CORRELATION BETWEEN THE CHEMICAL STRUCTURE OF SOME SULPHUR-CONTAINING COMPOUNDS AND THEIR ACTIVITY AS ACCELERATORS OF NATURAL RUBBER PLASTICIZATION*

A. S. PRASHCHIKINA, A. YE. GRINBERG and I. M. MAKAROVA Scientific Research Institute of Rubber and Latex Goods
(Received 21 Aiareh 1962)

WE HAVE demonstrated [1, 2] that dibcnzoylsulphide and certain metallic salts of thiobenzoic acid accelerate the process of natural rubber plasticization (NR). It seemed desirable to continue the work in the direction of a study of other sulphur-containing compounds, differing in chemical constitution, as plasticization accelerators. A large number of materials have been described in the literature [3, 4], which act as N R plasticization accelerators to varying degrees. However, ao systematic investigation of individual classes or groups of compounds has been undertaken, nor has any a t t e m p t been made to explain the dependence of their activity as rubber piasticization accelerators on their chemical constitution. This makes it rather difficult to study the mechanism of reactions where the plasticization accelerators interact with the rubber during the plasticization process. It is therefore important to accumulate experimental information which would establish a regular correlation between the chemical constitution of sulphur-containing compounds and their activity as N R plasticization accelerators, both from the practical and theoretical points of view. We have synthesized and studied the 16 compounds whose structures are given in Table 1. The radicals C~HsC(0)S-- and CeH5CH2S-- are contained in most of them. The accelerating effect of the compounds was studied in a wide temperature and concentration range during N R plasticization oil a laboratory mill and in a mixer (Table 2). The efficiency of the various compounds was assessed from the increase in the plasticity of the rubber treated, as compared with that treated without their addition. The compounds studied can be divided into three groups according to their activity as NI~ plasticization accelerators. The first groups comprises I, II and III. The efficiency of this group rises with concentration and plasticization temperature. * Vysokoraol. soyed. 5: No. 11, 1641-1644, 1963. 751

752

A. S. P R A S H C H I K I N A e$ al. T A B L E I. C O M P O U N D S E X A M I N E D AS N R PLASTICIZATION A C C E L E R A T O R S

Compound Thiobcnzoic acid I Dibenzoylsulphide I I Dibenzoyldisulphide I I I Sodium thiobenzoate IV Ammonium thiobenzoate V Zinc thiobenzoate VI Nickel thiobenzoato V I I Cadrnimn thiobenzoate V l n Lead thiobenzoate I X Benzylthiobenzoate X bis-thiobenzoatebenzylidenc X I Trithiobenzoatemethane X I I Dibenzylsulphide X I I I Zinc dibenzylmercaptide XIV 2,4-dinitrophenylthiobenzoate XV
2,2', 4,4'-tetranitrodiphenylsulphide

Formula

M.p., C 23-24 46-48 128-129

CeHsCOSH (CeH~C0)~S (CeH~COS)2 CeH5COSNa C~HsCOSNH4 (C6H5COS)2 Ell (CsHsCOS)~ Ni (C6H~COS)~Cd (CsH5COS)2 Pb CsHsCOSCH~CeH5 (Cell5COS)3 CHCsH5 (C6H5COS)3 CH (CeHsCH~)~ S (CsHsCH2S)~ Zn CeHsCOSCaHs(NO~)~
-2.4

108-110 158-162 205-207 144-148 39-140 139-40

119-120

46-48 220 110-111 194-196

[2.4-(N0,),C~H.], S

XVI

TABLE 2. TESTING CONDITI01~S FOR SULPHUR-CONTAINING COMPOUNDS AS N R PLASTICIZATION ACCELERATORS

Compound

Temperature,

Concentration,

Equipment

wt. %
40-120 40-140 40-140 100-120 100 40-140 40-140 40-140 40-140 100-120 100-120 10O 100 100 100 100 0"2-1.0 0"1-3.0 0-1-3.0 0.2-0-6 0.1-0.6 0.1-3.0 0.1-3.0 0.1-3.0 0.1-3.9 0.1-0-1 0.1-0.6 0.15-0.4 0.1-0.6 0-3 0.1-0.1 0.1-0.1 Mill and mixer
p~ p~

I II HI IV V VI VII VIII IX X XI XlI XIII XIV XV XVI

Mill Mill and mixer

~p ~P 9~

Mill

Sulphur-containing compounds as accelerators of natural rubber plasticization

753

T h e second g r o u p c o n t a i n s t h e salts of t h i o b e n z o i e acid. T h e y are effective as p l a s t i c i z a t i o n a c c e l e r a t o r s e v e n a t t e m p e r a t u r e s of a r o u n d 30 , a n d t h e r e is v e r y little v a r i a t i o n f r o m 30-100 . I f t h e c o n c e n t r a t i o n of t h e c o m p o u n d is raised a b o v e a c e r t a i n level (0.3-0.6 wt. ~/o) t h e i r a c c e l e r a t i n g efficiency is n o t increased b u t m a y e v e n be r e d u c e d in s o m e cases. I n o t h e r words, this g r o u p e x h i b i t s a c o n c e n t r a tion o p t i m u m . T h e t h i r d g r o u p c o m p r i s e s c o m p o u n d s X - X V I , which h a d a b s o l u t e l y no effect as accelerators. T h e results of t h e s t u d y are s h o w n in Figs. 1 a n d 2. I t is n o t n e c e s s a r y t o give t h e a c c e l e r a t i n g effect of all t h e t e s t c o m p o u n d s , as t h e r e was v e r y little difference w i t h i n e a c h group. T h e F i g u r a s t h e r e f o r e j u s t show t h e a c c e l e r a t i n g effect of t w o to t h r e e r e p r e s e n t a t i v e s of e a c h group. T h e e x p e r i m e n t a l figures i n d i c a t e a r e g u l a r c o r r e l a t i o n b e t w e e n t h e c h e m i c a l s t r u c t u r e of a c o m p o u n d a n d its a c t i v i t y as a r u b b e r plasticization accelerator. I a n d its m e t a l l i c salts are effective NI- p l a s t i c i z a t i o n accelerators. I f t h e h y d r o g e n a t o m on t h e thiol s u l p h u r is r e p l a c e d b y benzyl, d e n i t r o p h e n y l , thioa .~ -~~-~-2

O"
~:~0
,~0'2[

4
, , , , ,

<

0 0.2 0.4 0.6 0-8 t

0 0-2 0.4 0-608 I 0 0.2 0.4 0.6 0.8 ! Concentration of compounds, wt %

FIS. 1. Accelerating effect of sulphur-contalning compounds with NR plasticization in a mill (temperature 100): 1--thiobenzoic acid; 2--dibenzoylsulphide; 3--zinc thiobenzoate; g-cadmium thiobenzoate; 5-- nickel thiobenzoate; 6-- benzylthiobenzoate; 7-- dibenzylsulphide; 8-- bis-thiobenzoatebenylidene.
a a b

~
"~

0"5

5 7

|
j I J
II I J

~. 0"3[-

30

50 70

I00

30

50 70

I00

80

IO0

130

Plo~Mc]zaHon tempervtupe , C

FIG. 2. Accelerating effect of sulphur-containing compounds with NR plasticization in a mill (a) and in a mixer (b) (concentration of compounds 0"3 wt. %). a: 1-- dibenzoylsulphide; 2-- dibenzoyldisulphide; 3--zinc dibenzylmercaptide; g--rubber plasticized with additive; 5--zinc thiobenzoate; 6--sodium thiobenzoate; 7--cadmlum thiobenzoate; b: 1--dibenzoylsulphide; 2 -- zinc thiobenzoate; 3-- dibenzoyldisulphide; 4 -- bis-thiobenzoatebenzyl; 5-- rubber plasticized without additive.

754

A. S. PRASHCBIKINA et ~Z:

benzoylphenyhnethyl or dithiobenzoylmethyl radicals, the activity of thiobenzoic acid as a plasticization accelerator is completely nullified. I I and I I I are as good as I. Of the three monosulphides studied, II, X I I I and XVI, only I I is an accelerator. Looking at our experimental results it can thus be seen that some of the compounds act as plasticization accelerators while others do not. This shows that there is a connection between the chemical structure of sulphur-containing compounds and their activity as plasticization accelerators. I t is suggested that this regular correlation is due to the tendency of the compounds to decompose into free radicals under the conditions of plasticization. The ones which most easily decompose are the best accelerators. This also explains the relation between the accelerating efficiency of the compound and the plasticization temperature. Those materials which decompose to form free radicals at a low temperature, I and salts for instance, accelerate N R plasticization at 30-40 , while I I I only has this effect at temperatures above 80 .
CONCLUSIONS

(1) A study has been made of the relation between the activity of certain sulphur-containing compounds as N R plasticization accelerators, and their chemical structures. (2) I t has been found that thiobenzoic acid and its salts, and also dibenzoylsulphide and dibenzoyldisulphide, are efficient accelerators. The accelerating effect of thiobenzoic is completely nullified if the hydrogen atom at the thiol sulphur is substituted b y benzyl, dinitrophenyl, thiobenzoylphenyhnethyl or dithiobenzovlmethyl radicals. (3) I t is suggested that the efficiency of a given group of compounds as accelerators is connected with their capacity to decompose o free radicals under plasticization conditions. Trans~a~ by V. ALFORD
REFERENCES

1. 2. 3. 4.

A. Ye. GRINBERG and A. I. TSVETKOV et al., Kauchuk i rezina, No. 10, 35, 1959 A. S. PRASHCHIKINA and E. Ye. GRINBERG, Kauchuk i rezina, No. 4, 23, 1963 M. PIKE and W. F. WATSON, J. Polymer Sci. 9- 229, 1952 J. WILLIAMS and S. SMITH, Industr. and Engng Chem. 27: 1317, 1935