Ultraviolet Spectra of Elastomers

and Rubber Chernicals

Ultraviolet Spectra of Elastomers
and Rubber Chemicals

V. S. Fikhtengol'ts, R. V. Zolotareva,
and Yu. A. L'vov
All-Union Synthetic Rubber Research Institute, Leningrad

Translated from Russian by

A. Eric Stubbs
Senior Scientific Translator

1:1
PLENUM PRESS DATA DIVISION
NEW YORK' 1966
 Library of Congress Catalog Card Number 66-12889

The original Russian text was published for the All-Union Synthetic
Rubber Research Institute by Khimiya Press in Moscow in 1965.
ULTRAVIOLET SPECTRA OF ELASTOMERS AND RUBBER CHEMICALS

ATLAS UL'TRAFIOLETOVYKH SPEKTROV POGLOSHCHENIYA VESHCHESTV,

PRIMENYAYUSHCHIKHSYA V PROIZVODSTVE SINTETICHESKIKH KAUCHUKOV

ATnAC YJlbTpalj>HOJleTOBblX cneKTpOB nOrJlow.eHHSI Bew.eCTB,

npHMeHSlIOw.HXCSI B npOH3BO.llCTBC CHHTeTH'IeCKHX KaY'IYKOB

B. C. 4>uxmenZOAbt{. P. B. 30Aomape8a.
10. A. J1b808
ISBN-13: 978-1-4615-9593-9 e-ISBN-13: 978-1-4615-9591-5
001: 10.1007/978-1-4615-9591-5

© 1966 Plenum Press Data Division

Soflcover reprint of the hardcover 1st edition 1966

A Division of Plenum Publishing Corporation

227 West 17 Street, New York, N. Y. 10011
All rights reserved

No part of this publication may be reproduced in any

form without written permission from the publisher
 PREFACE
In the modern organic synthesis industries, one of which is
the synthetic rubber industry, ever increasing use is made of
physical and physicochemical methods of analysis, which sur-
pass chemical methods in speed, accuracy, and sensitivity. By
these methods it is often possible to arrive at the solution of
problems in the investigation of complex mixtures of organic
products which are not amenable to the usual chemical methods
of analysis.
One such physical method is ultraviolet spectrophotometry.
The field of application of this method is restricted, in the main,
to aromatic compounds and to systems containing double bonds
conjugated among themselves or with functional groups. In the
synthetic rubber industry ultraviolet spectroscopy finds appli-
cation in the analysis of a great variety of substances used in
that industry: for the determination of impurities in monomers
and intermediate products, in the study of the composition of
certain polymers, for the quantitative estimation of various
ingredients in rubbers, in the control of certain copolymeriza-
tion processes, and for many other purposes. The method
can be used for the identification of certain compounds and
can be applied in the determination of the composition of syn-
thetic rubber samples. Shortcomings of the method, which
limit its analytical application in certain cases, are the super-
position of absorption spectra and their inadequate selectivity.
The atlas gives absorption spectra in the near ultraviolet
(200-400 mil) for 141 different substances met in synthetic
rubber manufacture: monomers, polymers, various antioxi-
dants, and other substances used in the synthesis of rubbers
(emulsifiers, initiators, regulators, various auxiliary ma-
terials, etc.).
All the spectra are represented in the form of graphs of

v
PREFACE

the relation a =f (/\), in which a is the specific extinction co-

efficient (optical density of a solution containing 1 g of the
substance in 1 liter at a layer thickness of 1 cm) and A is
wavelength (mIL). The scales of the spectra vary: they were
chosen so as to reveal the characteristics of the spectrum as
clearly as possible. The spectra shown in the atlas were deter-
mined by the authors in the laboratories of the All-Union
Synthetic Rubber Research Institute with an SF -4 spectro-
photometer at room temperature (20 ± 3°C). Many of them
were determined for the first time. The relative error in the
determination is up to 5%. which is usual for the SF -4. In some
cases our results do not agree with data in the literature (which
are cited in footnotes to the tables). It should be noted that in
a number of cases we had to deal with technical products or
with substances of unknown purity. This refers mainly to anti-
oxidants and to various ingredients used in the synthesis of
rubbers.
Apart from the spectra. at the beginning of each section a
table is given which states the solvent in which the measure-
ment was conducted. the wavelength Amax at each absorption
maximum, and the specific a and molecular ( extinction co-
efficients at each maximum.
In the legends to the figures we state, successively, the
solvent, the concentration c, and the thickness d of the layer
of solution.
The atlas does not give the spectra of some aromatic
hydrocarbons used in the synthetic rubber industry as solvents
or for other purposes (e.g., benzene and toluene) because
their spectra can be found in a readily available atlas [1]. The
general laws of electronic spectra and the experimental tech-
niques, which have been described in the literature [2, 3], are
not expounded here.

vi
 PREFACE

The authors hope that, despite possible shortcomings, this

atlas will be found useful in the practical work of spectros-
copists' not only in the synthetic rubber industry, but in allied
fields (plastics, petrochemicals, etc.) in which the compounds
whose spectra are given in the atlas can be met.

vii
 Contents
I. Monomers • • • • • • • • • • • • • • • • • • • • • • 1
Spectral Characteristics of Monomers • . . . • • • . . . . 2

II. Polymers • • • • • • • • • • • • • • • • • • • • 19
Spectral Characteristics of Polymers. 20

III. Organosilicon Compounds. . • • • • • • • • • • • • • • • • • • 29

Spectral Characteristics of Organosilicon Compounds in
Copolymers Containing Dimethylsiloxane Units. . . 30

IV. Antioxidants. • • • • • • • • • • • • • • • • • • • • • • • • • • • 57
Spectral Characteristics of Antioxidants - Secondary
Amines . . . • . . . • . . . . . . . • . . . . . . . . . . . • . 59
Spectral Characteristics of Antioxidants - p-Anisidine
Derivatives • • . . . . . . . . . . . • . . . . • • . . . . . . 67
Spectral Characteristics of Antioxidants - p-Phenyl-
enediamine Derivatives. . . • . . . • • . . • . . • • . • . 74
Spectral Characteristics of Antioxidants - Phenol
Derivatives . . • . . . . . • . • . • . • • • • . . . . . . . . 88
Spectral Characteristics of Antioxidants - Phospho-
rous Esters . . . • . . 104
Spectral Characteristics of Antioxidants - Hydroqui-
none Derivatives • . . . . . . . . . . . . . . . . . . . . . 108
Spectral Characteristics of Antioxidants - Sulfides .. 112
Spectral Characteristics of Antioxidants - Hydroquin-
oline Derivatives. . . . . . . . . . . . . . . . . . . . • .. 118
Spectral Characteristics of Various Antioxidants. • .• 125

ix
CONTENTS

V. Various Substances Used in Synthetic Rubber Manufacture. 131

Spectral Characteristics of Various Substances Used
in Synthetic Rubber Manufacture. . . . . . . . 132

VI. Various Substances Met as Intermediate Products,

By-Products, and Impurities. • • • • • • • • • • • • • • • • • •• 149
Spectral Characteristics of Various Substances Met as
Intermediate Products, By-Products, and Impuri-
ties . . . . 150

Literature Cited. 169

x
 I. MONOMERS
The monomers used in the preparation of synthetic rubbers
(Table 1) are substances containing a system of conjugated
double bonds or a double bond conjugated with a triple. The
absorption spectra of all of them therefore contain strong K
bands. When the substance contains a double bond conjugated
with a benzene ring, a B band appears in addition to the K band.
When the double bond is conjugated with a carbonyl group
(acrylic compounds), the K band is considerably weaker.
The character of the absorption spectrum is also affected
by the substituents situated at the conjugated bond. When there
is a substituent on the second carbon atom of a dienic system,
a bathochromic shift in the absorption band is observed
(isoprene, chloroprene). Also, substitutents such as methyl
or chloro bring about a reduction in the strength of the absorp-
tion band. When the methyl group is on the first carbon atom
of the dienic system a bathochromic shift in the absorption
band is again observed, and there is a still greater reduction
in its strength (piperylene). A methyl group on the second
carbon atom at a double bond conjugated with a benzene ring
brings about only a slight reduction in the strength of the two
bands (K and B), but in this case there are hypsochromic shifts
in the absorption bands (a-methylstyrene).
When the double bond is conjugated with a pyridine ring,
the strengths of the K and B bands are much lower than in the
case of conjugation with a benzene ring, and the absorption
bands are shifted considerably toward the longer waves.
Since the polymerization of a monomer destroys the conju-
gated system of bonds, polymers do not give K absorption bands.
It is therefore possible to estimate the amount of unchanged
monomer from the strength of the absorption band and to follow
the progress of the polymerization. Similarly, the residual
monomer content of a polymer can be determined spectro-
photometrically [4].
1
MONOMERS

TABLE 1
SPECTRAL CHARACTERISTICS OF MONOMERS

Figure Monomer Solvent Amax' mp. a

1 1,3-Butadiene Ethanol 218 570 30,750*
2 Isoprene (2-methyl- Ethanol 223 316 21,500t
1,3-butadiene)
3 Chloroprene (2-chloro- Ethanol 223 240 21,250
1,3-butadiene)
4 Piperylene, 93'70 of trans Ethanol 220 250 16,850+
form (trans-1,3-penta-
diene)
5 Piperylene, 77.5'70 of cis Ethanol 225 235 16,000+
form (ci s-l, 3-penta-
diene)
6 Styrene Ethanol 208 203 21,100
248 150 15,500§
Dioxane 248.5 137 14,300
7 a-Methyl styrene Ethanol 206 170 20,000
243 103 12,150
8 Methacrylic acid Ethanol 207.5 92 7,900
9 Methyl methacrylate Ethanol 207.5 84 8,400
(technical)
10 Butyl methacrylate Ethanol 207.5 66 8,300
(technical)
11 Acrylonitrile Ethanol 205 90 4,750
i2 2-Vinylpyridine Chloroform 238 109 11,450
278.5 48 5,050
13 5-Vinyl-2-picoline Chloroform 244 140 16,650
284 37 4,400
14 2-Methyl-5-hexen-3-yn- 50'70 Ethanol 221.5 138 15,200
2-01 230.5 111 12,200
15 p-(l, I_Dimethyl-4_penten_ 50'70 Ethanol 223.5 107 19,900
2-ynyl) phenol 275.5 10 1,850

*In hexane Amax= 217 mp., (= 20,900 [5].

tIn hexane Amax= 220 !IlJ1, (= 23,900 [5]. In hexane Amax = 220 mp., (= 21,000 [6].
tIn alcohol Amax= 223.5 mp., ( = 23,000 [8].
§In alcohol Amax= 244 mp., ( = 13,000 [9].

2
 MONOMERS

a 600

500
II
/\
J 1\
I '\
400

300
I

200

~
'C
100

o
200 2tD 220 230 2~0 250 260
A. mp.

Fig.!. l,3-Butadiene

Ethanol
C = 0.15 g/liter
CH 2 = CH - CH = CH 2 d= 0.58 mm

3
MONOMERS

3001---t-----l;~:__+_-_+_-___4

IOOt-''"--+---+--+-+--+----I

Fig. 2. Isoprene (2-methyl-I,3-butadiene)

Ethanol
CH,
I C = 0.15 g/liter
CH 2 =C - CH = CH 2 d =.0.58 mm

4
 MONOMERS

a2tO

/ ~\
I
200

f60 \
J \
/ \
120

80

40
7
\
o
200 2tO 220 230
I~
2~0 250 260
~. mIL

Fig. 3. Chloroptene (2-chloro-l.3-butadiene)

Cl Ethanol
I C = 0.82 g/liter
CH2 =C-CH=CH 2 d = 0.058 mm

5
MONOMERS

a 250
f
lOO ~\
150 1\
\
100

50 1
o \ "'-
210 220 230 250
A,mll

Fig. 4. trans-Piperylene (trans-l,3-pentadiene)

Ethanol
C = 0.77 g/liter
CH2 = CH - CH = CH - CH, d= 0.049 mm

6
 MONOMERS

a 250

V\
200

150
/ 1\
fOO

50 \
\
o '-....
210 220 230 240 -
250 260
A,fIl/l

Fig. 5. c;s-Piperylene (cis-l,3-pentadiene)

Ethanol
C = 0.78 g/liter
CH,=CH-CH=CH-CH. d= 0.049 mm

7
 MONOMERS

a 21.0 12

7'
lOO ~'0
~

f60 8

~ I/'r\ -\ ~
'\ 7
"
f20 V 6

\ J

'\ /
80

r\ V
17

40

\
2

\
~

o 0
200 210 22'0 23'0 240 25'0 250 270 280 290 3'00
A,mp.

Fig. 6. Styrene

Ethanol
C = 1.06 g/liter
d= 0.058 and 1.004 mm

8
 MONOMERS

a 200

I\
160
/\

f20

I~ / ~
\
80

\ /
V

'"
1,0

o r-
200 2tO 220 230 240 250 260 270 280 290 300
A,mll

Fig. 7. a-Methylstyrene

Ethanol
C = 1.016 g/liter
d = 0.058 mm

9
MONOMERS

a faa

'"
/"
/

I
75
'\
50 ~
'\

25 ~
~

o ~
200 210 220 230 21.0
A,mll

Fig. 8. Methacrylic acid

CH
Ethanol
I ",0
CH2 = C-C'- C = 1. 0 1 g/liter
'OH d= 0.112 mm

10
 MONOMERS

a 100

",--..
75 ~

I '\ 1\

'\
50

o
200 210 220 "'" ~~
230 21.O
A,mll

Fig. 9. Methyl methacrylate

CH,
I 0 Ethanol
CH, = c-c'" C = 1.96 g/liter
'OCH, d= 0.058 mm

11
MONOMERS

a7S
~

I
/ ~
~~
'"
25

o ~ """-
200 ZIO 220 230

Fig. 10. Butyl methacrylate

Ethanol
C = 2.64 g/liter
d= 0.058 mm

12
 MONmlERS

a 100

15 / 1\
7
'\
1\
\
50

25

o ~ t-....
200 210 220 230
A.mp.

Fig. 11. Acrylonitrile

Ethanol
C = 1. 79 g/liter
CH,z= CH-C=N d= 0.058 mm

13
 MONOMERS

a '25

~I\

\
tOO V

75 / \
50 1\
~ ~./V- ~

'"
25

o ...........
220 230 2'0 250 260 270 280 290 300 310
A,mll

Fig. 12. 2-Viny1pyridine

Chloroform
C = 1.00 g/liter
d= 0.058 mm

14
 MONOMERS

a '50

125
)r\
tOO / ~
75 ,
V \,
\

'"
50

""'"
""""--"'"

'"
25

o
220 230 250 260 270 280 290 300 310
A,mll

Fig. 13. 5-Vinyl-2-picoline

Chloroform
C = 0.10 g/liter
CH,C s H,NCH = CH2 d = 0.506 mm

15
MONOMERS

a 1!fO

~
125
/ \
~/
""'
7S \,
50 ~

25 \ "-
o
210 220 230
"-- - 250
A.mll

Fig. 14. 2-Methyl-5-hexen-3-yn-2-o1

CH,
I
50'70 ethanol
CH, = CH-C;: C-C-OH
I C = 1. 00 g/liter
CH, d= 0.058 mm

16
 MONOMERS

a 120 '2 a

A fa
V\
fOO
/ \
/
'"\
\ r-...

\
80 8
'-V
60

\
5
\
1,0

20 r\"- \ 2

o
m m ~ m ~ ~ m ~ ~
"- D
A,mll
0

Fi~:. 15. p-( 1,I-Dimethyl-4-penten-2-ynyl) phenol

CH,
I
50'70 ethanol
CH 2 = CH-C c' C-C-C.H.OH
I C = 1.00 g/liter
CH, d = 0.058 and 0.506 mm

17
 II. POLYMERS
In the polymerization of monomers containing conjugated
systems of bonds, the latter are destroyed and the associated
K absorption bands disappear. Usually, therefore, polymers
(Table 2) do not have absorption bands in the near ultraviolet.
However, in the polymerization or copolymerization of mono-
mers containing a benzene or pyridine ring in the molecule
the B band associated with this ring does not disappear in the
spectrum of the polymer. Hence, whereas the study of the
polymerization processes of monomers not containing benzene
or pyridine rings can be conducted only by determining the
content of unchanged monomer, when there are B bands it is
possible to determine directly the amount of monomer that
has polymerized [10].
It is interesting to note the difference in the spectra of
polystyrenes prepared by emulsion polymerization and by ca-
talytic polymerization in solution both in the position and in the
strength of the absorption bands. This points to a difference in
structure between the polymers. The character of the absorp-
tion bands is preserved even in copolymerization with other
monomers, depending on the method of polymerization.
The absorption bands in the spectra of thiokols arise from
the sulfide bonds; they are R bands.

19
POLYMERS

TABLE 2
SPECTRAL CHARACTERISTICS OF POLYMERS

Figure Structural unit Solvent "-max, ffi/1 a

16 Styrene, in emulsion copolymers Chlorofonn 255.7 1.85 190
262.5 2.20 230
269.5 1.60 165
17 Styrene, in products of catalytic Chlorofonn 254.5 7.05 730
copolymerization in solution
18 (3-p-Hydroxyphenyl-3-methyl-l- Chlorofonn 276 8.0 1500
butynyl) ethylene in copolymers 282.5 6.9 1300
with 1,3-butadiene
19 (2-Pyridyl) ethylene in copoly- Chlorofonn 258 32 3350
mers with 1,3-butadiene 263 33.5 3500
270 25 2600
20 (5-Methyl-2-pyridyl) ethylene in Chlorofonn 269.5 28 2500
copolymers with 1,3-butadiene 276 21.5 2550
21 Unit of thiokol T-l Dioxane 210 5.00 830
250 2.30 380
22 Unit of thiokol T-2 Dioxane 208 5.30 1350
250 1.85 470
23 Unit of thiokol T-3 Dioxane 207 3.90 1400
249 1.20 435

20
 POLYMERS

a 2.5

1\
\,
2.0

1.5
(
\\ /
/ V
1.0
/
o.s \

o
230 21,0 250 260 270
\ io-.
2tJO 290
A,mll

Fig. 16. Styrene unit in emulsion copolymers

Chloroform
C = 10.0 g/liter
d = 0.506 mm

21
POLYMERS

a6

6 :\
/~ I\.
~/ \
2 \ '\
o h
230 240 2~0 260 270 280 """"
290 300

Fig. 17. Styrene unit in products of catalytic copolymerization in solution

Chlorofonn
C = 0.94 g/liter
d = 1.012 mm

22
 POLYMERS

aB

I
7\~
I \
6

2
........ ./
/
\
o ~
2+0 250 260 270 260 290 JOO
A,mll

Fig. 18. (3-p-Hydroxyphenyl-3-methy1-1-butyny1) ethylene

unit in copolymers with l,3-butadiene

Chloroform
C = 1. 00 gil iter
d=1.012mm

23
POLYMERS

30 /' Y\
/ \.
zo / 1\
fO i'../
/ \\
o ~
130 2IJJ 250 260 210 280 290 300

Fig. 19. (2-Pyridyl) ethylene unit in copolymers with 1,3·butadiene

Chloroform
C = 0.96 g/liter
d= 0.210 mm

24
 POLYMERS

a 30

20 /
V~
V \
'0
" ~ ~

o
230 21.0 250 26IJ 270 280
" 290 300
A,mll

Fig. 20. (S·Methyl·2·pyridyl) ethylene unit in copolymers with l,3-butadiene

-CH-CH,- ] Chloroform
[
~5H3NCH3
C = 1. 20 g/li ter
d = 0.210 mm

25
POLYMERS

as {

\
3

'" '"
2

'\-/
o
" r--.
200 220 21,0 260 280 300 320
A,mll

Fig. 21. Unit of thiokol T-1

Dioxane
C = 10.0 g/liter
[-S(CH2)20CH20(C~)2S- ] d = 0.210 mm

26
 POLYMERS

a6

5
I't
I

J \
2
'\
'" '"
~ V--
I

o t----
200 220 240 260 280 300 320
A,mll

Fig. 22. Unit of thiokol T-2

Dioxane
C = 10.0 g/liter
d= 0.210 mm

27
POLYMERS

\
a

2 \
\
f

o
-- ,...- .....
~
~
200 220 240 260 280 300 320
"'ffiIl

Fig. 23. Unit of thiokol T-3

Dioxane
C = 10.0 g/Iiter
d = 0.210 mm

28
 III. ORGANOSILICON COMPOUNDS
The application of ultraviolet spectroscopy in the investi-
gation of organosilicon compounds is limited in the main to those
containing aromatic rings. However, the extensive application
of cocondensation reactions to give copolymers containing
dimethylsiloxane units and a great variety of aromatic siloxane
units opens up wide possibilities for the use of the absorption
spectra of the latter, both for the purpose of identifying these
aromatic derivatives and for their quantitative determination
in copolymers [11,12].
Nearly all the organosilicon compounds whose spectra are
given here (Table 3) are polysiloxanes. Their segregation in
a special section is justified by the specific structure of the
polymer chain. Also, the spectra of a few monomeric com-
pounds are given along with those of the corresponding poly-
siloxanes, which makes it possible to trace changes in the
spectrum due to the presence of various substituents on
silicon. In view of the fact that almost all of the polyarylsil-
oxanes given here are copolymers containing dimethylsiloxane
units, extinction coefficients were calculated in terms of one
arylsiloxane elementary unit.
The spectra of these compounds are essentially the spectra
of benzene or biphenyl containing one or more silicon sub-
stituents, and they contain B bands. The positions and intensi-
ties of the absorption maxima depend on the number and struc-
tures of the substituents in the benzene ring. The introduction
of CH 2 groups between the silicon atom and the aromatic ring
also has an effect. It is interesting that in this case a certain
alternation of properties is observed, as is found in some
homologous series: the absorption coefficients of compounds
containing an odd number of CH 2 groups between silicon and
phenyl are higher than those of adjacent compounds with an even

29
ORGANOSILICON COMPOUNDS

number of CH 2 groups [11, 13]. Moreover, the introduction of

CH 2 groups causes a smoothing-out of the spectrum, as also
does the introduction of a second substitutent into the phenyl
group.
Some of the organosilicon compounds whose spectra are
given here were synthesized at the All-Union Synthetic Rubber
Research Institute for the first time.

TABLE 3
SPECTRAL CHARACTERISTICS OF ORGANOSILICON STRUCTURAL
UNITS IN COPOLYMERS CONTAINING DlMETHYLSILOXANE UNITS
Structural unit
Figure Solvent >max. fn/l a
(or compound)
24 Methylpheny1siloxane unit Chloroform 253.5 1.45 197
259.0 2.10 286
264.0 2.25 306
270.5 1. 70 231
25 (Ch10romethyl) phenylsilox- Chloroform 254.0 1.30 222
ane unit 259.5 1.90 324
264.5 2.30 392
271.0 1.85 315
26 Ethylphenylsiloxane unit Chloroform 253.5 1.40 210
259.0 2.00 300
264.0 2.20 330
270.5 1.60 240
27 Phenylvinylsiloxane unit Chloroform 253.5 1.45 215
259.0 2.10 311
264.0 2.25 353
270.5 1. 70 251
28 Methyl (m-trifluoromethyl- Chloroform 259.0 1.80 367
phenyl) siloxane unit 264.5 2.30 469
271.0 1. 75 357
29 Benzylmethylsiloxane uni t Chloroform 261.0 2.25 337
267.0 2.80 420
274.0 2.40 360
30 (a-Methylbenzyl) methylsil- Chloroform 261.0 2.00 328
oxane unit 266.5 2.25 369
273.5 1.65 270
31 Methy1phenethylsiloxane Chloroform 262.5 1.65 270
unit 270.0 1.30 213
32 Methyl (3-phenylpropyl)_ Chloroform 261.5 1.75 308
siloxane unit 269.0 1.35 238

30
 ORGANOSILICON COMPOUNDS

Structural unit
Figure Solvent Ama x ,t11fL a
(or compound)

33 Methyl (4-phenylbutyl)- Chlorofonn 262.0 1.55 291

siloxane unit 269.0 1.20 226
34 (Anilinomethyl) methyl- Chloroform 248.0 80 13,200
siloxane unit 297.0 15 2,475
35 Methyl-1-naph thylsilox- Chloroform 273.5 36 6,750
ane unit 283.0 42 7,850
293.0 30 5,600
36 Diphenylsilanediol Chloroform 259.0 3.00 648
264.0 3.05 659
270.0 2.30 497
37 Diphenylsiloxane unit Chloroform 260.0 3.25 643
265.5 3.65 723
271.5 2.75 545
38 (Methylphenylsilylene) _ Chloroform 254.0 1. 70 483
(ethylene) (methy 1- 259.5 2.20 625
phenylsiloxane) unit 264.5 2.10 596
270.5 1.40 398
39 p-Phenylenebis [dimethyl- Chloroform 265.0 2.10 40,
silaneJ 270.0 2.25 437
276.5 1. 70 330
40 p-Phenylenebis [dimethyl- Chloroform 264.5 1.20 271
silanol] 269.5 1.45 .328
275.5 1.25 283
41 (Dimethylsilylene) (p- Chloroform 264.5 2.10 .437
phenylene) (dimethyl- 269.5 2.35 489
siloxane) unit 275.5 2.00 716
42 [Methyl (3,3, 3-trifluro- Chloroform 270.0 1.60 595
propyl) sily.lene] (p- 276.5 1.40 521
phenylene) [methyl-
(3,3, 3-tr~fluoroprOPYI)
siloxane unit
43 (Dimethylsilylene) (m- Chloroform 264.0 1.60 334
phenylene) (dimethyl- 269.0 1. 70 354
siloxane) unit 275.0 1.20 250
44 414 '-Biphenylylenebis- Chlorof orm 265.0 9.50 2,550
dimethyl silane]
45 4,4 ~BiphenYlylenebis- Chloroform 260.0 4.75 1,700
[ chlorodimethylsilane]
46 (OXYf,i-p-phenYlene)- Chloroform 218.0 57 18,100
bis dimethylsilanol]
47 (Dimeth ylsilylene)-p- Chloroform 218.5 62.5 18,750
phenylene-oxy-p-phenyl- 239.0 57.5 17,250
ene (dimethylsiloxane)
unit

31
ORGANOSILICON COMPOUNDS

a 2.5

f\

I
2
V
fj
\
V
~
'\
./

0.5 /
/ \
\
'-'

o I'--
230 21,0 250 260 270 280 290
1\, mIL

Fig. 24. Methylphenylsiloxane unit

C6Hs ]
[ -~i-O- Chlorofonn
C = 10.0 g/liter
CH, d = 0.205 mm

32
 ORGANOSILICON COMPOUNDS

a 2.5

2 A
1.5 /~ \ I~
;1
\.

\ / \
0 V
,,~
o
230 21,0 250 260 270 280 290
A,mll

Fig. 25. (Chloromethyl) phenylsiloxane unit

C6Hs ]
[ -~i-O- Chloroform
C = 10.2 g/liter
CH2 Cl d= 0.205 mm

33
ORGANOSILICON COMPOUNDS

a 2.5

1\ 1\
I ~\
2

(5

f' V

"
V
f

0.5 \ \

"
\../
o
230 240 250 260 270 280 290
/t,m/,-

Fig. 26. Ethylphenylsiloxane unit

C6Hs ]
[ -~i-O- Chloroform
C = 9.25 g/liter
C2 HS d = 0.205 mm

34
 ORGANOSILICON COMPOUNDS

a 2.5

'" ~f\
I
2

\ ~
V"
(5
V
/

0.5 \ I 1
o
\../
230 2~0 250 260 270
\ 280 290
A.mIL

Fig. 27. Phenylvinylsiloxane unit

C6Hs ]
[ -~i-O- Chlorofonn
C = 10.0 g/liter
CH = CH, d = 0.205 mm

35
ORGANOSILICON COMPOUNDS

a 2.5

2 1\
1.5
( ~~ r\
/
0.5
~V
/ \\.
o
230 240 250 260 270 280
" 290
A,mll

Fig. 28. Methyl (m-trifluoromethylphenyl) siloxane unit

Chloroform
C = 50.0 g/liter
d = 0.107mm

36
 ORGANOSILICON COMPOUNDS

a3

2.5 \ f\
2
/J
1.5 \ // V

'v
0.5 \
"'-...
o
230 21.0 250 260 270 280 290
A,mll

Fig. 29. Benzylmethylsiloxane unit

Chloroform
C = 9.25 g/liter
d= 0.205 mm

37
ORGANOSILICON COMPOUNDS

a 3

2.5

/\
2
- \
\'-- /
/ "
f

OJ \
\
o ~
230 21,0 250 260 270 280 290
A,ml1

Fig. 30. (a-Methylbenzyl) methylsiloxane unit

~H-C6H5
CH, ]
[
-Si-O- Chlorofonn
I C = 9.95 g/liter
CH, d = 0.205 mm

38
 ORGANOSILICON COMPOUNDS

a 3

lI\.
[7 ~

."
0.5
'V \
o
230 21.0 250 260 270 280 290
A,mll

Fig. 31. Methylphenethylsiloxane unit

Chloroform
C = 9.95 g/liter
d= 0.510 mm

39
ORGANOSILICON COMPOUNDS

a 2.5

\
\
2

1.5 1\ /
\J V \v-
\
\
"
0.5

o
230 240 250 260 270
"'-290
280
A,mll

Fig. 32. Methyl (3-phenylpropyl) siloxane unit

Chloroform
C = 10.6 g/liter
d = 0.205 mm

40
 ORGANOSILICON COMPOUNDS

\ """"
,\ £ iL
£5

"V \
"
Q5

o ~
230 2f,(} 250 260 270 280 290
A,mil

Fig. 33. Methyl(4-phenylbutyl) siloxane unit

Chloroform
C =11.3 g/liter
d= 0.205 mm

41
ORGANOSILICON COMPOUNDS

80
V r\
a

"~
60

40 1/ ~

20
"-
o
230 240 250 260 270 280 290 300 3'0
A,mll

Fig. 34. (Anilinomethyl) methylsiloxane unit

Chlorofonn
C = 1. 05 g/liter
d= 0.107 mm

42
 ORGANOSILICON COMPOUNDS

a 50

30
V0 \
2f) 1\ ~ \\
\. /
"
10 \.

o "'-
2+0 250 260 270 280 290 JOO 310 320
A,mIL

Fig. 35. Methyl-l-naphthylsiloxane unit

C,oH, ]
[ -~i-O- Chloroform
C = 5.84 g/liter
CH, d = 0.066 mm

43
ORGANOSILICON COMPOUNDS

as

7
J

\ ~
2

, '\ L/v ~

~
o
2.30 21,0
~ ~
250 260 270 280 290
A,mll

Fig. 36. Diphenylsilanediol

C6H S
I
HO-Si-OH Chlorofonn
I C = 10.0 g/liter
C6 HS d = 0.212 mm

44
 ORGANOSILICON COMPOUNDS

a 5

3 ~I\
2
\
) \
~
\ / V
\
\
f

o
230 21,0 25f) 260 '70 280 2!J(J
A,mfl

Fig. 37. Diphenylsiloxane unit

C6Hs ]
[ -~i-O- Chloroform
C = 10.0 g/liter
C6 HS d= 0.212 mm

45
ORGANOSILICON COMPOUNDS

a3

2.5

I
IV\
1\

r1
2

\ \
'''-./
f \
Q5 \
o '--- ~

230 240 250 260 270 280 290

A,mll

Fig. 38. (Methylphenylsilylene) (ethylene) (methylphenylsiloxane) unit

[
C6Hs C 6H S
-~i -CH, -CH, -~i-O-
J Chloroform
C = 8.40 g/liter
CH 3 CH, d= 0.112 mm

46
 ORGANOSILICON COMPOUNDS

a2 oJ

2
,J~
,/
/ ~
\-/
f. 5

0.,
o2'0 250 260 270 "--
280 290 JO()
A,mll

Fig. 39. p-Phenylenebis [dimethylsilane]

CH3 CH 3
I I
Chlorofonn
H -Si-C 6 li. -Si-H
I I C = 10.4 g/liter
CH3 CH 3 d = 0.506 mm

47
ORGANOSILICON COMPOUNDS

300
A,mlL

Fig. 40. p-Phenylenebis [dimethylsilanol]

CH. CH.
I I
HO - Si - CoHo - Si - OH Chloroform
I I C = 5.11 g/liter
CH. CH. d = 0.506 mm

48
 ORGANOSILICON COMPOUNDS

a 2.5

~1\
V '\
r

\
V
/
~
0)
\

o ~-
240 250 260 270 280 290 300
A,mll

Fig. 41. (Dimethylsilylene) (p-phenylene) (dimethylsiloxane) unit

[
CH3
-~i-C.H4-~i-O-
CH3 J Chloroform
C = 10.43 g/liter
CH 3 CH 3 d= 0.212 mm

49
ORGANOSILICON COMPOUNDS

a2

.5

1
/ ~
a \
/
/ 1\

lJ
~ ~-
240 260 Z70 280 290 300
A.mll

Fig. 42. [Methyl(3.3.3-trifluoropropyl) silylene] (p-phenylene)

[methyl(3. 3. 3-trifl uoropropyl) siloxane] unit

Chloroform
C = 10.03 g/liter
d = 0.506 mm

50
 ORGANOSILICON COMPOUNDS

aZ

1.5 A£
, /
/ I~
0.5 1\
- /V \
o
2'0 250 260 270
"- -
280 290 300
A,mll

Fig. 43. (Dimethylsilylene) (m-phenylene) (dimethylsiloxane) unit

[
CH, CH,
-~i-C.H4-~i-O-
J Chloroform
C = 10.86 g/liter
CH, CH, d = 0.506 mm

51
ORGANOSILICON COMPOUNDS

fa
\
a

/ hi\
\\
8

2 ~
a ~
2/,0 250 260 270 280 290 300
A.mf.L

Fig. 44. 4.4'-Biphenylylenebis [dimethylsilane]

CH, CH,
I I
Chloroform
H-Si-C.H.C.H.-Si-H
I I C = 11.4 g/liter
CH, CH, d= 0.212 mm

52
 ORGANOSILICON COMPOUNDS

a6

\,
" \\
5
V
"-

1
I'"'",
o
21.0 250 260 270 280 290 300
A,mll

Fig. 45. 4,4'·Biphenylylenebis [chlorodimethylsilane]

CH, CH,
I I Chloroform
Cl-Si-C.H.C.H. -Si -Cl C = 12.4 g/liter
I I
CH, CH, d= 0.112 mm

53
ORGANOSILICON COMPOUNDS

a 60

(\

"
I
1,0 ~
'\
1\
_\
30

20 \

~ .........
-- I'--
fO

o
210 220 230 240 250 260 270 280 290
A,mfl

Fig. 46. (Oxydi-p-phenylene) bis [dimethylsilanot]

CH, CH,
, I
Chlorofonn
HO -fi-C6H40C6H4 -~i-OH
C = 3.06 g/liter
CH, CH, d = 0.058 mm

54
 ORGANOSILICON COMPOUNDS

a 62.5

50
(
1 "- y ~
'\ 1\
37.5

25 \
12.5
"~
"- ~
o
210 220 230 240 250 250 270
""'-
280 2!JO
A,mll

Fig. 47. (Dimethylsilylene)-p-phenylene-oxy-p-phenylene (dimethylsiloxane) unit

CH, CH, ]
[ -~i-C H OC H - ~i-O-
6 4 6 4
Chloroform
I I C ~ 3.05 g/liter
CH, CH, d = 0.058 mm

55
 IV. ANTIOXIDANTS
The aging of polymers, which is manifested by the worsen-
ing of the physicomechanical, dielectric, optical, and other
properties of polymeric materials during storage, treatment,
or use, is the result of the occurrence in these materials of
various processes induced by heat, light, atmospheric oxygen
and ozone, and other external factors.
Many of the antioxidants used for the protection of rubbers
from thermal and oxidative aging possess a combination of
various properties and are used for the protection of nurtlerous
polymeric materials from aging by light, ozone, and other
agencies. For this reason the material in this section will be
of interest to a large number of investigators working on the
stabilization of high-polymer materials.
In this section we present the ultraviolet spectra of the most
widely used antioxidants produced in the Soviet Union and
abroad. We have also determined and published the spectra
of products not yet in commercial production. This applies
mainly to p-phenylenediamine and p-anisidine derivatives a~d
to phosphorous esters.
We have classified antioxidants as follows in accordance
with their chemical structures:
1) secondary amines (Table 4)
2) p -anisidine derivatives (Table 5);
3) p -phenylenediamine derivatives (Table 6);
4) phenol derivatives (Table 7);
5) phosphorous esters (Table 8);
6) hydroquinone derivatives (Table 9);
7) sulfides (Table 10);
8) hydroquinoline derivatives (Table 11);
9) various antioxidants (Table 12).

57
ANTIOXIDANTS

From our point of view this is the most convenient classifica-

tion, for it allows the antioxidants to be grouped not only in
accordance with the form of the spectral curve, but usually
also in accordance with the mechanism of the inhibiting action
on the oxidation process in rubber.
In the main, these spectra were determined for technical
products whose purities we did not establish. The data obtained
can be used successfully for the identification and quantitative
determination of antioxidants in high-polymer materials.
In view of the fact that all antioxidants are aromatic com-
pounds, their spectra contain not only K bands, but also B bands.
The position of the bands and the form of the spectral curves
are determined by the various peculiarities of structure and
the nature of the substituents in the aromatic rings. In these
spectra the relation of the character of the spectrum to the
structure of the molecule shows up most clearly.
We must point out the peculiar properties of the spectra
of antioxidants containing free hydroxy groups (phenol and
hydroquinone derivatives and thiodiphenols) and of phosphorous
esters. These show as changes in the spectrum in alcoholic
alkaline solution, and the changes depend on the structure of
the antioxidant molecule - the more highly screened the
hydroxyl by substituents, the less the change in the spectrum.
Data on the change in the spectrum on addition of alkali can be
applied for the quantitative determination of these antioxidants
by the differential method in presence of other substances which
interfere in the direct determination [14]. For this reason,
the spectra of antioxidants containing hydroxy groups and of
phosphorous esters were determined both in neutral (solid line)
and in alkaline (broken line) alcoholic media.

58
 ANTIOXIDANTS

TABLE 4
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - SECONDARY
AMINES

Figure Antioxidant Solvent .\max, ffi/1 a

48 Neozone A (N-phenyl-1- Ethanol 253 79 17,300

naphthy1amine) 340 39.5 8,650
49 Neozone D (N-phenyl-2- Ethanol 272.5 122 26,700
naphthyl amine) 310 105 23,000
348 20 4,400
50 p-Hydroxyneozone [N-p- Ethanol 259 111 25,850
hydroxyphenyl-2- 304 98 23,000
naphthyl amine, p-(2-
naphthyl amino) phenol]
51 p-Hydro xydiphenylamine- Ethanol 283 85 15,700
(p-anilinophenol)
52 Agerite Sta1ite (octyl- or Ethanol 288 61
heptyl-substituted
diphenylamine)
53 Antioxidant BLE (pro- Ethanol 289 95
duct of the condensa-
tion of diphenylamine
with acetone)
54 Antioxidant BLE-25 Ethanol 287 105
(product of the conden-
sation of diphenylamine
with acetone)

59
ANTIOXIDANTS

a fDO

\ /' \
75 /"'\.

50

\
'"~
~
25 .......... .-/

o r-.-
220 240 260 280 300 320 340 360 380 400
A,mll

Fig. 48. N eozone A (N-phenyl-l-naphthylamine)

Ethanol
C = 0.79 giliter
d = 0.117 mm

60
 ANTIOXIDANTS

a 150

125

100
/1 /"\

/ /f \

J
75

50
V \
25 ~
'- ,...--.......
o ~ ~

220 2;.0 260 280 300 320 34.0 360 380 400
A,mfJ-

Fig. 49. Neozone D (N-phenyl-2-naphthylamine)

Ethanol
C = 0.79 g/liter
d = 0.049 mm

61
ANTIOXIDANTS

a '20

\ -
\
tOO

80
l /
/ i\
60
\/ \
1,0 \
20
\ -............
o
220 21.0 260 280 JOO 320 )1,0 360 J80
A,mll

Fig. 50. p-Hydroxyneozone [N-p-hydroxyphenyl-2-naphthylamine,

p-(2-naphthylamino) phenol]

Ethanol
C = 0.166 g/liter
d = 0.214 mm

62
 ANTIOXIDANTS

a tOO

80 Ir"\.

60 / \
40
/ 1\
20
'-'
.-/
\
a
~ r--
220 21,0 260 JOO 320 31.0 360
A. mJl.

Fig. 51. p-Hydroxydiphenylamine (p-anilinophenol)

Ethanol
C = 0.204 g/liter
d=0.214mm

63
AN TIOXIDAN TS

a 75

60
1/
\
J
/ 1\
"'- \'-:
30

'5
~
V
o ~
220 24.0 260 280 300 J20 340 360
A,mll

Fig. 52. Agerite Stalite

Ethanol
C = 2.60 g/liter
d = 0.66 mm

64
 ANTIOXIDANTS

afOO

•. 1\
." / \
// ~
'"
40

~ \
'"
20

O r0-
ZZD 21,0 Z60 ZM} 300 320 31,0 JtIO
A.mll

Fig. 53. Antioxidant BLE

Ethanol
C = 1.00 g/liter
d = 0.205 mm

65
ANTIOXIDANTS

a 120

.... 1/"'\

I \
/
IJ(J

~
/ \\
6

40 "-
.......... --./
20 I\..
0
220 2~ 260 280 3IJ() 320
"'"
~
~

36D
A.m/1

Fig. 54. Antioxidant BLE-25

Ethanol
C = 1. 00 g/lite r
d=0.107mm

66
 ANTIOXIDANTS

TABLE 5
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - p-ANISIDINE
DERIVA TIVES
Figure Antioxidant Solvent Amax,m/1 a
55 N-Heptyl-p-anisidine Ethanol 242 52 11,550
308 12 2,650
56 N -Cyc!ohexyl-p-ani sidine Ethanol 242 73 15,000
300 16.5 3,400
57 N -s -Octyl-p-anisidine Ethanol 242 50 11,800
302 10 2,350
58 N -<z-Methylbenzyl-p- Ethanol 244.5 52 15,100
anisidine 313 10 2,900
59 N _Isopropy1-p-anisidine Ethanol 242 60 10,150
300 11 1,850
60 N-Alkyl-p-anisidine Ethanol 244 46
310 8.5

67
ANTIOXIDANTS

a 60

~
50

/\
-/ \
'0

sn

20
/ ~

.. \'- ~
..--.......
0
~~
220 ]1,0 260 261) 300 320 3'0 360 310
A,mll

Fig. 55. N-Heptyl-p-anisidine

Ethanol
C ~ 0.542 g/liter
d ~ 0.214 mm

68
 ANTIOXIDANTS

a 80

I r\
/ \,
60

40 17

20 ~
o
220 21,{)
"-V "'-
"'-
280 3IXJ 320 31.0 360
A,rnp.

Fig. 56. N-Cyc1ohexyl-p-anisidine

Ethanol
C = 0.592 g/liter
d = 0.214 mm

69
ANTIOXIDANTS

40 / '\
/ \
\
30
/
20

1\
""
to

o '-. / ~
220 21,0 260 280 300 320 31,0 360
A,mll

Fig. 57. N-s-Octyl-p-anisidine

Ethanol
C = 0.650 g/li ter
d= 0.214 mm

70
 ANTIOXIDANTS

aDa

a r\.

\
5

~J
/ \\

\
'0

" '"
'0
V
0
V
220 21,0 280 300 320 340 360
A.mp.

Fig. 58. N-a-Methylbenzyl-p-anisidine

C.Hs
I
Ethanol
CH 3 0C.H.NHCH
I C = 0.592 g/liter
CH, d = 0.214 mm

71
ANTIOXIDANTS

/ '\
a60

~o

I
30 / \
20
II \
~
""--
fO

o
220 240 260
'-V 280 300 320 31,0 360
A. mil

Fig. 59. N-Isopropyl-p-anisidine

CH 3
Ethanol
CH 3 0C.H.NHCH
C =0.536 g/li ter
CH 3 d = 0.214 mm

72
 ANTIOXIDANTS

a 50

40 I t\
.." / \
20 / \
~

'"
to
'-V
-
0 ~
260 280 300 320

Fig. 60. N-Alkyl-p-anisidine

Ethanol
C = 0.536 g/liter
d= 0.214 mm

73
ANTIOXIDANTS

TABLE 6
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - p-
PHENYLENEDIAMINE DERIVATIVES

Figure Antioxidant Solvent Amax, mil a

61 Antioxidant DFFD(N,N'-diphenyl-p- Ethanol 304 105 27,300
phenylenediamine)
62 Antioxidant 4010 (N-cyc1ohexyl-N'- Ethanol 290 70 18,600
phenyl-p-phenylenediamine) Ethanol
63 Antioxidant 4010-NA (N-isopropyl- Ethanol 290 83 18,850
N'-phenyl-p-phenylenediamine)
64 N -Pent y1-N '-pheny 1-p-phen ylene- Ethanol 290 53.5 13,650
diamine
65 N-Hexyl-N'-phenyl-p-phenylene- Ethanol 290 77 20,700
diamine
66 N -octyl-N'-ph eny1-p-ph enyl ene- Ethanol 290 55 16,350
diamine
67 N-Decyl-N'-phenyl-p-phenylene- Ethanol 290 54 17,550
diamine
68 N-Alkyl-N'-phenyl-p-phenylene- Ethanol 290 55
diamine (technical product)
69 N,N'-Dipentyl-p-phenylenediamine Ethanol 259 27.5 6,850
70 N,N'-Dioctyl-p-phenylenediamine Ethanol 259 38.5 12,800
71 N,N'-Dinonyl-p-phenylenediamine Ethanol 259 33 11,900
72 Agerite white (N,N'-di-2-naphthyl- Ethanol 80'70 246 74 27,000
p-pheny1enediamine) + chloro- 274 63 23,000
fonn (20'70) 318 69.5 25,300
73 Aranox [N-phenyl-N'-(p-tolylsul- Ethanol 227 46 15,550
fonyl)-p-phenylenediamine,N- 293 54 18,250
(p-anilinopheny1)-p-toluenesul-
fonamide]

74
 ANTIOXIDANTS

af.'20

'00 1'~

-
lin / \
-
V \
'\\
lUI

....
In /
'- ~ /
\
20

a "-
260 280 300 320 340 360
X,mp.

Fig. 61. Antioxidant DFFD (N,N'-diphenyl-p-phenylenediamine)

Ethanol
C = 0.10 g/liter
d= 0.107 mm

75
ANTIOXIDANTS

a8u

0 A
0
V 1\
---/
~ \
"-
a
220 21,(} 260 280 300 320 """
34(J 360
A.mp.

Fig. 62. Antioxidant 4010 (N-cyclohexyl-N'-phenyl-p-phenylenediamine)

Ethanol
C = 2.00 g/liter
d= 0.066 mm

76
 ANTIOXIDANTS

a 100

/'\.
80
V \
60 /
./
V \
1'--""
V
\
'"
'0

0 ~
220 240 2~O 300 320 340 J6()
A.mll

Fig. 63. Antioxidant 401 O-N A (N-isopropyl-N '-phenyl- p-phenylenediamine)

CH,
I Ethanol
C.Hs NHC.H4NH~H C = 1.00 g/liter
CH, d = 0.066 mm

77
ANTIOXIDANTS

a 60

~
I
J ~

30 ! 1
20 I ... --..,....
V
l...--/ \\
~

'""'-
fO

o
220 240 260 280 300 320 31,0 360
A.mll

Fig. 64. N-Pentyl-N'-phenyl-p-phenylenediamine

Ethanol
C = 0.410 g/liter
d= 0.214 mm
 ANTIOXIDANTS

80
)V\
a

l,.-/
/ 1\\
"
I~
-..../'"

20
~
o ~
no 240 260 280 300 320 340 360 380
A.mJl

Fig. 65. N-Hexyl-N'-phenyl-p-phenylenediamine

Ethanol
C = 0.472 g/liter
d = 0.117 mm

79
ANTIOXIDANTS

a 50

50 1\
/ \
V \
,,0

30

1"- V \
\
20

fO
'\
o ~
220 240 260 2130 300 320 340 360
A,mll

Fig. 66. N-Octyl-N'-phenyl-p-phenylenediamine

Ethanol
C = 0.460 g/liter
d = 0.117 mm

80
 ANTIOXIDANTS

a 60

50
If
/\ ,
J r\
3D
/ \
20 I .... -
~
V
\
1\
"
'0

o i'-
220 260 280 300 320 31.0 360
A.mll

Fig. 67. N-Decyl-N'-phenyl-p-phenylenediamine

Ethanol
C = 0.240 g/liter
d = 0.509 mm

81
ANTIOXIDANTS

a 50

50 1/\
/ \
V
40

30 \
'--J
V- \
\
20

fO
"-
o ~
220 240 260 280 JOO 320 360
A,mll

Fig. 68. N-Alkyl-N!phenyl-p-phenylenediamine (technical product)

Ethanol
C = 0.636 g/liter
d = 0.117 mm

82
 ANTIOXIDANTS

aJO

/ 1\
I \
25

20

15
V \
10
J 1\'-..
---.... ...........
----
......
i'--
o
220 240 260 280 300

Fig. 69. N,N'-Dipentyl-p-phenylenediamine

Ethanol
C = 0.3376 g/liter
d= 0.509 mm

83
ANTIOXIDANTS

I~
\
30

j
/
J
~ ~
~
0
i'........ -
220 2itO 260 280 J()O 320 360 180
A,mll

Fig. 70. N,N'-Dioctyl-p-phenylenediamine

Ethanol
C = 0.492 g/liter
d = 0.509 mm

84
 ANTIOXIDANTS

4U

/ t\

/ \ \~
JO

2< V

"J --- ~ t'--

0
220 21JJ 260 280 JOO 320 340 360 380
A,mll

Fig. 71. N,N' -Dinonyl-p-phenylenediamine

Ethanol
C = 0.398 g/liter
d = 0.214 mm

85
ANTIOXIDANTS

a 80
'- ~
"---. /' r\
\
6,
V
~
'",
"1.1

....
"",

l
"- i'---
220 2110 260 280 300 320 360 380 400
A,mll

Fig. 72. Agerite white (N,N' -di-2- naphthyl-p-phenylenediamine)

80'70 ethanol, 20'7, chloroform

C = 0.1244 g/liter
d = 0.509 mm

86
 AN TIOXIDAN TS

aBO

50 /\

40 \
/ \
\ / \
\
30

20 \ /y
~ \

"
10

o r-..
220 240 260 280 300 320 Jl,0 360
A,mll

Fig. 73. Aranox [N-phenyl-N'-(p-tolylsulfonyl)-p-phenylenediamine,

N-(p-anilinophenyl)-p-toluenesulfonamide]

Ethanol
C = 0.0231g/liter
d= 5.01 mm

87
ANTIOXIDANTS

TABLE 7
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - PHENOL
DERIVA TIVES

Neutral alcoholic Solution in 0.1 N

solution alcoholic alkali
Figure Antioxidan t
>max, a )'max' a
mil mil
74 lonol, Antioxidant P-21 (2,6-di-t- 278 8.0 1,760 278 8.0 1,760
butyl-p-cresol) 307 2.0 440
75 Antioxidant P-23 (2,4,6-tri-t- 274.5 7.0 1,760 274.5 7.0 1,760
butylpheno1) 302 2.0 500
76 Ar.tioxidant 425 (2,2'-memy1enebis- 282 13.0 4,780 286.513.0 4,780
6-t-butyl-4-ethylphenol ) 307 17.0 6,250
77
1
Antioxidant 2246 (2 2'-methYlenebis-
[6-t-butyl-p-cresol )
281 12.0 4,080 287 12.0 4,080
308 17.0 5,780
78 Bukremet (4,4'-methylenebis [6-t- 279 10.7 3,600 255 31.7 10,700
butyl-o-cresol]) 293 14.0 4,750
79 Stntowhite powder (4,4'-butylidenebis- 281 1.3 5,000 287 13.5 5,150
6-t-butyl-m-cresol])

I
80 P,p'-Dihydroxybiphenyl (p,p'-biphenol) 264 126 23,500 293 153 28,500
81 Wing-Stay S} Mixtures of mono-, di-, and 280 8.5 302 15.0
82 Montac1ere tri-styryl derivatives of 279.5 8.0 303 18.2
phenols
83 Styphen I 282 6.2 306 10.2
84 N,no. EX P,od",. ,f " " " ..,,'" 281 14.0 302 19.5
85 Nonox EXN of phenols with aldehydes 283 17.0 301 21.0
86 Nonox WSL 280 9.3 287 9.5
301 9.3
87 Nonox WSP 283 11.5 288 11.7
310 15.3
88 Agerite Super lite (polyalkylated poly- 280 11.2 285 11.0
phenol)

88
 ANTIOXIDANTS

dO

/1
Z5 I~ ~
I
I, I
/
~

, I

V
II
bl
.. J
1
\
\\
25

o
1k/ ~
......,,
\
1' ...
220 240 260 280 31)0 320 3'0
A, mp.

Fig. 74. lonol, Antioxidant P-21 (2,6-di-t-butyl-p-cresol)

OH

(CH 3) , C ¢ C ( C H 3 )3 Ethanol (a), 0.1 N ethanolic KOH (b)

C = 3.67 g/liter
CH 3 d = 0.214 mm

89
ANTIOXIDANTS

a 10

7.5
,
I
,
I
b ,," /r,
/
-' \
\
\
\
2.5

k/ (
,
~,

\ ,
o
Z20 240 260 280 300
' ..
320
-- -
31.0 360
A,mlL

Fig. 75. Antioxidant P-23 (2,4,6-tri-t-butylphenol)

OH

(CH,)' c-O-C(CH,), Ethanol (a), 0.1 N ethanolic KOH (b)

C ~ 14.00 g!liter
C(CH,l. d ~ 0.049 mm

90
 ANTIOXIDANTS

20
\
\
\
\ , I" \

" h, ,
\ ,I \
~~-" \
~\..b \

1
to
,
\

"
\:J~ \\
o
220 260 280 3IJ()
- 320
'-
340
- 360
A,mp.

Fig. 76. Antioxidant 425 (2,2'-methylenebis [6-t-butyl-4-ethylphenol))

OH OH

(CH,), C-¢-CH2-¢-C(CH')' Ethanol(a), 0.1 N ethanolic KOH (b)

C = 7.90 g/liter
C 2 H, C 2 H, d = 0.066 mm

91
ANTIOXIDANTS

a 25

\
20
\ "
\ II '\

,,
15
\ \
\b I \
I A-'
\

'Ii \
a \
fO
\
\
, I \
.."

\
5 I \
V \\
.
o
220 240 200 280 300 320
'-3/.0-- 360
A,mp.

Fig. 77. Antioxidant 2246 (2,2' -methyle nebis[6 - t-butyl-p- cresol])

OH OH

(CH,), C-¢--CH 2 - Q- C(CH'h Ethanol (a), 0.1 N ethanolic KOH (b)

C = 1. 48 g/liter
CH, CH, d = 0.214 mm

92
 ANTIOXIDANTS

0"0
\
nv \ \ ""
,\ I
I
i', b
\ I
\
\
a \
'''',.... -~
\ i,
",
0
lZO
~V
240 260 280
\ 300
,
320
"" ....... _-
31.0 JIiO
x, mil

Fig. 78. Bukremet (4,4'-methylenebis [6-t-butyl-o-creso1])

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 0.734 g/liter
d = 0.509 mm

93
ANTIOXIDAN TS

a 'S

\~j ~\\,

/v
10
a
1
\
"',

o
l \ ~
\
,
\

" .... -
2f,{} 260 280 JOO 320

Fig. 79. Santo white powd e r (4,4'-butylidenebis [6-t-butyl-m-cres0!J)

C( CH,l, C( CH,),

Ho.hYH A-oH Ethanol (a), 0.1 N ethanolic KOH (b)

'=(
C,H-:\=I C = 0.800 g / liter
CH, CH, d = 0.509 mm

94
 ANTIOXIDANTS

a 200

.....
.r"
i.'
- ,
\

I ~'
\
\

V ,
txJ I '\ \
\ b
, I

1\
\ I
a , I
1\
5u
,,
V
\
.......... 41" \

0
.20 2t.O 260 2(J()
.........
JOG 320
' ...

3/.0
-- 36IJ
A.mjL

Fig. 80. PIP' -Dihydroxybiphenyl (P,P' -biphenol)

Ethano l (a), 0.1 N ethanolic KOH(b)

C = 0.79 g/lite r
d = 0.066 mm

95
 ANTIOXIDANTS

alO
\
\

15
\ / .,\
\b
\ I \
/ \
to
\a \
" /
/
\
\ \\
\. - / r\ \

o
220 2110 26lJ 280
\ 300
\

320
~,
,
' ..
340
- 360
A,mJl

Fig. 81. Wing-Stay S

Ethanol (a) 0.1 N ethanolic KOH (b)

C = 0.78 g/liter
d = 0.214 mm

96
 ANTIOXIDANTS

a2tJ
f\b ...,
\ /
\
\,
la
/ \
'5
, /
I
\\
\
- \

\\
·'u

~ / 1\
\
5
V \
\ ,
0
220 21,0 260 280 300 320
""3/.0
A,mll

Fig. 82. Montaclere

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 0.82 g/liter
d = 0.214 mm

97
ANTIOXIDANTS

a 12.5

10
\b
\
-. \
a
\ 1/ \
7.5
\
- f \
\
\ / \ \,
2.5
'v ,/
\ \
,
\-
\

' .... --
o
220 260 280 300 320 31.0 360
A.m(l

Fig. 83. Styphen I

Ethanol (a). 0.1 N ethanolic KOB (b)

C = 10.0 g/liter
d = 0.066 mm

98
 ANTIOXIDANTS

a 20
I
I "\\

I \
I
\
'5 ,b -I
\
a
\ /~ \
\
l'
10 \
\

\ ,
\
5
0 II \
\ ,
' ...... 1--_
o 320 3/.0 360
220 2110 260 280 300
A,mll

Fig. 84. N onox EX

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 0.1006 g/liter
d = 5.01 mm

99
ANTIOXIDANTS

a 25

10 :, --,
I't".

,
1 J \
I
)(\ / \

\:, I
\
15
}
1
\
\
I
\
a

VJ
f(}
/

\
\
\
\ '-J
J
\ \
\

~ ' ....... --
o
220 240 260 280 320 31.0 J60
A.mp.

Fig. 85. Nonox EXN

Ethanol (a). 0.1 N ethanolic KOH (b)

C = 7.9 g/liter
d = 0.066 mm

100
 ANTIOXIDANTS

a 20

,
\
\. /\
I

h
\
a \I

'f K'"
10
too,
\
, \ \

"-
\ 11 \
\

0
210 21.0
U 260 210 300
\
320
t"--
31.0 360
A,mll

Fig. 86. Nonox WSL

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 10 g/liter
d = 0.066 mm

101
ANTIOXIDANTS

aZO
•
I

~,
\
15
\b
, I
I \
,
I

,,
a \
\

\; \
rx-".,.I
\
\
10

\ '
'- '" I \
\
/
\
\

,
\

~
\

o "... -
220 2tO 260 280 JOO 320 360

Fi g. 87. N o n o x WSP

Ethano l (a). 0 .1 N eth a n o li c KOH (b)

C = 10 g/liter
d = 0 . 066 mm

102
 ANTIOXIDANTS

a t'(;
\
\b /~\\
'1' ,,
0
\ \

- "

I
8
\
I
a \
\

\\.;Vil
6
\
\
\
~
\
'.
,
\
2

0
"..........
260 280 300 320 3"0
A.mp.

Fig. 88. Agerite Superlite (polyalkylated polyphenol)

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 0.722 g/li ter
d = 0.509 mm

103
ANTIOXIDAN TS

TABLE 8
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - PHOSPHOROUS
ESTERS
Neutral alcoholic Solution in 0.1 N
solution alcoholic alkali
Figure Antioxidant
Amax, mil a f Amax, mil a f

89 Polygard (tris-p-nonylphenyl 272 4.0 2,750 295 8.5 5,850

phosphite)
90 lonol pyrocatechol phosphite 272 11.0 3,950 Destroyed
(2, 6-di -t-bu ty lop-to 1y 1-0- 277 9.5 2,500
phenylene phosphite)
91 Phosphite, Antioxidant P-24 269 6.2 300 12.2
(phosphorous ester of 279 6.8
styryl-substituted phenol)

104
 ANTIOXIDANTS

'0
,
I , ... \
I
,,
I
l

a
,
Ib
,I
I
I
,
\
,
I
j
I
\~
2.5 \
~ \\
~
280 300
'. ...
~
320
--- ~
340
A,ml-'

Fig. 8 9 . Polygard (tris-p-no n y lphenyl phosphite)

Ethanol (a), 0.1 N ethan o lic KOH (b)

C = 4.0 g/liter
d = 0.214 mm

105
AN TIOXIDAN TS

a 12

10 h
8 \ / ~
6
I
/
\, J ~
2 \ / \
o
230 240
\...., 'I
250 260 270 280
\ I'-.....
290 300
A,mp.

Fig. 90. Ionol pyrocatechol phosphite (2,6-di-t-butyl-p-tolyl-o-phenylene phosphite)

T(CH,),

~I
V-O'"
0, P-0-o-CH
, Ethanol
C = 0.1204 g/liter
C(CH,), d=S.Olmm

106
 ANTIOXIDANTS

a 15

\
12,5
\
\ , '\
I
\
/
\b

10 \ \
\, I
I \
\
\
a ,~
"
I
\,
~ l/~ ••
\

25
'\J
\ •,
,
a220
240 Z6Q 280
\~ 300 320
\
".-. ~
360
A,mJl

Fig. 91. Phosphite, Antioxidant P-24

Ethanol Cal, 0.1 N ethanolic KOH Cb)

C = 0.164 g/liter
d= 5.01 mm

107
ANTIOXIDANTS

TABLE 9
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - HYDROQUINONE
D ERIV ATIVES
Neutral alcoholic Solu lion in 0.1 N
solution alcoholic alkali
Figure Antioxidant
-\max' mJ1 a Amax, mJ1 a
92 Agerite Alba [p-(benzyloxy)- 291 13 2,600 308 14 2,800
phenol]
93 Santovar 0, Antioxidant P-20 294 21 4,650 252 27 6,000
(2, 5-di-t-buty lhydroquinone) 324 47 10,400
94 Santovar A (2,5-di-t- 230 18 4,500 256 22 5,500
pentylhydroquinone) 294 19 4,750 324.5 35 8,750

108
 ANTIOXIDANTS

a '5
,"'\
1\ ' '.

1/ I
\
\
a \
1\ b
fO
\ I
\ I \
\ ! \

\L.
zs J

I
I
\
\
I
\
~V
\
2.S ~ \
\
o
2ZQ lJ,(J 260 280 3fJO
~ 320
\

"-
1UJ 160
A.mll

Fi g. 92. Age rite Alba [p-(ben z yloxy)phe nol]

Ethano l (a). 0 . 1 N ethano lic KOH (b)

C = 0.682 g/liter
d = 0.509 mm

109
AN TIOXIDAN TS

a50
if ....,

i
I
/ \
\
,,,
I \,
,,
3D
, ",", :
,
-
I

20 'x""
\
b
I

"\ , V) ,
\

\/ I
I
\ \"- '

\
/
~ ~" ... '
o
Z20 ;'0 Z60 280 300 3Z0 JlJO 160
A,mp.

Fig. 93. S a nto var 0 , Antioxidant P-20 ( 2,S-di-t-butylhy dro quin o ne)

OH

O
I
-c(CH,),
E t han o l (a) , 0.1 N etha noli c KOH (b )
(CH,), C -:::::,..
I
C ~ 7 . 9 g/ lite r
OH d ~ 0 . 0 66 mm

110
 ANTIOXIDANTS

a 40
, ...
J
~ \ \

/ \
\

....... ,
I \
\
I \
20
;
\b
V' 'v/
\
V\~. \
\ \
a \ / \
0

I ~ /'
,-"if!'
1--"-
/' .~
0
220 21,0 260 Z80 300 320 31,0 360
A.mJL

Fig. 94. Santovar A (2.5-di-t-pentylhydroquinone)

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 7.9 g/liter
d = 0.066 mm

111
ANTIOXIDANTS

TABLE 10
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - SULFIDES

Neutral alcoholic Solution in 0.1 N

solution alcoholic alkali
Figure Antioxidant
a

95 Antioxidant SAO-6 (2,2'- 292 14.5 5,200 298 17.2 6,150

thiObij[ 6-t-butyl-p- 319 18.5 6,600
cresol)
96 Antioxida t AN-6 (2,2' 294 7.0 3,375 298 5.5 2,650
thiobis [;,-(a,a -dimethyl- 317 6.5 3,150
benzyl)-p-cresol b
97 Santowhite crystals (4,4'- 249 47.0 16,800 269 59.0 21,100
thiobis [6-t-butyl-m- 281 21.5 7,700
cresol])
98 Santowhite eM (6,6' - 236 56.0 13,800 266 108.0 26,600
thiodi-o-cresol) 251 60.0 14,750
99 Santowhite MK (product 284 19.0 251 37.5
of reaction of sulfur
chloride with 6-t-
butyl-m-cresol)

112
 ANTIOXIDANTS

alO
,'" ,
1\ /" ,/ \
,
\
16 I ~"

12
1\
\ /\ \
\
\ V\
\ b \
\ \
\ \
\

\ / \
8
\\
\ \,
I'-""

o '. ----
240 260 280 300 320 340

Fig. 95. Antioxid a nt SAO-6 (2,2'-thiobis [6-t-butyl-p-c resol])

(CH,), C --0- --0-

OH
I
S
OH
I
CC CH ,), Ethanol (a), 0 . 1 N ethanolic KOH (b)
C = 0 . 611 2 g/liter
CH, CH, d = 0.509 mm

113
ANTIOXIDANTS

a 8 r---~r----'----~-----r-----r----~

Zr---~----+----1---T-r----~,~~
,,
"
~~'~O--~~O--~MbO~-J~O~O--~~bO~~J~'O~=~~O
A,ml-'

Fig. 96. Antioxidant AN-6 (12,2' -thiobis [6-(a,a-dimethylbenzyl)-p-cresol])

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 0.777 g/Iite r
d = 1.016 mm

114
 ANTIOXIDANTS

a 60 ,"'\
\ I ' \\
\\

L
50
!(v' \
\
\
1.0 ,, \

\
\ b //\ \
\
JO \, ..
~
\
\\

'\
20
\

I"
\
\
10
,
o
220 21.0 160 c80 JOO
-" ' ....
J20 340
A.mll

Fig. 97. Santo white crystals (4.4' -thiobis [6-t- butyl-m-cresolh

-o-
fH, yH,
0H Ethanol (a), 0.1 N ethanolic KOH (b)
HO-(0- S
I I
C = 0.1004 g/liter
C(CH,), C(CH,), d = 1.016 mm

115
ANTIOXIDANTS

a 120

,..
I '.
100
\
\
I \
80 ,I \

I
I \
I

Iv'1\
\
60
\ \
I 1\ "
\
'" ,
\
-"
/ b

~I"'\. ,
\ ,
'""-
20
"i', .....
--
°
f-. ... ~
220 240 260 280 JOO 320 340 360
A,mJl

Fig. 98. Santo white CM (6,6 '-thiodi-o-cres o l)

-O-s-O-CH,
OH OH
I I
Ethan o l (a), 0.1 N ethanolic KOH (b)
CH, C = 0.112 g/liter
d = 1.01 6 mm

116
 ANTIOXIDANTS

,----',
1\ " ...'\
,
\
b

" ..........
20
a
'"
'--
~ ",

"
' .... .... - ---. -- ...
10

---
.........
" I'-- ..........

o
i'--....
220 21,.0 260 280 300 320 .340 JDO 380 400
A,mll

Fig. 99. Santo white MK

Ethanol (a), 0.1 N ethanolic KOH (b)

C = 0.796 g/liter
d = 0.214 mm

117
ANTIOXIDANTS

TABLE 11
SPECTRAL CHARACTERISTICS OF ANTIOXIDANTS - HYDROQUINOLINE
DERIVA TIVES
Figure Antioxidant Solvent Amax. mfl a
100 Santoflex AW (6-ethoxy-l.2-dihydro- Ethanol 229 100 21.800
2. 2.4-trimethylquinoline) 350 11 2.400
101 Santoflex DD (6-dodecyl-1.2- Ethanol 233 78 26,600
dihydro- 2, 2, 4-trimethylquinoline) 342 5 1,700
102 Agerite Resin D Ethanol 236 89 15,400
296 13 2,250
103 Flectol B Ethanol 232 143 24,750
310 12 2,075
322 12 2,075
104 Antox (product of condensation of Ethanol 231 98
aniline with butyraldehyde) 235 102
248 32
305 15
318 15
105 Antioxidant 1-18 (product of con- Ethanol 247 60
densation of aniline with iso- 299 15
prene)

118
 ANTIOXIDANTS

tOO
1/\
a

80

60 ~
\
20 \ '-..
~ ...............
o ~.
220 21,0 260 280 300 320 360 380 4(J(J
A.ffi/.L

Fig. 100. Santoflex AW (6-ethoxy-1.2-dihydro-2.2.4-trimethylquinoline)

CfH.
C2Hs0-CO
~ N
I
).... CH.
.... CH
•
Ethanol
C = 0.1572 g/liter
d= 0.509 mm
H

119
ANTIOXIDANTS

7\
a 80

60 [7

~
\
"
20

o
220 240 260 280 100 320 350 380
A,mt'-

Fig. 101. Santoflex DD (6-dodecyl-l,2-dihydro-2,2,4-trimethylquinoline)

?H,
C12H25-(O~ CH

~ N
I
"'CH', Ethanol
C = 0.021 g/liter
H d= 5.01 mm

120
 ANTIOXIDANTS

a fDa

80
f\

60
II ~
~
\
~
20
"- - -........ """--
o
Z20 21,.0 260 280 JOO 320 340 360
A,mIL

Fig. 102. Agerite Resin D

CH, ]
[ a)~CH' Ethanol
I CH,
C = 0.91 g/liter
H n d = 0.214 mm

121
ANTIOXIDANTS

a 150

125 f\
I \
100

\
75

,
50

25
\
~

o r--
220 240 260 280 300 320 3J.O 360 380
/..,mp.

Fig. 103. Flectol B

Ethanol
C = 0.1464 g/liter
d = 0.509 mm

122
 ANTIOXIDANTS

a 120

11
100

80

60

20 ~
f\....
~
o '-.....
220 2t.D 260 280 ]00 320 J!.,l)
A,mll

Fig. 104. Antox

Ethanol
C = 0.152 g/hter
d = 1.016 mm

123
ANTIOXIDANTS

V\
a 60

/
50
\
30
IJ
20

fO \ '-~
/ ~
\
o
220 21.0 260 280 "-
320 3/,Q
/I.,mll

Fig. 105. Antioxidant 1-18

Ethanol
C = 0.922 g/liter
d= 0.117 mm

124
 ANTIOXIDANTS

TABLE 12
SPECTRAL CHARACTERISTICS OF VARIOUS ANTIOXIDANTS

Figure Antioxidant Solvent Amax, mfL a

106 Mercaptobenzimidazole (2- Ethanol 246 90 13,400
benzimidazolethiol) 305 194 28,900
107 Flexamine (mixture of 65'7, Chloroform 295 71.5
of product of condensa-
tion of a diarylarnine witq
a ketone and 35% of N,N-
diphenyl-p-phenylene-
diamine)
108 Akroflex C (mixture of 65% Ethanol 252 63
of Neozone A and 35% of 304 50
N,N'-diphenyl-p-
phenylenediamine)
109 Santoflex ax (mixture of Ethanol 234 37.5
the antioxidant Santoflex 301 45
a andN,N'-diphenyl-p-
phenylenediamine)

125
ANTIOXIDANTS

aawr---~-----r----'-----~----r----'

~~2~O--~~~O~~~~2~oo~~~=a~~~-~~o
A,mll

Fig. 106. Mercaptobenzimidazole (2-benzimidazoletbiol)

Ethanol
~N>C_SH C = 0.216 g/liter
VNH d=0.214mm

126
 ANTIOXIDANTS

a BO

60 / "-
\ . . . r--""
/ \ \

20

o
220 21.0 260 280 JOO 320
" ~
:MO 360 380
A.mll

Fig. 107. Flexamine

Chloroform
C = 0.754 g/liter
d= 0.117 mm

127
ANTIOXIDANTS

a 80

V\
/'\.
60
~
\ / ' -........ '"

"'"
"'- I'"

10
"-
~
280 300 320 340 360 380
A,mll

Fig. 108. Akroflex C

Ethanol
C = 0.470 g/liter
d = 0.117 mm

128
 ANTIOXIDANTS

aSO

/ '\
/ \
40

30 ~~
\
II

20 / \
\
""- . /
10
~
o
220 240 260 280 300 320 JI10 360
A.mll

Fig. 109. Santoflex BX

Ethanol
C = 1.50 g/liter
d = 0.107 mm

129
 V. VARIOUS SUBSTANCES USED IN SYNTHETIC
RUBBER MANUFACTURE
This section contains the spectra of various substances
(Table 13) used as emulsifiers and polymerization initiators,
regulators, and short-stoppers in the production of synthetic
rubbers by emulsion polymerization. By spectrophotometric
methods of analysis both the purities of these substances and
their concentrations in mixtures and solutions used in the
polymerization can be determined. Moreover, some of them
remain in the finished rubber, and their contents can be
determined [14].
Many of the compounds listed are aromatic and their ab-
sorption spectra contain both K and B bands. The absorption
spectra of a number of compounds containing a disulfide bond
have particular characteristics due to the interaction of the
unshared electron pair of nitrogen or oxygen with the C=S
bond. The disulfide bond also appears to have an effect on the
latter. In alkaline alcoholic solutions the spectra of these
compounds change, which makes it possible to determine them
in presence of other radiation-absorbing substances by the
procedure used for phenolic antioxidants.
The analysis of modified rosin used as an emulsifier is
conducted with the aid of the spectra of rosin acids given
here [15].

131
VARIOUS SUBSTANCES USED IN MANUFACTURE

TABLE 13
SPECTRAL CHARACTERISTICS OF VARIOUS SUBSTANCES USED IN
SYNTHETIC RUBBER MANUFACTURE
Figure Roduct Solvent AmaX'rry.t a [

110 Neka1 BXG (sodium 6,7- Ethanol 232 210 72,000

dibutyl-2-naptha1ene- 2"89 20 6,900
sulfonate)
Water 229.5 164 56,000
290 21 7,200
111 Leucano1(disodium 6,6'- Ethanol 227 235 111,000
methy1enedi-2- 275 17 7,900
naptha1enesulfonate)
112 Azo1yat A (sodium a1- Ethanol 262 2.30 710
ky1benzenesulfonates) 269 2.70 835
277 2.30 710
Water 263 2.35 725
270 2.80 865
277.5 2.20 680
113 Abietic acid Ethanol 234 72 19,450
241 77 20,800
114 Neoabietic acid Ethanol 250 80 21,600
115 Dehydroabietic acid Ethanol 268 2.2* 590
275.5 2.3 620
116 Emulsifier OP-4 Ethanol 206 28.6 12,500
225 22.9 10,000
276 3.5 1,500
282 3.0 1,300
117 Emulsifier OP-10 Ethanol 206 136 9,550
225 12.5 8,750
276 2.1 1,475
282 1.8 1,250
118 Dipropoxide [bis- Ethanol 238 94 25,400
(isopropoxythiocar- 286 46 12,400
bony1)disulfide] 0.1 N ethanolic 228.5 97 26,200
KOH 304 121.5 32,800

132
 VARIOUS SUBSTANCES USED IN MANUFACTURE

Figure Product Solvent -\nax' mil a

119 BEK [bis( ethoxythio- Ethanol 237 92 22,250
carbonyl) disulfide1 284 43 10,400
0.1. N ethanolic 226 89 21,550
KOH 302 122.5 29,650
120 Thiuram D [bis- Ethanol 272-280 43.5 10,450
(dim ethylthiocarbam-
oyl) disulfide 1 0.1 N ethanolic 255 81 19,500
KOH 285 75 18,000
121 Thiuram E [bis- Ethanol 216.5 73 21,600
(diethylthioc arbam-
oyl) disulfide) 0.1 N ethanolic 259 71.5 21,150
KOH 287 64 18,950
122 Sodium diethyldithio- Ethanol 253.5 79 13,500
carbamate 287 85 14,500
123 Hydroquinone Ethanol 225 55 6,050
294 26 2,850**
0.1 N ethanolic 209 75 8,250
KOH 242 62 6,800
320 24 2,650
124 Cumene hydroper- Ethanol 246 1.90 290
oxide (a,a-dimethyl- 251 2.00 305
benzyl hydroperoxide) 257 2.05 310
264 1.45 220

'In alcohol Amax=268 ffij1 and 275.5 mil, a = 2.3 and 2.2 [16].
In alcohol Amax=275 ffij1, a =2.4 [17].
**In alcohol Amax=294 ffij1, f=3,100 [18).

133
VARIOUS SUBSTANCES USED IN MANUFACTURE

a 21,0 30a

200 '" 25

J
/
160 20

120
/ ~ 15

BO I
I
\\ fa
/ \.

o
210 230
\ 250 270 290 310 '" i'- o
330 350
A,mll

Fig. 110. Nekal BXG (sodium 6,7-dibutyl-2-naphthalenesulfonate)

Ethanol
C = 1.66 g/liter
d = 0.049 and 0.509 mm

134
 VARIOUS SUBSTANCES USED IN MANUFACTURE

a250 25 a

200 II
1/ 20

cr, /\

/ /'
\ "
~.,

00 \/
/ \
fO

0 5
\ \
~o
0
200 220 240 260 280 300 320
A,mll

Fig. 111. Leucanol (disodium 6,6' -methylenedi- 2-naphthalenesulfonate)

Ethanol
~-c~~ C = 0.56 g/liter
NaO,S~ ~-SO.Na d = 0.058 and 0.506 mm

135
VARIOUS SUBSTANCES USED IN MANUFACTURE

aJ

\ r
\ ~ .~
2

l5 l\'-V
)

\
1

0.5
230 240 250 260 270 280 290
>t.m/-,-

Fig. 112. Azolyat A (sodium alkylbenzenesulfonates)

ClOH21~
Ethanol
V-SO,Na
C = 0.20 g/liter
- 60'7, -40% d= 9.99 mm

136
VARIOUS SUBSTANCES USED IN MANUFACTURE

a BO,----,-----y---r------.----,

20r---~--_+----+_~~--~

D~--~--~--__~--~~~
220 230 240 250 270
A,mll

m
CH, COOH
Fig. 113. Abietic acid

CH
~H'
I
CH, Ethanol [24]

137
VARIOUS SUBSTANCES USED IN MANUFACTURE

a80.---~---'r---~--~----,----.

20'~--~---4----+---~--4rl~~

OL-__- L____~__~__~~__~~~
220 230 240 250 260 280
A,mll

Fig. 114. Neoabietic acid

CH 3 COOH

M CH 3

~=-~ I
CH 3 Ethanol [24]

138
 VARIOUS SUBSTANCES USED IN MANUFACTURE

aJ

2.5

,
1\ ~
JJ IV
2 1\

f. 5
~
~
V \,
f

aJ ~
'-
0
220 230 240 250 260 270 280 290
A.mll

Fig. US. Dehydroabietic acid

7Y)0\
~~H I
Ethanol
C = 1.034 g/liter
CH. d = 1.012 mm

139
VARIOUS SUBSTANCES USED IN MANUFACTURE

a30 6a

25 J\ 5

20
\ V\
1\../
~ /\
\ \
5 J

/
\ \' - \,
V 2
/
/ f
\ V
0 i'- o
200 210 220 230 240 250 260 270 280 290 300
A,mll

Fig. 116. Emulsifier OP-4

Ethanol
C = 10.2 g/liter
d= 0.112 and 0.210 mm

140
 VARIOUS SUBSTANCES USED IN MANUFACTURE

at5 3a

A
:\ /\
".
""
fa \~ /'\
V \ Z

\ ) r\ 1.5

\ /1
l5 1

5 ,
2.5
\~
\
~ \ 0.5

a ~a
zoo 210 220 230 21,0 250 260 270 280 290 300
A,mll

Fig. 117. Emulsifier OP-IO

Ethanol
C = 10.0 g/Iiter
d = 0.112 and 0.210 mm

141
VARIOUS SUBSTANCES USED IN MANUFACTURE

a f2'
~'\
t \,
100
,,
f\\1\
I I

,
,:
I

75 I

50
\ b I
I
I
\,
,,
1'-.-
1'\ "
\
\ \
\, ,,

'"
I ~
25
,, I
I
,
o "-"' '-
220 240 260 280 300 320 340
A,mp.

Fig. 118. Dipropoxide [bis(isopropoxythiocarbonyl) disulfide]

Ethanol (a), 0.1 N ethanolic KOH (b)

(CH')2CHOCSSCOCH (CH')2
II II C = 1. SO g / liter
S S d = 0.049 mm

142
VARIOUS SUBSTANCES USED IN MANUFACTURE

a 125
,,..,
, ,
I
\
\

- I'\a ,,: ,I
,,,
I~ I
I ,
,
I
75
, \
\
I
~ ,
\,
-, /'\.
\ ~ !
"- J ,,
,
,b
'.
,,
\
\\
,, ,
~ r-,' ..
-'
260 280 300 320 31JJ
A,m,.,.

Fig. 119. BEK [bis(ethoxythiocarbonyl) disulfide]

Ethanol (a), 0.1 N ethanolic KOH (b)

C 2 H.OCSSCOC2 H.
II II C = 1.58 g/liter
S S d = 0.049 mm

143
VARIOUS SUBSTANCES USED IN MANUFACTURE

a 100

b
/',
75 I' ,
I \

I~
- N
10-/ \
\./ I
\
\
\
50 ........

~
""----

o ~ 1'--... -
i'-...
......
--
220 240 260 2M 300 320 3t.Q 360
A. m/-l

Fig. 120. Thiuram D [bis (dimethylthiocarbamoyl) disulfide]

Ethanol (a). 0.1 N ethanolic KOH(b)

(CH')2NCSSCN (CH,),
II II C = 0.98 g/liter
S S d=0.107mm

144
 V ARIOUS SUBSTANCES USED IN MANUFACTURE

2j~--+---~---+----~--~--~--~

o~ __ __ ____ __ __ ____ __
~ ~ ~ ~ ~ ~ ~

200 220 21,0 260

Fig. 121. Thiuram E [bis(diethylthiocarbamoyl) disulfide]

(C,H. ),NCSSCN (C,H. ), Ethanol (a), 0.1 N ethanolic KOH (b)

" II
C = 0.97 g / liter
S S d= 0.112 mm

145
VARIOUS SUBSTANCES USED IN MANUFACTURE

a 100

/"\ {\
15
j' V

50 \V / ~J
\,
o
200 220 21,O 260 280
~
300 320
A,mll

Fig. 122. Sodium diethy1dithiocarbamate

(C,Hs),NCSNa Ethanol
II C = 1.07 g/liter
S d = 0.058 mm

146
 VARIOUS SUBSTANCES USED IN MANUFACTURE

a 75
tIl
I I

,,r"\\
\

\
50
\\ 1/\ iI \

\...,I ~\
\
\b
\
31.5
\ \
\0

V--; 1\ ........ - "

~-
25
,,
\
\ .....
ko- ......
..... "-

IZ) "

"'- /
\

~
\

o ' ...
200 220 21,0 260 280 300 320 Jl,O 360
A. mll-

Fig. 123. Hydroquinone

Ethanol (a), 0.1 N ethanolic KOH (b)

HOOOH C = 0.884 g/li ter
d = 0.210 mm

147
VARIOUS SUBSTANCES USED IN MANUFACTURE

aJ

\
2

(5
\
~ L.-JV V\
f
V\
\ 1\
0.5

o
'-i'-t--
220 230 2~O 250 260 270 280 290 J(J()
A.mp.

Fig. 124. Cumene hydroperoxide (a.a-dimethylbenzyl hydroperoxide)

CH,
I
C.H. -C-Q-OH Ethanol
I C = 36.6 g/liter
CH, d= 0.049 mm

148
VI. VARIOUS SUBSTANCES MET AS INTERMEDIATE
PRODUCTS, BY -PRODUCTS, AND IMPURITIES
The acetylene derivatives whose spectra are given here
(Table 14) are either intermediate products used in the produc-
tion of chloroprene rubber (butenyne) or impurities formed
in the course of syntheses (1,5-hexadien-3-yne, ethynylbenzene,
butadiyne). A spectrophotometric method has been devised
for the determination of the latter as impurities [19].
All these compounds show very strong K bands due to the
conjugation of a triple bond with a double bond or a benzene
ring. When there are two conjugated triple bonds (butadiyne)
the strength of the band is greatly reduced.
This section includes also spectra of by-products formed in
the synthesis of monomers and other substances used in syn-
thetic rubber production, and also of substances formed by the
decomposition of compounds used in polymerization processes.
Spectral analysis is used both to determine the purities of
compounds [20], and also to determine the polymerization
mechanism from the identity of the products of the decom-
position of compounds taking part in this process.

149
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

TABLE 14
SPECTRAL CHARACTERISTICS OF VARIOUS SUBSTANCES MET AS
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

Figure Compound Solvent \nax' mil a

125 Vinylacetylene Methanol 218 266 13,800*
(butenyne) 227 205 10,650
126 Divinylacetylene (1,5- Methanol 252 188 14,700
hexadien-3-yne) 265 172 13,400
127 Phenylacetylene (ethy- Methanol 234.5 256 26,100
nylbenzene) 245 229 23,350
128 Diacetylene Methanol 223.5 9.5 475
(butadiyne) 234 10.5 525
246 5.0 250
129 Acetaldehyde Water 276.5 0.17 7.5
130 Butyra1dehyde Water 282 0.15 10.8
131 Crotonaldehyde Ethanol 219 275 17,250 2*
132 Acetone Water 264 0.3 17.4
133 Cyc10pen tadiene Isopentane 239 45 3,000'*
134 Benzoic acid Ethanol 272 7.50 915
280 6.20 755
0.1 N ethanolic 262 4.80 585
KOH 269 4.50 550
276 3.25 395
135 Acetophenone Water 245 93 11,150
136 a,a-Dimethy1benzy1 Water 250.5 1.45 200
alcohol 256 1.55 210
137 Ch1orobenzene Ethanol 251 1.20 135
257.5 2.00 225
264 2.55 285
271 1.85 210
138 p-Dichlorobenzene Ethanol 258.5 1.85 270
265 2.75 425
272.5 3.70 545
280.5 3.05 470
139 0- Dichlorobenzene Ethanol 262.5 2.05 320
269.5 2.55 375
277 1.95 305
140 5-Ethyl-2-picoline Ethanol 268 50 6,000
141 2-Nitropropene Ethanol 222 48 4,200 4 *

*\nax = 219 mil, = 6400 [7].

2* In alcohol Amax ~ 217 mil, f = 15,650 [21].

'* In hexane A max = 238.5 mil, f = 3400 [22].

4* In alcohol Amax = 22 ~ mil, f = 3300 [23].

150
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

a JI1)

250 ,/"\.

.""
...." 1\'--
\
f50

\
\
tf1J

'" -
50

D
215 220 225 230 235 2~ 250
A.mp.

Fig. 125. Vinylacetylene (butenyne)

Methanol
C = 1.12 g/liter
CH"'C-CH=C~ d= 0.049 mm

151
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

a 2fl)

X\ f\
'J \ V\
'50

\
1\
."1111.
V
50 \..

- /
\ i'--
0
210 220 230 240 250 260 270 280 290
A,mll

Fig. 126. Divinylacetylene (1,5-hexadien-3-yne)

Methanol
C = 1.48 g/liter
CH2 = CH - C= C-CH = CH2 d = 0.049 mm

152
 INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

aJDO

-
J \-
'50

I~
/ \
2fJO
'V

ttll 1/ \
-...
/ \,
/, ~
ZI5 220 225 230 2J5 2/,0 21,5 250 255 260
A. rnp..

Fig. 127. Phenylacetylene (ethynylbenzene)

Methanol
C = 0.96 g/liter
d= 0.049 mm

153
 INTERMEDIATE PRODUCTS, BY .PRODUCTS, AND IMPURITIES

a 12.5

10
.,-

7.5
./
V ~
V \ \
5

" '"
'"
2.5

o ~-
215 220 225 230 235 240 245 250 255 260
A.m/i

Fig. 128. Diacetylene (butadiyne)

Methanol
C = 8.16 g/liter
CH",C-C"'CH d = 0.049 mm

154
INTERMEDIA TE PRODUCTS, BY -PRODUCTS, AND IMPURITIES

a02

r ~

a , I
V
\
/ ~
\
11.05

-- ./
I

o ~
2fJ(J 220 Z60 280 3IJO 320 3/,(J
A,Inf1

Fig. 129. Acetaldehyde

Water
c= 32.5 g/liter
CH 3 CH=O d = 1.004 mm

155
INTERMEDIATE PRODUCTS, BY .PRODUCTS, AND IMPURITIES

A,mll

Fig. 130. Butyraldehyde

Water
C = 5.04 g!liter
CH3 CH,CH2 CH=O d= 9.99 mm

156
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

a 300

/ 1\
V\
250

\
200

/
/
150

fDa \
\\
I

50

a ~
200 210 220 230 240 250 260
A,mll

Fig. 131. Crotonaldehyde

Ethanol
C =0.804 g/liter
CH 3 CH= CHCHO d = 0.058 mm

157
INTERMEDIATE PRODUCTS, BY -PRODUCTS, AND IMPURITIES

I \\
aO)

/
0.25

/ \
0.2

a15

a1 J _\
0.05
V
/ \\
~
~
o
200 220 240 260 280 300 320
A,mll

Fig. 132. Acetone

Water
C=4.85 g/liter
(CH')2 C =O d=5.00 mm

158
INTERMEDIATE PRODUCTS, BY·PRODUCTS, AND IMPURITIES

a 50

0 /" ~
-
SIl /
V'
~
20 '- V ~
fa \
0
200 210 220 230 21,0 250
~270
260
I--
280
A.fn/l.

Fig. 133. Cyclopentadiene

CH-CH
II 1/
lsopentane
CH
, /
CH
c= 2.27 g/liter
d=O.112 mm

159
INTERMEDIATE PRODUCTS, BY-PROD UCTS, AND IMPURITIES

a fO
\J
\
8

y r\
~ V ... -, b
_- \
\
v\ \
,_\-
2
\
o .....
21.0 250 250 270 Z80 290 J{)()
h. m,.,.

Fig. 134. Benzoic acid

Ethanol (a). 0.1 N ethanolic KOH (b)

C = 10.0 g/liter
d = 0.107 mm

160
 INTERMEDIA TE PRODUCTS, BY -PRODUCTS, AND IMPURITIES

a foo

/
f\ 1\

50 / \
I
\
I ~

o
II
220 230 2t.() 2~0
"
260 270 280
r---
2g0 300 310
A.mp.

Fig. 135. Acetophenone

Water
, C=O.33 g/Uter
CH 3 d=O.212 mm

161
INTERMEDIATE PRODUCTS, BY·PRODUCTS, AND IMPURITIES

a2

A
f5

) ~\
I'\.

\
1
/
0.5 \'--' ~ \

o ~
220 230 240 250 260 270 280 290 300 310
A,mfL

Fig. 136. a,a-Dimethylbenzyl alcohol

CH,
I
C.Hs -C-OH Water
I C= 1.05 g/liter
CH, d=S.OO mm

162
INTERMEDIATE PRODUCTS, BY·PRODUCTS, AND IMPURITIES

a"
J

;
2

\ J\ \~
\.
1

~V
o
220 230 2'0 250 260 210 280 290
A.,mll

Fig. 137. Chlorobenzene

Ethanol
C =25.9 g/liter
C.Hs CI d= O. 049 mm

163
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

a 4

J A
2
tv \/-
/~
f
\ \
~
o
230 240 250 260 270 280
"
290 JOO
.A. mil

Fig. 138. p-Dichlorobenzene

Ethanol
C =38.7 g/li ter
d= O.049mm

164
INTERMEDIATE PRODUCTS, BY .PRODUCTS, AND IMPURITIES

\ J\
\ V'
2

i'... ./
~i\

o
230 240 250 260 270 280
~- 290 300
A,mll

Fig. 139. o-Dichlorobenzene

Ethanol
C=41.8 g/liter
d=O.049 mm

165
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

/
0

'1/

J,~I\
J I"
v~
V
0,,-
,
2
[7
~ \
'0

a i'-
220 23'0 240 250 26'0 27'0 280 290
A,mil

Fig. 140. 5-Ethyl-2-picoline

Ethanol
C = 1.58 g/liter
d= 0.049

166
INTERMEDIATE PRODUCTS, BY-PRODUCTS, AND IMPURITIES

'" 50
/ r'\
311
\
\
,
2u

0
1\
0 :----
200 220 21,0 280 280 300
A,mll

Fig. 141. 2-Nitropropene

CH,=C-CH, Ethanol
I C = 2.15 g!liter
NO, d = 0.112 mm

167
 LITERA TURE CITED

1. M. M. Kusakov, N. A. Shimanko, and M. V. Shishkina, Ultra-

violet Absorption Spectra of Aromatic Hydrocarbons, (Izd.
AN SSSR, 1963).
2. A. Gillam and E. S. Stern, Introduction to Electronic Absorp-
tion (St. Martins), [Russian translation: Electronic Absorp-
tion Spectra of Organic Compounds (IL, 1957)]; E. A.
Braude and F. C. Nachod, Determination of Organic Struc-
tures by Physical Methods, Ch. 4, N.Y., 1955.
3. V. M. Peshkova and M.1. Gromova, Practical Handbook on
Spectrophotometry and Colorimetry, MGU, 1961.
4. V. N. Mironova and V. V. Zharkov, Vysokomol. soed., 2(7):
1013 (1960).
5. Smakula, Angew. Chern., 47:653 (1934).
6. A. Gillam and E. S. Stern, op. cit. [Russian translation]
p.229.
7. Ibid., p. 132.
8. Booker, Evans, and Gillam, J. Chern. Soc., 1940:1453.
9. Koch, J. Chern. Soc., 1949:387; Robertson and Matsen, J.
Am. Chern. Soc., 72:5250 (1950).
10. L. M. Pyrkov, S. E. Bresler, and S. Ya. Frenkel', Zhur. Org.
Khim. 29(8):2750 (1959).
11. V. S. Fikhtengol'ts and R. V. Zolotareva, Spectrophotometric
Investigation and Analysis of Polyarylmethylsiloxanes, in
the Collection "Physicochemical Methods for the Analysis
and Investigation of Substances Used in Synthetic Rubber
Manufacture," Goskhimizdat, 1961.
12. S. B. Dolgoplosk, A. L. Klebanskii, L. P. Fomina, V. S.
Fikhtengol'ts, and E. Yu. Shvarts, Doklady Akad. NankSSSR
150(4):813 (1963). [English translation: DokladyChemistry
150:461 (1963).]
13. S. N. Borisov, A. V. Karlin, E. A. Chernyshev, and V. S.
Fikhtengol'ts, Vysokomol. soed., 4(10):1507 (1962).

169
LITERATURE CITED

14. V. S. Fikhtengol'ts and R. V. Zolotareva, Spectrophotometric

Methods for the Analysis of Synthetic Rubbers, in the
Collection n Physicochemical Methods for the Analysis and
Investigation of Substances Used in Synthetic Rubber
Manufacture," Goskhimizdat, 1961.
15. V. S. Fikhtengol'ts, Zav. lab., 27(4):400 (1961). [English
translation: Industrial Laboratory 27(4):402 (1961).]
16. Fieser and Campbell, J. Am. Chern. Soc., 60:159 (1938).
17. Ahlers and O'Neill, J. Oil and Col. Chern. Assoc. 37:552
(1954).
18. Morton and Stubbs, J. Chern. Soc., 1940:1349; Morton and
Sawires, J. Chern. Soc., 1940:1952.
19. 1. Va. Poddubnyi, I. V. Nel'son, and R. V. Zolotareva,
Spectrophotometric Method for the Determination of
1,5-Hexadien-3-yne and Butenyne Impurities, in the Col-
lection "Physicochemical Methods for the Analysis and
Investigation of Substances Used in Synthetic Rubber Manu-
facture, n Goskhimizdat, 1961.
20. V. S. Fikhtengol'ts and R. V. Zolotareva, Spectrophotometric
Control of Chlorobenzene Production, in the Collection
"Physicochemical Methods for the Analysis and Investiga-
tion of Substances Used in Synthetic Rubber Manufacture,"
Goskhimizdat, 1961.
21. Hausser, Kuhn, Smakula, and Hoffer, Z. phys. Chern.,
B29:371 (1935).
22. Scheibe, Ber., 59:1333 (1926).
23. Braude, Jones, and Rose, J. Chern. Soc., 1947:1104.
24. S. Harrison and T. Sanderson, J. Am. Chern. Soc., 70:334
(1948).

170