... Acta, Part A, 23, 921 (1967). (6) PA Mullen and M. K. Orloff, J. Chem. ... XVII. Thermal Deco... more ... Acta, Part A, 23, 921 (1967). (6) PA Mullen and M. K. Orloff, J. Chem. ... XVII. Thermal Decomposition of Cyclic Azo Compounds' ,2 Robert C. Neuman, Jr.,* and Ernest W. Ertley3 Contribution from the Department of Chemistry, University of California, Riverside, California 92502. ...
ABSTRACT 1H NMR and 13C NMR have been used to study the end groups and tacticity in PMMA macromon... more ABSTRACT 1H NMR and 13C NMR have been used to study the end groups and tacticity in PMMA macromonomers and oligomers. These macromonomers are terminated almost exclusively in one vinylidene group per chain. The end group signals from the macromonomers are identified in both the 13C and 1H NMR spectra. The spectra of the purified oligomers (n = 1-4) were used to aid in assignment. The macromonomers are predominantly syndiotactic, and the tacticity measured is consistent with Bernoullian statistics. The tetramer is a mixture of r and m isomers in a 4:1 ratio. It is shown that T1 experiments can provide a useful method of distinguishing resonances due to low molecular weight impurities from those due to stereochemical or isomeric effects in macromonomers. The absence of internal double bonds was confirmed by isomerizing the vinylidene group of several oligomers and of the macromonomer, and verifying the absence of the isomerized signals in the NMR spectra of the original materials.
50 pmol) in 2 mL of the solvent was added to it under argon and stirred under gentle reflux; 200 ... more 50 pmol) in 2 mL of the solvent was added to it under argon and stirred under gentle reflux; 200 pmol of the acid was then added to the reaction mixture, and the reflux was continued for 30 min.
In a study of the effects of pressure on the thermolysis of a six-membered cyclic azo compound, p... more In a study of the effects of pressure on the thermolysis of a six-membered cyclic azo compound, pressure increased the yield of 1,2-diphenylcyclobutane compared to styrene (Fig. 1). 2 This is consistent with the sole intermediacy of a 1,4-diradical, but styrene formation from a possible concurrent concerted three-bond scission reaction could not be ruled out. Because 1,4-diradicals are intermediates in the photolysis of phenyl alkyl ketones, 3 we decided that pressure effects on the products of these diradicals might provide insight into the cyclic azo canpound results.
Journal of the American Chemical Society, Aug 1, 1979
Page 1. 5162 Journal of the American Chemical Society 1 101:18 1 August 29, 1979 Acknowledgment. ... more Page 1. 5162 Journal of the American Chemical Society 1 101:18 1 August 29, 1979 Acknowledgment. This work was supported by Grant GM 24862 from the National Institutes of Health. References and Notes (1) Department ...
The present invention concerns a process for polymerizing INITIATED BY FREE RADICAL Unsaturated s... more The present invention concerns a process for polymerizing INITIATED BY FREE RADICAL Unsaturated species characterized by use of the compound of formula (I) as transfer agents chain, where X is selected from hydrogen, CN, ARIL optionally substituted, COOH , COOR, C (O) NHR SUP {6}, C (O) NR SUP {7} R {SUP, 8}, and halogen; Q is selected from COOR SUP {1}, CN, YC (O) NR SUP {7} R {SUP, 8}; Y is selected from hydrogen, alkyl C {SUB 1} AC {SUB, 6}, alkyl C {SUB 1} AC {SUB, 6} substituted with one or more substituents selected from hydroxy, amino, C {SUB, 1} {SUB AC, 6}, {alkoxycarbonyl C SUB, SUB 1} {AC, 6}, halogen, CN and aryl optionally substituted; Alkenyl C {SUB, SUB 1} {AC, 6}, and alkenyl C {SUB, SUB 1} {AC, 6}; Z is selected from COOR SUP {2}, CN, and aryl optionally substituted; R SUP {3} {SUP YR, 4} may be the same or different and are selected from hydrogen, alkyl C {SUB, SUB 1} {AC, 4} and halogen; OR SUP {3} {SUP YR, 4} JOINTS WITH CARBON TO ATOM are attached form part of a...
POLYMERIZATION an improved method ELEMENTAL IN THE PRESENCE OF DRIVEN macromonomer relatively low... more POLYMERIZATION an improved method ELEMENTAL IN THE PRESENCE OF DRIVEN macromonomer relatively low molecular weight AS CAN BE DONE WITH A CHAIN transfer catalyst metal chelate. This method has several uses including reducing the molecular weight of A VARIETY OF crosslinkable polymers and copolymers.
... Acta, Part A, 23, 921 (1967). (6) PA Mullen and M. K. Orloff, J. Chem. ... XVII. Thermal Deco... more ... Acta, Part A, 23, 921 (1967). (6) PA Mullen and M. K. Orloff, J. Chem. ... XVII. Thermal Decomposition of Cyclic Azo Compounds' ,2 Robert C. Neuman, Jr.,* and Ernest W. Ertley3 Contribution from the Department of Chemistry, University of California, Riverside, California 92502. ...
ABSTRACT 1H NMR and 13C NMR have been used to study the end groups and tacticity in PMMA macromon... more ABSTRACT 1H NMR and 13C NMR have been used to study the end groups and tacticity in PMMA macromonomers and oligomers. These macromonomers are terminated almost exclusively in one vinylidene group per chain. The end group signals from the macromonomers are identified in both the 13C and 1H NMR spectra. The spectra of the purified oligomers (n = 1-4) were used to aid in assignment. The macromonomers are predominantly syndiotactic, and the tacticity measured is consistent with Bernoullian statistics. The tetramer is a mixture of r and m isomers in a 4:1 ratio. It is shown that T1 experiments can provide a useful method of distinguishing resonances due to low molecular weight impurities from those due to stereochemical or isomeric effects in macromonomers. The absence of internal double bonds was confirmed by isomerizing the vinylidene group of several oligomers and of the macromonomer, and verifying the absence of the isomerized signals in the NMR spectra of the original materials.
50 pmol) in 2 mL of the solvent was added to it under argon and stirred under gentle reflux; 200 ... more 50 pmol) in 2 mL of the solvent was added to it under argon and stirred under gentle reflux; 200 pmol of the acid was then added to the reaction mixture, and the reflux was continued for 30 min.
In a study of the effects of pressure on the thermolysis of a six-membered cyclic azo compound, p... more In a study of the effects of pressure on the thermolysis of a six-membered cyclic azo compound, pressure increased the yield of 1,2-diphenylcyclobutane compared to styrene (Fig. 1). 2 This is consistent with the sole intermediacy of a 1,4-diradical, but styrene formation from a possible concurrent concerted three-bond scission reaction could not be ruled out. Because 1,4-diradicals are intermediates in the photolysis of phenyl alkyl ketones, 3 we decided that pressure effects on the products of these diradicals might provide insight into the cyclic azo canpound results.
Journal of the American Chemical Society, Aug 1, 1979
Page 1. 5162 Journal of the American Chemical Society 1 101:18 1 August 29, 1979 Acknowledgment. ... more Page 1. 5162 Journal of the American Chemical Society 1 101:18 1 August 29, 1979 Acknowledgment. This work was supported by Grant GM 24862 from the National Institutes of Health. References and Notes (1) Department ...
The present invention concerns a process for polymerizing INITIATED BY FREE RADICAL Unsaturated s... more The present invention concerns a process for polymerizing INITIATED BY FREE RADICAL Unsaturated species characterized by use of the compound of formula (I) as transfer agents chain, where X is selected from hydrogen, CN, ARIL optionally substituted, COOH , COOR, C (O) NHR SUP {6}, C (O) NR SUP {7} R {SUP, 8}, and halogen; Q is selected from COOR SUP {1}, CN, YC (O) NR SUP {7} R {SUP, 8}; Y is selected from hydrogen, alkyl C {SUB 1} AC {SUB, 6}, alkyl C {SUB 1} AC {SUB, 6} substituted with one or more substituents selected from hydroxy, amino, C {SUB, 1} {SUB AC, 6}, {alkoxycarbonyl C SUB, SUB 1} {AC, 6}, halogen, CN and aryl optionally substituted; Alkenyl C {SUB, SUB 1} {AC, 6}, and alkenyl C {SUB, SUB 1} {AC, 6}; Z is selected from COOR SUP {2}, CN, and aryl optionally substituted; R SUP {3} {SUP YR, 4} may be the same or different and are selected from hydrogen, alkyl C {SUB, SUB 1} {AC, 4} and halogen; OR SUP {3} {SUP YR, 4} JOINTS WITH CARBON TO ATOM are attached form part of a...
POLYMERIZATION an improved method ELEMENTAL IN THE PRESENCE OF DRIVEN macromonomer relatively low... more POLYMERIZATION an improved method ELEMENTAL IN THE PRESENCE OF DRIVEN macromonomer relatively low molecular weight AS CAN BE DONE WITH A CHAIN transfer catalyst metal chelate. This method has several uses including reducing the molecular weight of A VARIETY OF crosslinkable polymers and copolymers.
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