (4) in methyl methacrylate (MMA) [12][13][14] or other polymerizations or on the dependence of these parameters on macromonomer molecular weight or reaction temperature.…”

Section: Introductionmentioning

confidence: 99%

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Chain Transfer Activity of ω-Unsaturated Methyl Methacrylate Oligomers

et al. 1996

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The chain transfer activities of a series of ω-unsaturated methyl methacrylate oligomers [(dimer (1), trimer (2), tetramer (3), and a methyl methacrylate macromonomer with average chain length of 24 units (4)] have been evaluated in methyl methacrylate polymerizations over the temperature range 45−100 °C. Transfer constants were determined by analysis of the ln chain length distributions. The dimer (1) was found to be substantially less effective as a chain transfer agent than the trimer (2) or the higher macromonomers (3, 4) [C T(60 °C) 1, 0.013; 2, 0.19; 3, 0.31; 4, 0.21]. The transfer constants show only a small temperature dependence and no variation with conversion. No discernible retardation was observed in these polymerizations. A reduced yield of polymer observed at conversions >10% in bulk polymerizations of MMA carried out in the presence of 1 − 4 can be attributed to the absence of the gel (Trommsdorff) effect. The results are interpreted in terms of the addition−fragmentation mechanism for chain transfer.

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“…Methyl methacrylate macromonomers of general structure ( 4 ) have recently become of importance as precursors to block − and graft copolymers − and as chain transfer agents. ,, …”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chain Transfer Activity of ω-Unsaturated Methyl Methacrylate Oligomers

et al. 1996

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“…Macromonomers with end group structure 2 have utility as chain transfer agents [1][2][3][4][5][6][7] and as precursors to block, [8][9][10] graft, 1,2,[10][11][12][13][14][15][16][17][18] and end-functional polymers. [19][20][21] Polymerizations of methacrylate esters [e.g.…”

Section: Introductionmentioning

confidence: 99%

“…Macromonomers with end group structure 2 have utility as chain transfer agents − and as precursors to block, − graft, ,,− and end-functional polymers. − Polymerizations of methacrylate esters [e.g. methyl methacrylate (MMA); Y = CO 2 Me)] and some other monomers with an α-methyl group in the presence of cobaloximes as chain transfer catalysts can provide such macromonomers in high yield.…”

Section: Introductionmentioning

confidence: 99%

Binary Copolymerization with Catalytic Chain Transfer. A Method for Synthesizing Macromonomers Based on Monosubstituted Monomers

et al. 2005

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With appropriate choice of conditions, copolymerization of monosubstituted monomers [CH2CHX: e.g., styrene, butyl acrylate (BA)] in the presence of small amounts of an α-methylvinyl monomer [CH2C(CH3)Y: e.g., α-methylstyrene (AMS), methyl methacrylate (MMA), methacrylonitrile (MAN)] and a cobaloxime as chain transfer catalyst provides a route to macromonomers that are composed largely of the monosubstituted monomer and yet have a chain end derived from the α-methylvinyl monomer (−CH2−C(CH2)Y). The various factors (temperature, concentrations, type of cobaloxime, types of monomer) that influence molecular weight and end group purity and the importance of the various side reactions that may complicate the process are described. Macromonomer purity is enhanced by increasing the concentration of the α-methylvinyl monomer and reducing the cobaloxime concentration. It also depends on the structure of the cobaloxime, increasing in the series where the ligands are derived from dimethyl glyoxime < diethyl glyoxime ∼ diphenyl glyoxime, and the α-methylvinyl monomer, increasing in the series where Y is CO2R < CN < Ph. For styrene−AMS copolymerization, macromonomer purity (the fraction of AMS-derived ends) was enhanced by increasing the reaction temperature. For BA−AMS copolymerization, macromonomer purity was enhanced by decreasing the reaction temperature. However, it is necessary to use a high reaction temperature to limit the extent of macromonomer copolymerization that occurs as a side reaction at high monomer conversion. High purity, AMS terminal BA macromonomers can be prepared by BA−AMS copolymerization at 125 °C with as little as 2 mol % AMS. We also show how the overall composition, molecular weight, and end group functionality of copolymers formed in the presence of a chain transfer agent can be predicted using classical statistics and point out some problems with previous treatments. Analytical expressions which describe zero conversion binary copolymerization in the presence of a transfer agent are derived and successfully applied to the above-mentioned system. The effective transfer constants of cobaloxime transfer catalysts are reported. Those observed in copolymerizations of vinyl and α-methylvinyl monomers are reduced with respect to values observed in homopolymerization of α-methylvinyl monomers because of reversible consumption of the cobalt complex as an adduct to the vinyl monomer. Transfer constants of macromonomers with AMS end groups in styrene polymerization at 120 °C are in the range 0.11−0.15. At lower temperatures (80 °C), macromonomer copolymerization dominates over chain transfer and the effective transfer constant is ∼0.

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“…Methacrylate macromonomers of general structure (RMA n ) have found importance as chain transfer agents − and as precursors to block, − graft, ,,,− and end-functional polymers. ,− An excellent summary of their synthesis and application is provided by Gridnev and Ittel in their recent review on catalytic chain transfer. We 3 have previously reported on the chain transfer activity of MMA macromonomers (MMA n , n = 2, 3, 4, >4) in MMA polymerization.…”

Section: Introductionmentioning

confidence: 99%

Chain Transfer Activity of ω-Unsaturated Methacrylic Oligomers in Polymerizations of Methacrylic Monomers

et al. 2004

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Chain transfer constants have been determined for an unsaturated methyl methacrylate trimer, CH2dC(CO2Me)CH2[C(CO2CH3)(CH3)CH2]2H (MMA3), in polymerizations of methacrylate esters (ethyl, EMA; BMA; tBMA; EHMA) and for the analogous trimers of butyl methacrylate (BMA3) and methacrylic acid (MAA3), a hydroxyethyl methacrylate dimer (HEMA2), a hydroxyethyl methacrylate-methyl methacrylate-hydroxyethyl methacrylate trimer (HEMA-MMA-HEMA), and a HEMA macromonomer in methyl methacrylate (MMA) polymerization. These data have been assessed with reference to our previously reported data on chain transfer of MMA macromonomers in MMA polymerizations. The transfer constants (Ctr) for MMA3 in polymerizations of methyl, ethyl, n-butyl, tert-butyl, and 2-ethylhexyl methacrylate at 60 °C are similar (∼0.18). The Ctr of MAA3 (0.28 at 60 °C in 2-butanone solvent) in MMA polymerization is ca. 50% higher than that of MMA3 under similar conditions. Other trimers (BMA3, HEMA-MMA-HEMA) and a low molecular weight HEMA macromonomer (degree of polymerization ca. 7) have Ctr similar to that of MMA3. The transfer constants for the various trimers show no significant temperature dependence over the range 60-100 °C. The Ctr of the dimers (MMA2, HEMA2) in MMA polymerization are an order of magnitude lower than those of the corresponding trimers. The Ctr of HEMA2 (0.018 at 60 °C) in MMA polymerization is ca 50% higher than that of MMA2 (0.013 at 60 °C). The Ctr of both dimers increases with increasing temperature between 60 and 100 °C (Ctr HEMA2 0.031, MMA 0.018 at 60 °C). Issues relating to the synthesis and characterization of trimers (RMA3) by catalytic chain transfer are discussed. Methods for synthesis of di-end-functional trimers MAA-MMA-MAA, HEMA-MMA-HEMA based on selective hydrolysis and reesterification are described. These trimers may find use in telechelic synthesis.

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Synthesis and copolymerization of 2,2-dimethyl-4-methylene glutaric anhydride

Cited by 6 publications

References 0 publications

Chain Transfer Activity of ω-Unsaturated Methyl Methacrylate Oligomers

Chain Transfer Activity of ω-Unsaturated Methyl Methacrylate Oligomers

Binary Copolymerization with Catalytic Chain Transfer. A Method for Synthesizing Macromonomers Based on Monosubstituted Monomers

Chain Transfer Activity of ω-Unsaturated Methacrylic Oligomers in Polymerizations of Methacrylic Monomers

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