Vulcanization of Crepe Rubber by Sulfur Monochloride. II. The Dilatometric Method

1955 ◽  
Vol 28 (3) ◽  
pp. 850-864 ◽  
Author(s):  
J. Glazer
Keyword(s):  
Cross Linking ◽  
Kinetic Behavior ◽  
High Dilution ◽  
Dilute Solutions ◽  
Volume Contraction ◽  
Sulfur Monochloride ◽  
Dilatometric Method ◽  
The Cross ◽  
Vulcanization Process ◽  
Large Contraction

Abstract The vulcanization of rubber by sulfur monochloride is believed to consist of the cross-linking of adjacent isoprene units by thio-ether bonds. Such a reaction, involving polymer aggregation, should be accompanied by an increase of the density of the rubber, and, by choosing a suitably delicate technique, it should be possible to measure the rate of vulcanization by observing density changes. A dilatometric method seemed most suitable, and it was found that the reaction could indeed be followed by observing the rate of decrease of volume of the system rubber-sulfur monochloride when dissolved in a suitable solvent. Initial experiments showed that, during cold vulcanization, the system underwent a volume contraction which was of the order of 10 per cent with respect to the rubber. This comparatively large contraction allowed one to work with extremely dilute solutions (<0.3% w/w) of rubber. It thereby became possible to study the systems under more ideal kinetic conditions of high dilution than has been hitherto possible. In the present investigation, it has not been possible to do more than establish the broad outlines of the kinetic behavior of the system, and, on this basis, to propose feasible mechanisms for the cold vulcanization process.

Dilatometric Measurement of the Rate of Vulcanization of Crepe Rubber by Sulfur Monochloride

1952 ◽  
Vol 25 (1) ◽  
pp. 48-49
Author(s):  
J. Glazer
Keyword(s):  
Chemical Analysis ◽  
Cross Linking ◽  
Mustard Gas ◽  
Dilatometric Measurement ◽  
Sulfur Monochloride ◽  
Dilatometric Method ◽  
The Cross ◽  
Kinetics Of ◽  
Vulcanization Process

Abstract The cold vulcanization of rubber by sulfur monochloride is believed to consist essentially of the cross-linking of adjacent polyisoprene units by a series of sulfide bonds. Chemical analysis of the product suggests that the cross-linking process is analogous to the mustard gas reaction of ethylene with sulfur monochloride, thus: (see PDF for diagram) Nothing is known, however, about the kinetics of this vulcanization process. General considerations lead one to expect that such a reaction, involving polymer aggregation, should be accompanied by an increase in the density of the rubber; moreover, by choosing a suitably delicate technique, it should be possible to utilize such density changes for rate determinations. A dilatometric method seemed most suitable, and the experiments described here show that the vulcanization process is, indeed, accompanied by a decrease in volume of the reaction mixture, and that the reaction may be followed quantitatively using a tap dilatometer.

scholarly journals Investigation of the functional network modifier loading on the stoichiometric ratio of epoxy resins and their dielectric properties

2021 ◽  
Author(s):  
Istebreq A. Saeedi ◽  
Sunny Chaudhary ◽  
Thomas Andritsch ◽  
Alun S. Vaughan
Keyword(s):  
Glass Transition ◽  
Dielectric Properties ◽  
Electrical Properties ◽  
Epoxy Resins ◽  
Functional Network ◽  
Cross Linking ◽  
Network Modifier ◽  
Epoxy Resin System ◽  
The Cross ◽  
The Impact

AbstractReactive molecular additives have often been employed to tailor the mechanical properties of epoxy resins. In addition, several studies have reported improved electrical properties in such systems, where the network architecture and included function groups have been modified through the use of so-called functional network modifier (FNM) molecules. The study reported here set out to investigate the effect of a glycidyl polyhedral oligomeric silsesquioxane (GPOSS) FNM on the cross-linking reactions, glass transition, breakdown strength and dielectric properties of an amine-cured epoxy resin system. Since many previous studies have considered POSS to act as an inorganic filler, a key aim was to consider the impact of GPOSS addition on the stoichiometry of curing. Fourier transform infrared spectroscopy revealed significant changes in the cross-linking reactions that occur if appropriate stoichiometric compensation is not made for the additional epoxide groups present on the GPOSS. These changes, in concert with the direct effect of the GPOSS itself, influence the glass transition temperature, dielectric breakdown behaviour and dielectric response of the system. Specifically, the work shows that the inclusion of GPOSS can result in beneficial changes in electrical properties, but that these gains are easily lost if consequential changes in the matrix polymer are not appropriately counteracted. Nevertheless, if the system is appropriately optimized, materials with pronounced improvements in technologically important characteristics can be designed.

scholarly journals The Effect of Surfactant-Modified Montmorillonite on the Cross-Linking Efficiency of Polysiloxanes

Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2623
Author(s):  
Monika Wójcik-Bania ◽  
Jakub Matusik
Keyword(s):  
Total Pore Volume ◽  
Cross Linking ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
The Cross ◽  
Chain Lengths ◽  
First Time ◽  
Substituent Influence ◽  
Benzyl Substituent

Polymer–clay mineral composites are an important class of materials with various applications in the industry. Despite interesting properties of polysiloxanes, such matrices were rarely used in combination with clay minerals. Thus, for the first time, a systematic study was designed to investigate the cross-linking efficiency of polysiloxane networks in the presence of 2 wt % of organo-montmorillonite. Montmorillonite (Mt) was intercalated with six quaternary ammonium salts of the cation structure [(CH3)2R’NR]+, where R = C12, C14, C16, and R’ = methyl or benzyl substituent. The intercalation efficiency was examined by X-ray diffraction, CHN elemental analysis, and Fourier transform infrared (FTIR) spectroscopy. Textural studies have shown that the application of freezing in liquid nitrogen and freeze-drying after the intercalation increases the specific surface area and the total pore volume of organo-Mt. The polymer matrix was a poly(methylhydrosiloxane) cross-linked with two linear vinylsiloxanes of different siloxane chain lengths between end functional groups. X-ray diffraction and transmission electron microscopy studies have shown that the increase in d-spacing of organo-Mt and the benzyl substituent influence the degree of nanofillers’ exfoliation in the nanocomposites. The increase in the degree of organo-Mt exfoliation reduces the efficiency of hydrosilylation reaction monitored by FTIR. This was due to physical hindrance induced by exfoliated Mt particles.

Effects of a crosslinking agent on a supramolecular gel to control lost circulation

2021 ◽  
Vol 45 (16) ◽  
pp. 7089-7095
Author(s):  
Bo Wang ◽  
Jinsheng Sun ◽  
Kaihe Lv ◽  
Feng Shen ◽  
Yingrui Bai
Keyword(s):  
Crosslinking Agent ◽  
Network Density ◽  
Cross Linking ◽  
Supramolecular Gel ◽  
Lost Circulation ◽  
The Cross

The Cr3+ can improve the cross-linking degree and network density of the GP-A gel, and enhance its strength and plugging ability to control lost circulation.

scholarly journals Effect of the Cross-Linking Density on the Swelling and Rheological Behavior of Ester-Bridged β-Cyclodextrin Nanosponges

Materials ◽  
2021 ◽  
Vol 14 (3) ◽  
pp. 478
Author(s):  
Gjylije Hoti ◽  
Fabrizio Caldera ◽  
Claudio Cecone ◽  
Alberto Rubin Pedrazzo ◽  
Anastasia Anceschi ◽  
...  
Keyword(s):  
Scale Up ◽  
Future Application ◽  
Cross Linking ◽  
Synthesis Reaction ◽  
Dependent Behavior ◽  
Cyclodextrin Nanosponges ◽  
Potential Applications ◽  
Cross Linker ◽  
The Cross ◽  
Shed Light

The cross-linking density influences the physicochemical properties of cyclodextrin-based nanosponges (CD-NSs). Although the effect of the cross-linker type and content on the NSs performance has been investigated, a detailed study of the cross-linking density has never been performed. In this contribution, nine ester-bridged NSs based on β-cyclodextrin (β-CD) and different quantities of pyromellitic dianhydride (PMDA), used as a cross-linking agent in stoichiometric proportions of 2, 3, 4, 5, 6, 7, 8, 9, and 10 moles of PMDA for each mole of CD, were synthesized and characterized in terms of swelling and rheological properties. The results, from the swelling experiments, exploiting Flory–Rehner theory, and rheology, strongly showed a cross-linker content-dependent behavior. The study of cross-linking density allowed to shed light on the efficiency of the synthesis reaction methods. Overall, our study demonstrates that by varying the amount of cross-linking agent, the cross-linked structure of the NSs matrix can be controlled effectively. As PMDA βCD-NSs have emerged over the years as a highly versatile class of materials with potential applications in various fields, this study represents the first step towards a full understanding of the correlation between their structure and properties, which is a key requirement to effectively tune their synthesis reaction in view of any specific future application or industrial scale-up.

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