RATES OF POLYMERIZATION OF ACRYLATES AND METHACRYLATES IN EMULSION SYSTEMS

1964 ◽  
Vol 42 (4) ◽  
pp. 825-829 ◽  
Author(s):  
K. G. McCurdy ◽  
K. J. Laidler
Keyword(s):  
Steric Hindrance ◽  
Steric Effects ◽  
Hydroxyl Group ◽  
Methyl Ethyl ◽  
Initial State ◽  
Emulsion Systems

The microcalorimeter has been used to obtain rates of polymerization of a number of monomers in emulsion systems. The rates with the acrylates are consistently higher than those with the methacrylates, and this is attributed to less steric hindrance. Low rates found with monomers containing a hydroxyl group are explained as due to solvation in the initial state. In both the acrylates and methacrylates the rates go through a maximum as one goes up the series methyl: ethyl: butyl: hexyl. This is discussed in terms of inductive and steric effects.

Steric effects in quaternizations. Alkylation of pyridine, thiazole, isothiazole and some benzologues with methyl, ethyl and isopropyl iodides

1976 ◽  
Vol 29 (8) ◽  
pp. 1745 ◽  
Author(s):  
LW Deady ◽  
DC Stillman
Keyword(s):  
Steric Hindrance ◽  
Electronic Effect ◽  
Alkyl Halide ◽  
Steric Effects ◽  
Methyl Ethyl ◽  
Rate Retardation

Results of quaternization reactions in sulpholane at 65� are reported. A large steric hindrance is noted for quinoline relative to pyridine. A much smaller variation in rate with change in alkyl halide is seen in the benzothiazole/thiazole pair. Steric effects are very small and the rate retardation resulting from benzofusion is ascribed largely to an electronic effect. 2,l-Benzisothiazole reacts at essentially the same rate as isothiazole under these conditions.

Studies of the Wallach Transformation. II. Steric Effects in Some Symmetrically Disubstituted Azoxybenzenes

1951 ◽  
Vol 4 (2) ◽  
pp. 185
Author(s):  
PH Gore ◽  
GK Hughes
Keyword(s):  
Sulphuric Acid ◽  
Important Influence ◽  
Steric Effects ◽  
Hydroxyl Group ◽  
Azoxy Compounds ◽  
Point Of Entry ◽  
Substituent Group

Study of the behaviour of symmetrical azoxy compounds in the Wallach Transformation shows the important influence of size of a substituent group ortho to the point of entry of the hydroxyl group.�The various processes known to occur in a solution of azoxybenzene in sulphuric acid are discussed.

scholarly journals On the nature of the electronic effect of multiple hydroxyl groups in the 6-membered ring – the effects are additive but steric hindrance plays a role too

2017 ◽  
Vol 15 (5) ◽  
pp. 1164-1173 ◽  
Author(s):  
Christian Marcus Pedersen ◽  
Mikael Bols
Keyword(s):  
Steric Hindrance ◽  
Electronic Effect ◽  
Membered Ring ◽  
Steric Effects ◽  
Hydroxyl Groups ◽  
Base Strength ◽  
Electronic And Steric Effects

Electronic and steric effects each play important roles in determining the base strength in piperidines.

scholarly journals Synthesis of Siloxyalumoxanes and Alumosiloxanes Based on Organosilicon Diols

2017 ◽  
Author(s):  
Galina I. Shcherbakova ◽  
Pavel A. Storozhenko ◽  
Alexander V. Kisin
Keyword(s):  
Steric Hindrance ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
High Polymer ◽  
Cyclic Structure ◽  
Reaction Products ◽  
Equimolar Ratio ◽  
Aluminum Alkyl ◽  
A Chain ◽  
Alkyl Residue

We have drawn a few interesting conclusions while studying reaction products of Ph2Si(OH)2 with Al(iBu)3 and tetraisobutyl alumoxane. In the first place, this is the production (at Ph2Si(OH)2 and Al(iBu)3 equimolar ratio) of oligomer alumoxanesiloxane structure with alternating four- and six-member rings, as well as isobutyl and phenyl groups migration between aluminum and silicon due to formation of intramolecular four-member cyclic alumosiloxane complex [Ph2(OH)SiO]Al(iBu)2 → [(iBu)Ph(OH)SiO]Al(iBu)Ph. Ph2Si(OH)2 interaction with Al(iBu)3 not only starts from intramolecular alumosiloxane complex production, but the chain is terminated for the same reason, which in the case of Ph2Si(OH)2 reaction with tetraisobutylalumoxane results in failure of obtaining high-polymer alumosiloxane compounds. When Al(iBu)3 interacts with α- and γ-diols, no oligomer compounds are produced. Al(iBu)3 reaction with α, γ-diols results in monomer compounds that are likely to have cyclic structure. Notably at Al(iBu)3 interaction with α-diol only double excess of Al(iBu)3 allows full replacement of hydrogen in α-diol hydroxyl groups by aluminum alkyl residue with 1,3-bis(diisobutylalumoxymethyl)-1,1,3,3-tetramethyldisiloxane production. At equimolar ratio of initial reagents the second isobutyl radical at Al does not interact with the second hydroxyl group of α-diol, apparently due to steric hindrance and 1-(diisobutylalumoxymethyl)-3-(hydroxymethyl)-1,1,3,3-tetramethyl-disiloxane is produced. Al(iBu)3 reactions with γ-diol also result in monomer compounds but the presence of a chain consisting of three СН2-groups between Si and hydroxyl group facilitates interaction between the second hydroxyl group of γ-diol and the second isobutyl radical Al(iBu)3. Tetraisobutylalumoxane reactions with α- and γ-diols results in oligomer compounds.

Effect of Alkyl Group Structure on Cure Characteristics of N,N-Dialkylthio-Carbamyl-N′,N′-Dialkylsulfenamide Vulcanization Accelerators

1974 ◽  
Vol 47 (4) ◽  
pp. 906-910 ◽  
Author(s):  
R. D. Taylor
Keyword(s):  
Carbon Atom ◽  
Steric Hindrance ◽  
Alkyl Group ◽  
Group Structure ◽  
Substituent Effects ◽  
Steric Effects ◽  
Alkyl Groups ◽  
Inductive Effects ◽  
Cure Rates ◽  
Alpha Carbon

Abstract Wide variations in scorch times and cure rates can be attained with tetraalkylthiocabamylsulfenamides through variation in alkyl groups. Substituent effects are substantial on either the carbamate nitrogen or on the sulfenamide nitrogen. Both inductive effects and steric effects influence the scorch times and cure rates. Positive inductive effects shorten scorch times and increase cure rates. Steric hindrance at the sulfenamide nitrogen increases the scorch time. Branching at the carbon atom beta to the nitrogen has a larger effect on scorch time than branching at the alpha carbon. Thiocarbamylsulfenamides can give appreciably higher cure rates and cure efficiencies than their benzothiazole sulfenamide analogs.

Effect of Third Monomer Type and Content on Peroxide Crosslinking Efficiency of EPDM

2003 ◽  
Vol 76 (1) ◽  
pp. 132-144 ◽  
Author(s):  
Martin van Duin ◽  
Herman G. Dikland
Keyword(s):  
Molecular Weight ◽  
Steric Hindrance ◽  
Radical Addition ◽  
Steric Effects ◽  
Low Molecular Weight ◽  
Comprehensive Overview ◽  
Model Studies ◽  
The Third ◽  
Peroxide Curing ◽  
Weight Model

Abstract Peroxide crosslinking of EPDM is commonly applied in rubber practice. Although the presence of a diene termonomer is not a prerequisite for peroxide crosslinking, it does provide a significant increase of the peroxide crosslinking efficiency. Different explanations for the effect of the type and the amount of the third monomer on the peroxide curing efficiency have been put forward; but, a comprehensive overview and an acceptable explanation of all the effects observed are still lacking. In the present paper, this gap is filled by combining results from low-molecular-weight model studies and rheometer experiments with information from the literature. It is shown that peroxide crosslinking of EPDM proceeds via the combination of two EPDM macro-radicals and the addition of an EPDM macro-radical to the residual EPDM unsaturation. The extent to which the latter radical addition occurs, is governed by the amount of the third monomer and by the steric hindrance of the residual unsaturation of the EPDM, i.e. the lower the number of ipso- and β- alkyl substituents on the unsaturation, the higher the rate of addition. This explains why EPDMs containing termonomers with terminal unsaturations are more reactive than those with internal unsaturations. The same approach was followed to assess the peroxide curing efficiency of polydiene elastomers. It was found that the same steric effects govern peroxide crosslinking of polydiene elastomers, such as NR, IR and BR.

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