The Chemistry of Vulcanization. VII. Role of Zinc Butyrate in the Reaction of Diphenylmethane, Sulfur and 2-Mercaptobenzothiazole

1960 ◽  
Vol 33 (1) ◽  
pp. 217-228 ◽  
Author(s):  
Jitsuo Tsurugi ◽  
Haruko Fukuda
Keyword(s):  
Zinc Oxide ◽  
Kinetic Study ◽  
Butyric Acid ◽  
Model Compound ◽  
Reaction System ◽  
The Other ◽  
Zinc Salt ◽  
Reaction Products ◽  
Molecular Dispersion

Abstract In previous Parts of this series, the accelerating mechanism of thiazole type accelerators, namely, 2-mercaptobenzothiazole (MBT), 2,2′-benzothiazolyl disulfide (MBTS) and zinc salt of 2-mercaptobenzothiazole (ZMBT) in the absence of zinc oxide or zinc soap, was investigated with diphenylmethane (DPM) as a model compound of rubber hydrocarbon. The significance of DPM as a model was discussed in some of the earlier papers. Parts IV, V and VI of this series indicated that 2-mercaptobenzothiazolyl radical generated from accelerators splits the sulfur ring, and that the processes by which accelerators generate the radical differ with each other according to their types. These results were obtained in the absence of zinc oxide or zinc soap. The present study will report the role of zinc butyrate in the reaction involving DPM, sulfur and MBT. Experience in the industry indicates that zinc oxide (or zinc soap) is indispensable to the thiazole type accelerators and that the efficiency of zinc oxide or soap is more prominent in MBT than in MBTS or ZMBT. The results obtained in the previous papers also suggest that zinc oxide or soap may have an influence on the rate at which the accelerator generates 2-mercaptobenzothiazolyl radical, since it is shown in Parts IV, V and VI that the radical has an accelerating effect. Therefore, it may be considered that zinc oxide or zinc soap activates MBT more effectively than does the other thiazole type accelerators in order to produce this radical. As will be seen later in this study, interaction of MBT with zinc butyrate in the absence of sulfur produces ZMBT and butyric acid. The ZMBT will interact with sulfur and generate the 2-mercaptobenzothiazolyl radical as reported in Part VI. The zinc salt thus formed will be dispersed in a state of molecular dispersion in the reaction system, while the same compound prepared in Part VI was not dissolved in DPM even at the reaction temperatures. In this respect the former is considered more effective than the latter. In order to verify the above assumptions the reaction involving DPM, sulfur and MBT in the presence of zinc butyrate were investigated. The reaction products and mechanism were compared with those in the absence of zinc soap. Since zinc butyrate is soluble in the reaction system at the reaction temperatures, a kinetic study also was carried out and compared with that in the absence of zinc soap.

The Chemistry of Vulcanization. VIII. Role of Zinc Butyrate in the Reaction of Diphenylmethane, Sulfur and 2-Benzothiazolyl Disulfide

1961 ◽  
Vol 34 (2) ◽  
pp. 648-657
Author(s):  
Haruko Fukuda ◽  
Jitsuo Tsurugi
Keyword(s):  
Zinc Oxide ◽  
Reaction Mechanism ◽  
Butyric Acid ◽  
Rate Equation ◽  
Experimental Results ◽  
Zinc Salt ◽  
Elementary Sulfur ◽  
Rate Determining Step

Abstract Diphenylmethane (DPM) which contains α-methylenic hydrogen has been used as a model of rubber hydrocarbon, and reactions involving DPM, sulfur and thiazole type accelerators in the absence of zinc oxide or soap were reported in previous papers. These papers reported that 2-mercaptobenzothiazole (MBT), 2-benzothiazolyl disulfide (MBTS) and zinc salt of 2-mercaptobenzothiazole (ZMBT) generate the same radical, i.e., 2-benzothiazolesulfenyl which has the accelerating effect. This radical opens the ring of elementary sulfur and thus accelerates vulcanization since the spontaneous splitting of the sulfur ring molecule to a biradical was found to be the rate determining step in the reaction of DPM with sulfur alone. Processes by which accelerators generate this radical differ from each other owing to the types of accelerators, that is, mercaptan, disulfide and zinc mercaptide type. The previous paper reported the reaction involving DPM, sulfur and MBT in the presence of zinc butyrate. According to this, MBT first reacts with zinc butyrate to form butyric acid and ZMBT, the latter then generating the effective benzothiazole-sulfenyl radical. Thus, even in the presence of zinc soap, the essential mechanism of acceleration is the same as in the absence of zinc soap, though the process and rate for forming benzothiazolesulfenyl radical are different in the absence of zinc soap. In the present paper the reaction of DPM, sulfur and MBTS in the presence of zinc butyrate are reported. The reaction mechanism will be deduced from the experimental results obtained here and from conclusions obtained in the previous papers. The rate equation for MBTS consumption and equation for the accelerating efficiency for this accelerator are derived from the mechanism. The theoretical equations were examined by experiments.

scholarly journals Zinc Oxide Supported onto Biogenic Silica from Gigantochloa atroviolacea Leaves: Preparation, Characterization and Antibacterial Activity

2019 ◽  
Vol 31 (10) ◽  
pp. 2197-2200
Author(s):  
Elsa Sriwahyuni ◽  
Anti Kolonial Prodjosantoso ◽  
Dewi Sasmita
Keyword(s):  
Zinc Oxide ◽  
Antibacterial Activity ◽  
Staphylococcus Epidermidis ◽  
Biogenic Silica ◽  
Antibacterial Activities ◽  
The Other ◽  
Raw Material ◽  
Zinc Salt ◽  
Impregnation Method ◽  
Bamboo Leaves

Bamboo rod is a well known raw material utilized to make houses, papers, handicrafts, chopsticks and medicines. On the other hand, the utilzation of leaves, which are often considered as garbages, receive less attentions. Even though, bamboo leaves are good sources of SiO2 or silica. This work reports the preparation of zinc oxide (ZnO) supported onto biogenic silica (SiO2) from leaves of Gigantochloa atroviolacea, characterization and the antibacterial activities of ZnO@SiO2 against Staphylococcus epidermidis. The ZnO was supported onto biogenic SiO2 by using impregnation method of SiO2 in zinc salt [Zn(NO3)2·6H2O] solution. A combination XRD and SEM-EDX techniques were used to confirm the formation of ZnO on ZnO@SiO2. Investigations indicate that the as prepared ZnO@SiO2 revealed significant antibacterial activity against Staphylococcus epidermidis bacterial strain.

A Study of Vulcanization Accelerators. I. Compounds Which React Analogously to Rubber

1957 ◽  
Vol 30 (3) ◽  
pp. 952-961
Author(s):  
J. Shimozato ◽  
K. Ura
Keyword(s):  
Zinc Oxide ◽  
Zinc Sulfide ◽  
Hydrogen Abstraction ◽  
Reaction System ◽  
Detailed Examination ◽  
The Other ◽  
Chemical Behavior ◽  
Model Compounds ◽  
Rapid Decomposition ◽  
Series Of Experiments

Abstract 1. To elucidate the chemical behavior of rubber toward sulfur, a series of experiments was carried out using model compounds : tetralin, toluene, xylene, aniline, phenol, chlorobenzene, dichlorobenzene and naphthalene. Similar reactivities between rubber and the model compounds were observed. 2. The effects of the accelerators in the reactions of the model compounds with sulfur were different according to whether or not zinc oxide was present in the reaction system. 3. A detailed examination of the quantities of zinc sulfide formed in the reaction of tetralin with sulfur in the presence of zinc oxide showed that several vulcanization accelerators have similar activating effects in rubber vulcanization. 4. With tetralin as reactant, the quantity of zinc sulfide decreased suddenly at the reaction temperature 150° C, which was ascribed to the rapid decomposition of tetralin peroxide at this temperature. 5. The accelerating action of CPB, contrary to that of the other accelerators, was promoted by tetralin peroxide. 6. Tetralin peroxide had only a small inhibiting influence upon reactions with the amine accelerators, which is ascribed to the antioxidative nature of the amine derivatives; the inhibiting influence becomes larger in reactions with thiol derivatives or without any added accelerators. 7. Substituent effect on the hydrogen abstraction of the model compounds was primarily determined by the negativity of the relevant carbon atom. The order of the reactivity was found to be in accord with that toward the general “cationoid reagents”. 8. Analytical methods during and after the reactions were simplified for industry use.

scholarly journals The effect of the components of the PdCl2/Fe/I2/Py catalytic system on nitrobenzene carbonylation to ethyl N-phenylcarbamate

2005 ◽  
Vol 3 (1) ◽  
pp. 28-39 ◽  
Author(s):  
Jadwiga Skupińska ◽  
Monika Karpińska ◽  
Maria Ołówek ◽  
Teresa Kasprzycka-Guttman
Keyword(s):  
Catalytic System ◽  
Considerable Increase ◽  
Constant Level ◽  
The Other ◽  
Reaction Products ◽  
Highly Active

AbstractThe PdCl2/Fe/I2/Py catalytic system (Py-pyridine), reported to be highly active in the reaction of nitrobenzene carbonylation to ethyl phenylcarbamate was studied. The present paper describes the role of catalyst components and its effect on the activity and selectivity of the catalyst. The increase in the amount of PdCl2 in the system while retaining a constant level of the other catalyst components, results in the increase of both carbamate and aniline yields. The increase in the amount of iron while retaining the other components constant, initially causes an increase in the carbamate yield; however, at Fe: Pd ratios higher than 36, the carbamate yield remains constant. The change in the amount of iron has no effect on the amount of aniline formed in the system. An increase in the amount of iodine in the system while retaining the other components constant, results in a decrease in carbamate yield and a considerable increase in the aniline yield of the reaction products.

ZINC OXIDE VERSUS MAGNESIUM OXIDE REVISITED. PART 1

2012 ◽  
Vol 85 (1) ◽  
pp. 38-55 ◽  
Author(s):  
Manuel Guzmán ◽  
Berta Vega ◽  
Núria Agulló ◽  
Ulrich Giese ◽  
Salvador Borrós
Keyword(s):  
Zinc Oxide ◽  
Environmental Impact ◽  
Natural Rubber ◽  
Metal Oxides ◽  
Environmental Effects ◽  
Model Compound ◽  
Rubber Industry ◽  
Sulfur Vulcanization ◽  
Activator System

Abstract Zinc oxide is a widely used compound in the rubber industry due to the excellent properties that it shows as activator, and consequently, its role in the mechanism of accelerated sulfur vulcanization has been extensively studied. Due to the increased concern about its environmental effects, several research studies have been carried out in order to substitute it with different metal oxides such us MgO. The effect of the activator system in order to minimize the environmental impact of the rubber goods has been explored. The work developed is presented in two parts. In Part 1, the influence of different mixtures of ZnO and MgO on the vulcanization of natural rubber has been investigated. In Part 2, model compound vulcanization has been used to study the role of MgO on the mechanism to gain a better understanding of the differences shown in Part 1.

ZINC OXIDE VERSUS MAGNESIUM OXIDE REVISITED. PART 2

2012 ◽  
Vol 85 (1) ◽  
pp. 56-67 ◽  
Author(s):  
Manuel Guzmán ◽  
Berta Vega ◽  
Núria Agulló ◽  
Salvador Borrós
Keyword(s):  
Zinc Oxide ◽  
Environmental Impact ◽  
Natural Rubber ◽  
Metal Oxides ◽  
Environmental Effects ◽  
Model Compound ◽  
Rubber Industry ◽  
Sulfur Vulcanization ◽  
Activator System

Abstract Zinc oxide is a widely used compound in the rubber industry due to the excellent properties that it shows as an activator and, consequently, its role in the mechanism of accelerated sulfur vulcanization has been extensively studied. Due to the increased concern about its environmental effects, several research studies have been carried out in order to substitute it with different metal oxides such us MgO. The effect of the activator system in order to minimize the environmental impact of the rubber goods has been explored. The work developed is presented in two parts. In Part 1, the influence of different mixtures of ZnO and MgO in the vulcanization of natural rubber has been investigated. In Part 2 of the study, model compound vulcanization has been used to study the role of MgO on the mechanism to gain a better understanding of the differences shown in the first part.

The Determination of Zinc Oxide in Rubber Vulcanizates by X-Ray Diffraction

1960 ◽  
Vol 33 (3) ◽  
pp. 890-898
Author(s):  
Stephen H. Laning ◽  
Melvin P. Wagner ◽  
John W. Sellers
Keyword(s):  
Zinc Oxide ◽  
Quantitative Analysis ◽  
Analytical Method ◽  
Direct Determination ◽  
Zinc Stearate ◽  
Photographic Film ◽  
Reaction Products ◽  
X Ray

Abstract Zinc oxide is a necessary component in most accelerator-sulfur vulcanization systems. While it is not an accelerator, its presence leads to increased modulus, i.e., tighter cures. The manner in which it can effect this better cure is not completely clear. Some insight into the role of zinc oxide has been gained through the analysis of the vulcanizate for reaction products of zinc, such as zinc stearate, the zinc salts of the accelerators, and zinc sulfide. However, these products may not account for all of the zinc oxide which has reacted. An analytical method for the direct determination of unreacted zinc oxide in vulcanizates was therefore needed. The determination of zinc oxide in rubber vulcanizates has received scant attention. Wet-chemical techniques for analysis of the sample after ashing provide only the total amount of zinc from which the amount of unreacted zinc oxide cannot be determined. Endter has reported the use of the Debye-Scherrer x-ray technique for the identification of zinc oxide in rubber samples. While similar to the method developed in this laboratory, Endter employed photographic film for recording the diffraction pattern, and special sample preparation was required to accommodate the photographic technique. This method was satisfactory for qualitative identification of zinc oxide, but was difficult to use for quantitative analysis. Subsequent to this investigation Hagino et al. described the use of x-ray diffractometry for the determination of the mixing ratio of ingredients compounded in rubber. This method was also suggested for the quantitative analysis of zinc oxide, but no studies were reported. During a study in this laboratory to determine the role of zinc oxide in the vulcanization of rubber, a new analytical method, based on x-ray diffractometry, was developed. The method was rapid, nondestructive, and simple. The data were reliable and accurate.

Plasma Levels of Protein S, Protein C, and Factor X: Effects of Sex, Hormonal State and Age

1995 ◽  
Vol 74 (05) ◽  
pp. 1271-1275 ◽  
Author(s):  
C M A Henkens ◽  
V J J Bom ◽  
W van der Schaaf ◽  
P M Pelsma ◽  
C Th Smit Sibinga ◽  
...  
Keyword(s):  
Regression Analysis ◽  
Postmenopausal Women ◽  
Protein C ◽  
Blood Donors ◽  
Premenopausal Women ◽  
Protein S ◽  
The Other ◽  
Factor X ◽  
Normal Ranges

SummaryWe measured total and free protein S (PS), protein C (PC) and factor X (FX) in 393 healthy blood donors to assess differences in relation to sex, hormonal state and age. All measured proteins were lower in women as compared to men, as were levels in premenopausal women as compared to postmenopausal women. Multiple regression analysis showed that both age and subgroup (men, pre- and postmenopausal women) were of significance for the levels of total and free PS and PC, the subgroup effect being caused by the differences between the premenopausal women and the other groups. This indicates a role of sex-hormones, most likely estrogens, in the regulation of levels of pro- and anticoagulant factors under physiologic conditions. These differences should be taken into account in daily clinical practice and may necessitate different normal ranges for men, pre- and postmenopausal women.

On the role of the dispute between "non-possessors" and "Josephites" in the culture of Moscow's prediction

1998 ◽  
pp. 61-62
Author(s):  
N. S. Jurtueva
Keyword(s):  
The Other ◽  
Moral Transformation ◽  
15Th Century ◽  
The Future ◽  
Secular Power

In the XIV century. centripetal tendencies began to appear in the Moscow principality. Inside the Russian church, several areas were distinguished. Part of the clergy supported the specificobar form. The other understood the need for transformations in society. As a result, this led to a split in the Russian church in the 15th century for "non-possessors" and "Josephites". The former linked the fate of the future with the ideology of hesychasm and its moral transformation, while the latter sought support in alliance with a strong secular power.

From Container to Claustrum: Projective Identification in Couples

2014 ◽  
Vol 4 (2) ◽  
Author(s):  
Tamara Feldman
Keyword(s):  
Psychological Health ◽  
Projective Identification ◽  
The Self ◽  
The Other ◽  
Intimate Partners ◽  
And Control ◽  
The Relationship ◽  
As If

This paper is a contribution to the growing literature on the role of projective identification in understanding couples' dynamics. Projective identification as a defence is well suited to couples, as intimate partners provide an ideal location to deposit unwanted parts of the self. This paper illustrates how projective identification functions differently depending on the psychological health of the couple. It elucidates how healthier couples use projective identification more as a form of communication, whereas disturbed couples are inclined to employ it to invade and control the other, as captured by Meltzer's concept of "intrusive identification". These different uses of projective identification affect couples' capacities to provide what Bion called "containment". In disturbed couples, partners serve as what Meltzer termed "claustrums" whereby projections are not contained, but imprisoned or entombed in the other. Applying the concept of claustrum helps illuminate common feelings these couples express, such as feeling suffocated, stifled, trapped, held hostage, or feeling as if the relationship is killing them. Finally, this paper presents treatment challenges in working with more disturbed couples.

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