JPRS ID: 9223 USSR REPORT CHEMISTRY

• Document Type: CREST
• Collection: JPRS
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00850R000300010006-1
• Release Decision: RIF
• Original Classification: U
• Document Page Count: 34
• Document Creation Date: November 1, 2016
• Sequence Number: 6
• Content Type: REPORTS

APPROVE~ FOR RELEASE: 2007/02/08: CIA-R~P82-00850R0003000'10006-'1
~'Ut'~ ~ F~U~ ~ ~

APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2047/02108: CIA-RDP82-00850R000300010006-1
FOR OFEICIaL USE ONL1'
_ JPRS L/9223
25 July 1980
~ USSR ~e ort
p
CHEMISTRY -
CFOUO 2/80)
,
FBIS FOREIGN BROADCAST lNFORMATION SERViCE
FOR OFFICiAL USE OIYLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
NOTE
JPRS publications contain iniormation primarily from foreign
- newspapers, periodicals and books, but also from news agency
transmissions and broadcasts. Materials from foreign-language -
sources are translated; those from English-language sources
are transcribed or reprinted, with the or~ginal phrasing and
other characteristics retained.
_ Headlines, editorial reports, and material enclosed in brackets -
are supplied by JPRS. Processing indicators such as [Text) ~
or [Excerpt) in the first line of eacr item, or following the
last line of a brief, indicate how the original information was
processed. Where no processing indicator is given, the infor-
mation was summarized or extracted.
~ Unfamiliar names rendered phonetically or transliterated are
enciosed in parentheses. Words or names preceded by a ques-
tion mark and enclosed in parentheses were not clear in the
original but have been supplied as appropriate in context. -
- Other unattributed parenthetical notes with in the body of an
_ item originate with the soi~rce. Times within it~ms are as
given by source. -
The contents of this publication in no way represent the poli- -
cies, views or attitudes of the U.S. Government.
Fc~r f:irther information o~ report content
c~ill (703) 351-2938 (economic) ; 3468
(political, sociological, military); 2726
(l.ife sciences); 2725 (physical sciences).
- COPYRIGHT LAWS AND REGULATIONS GOVERNING OWNERSHIP OF
MATERIALS REPRODUCED HEREIN REQUIRE THAT DISSEMINATION -
OF THIS PUBLICATION BE RESTRICTED FOR OFFICIAL USE OYLY. -
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
f
FOR OFFICIAL USE ONLY
- JPRS L/9223 `
25 July 1980
USSR REPORT
- CHEMISTRY
(FOUO 2/80)
CONTENTS ' . -
FUELS
Gasification of Low Oct~ne Liquid Fuels and Products of
Hydrogenation into a High Octane Gaseous Fuel for
Internal Combustion Engines 1
Graphite Complexes with Transition Metals - A New Class
of Organometallic Compounds 10
POLYMERS AND POLYMERIZATION
On the Mechanism of Low Temperature Solid Phase
Polymerization 19
Solid Phase Photosensitized Polymerization of Aerylonitrile
- at Cryogenic Temperatures 25
- a- (III - USSR - 21,B 5&T FOUO)
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
_ FUEL S
UDC 66.092+662.765
GASIFICATION OF LOW OCTANE LIQUID FUELS AND PRODU~TS OF HYDROGENATION Ii~TTO
A HIGH OCTANE GASEOUS FUEL FOR INTERNAL COMBUSTION ENGINES ,
~ Moscow KHIMIYA TVERDOGO TOPLIVA in Russian No 6, Nov-Dec 79 pp 47-52
manuscript received 2 Dec ?R
[Article by Ye.G. Gorlov, V.M. Antonova and Ya.M. Paushkin, Institute of
Fossil Fuels]
[7'.ext] A study is ma.de of the influence of temperature, the coefficient of
_ discharge of air and the nature of the column packing on the material ba-
lance and composition of a gas produced in the gasification of low hydro-
carbons, a petrole~ fraction and a hydrogenate of coal.
The substitution of liquid high octane fuel with less expensive fuel (not
inferior to it in octane number) and the problem of protecting the environ-
ment from toxic automobile exhausts can be solved by replacing this fuel
with gaseous fuel. At the present time the Siemens and Nissar Motor Co.
firms abroad and the Ukrainian SSR Academy of Sciences Institute of Gas in
the USSR are developing a process for producing gaseous fuel for internal
combustion engines, chiefly by means of the conversion of gasoline w~ith wa-
ter vapor in a catalyzez�, employing the heat of exhaust gases [1-3J.
However, the employment of water vapor complicates running these engines:
large tanks for storing water, problems relating to its freezing in winter
and to cleaning salts from the water, etc.
The purpose of this paper is to study the chemism of the process of the
gasification of low hydrocarbons of gasoline fractions and to determine the
optimal operating conditions of a gas generator which can be used together
with. an internal combustion engine.
Subjected to gasification were paraffins, naphthenes and aro~atic hydro-
carbons, as well as a petroleum fraction (70 to 220�) with the following
composition (in percentage by weight): unsaturated hydrocarbons four per-
- cent and aroma.tic 11; density of p`~p , 0.790; as well as a liquid frac-
tion produced in the hqdrogenation of coal (condensation point 300�) with
the following composition (in percent:age by weight): unsaturated
1
_ FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
hydrocarbons seven percent, aromatic 36, phenol~ 10 and sulfur 0.60; densi-
ty p~o , 0.860.
Gasification was carried out in a quartz reactor with a diameter of 20 mm
in the temperature range of 700 to 800� and urith volumetric rates of 3 to
6 h 1. The reactor was heated by means or an electric furnace, which was con- -
trolled automatically. The raw material was fed into the reactor by a dis-
pensing injector, and the air by a compressor. The gas produced and the
condensate were cooled and analyzed chromatographically. The coke content
was determined by weighing. The amount of gas was registered by a gas me-
ter. The gasification process was studied both in a hollow reactor and by
employing different column packings.
With incomplete combustion, part of the energy obtained from the raw ma- '
terial is converted into heat, whereby the total caloricity of the gas pro-
duced is lower than the caloricity of the original liquid fuel. With a co-
efficient of discharge of air of a> 0.4 , losses of heat make up a con-
sideratle part, since there is an increase in the role of endothermic clea-
vage reactions, which consume part of the heat prodt~ced in ~he dissociation
of products of high caloricity. On this basis, a should be as low as
possible.
With a= 0.1 , losses of heat are insignificant. A further drop in a
results in intensified formation of soot. For example, when a is low-
ered to 0.05, the amount of soot in a hollow reactor increases almost two-
fold as compared with a= 0.1 , and with a= 0.005 the reactor is c?ogged =
wi.th soot already after 30 min of operation (table 1).
At 800� is reached almost total conversion in a hollow reactor of the hydro-
- carbons studied, except the aromatic. The results have demonstrated that
an increase in the process's te~perature promotes gas formation for any
hydrocarbon. The reduction in coke formation with a rise in temperature is
apparently explained by the increase in the rate of reduction of carbon di-
oxide with the formation of carbon monoxide.
Coke formation depends on the degree of saturation of hydrocarbons, i.e.,
~n the ratio C:H. Maximum coke fo~ation is observed in aromatic hydro-
carbons.
With a rise in temperature the composition of the gas also changes: There
is an increase in the content of hydrogen, methane and ethylene.
However, the depth of conversion of hydrocarbons reached is insufficient for
stable operation of an engine. With a high yield of condensate having a
high octane nu~ml~er (the condensate can contain more than 70 percent aroma-
tic and unsaturated hydrocarbons), will be ebserved considerable soot form-
ation in the engine.
2
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
- FOR OFFICIAL USE ~NLY
Table 1. Material Balance of the Process of th.e Gasification of Hydrocar- -
bons in a Hollow Reactor and Composition of the Gas
2 1 Yrneeouo
1~ renraa _
IIapancerp~t zeMnepa
700 I 750 I 800 I 700 I 750 I 800
8)Koac~c~n~ueaT paczoRa eoaAyxa 0,0~ 0,1
9~blazep~a~aa~u 6aaasc, a~ac.ao:
10) raa 94,4 95,? 95,7 82,6 89,5 92.3
osAescaT 11) 5,2 4,3 4,1 17,? 10,4 7,6
12 ~oxc 0,4 0,3 0,2 0,2 0,1 0,1
CocTaa raaa, 06.%: 13)
14) HZ ~,4 6,8 7,4 6,1 8,4 9,4
CH~ 28,9 32,5 34,1 ' 13,8 17,2 2U,4
C:H~+CzH2 22,8 24,2 23~5 13,4 15,7 15,7
CZHe ~,5 1,9 i,i 2,1 1,9 1,5
EC, 2,6 0,2 - 3,7 1,6 1,~
E~~ - - � - 1,3 0,9 0,~
CO 5,0 6,8 6,8 8,4 8,9 9,4
COz - - - - - -
" NZ 29,4 27,4 27,0 48,4 43,2 40,8
- p2 0,4 0,1 0,1 1,8 1,7 0,9
po~u
_ ~ 4~ ueKan I 5~ AHK~oreKCas ronyon
rypa, 'C ~ ~
I 100 ('750 I 800 I 100 I 150 ( 800 75U S00
8) 0,1 0,1 0,1
9~10) 8U,4 84,9 89,4 80,7 83,4 88,2 39,1 47,7
11) 19,3 15,0 10,5 18,8 i6,3 11,6 60,5 52,0
12) 0,3 0,! 0,1 4,5 0,3 0,? 0,4 0,3 `
13~4~ 68 7,5 ~9,7 5,9 6,3 d,8 10,8 i4,2 ~
11,8 13,0 ii,6 10,8 !'!,4 14,9 14,3 15,1
12,1 13,8 10.7 17,6 18,7 19,6 0,3 0,6
1,3 1,1 1,0 2,9 2,5 ~1,7 0,1 -
3,1 2,9 2,5 l,7 1,5 d,3 - - -
0,7 0,8 0,4 1,7 i,5 ~1,3 - - ~
8,4 8,6 8,8 8,1 8,4 8,9 11,2 11,1 ~
1,9 1,8 0,5
Si,3 47,6 44,5 49,4 45,1 45,0 59,6 56,7
2,2 2,1 1,0 1,9 i,~ 0,7 3,8 2,3 "
[Key on following page]
3
FOR OFFICIAL US~ ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
Key:
l. Parameters 9. Material balance, Fercentage by
2. Hydrocarbons w~eight
~ 3. Hep tane 10 . Gas
4. Decane 11. Condensate
5. Cyclohexane 12. Coke
6. Toluene 13. Composition of gas, percentage by
7. Temperature, �C volume
8. Coefficient of discharge 14. H, CH , C H+C H, C,,H , EC , EC
of air C~, C02, N2,4022 2 ` 6 3 4,
Note: Parameter of process--volumetric rate, 3 h-1; duration of experiment,
3 h. �
For the purpose of increasing the yield of gas the process must be carried
out by using column packings, both inert and having a catalytic effect.
For this purpose we~e studied various types of packings: quartz, fireclay,
aluminum oxide, sil~ca gel, and commercial aluminosilicate (A1203, 11 to
13, and Si02, 88 to 86 percent by weight). ~
From fig 1 it is obvious that with an increase in the time the packing func-
tions the depth of conversion of the raw material and the yield of gas and
coke are reduced. The great^.st reduction is observed at the beginning of
the process (in the first 3(~ ~nin of operation). This is explained by the
fact that in the initial period the process of the gasification of hydro- -
carbons takes place on the entire active surface of the packing. As a re-
sult of this, the depth of conversion of hydrocarbons is increased. How-
ever, with time the coke formed in the process accumulates and partly de-
_ activates the surfsce of the packing. As a result there is a reduction in
the depth of cracking and accordingly in gas and coke formation. All this
is reflected also in the composition of the gas (cf. fig 1).
The reactions of isomerization, dehydrogenation and redistribution of hyd-
rogen take place preferredly on clean surfaces of the catalyzer. Zn pro-
portion to lengthening of the time the packing is used, the percentage of
these reactions is reduced and accordingly there is a reduction in the -
- yield of propane-propylene and butane-butylene fractions, and an increase
" in the content of hydroger~, methane and ethylene.
Since the normal operation of an engine depends not on the yield of any
single gas component, but on the stability of the gas's composition,-~hen
all investigations of gasification were made after the instant the gas
reached a steady composition, which equaled not less than 30 min of the
packing's functioning.
The results presented in tables 2 and 3 demonstrate that the employment of
packings increases the depth of conversion of hydrocarbons. This is evi-
denced especially considerably for aromatic hydrocarbons. The nature of
the packing exerts a great influence on the process.
4
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007/02148: CIA-RDP82-44850R000300014406-1
- FOR OFFICIAL USE ONLY
nracF%
a)
~on 1)
9s '
4
J
~ Z
1 x ,i
0
u6.�/, 2~ ;
40 y �
JO
10 Y~x S
~~tx~ 6
10 ~
B
9
D ~
60 110 1B0 240
_ BpeMA, MuN.
Figure 1. Influence of Duration of Functioning of the Column Packing
on the Process of Gasification of Heptane; a--material
balance; b--composition of gas: 1--gas, 2--coke, 3--con-
densate, 4--nitrogen, 5--methane, 6--ethylene, 7--hydrogen,
8--carbon monoxide, 9--propqlene, 10--ethane. Parameters
of process: packing A1203; temperature 800�C; a= 0.1 ;
volumetric rate 3 h 1.
Rey:
1. Percentage by weight 3. Time, min
2. Percentage by volume
Inert column packings such as quartz glass and fireclay influence the con-
version ~f hqdrocarbons insignificantly. Packings having a catalytic ef-
- fect increase the qield of gas on account of a considerable reduction in
the percentage of condensate.
At a process temperature of 700 to 800�, when a high depth of conversion
of hydrocarbons is reached, from the mechanism of both thermal and cata-
lytic cracking it is difficult~to distinguish considerable differences in
the nature of the effect of catalytic packings. But it is possib le to note
- that the best catalytic effect on the gasification of hydrocarbons is ex--
erted by aluminum oxide, which possesses aprotonic properties [4]. Further-
_ more the composition of the gas is changed in the direct~.on of an increase
in the content of hydrogen and ethylene.
5
- FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007/02148: CIA-RDP82-44850R000300014406-1
FOR OFFICIAL USE ONLY
Table 2. Material Balance and Composition oi Gas in the Gasification of
Heptane in Employing Different Column Packings
1` 2) , HacaAxa
_ IIapaMeTp~ ~pqeBOe 4 cxnaKa- oKaca n~oMO-
cxexao ~axor ~ renb Ia.vo~xxaxa~ canasar
8) liarepaa~as~a 6anaac,
xac. ao : �
9) raa 93.~ 90,6 94,4 '97,1 95,7
xosAeacaT 10~ 4,8 4,2 ?,1 0,7 2,3
xohc 1,7 5,2 3,5 2,2 2,0
_ 11) CocTas raaa, 06.% 12~
Hz 8,50 6,20 7,42 12,25~ ~ 8,70
CH~ ' 25,40 ~i9,2~- 24,53 59,10 22,60
CzH~+CZHz l~3,37 18,60~ 13,90 K6,6~+ K'1,18
CzHe 0,~0 0,80. 1,60 0,89 0,~0
ECs i,10 l,04 0,50 1,43 0,50
EC~ - - ~ - - 0~~ -
CO 8,78 8,84 8,40 9,20 9,?A
Oz 1,25 0,80 0,82 0,7~4 0,B4
- 13) Teunora cropasax raaa, 4910 4940 4880 54b0 5000
KKa.t~KM~
Key:
1. Parameters 8. Ma.terial balance, percentage by
2. Packing weight
3. Quartz glass 9. Gas
4. Fireclay 10. Condensate
_ 5. Silica gel 11. Coke
6. Aluminum oxide 12. Composition of ~as, percentage by
7. Aluminosilicate volume
13. Eeat of conbustion of gas, kcal/
/nm3
Note: Parameters of process--te~nperature 800�C; a= 0.1 ; time 3 h;
volumetric flowrate 3 h 1.
*C2H2 content less than one percPnt.
6
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007/02148: CIA-RDP82-44850R000300014406-1
FOR OFFICIAL USE ONLY
Table 3. Material Balance of the Process of Gasification of Hydrocarbons
with an A1203 Column Packing, and Composition of Gas
2 ~ . Yrneaouopon~
1~ ' 3~ remaa I 4) ~eKeg
IInpaMerpu ] ~ TeMaepaTypa,
' . 700 I 750 I 800 I 700 I 750 ( 800 .
10) Marepaa~s $ais 6anasc, s~ac.%:
raa 111 87,3 91,6 97,1 81,4 86,5 90,1
xoaAeacar 12~ 1,2 0,9 0,7 5,1 3,3 3,0
13) xoKC 11,5 ~ 7,5 2,2 13,5 f0,2 6,9
Cocraa raaa, 06.�,0: 14)
15) HZ � 1U,6 ii,3 12,3 6.9 8,1 9,6
CHa 14,4 47,8 19,1 14,6 16,7 l8,3
C:H~+C=H~ 16,8 17,3 16,6 14,7 15,6 16,4
C2He 2,3 !,7 0,9 1,1 1,0 0,8
EC, 2,6 1,4 1,4 2,0 2,0 1,9
- - - 0,5 0,5 0,3
CO+CO: 8;i . 8,9 9,2 10,7 ii,i 9,4
N= 43,6 40,7 39,2 48,6 44,2 43,9
0, 1,6 1,0 0,7 1;1 0,7 0,5
lo) Teanoza cropasax raaa; rcxa~/rcac' S000 5100 5100 4100 4200 49W
17 ) HII~( raaac~~ca~H$ 82 86 89 73 80 85 ,
~ 2 8) 9)
S~ANJI01'EItCaB I~~ TOJryOJI HE~TAABR rNApOCEHH38T
~paxRaR
-
I 100 I 750 I 800 I 750 I 80U T50 I 800 750 I 800
_ 1.~~
11) 81,1 85,9 88,7 50,0 76,9 79,7 89,8 76,2 86,9
12) 5,2 4,5 4,2 39,4 i4,9 10,4 4,8 13,5 6,1
13,7 9,6 7,1 10,6 8~2 9,9 6,4 10,3 7,0
~~~5) 6,T 7,0 7,4 16,3 18,2 6,2 7,8 5,8 6,2
l2,4 13,6 14,0 i4,6 16,? i8,8 23,7 l4,2 16,7
~ 16,6 19,0 23,3 0,5 0,3 i2,2 53,0 l3,7 16,1
1,4 0,8 0,5 0,6 0,5 1,3 0,5 0,9 0,6
2,6 !,3 0,6 1,5 0,6 i,6 0,6
2,! !,5 0,6 0,7 0,5 0,5 0,2 0,6 0,4
8,1 8,5 9,! 9,0 9,6 8,6 10,2 9,7 10,3 -
- 49,0 47,2 43,7 56,3 52,7 50,0 43,6 52,5 44,5
1,1 !,i 0,7 2,0 1,5 0,8 0,4 1,0 0,6
16 ) 5000 52(b 54IX3 3000 3700 4500 4700 4500 45(i0
1 7) j 72 79 83 3S 38 57 75 50 59
[Key on following page]
7
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007/02148: CIA-RDP82-44850R000300014406-1
FOR OFFICIAL USE ONLY
Key:
1. Parameters 11. Gas
2. Hydrocarbons 12. Condensate
3. Heptane 13. Coke
4. Decane 14. Composition of gas, percentage by
. 5. Cyclohexane volume
6. Toluene 15. H, CH[, , ~C2H4+C2H2 , C2H6, EC3,
7. Temperature, �C E~4, CO+C02, N2, 02 _
8. Petroleum fraction 16. Heat of combustion of gas, kcal/
9. Hydrogenate ~nm3
10. Material balance, percent- 17. Efficiency of gasification
age by weight
Note: Parameters of process--volumetric rate 3 h 1; a= 0.1 ; time 3 h.
1) The efficiency of gasification is given without taking the condensate
into account. 2) Content of C2H2 less than one percent by volume.
Table 4. Material Balance of Gasification of Heptane, Benzine and Hydro-
genate
~ 1~ Yr~esoafopous~
= IIapaMeTp~[ 3~ renTaa K C~Tft88H xnpo-
~paKqax reexaar
TeMUepaTypa, �C 700 750 800 800 800
~faTepga~ca~a o'a~zaac, xac.�(o:
raa 8) 88,6 92,8 95,7 88,8 i5,!
xo$Aesc T 9) 9,2 5,3 3.3 9,3 22,9
xoxc 10~ 2,2 1,9 1~0 1,9 2,0
11) CocTas raaa, 06.?'0:
Hz 5,3 7,1 9,7 6,2 7,5
CH~ 13,1 16,1 18,3 18,0 11,0
C=H~+C,HZ 12,0 t4,1 15,4 1i,7 12,i
CzHe 3,3 3,1 2,7 ?,1 5,0
EC, 5,5 4,1 3,6 5,2 2,3
EC~ 1,7 1,3 1,1 0,9 1,4
- CO 7,8 8,0 8,2 8,3 7,3
COz i,i 0,3 - - 1,4
NZ 49,5 45,0 40,3 47,2 51,3
O= 0,T 0,6 0,6 0,4 0,7
12~ TeIInoTa cropasasc raaa, rcxan/KM' ~280 5610 ~6�s0 5470 4660
13) xnA' ~ 80,5 83,2 87,0 72,0 53,0
[Kpy on following page] _
- *Efficiency of gasification given without taking condensate into account.
_ 8
FOR OFFICIAL US~ ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
I
FOR OFFICIr1L USE ONLY _
Key:
l. Parameters 10. Coke
" 2. Hydrocarbons 11. Composition of gas, percentage
3. Heptane by weight
4. Petroleum fraction 12. Heat of combustion of gas, kcal/
5. Hydrogenate /nm3 _
6. Temperature, �C 13. Efficiency
7. Material balance, percent-
age bq weight
- 8. Gas
9. Condensate
Note: Parameters of process--packing A1203; volumetric rate 6 h-1; time _
3h; a=0.1 .
Simultaneously was discovered an influence of the volumetric rate on the
coke formation process. A twofold increase in the volumetric rate dras-
tically reduces the yield of coke (tables 3 and 4).
Conclusions
1. In the incomplete oxidation of n-heptane, n-dECane and cyclohexane
chiefly gaseous hqdrocarbons are produced; the composition of the gas de-
- pends little cn the nature of the raw material.
2~ Under the conditions studied the best catalytic column packing is alum-
inum oxide.
_ 3. The gas generator reaches the stable mode after 30 min of operation.
Bibliography -
_ 1. Henkel, H.Y., Koch, Ch., Kosta, H. and Szabo, E.V. SIEMENS FORSCH.
UND ENTWICI~,-BER. , 2, 1, 1973.
2. French Patent No 2312553, 2 May 1975.
3. Maksimuk. B.Ya., Veselov, V.V., Nikolenko, A.A., Khorkin, A.P.,
Kalachev, S.I. and Kirichenko, G.N. KATALITICHESkAYA KGNVERSIYA UGLE-
VODORODOV, No 3, 1978.
4. Krylov, O.V. "Kataliz nemetallami" [Catalysis with Non-Metals],
Khimiya, Moscow, 1967. -
COPYRIGHT: Izdatel'stvo Nauka, KHIMIYA TVERDOGO TOPLIVA, 1979
[70-8831]
~ 8831
, CSO: 1841 -
9 _
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
GRAPHITE COMPLEYES WITH TP,AIVSITION METALS - A NEW CLASS OF ORGANOMETALLIC
COMPOUNDS '
Moscow VESTNIK AKADEMII NAUK in Russian No 3, 1980 pp 21-27
[Article by M. Ye . Vol' pin, Corresponding Member of the USSR Academy of
- Sciences]
[Text] Not so long ago it seemed that the foundation of chemistry had =
been built and all that remained to be done was to construct new stories
upon it. Al1 kinds of chemical bonds and their nature, a11 possible types
of compounds and basic classes of reactions were considered already known.
In recent decades a radical changs of many ide~s has occurred in chemistry.
One field which proceeded especially intensively was the chemistry of
organic compounds of transition metals, i.e. metals with unfilled inner
d-shells of the atoms, such as iron, cobalt, nickel, platinum, etc.
It turned out that these metals can yield compounds of an entirely new .
type, not predictable or explainable on the basis of classical ideas,
and not even representable by means of the familiar bond dashes. -
- The study of such compounds forced us, on the one hand, to rev.ise our
views on the na~ure of the chemical bond, and on the other hand it
revealed a whole class of new and amazing reactions of inetal-complex
catalysis passing through the intermediate f Grmation of compounds of this
type. Some amazing reactions proved to be possible such as, for example,
- the stereoregular polymerization of olefins, various reactions of cycliza-
tion of olefins and acetylenes, the disproportionation ("metathesis")
of olefins, and also the chemical fixation of molecular nitrogen. In
this way a vast field of new, nonclassical ideas developed in chemistry.
- Below we list some applications of these ideas in the investigation of
graphite, the form of free carbon most abundant on earth, a substance
which is well studied and widely used in technology.
Graphite represents an aggregate of flat polymeric molecules in which
- carbon atoms form reticular structures of hexagonal cells of benzene-
ring type. In such a system each carbon atom has a free pi-electron
' 10
FOR OFFICIAL USE ONLY
1
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007/02108: CIA-RDP82-00850R000300010006-1
I
FOR OFFICIAL USE ONLY
in a p-orbit perpendicular to the plane of the molecule. The pi-electrons
~ interact and form a single coupling chain which is responsible for the
electric conductivity as well as many other properties af graphite.
The parallel lattices of carbon atoms are interconnected not by chemical -
bonds but by weak Van der Waals forces. Therefore it is possible to
introduce various connectors into the space between the networks, such
as alkali metals, strong acids, halogenides of transition metals. In
this process the networks are as if pulled apart and so-called layered
compounds of graphite are formed in which there are no firm covalent
bonds in the perpendicular direction, i.e., between the inserted substance
and the carbon atoms.
- - - - ~ -
. ~ G
. I
` ~ , I _ ~ ' _ I 1 M
4y-
b~ ~~j~ ~
~ ~ _ ~ ~ b ~ ~ ~
- - - -
~ ~ ~ , ~
~ i ~
I ~ ~
~ ~c
~ - -
Cr j ~ ~ I ,t~~ I ~ -
~ ~ ~Y~ I
1 ' ~ - -
~,-1--~ ~
i ~ ~ i.
. ~
' .
A ~ - - B -
Figure 1. Structure of inetal-complex compounds.
A- complex of benzene with chromium -
(dibenzene chromium),
B- complex of graphite with a tran-
sition metal;
C- network of carbon atoms,
M - metal atoms,
= I~ - distance between the planes
Within the framework of the neoclassical ideas of modern chemistry of
transition metals, entirely new types of compounds are possible. By
analogy with the nonclassical monomolecular compounds ("sandwiches")
of the dibenzene chromium type (C6H6)2Cr, where chromium is linked with
two benzene rings,one may try to obtain a whole "flaky pie" where atoms
of a transition metal, filling strata between the graphite lattices, would
form pi-bonds with the carbon atoms in the perpendicular direction
(Figure 1). Such a task was undertaken by the author and Yu, N. Novikov
at the Institute of Organoelemental Compounds of the USSR Academy of
11
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
Sciences about ten years ago and they struggled with the solution for
a long t une. As a result they succeeded in developing various methods -
of synthesis of new type substances by reduction of stratified graphite
compounds with metal chlorides using various reducers: alkali metals, _
aromatic anion radicals, complex hydrides, etc, Recently such compounds
were also obtained by a direct method - introducing metal atoms between
the graphite layers. In this way, complexes of graphite with chromium,
tungsten, manganese, iron, cobalt, nickel, palladium, copper and other -
metals were obtained.
A difficult task was the investigation of the structure of the new com-
pounds that are solid insoluble powders. The physico-chemical methods '
usually employed in organic chemistry, such as nuclear magnetic resonance,
optical spectroscopy and mass spectroscopy, were not applicable here.
_ Investigation of the structure of these substances turned out to be possible
only by such methods as radiography, gamma resonance spectroscopy, X-ray
spectroscopy and magnetic methods. We will give only a few examples of
determining the structure of inetal complexes of graphite.
The transition from a compound of graphite with a metal chloride to
a compound with a 2ero-valent metal is accompanied by a substantial
decrease (2-2.5 times) of the thickness I~ of a filled layer in the
graphite (Table). Thus, in the initial stratified compination of graphite
with molybdenum chloride MoC15, where there is no chemical bond between -
the salt and the graphite, the distance Ic1 between ohe graphite lattices
is equal to the sum of the Van der Waals radii (9.5 A). In the reduction
- of this compound and formation of chemicg 1 bonds of molybdenum with carbon
the distance decreases to I~2 = 3.5-3.7 A, which is very close to the
inter plane dis~ance in the analogous monomolecular "sandwich", molybdenum
dibenzene (3.5 Magnetic data and the study of X-ray spectra also
- indicate formation of a pi-complex of graphite with molybdenum. In
contrast to the paramagnetic combination with MoC15, the complex of
graphite with molybdenum is dianagnetic similarly as is dibenzene molyb-
denum .
For the compound of graphite with palladium, investigations of the same
_ kind indicate formation of a pi-complex of graphite with monovalent
palladium. The inter-plane distance in such a compound (4.3 is very
close to the anadlogous parameter of the corresponding monomolecular
"sandwich" (4.4 A). In the investigation of the combination of graphite
with iron, Mossbauer and X-ray spectroscopy turned out to be very useful,
since they directly prove the presence of the chemical bond metal-carbon.
In this case both these bonds and the iron-iron bonds were detected, that
is, the iron atoms are arranged in the "pie" in a double layer.
Without dwelling on the demonstration of the structure of other complexes
with metals, although each of them has its specificity, cae turn to their
properties.
12
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
Thickness of the filled layers of stratif.ied compounds
of graphite with chlorides of transition metals and
with metals
Chlorides of Thickness of Transition Thickness of Thickness
transition the filled metals the filled difference
metals layer I~1 layer I~2 Ic � Ic1~Ic2
in A in A
- MoC15 9.3 Mo 3.7 5.6
_ MnC12 9.5 Mn 5.8 3.7 -
FeC13 9.4 Fe 5.9 3.5
CoC12 9.4 Co 5.9 3.5 '
NiC12 9.3 Ni 5.9 3.5
PdC12 9.9 Pd 4.3 5.6
CuC12 9.4 Cu 5.9 3.5
At present the catalytic properties of the graphite comple~ces have been
studied first. Indeed, looking at the layered structure of these compounds,
_ it could have been surmised beforehand that the location of the metal
atoms between the conducting carbon lattices would facilitate the reactions
of electron transfer from the metal (catalyst) to reacting substances.
The foxed distances I~ between the lattices (from 3.5 for molybdenum
to 6 A for iron and some other metals) allowed to consider the possibility _
of selective reactions where some molecules penetrate into the mid-layer
space easily and others with difficulty,
It developed that not only complexes of graphite with transition metals,
but also layered combination of graphite with salts of inetals have a
- number of interesting catalytic properties.
Combinations of graphite with halogenides of transition metals are very
soft catalysts of various cationic processes, for example, alkylation
and polymerization of unsaturated compounds. They are much more convenient
than the aluminum chloride and ferric chloride used in industry, as they
are more stable and difficult to hydrolyze, are less corroded and, most
important, they control the polymerization of highly reactive monomers
and catalyze selectively the alkylation and acylation of aromatic hydro-
carbons,
- Alkylation of benzene CeHe CHz=CIi~ CaIIeCHzCH~
Polymerization of isobutylene nCHz=C(CIi3)z (-CI~2-C(CH3)z-]n,
Polymerization of styrene nCaHbC1i=CIi1 (-iH-Cii~-)�
~=eHs
Polymerization of vinyl ethers nROCIi=CIiz (--CH - ~Hz -)n
I
o~
Amination of nitrochlorbenzenes ~ICaH~NOz + NH, ~VI1;C,H~N01
13
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
Epoxidation of olefins ~C=C~- IiOOH ~C C~ ~
/ \ . / \
.
C6HbCHzCH, 0, CeHSCHCHa
Oxidation of hydrocarbons ~
OOH ,
H+
Electrochemical reduction of nitrogen N~ NHZNH1
_ Hydrochlorination of olefins CH2-CH2 HCl CI~,CH2Cl
The compounds of graphite with transition metals can actively catalyze
various oxidation-reduction reactions. Thus, of great inte~est are the
properties of these compounds as electrodes, since they act simultaneously
as catalysts of electrochemical oxidation reactions of hydrogen in an '
acidic medium, and reduction of oxygen in an alkaline medium, The
activity of an oxygen electrode based on a graphite-cobalt compound in
- an alkaline medium reaches or even exceeds the acti~~ity of silver elec-
trodes. We wish to point out here that a layered cosnpound of graphite
with molybdenum pentachloride, introduced into an electrode, catalyzes
the electrochemical reduction of molecular nitrogen to a~monia and
hydrazine.
Compounds of graphite with cobalt, nickel and other metals, and also
with their oxides, catalyze actively and very selectively the dehydro-
genation of alcohols to aldehydes and ketones; dehydrogenation only
takes place, not accompanied by dehydration.
Hydrogenation of olefins RCH=CHR L H2 RCH, -CI::R
Hydrogenation of carbon monoxide CO I~, CH~ CZHa
Dehydrogenation of alcohols RCH~OH RCHt) H1
Electrochemical reduction of e,x,o `
oxygen , UK-
Oxidation of hydrogen 2Hz { Oz 2H2O -
If together with the transition metal an alkali metal, for instance
potassium, is introduced into the space between the layers, so that the
charge on the transition metal is changed, we obtain catalysts with
negatively charged iron, cobalt, nickel or other transition metals, which
are very active in the synthesis of am~monia from nitrogen and hydrogen.
They permit lowering considerably the process temperature as compared
to some industrial catalysts; c~iiich gives promise of obtaining low-
_ temperature catalysts for a~onia synthesis. Additionally, compounds of
graphite with transition metals and potassium are active catalysts fur
- the hydrogenation of carbon monoxide into hydrocarbons.
Synthesis of ammonia n'z 3H=- 2NH~
Hydrogenation of carbon monoxide CO Iiz CHi C~1ia
Hydrogenation of acetylenes IiC=CH H, CH,=CH2 _
14
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
~ Polymerization of isoprene nCHs-C(CIi,)CH=CHs [-CH,-CIi-J�
. I
C(CIi')-CHz '
- Finally, complexes of graphite with alkali metals, are very promising
as catalysts for polymerization reactions. Thus, in the polymerization
of organocyclosiloxanes, unlike other catalysts, these result in polymers ~
without terminal groups (possibly of cyclical structure) which are, even
without additional treatment, thermally more stable than the polysiloxanes
obtained with the usual catalysts.
Polymeriz3tion of cyclosiloxanes n(~5;0), [-litSiO-]4n
Polymerization of vinyl silanes nR3SiCH=CHz ~[-CH-CH,-jn �
. I
SiR,
Polymerization of butadiene �CH:=CHCH=CHs--~[-CH~-CH-In -
i
Polymerization of styrene CH=CH2 _
. nC6H6CH=CHZ [-CH-CHs-)n
I
C,H6
One unusual reaction catalyzed by compounds of graphite with transition
metals ought to be especially mentioned - the conversion of graphite into
- diamond. As is known, this conversion is thermodynamically impossible
under ordinary conditions and takes place only under pressures greater
than 50 kbar and at temperatures of 1500� C and above. This conversion
actually coiisists in cross-linking of graphite layers and formation of
chemical bonds between them (Figure 2). For this, however, such an
enormous activation energy must be overcome that without a catalyst these
reactions do not take place even under the indicated conditions of high
pressures and temperature. In the industry, metals are usually employed
as catalysts; they are introduced in powder form or as sma11 bits in
quantities up to 50�J, of the charge weight. It is thought that under
these conditions the metal fuses and graphite is dissolved in it and later
crystallizes in the form of diamond.
Together with Ya. A. Kalashnikov (MGU [Moscow State University]) the
question was raised: Could cross-linking of graphite layers be effected
by atoms of a metal included in the complex, thus avoiding any dissolution
of graphite in the metal? It turned out that complexes of graphite with
quite ordinary metals, e.g. iron, actually catalyze the conversion of _
graphite into diamond at pressures of 60-80 kbar and temperatures of
1200-1600� C. The quantity of the metal in the catalyst is only a few -
per cent and the reaction proceeds much faster than in the usual diamond
synthesis. It is interesting that transparen.t, well-facetted monocrys-
tallines are obtained in this way, of sizes up to 30 microns, characterized
by high purity.
15
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
~`i T--~;
, i
i ~~pa~NT-M
~
i i i i ~
i i i ii
~pa~Nr~K AnMa3~ ,
Figure 2. Scheme for the conversion of graphite into
diamond (dotted lines indicate the cross-
linking of graphite layers)
* graphite diamond
Thus, on the one hand, a basically new method of diamond formation was
found and on the other hand, diamonds were obtained which differ fr an
the ussal synthetic ones and in many respects are close to natural dia-
monds.
As under the action of complexes of transition metals graphite can be
converted into diamond, that is, its very structure can change under the
influence of such compounds, it is interesting to consider one more
reaction requiring destruction of graphite-like structures. We are
referring to the metiiods of converting coal into hydrocarbon fuel.
Due to depletion of crude oil sources we have an acute problem of coal
burning and its conversion into hydrocarbons; and processes which previously
were considered economically unprofitable are not developed further and ~
anew, taking into account the fact that the coal reserves on the earth
considerably exceed the oil reserves.
Twc~ basic methods of conversion of coal into liquid fuel are known at
present. One of them consists of direct hydrogenation of coal under
rather struct conditions - at a temperature of about 500� C under
hydrogen pressure (method of Bergius). Hydrogen is obtained by conversion
of coal with water yielding CO and H2; thereafter C0, reacting with
water, is converted into C02 and H2. In short a three-stage synthesis
must be carried out for the hydrogenation of coal.
Th~ other method, the Fischer-Tropsch reaction
nC0 + (2n +1)H2 CnH2n+2 + nH2O,
_ is thermodynamically possible at not very high temperatures, but it also
requires a separate production of hydrogen. By now the interest in this
reaction has increased again, although the hydrocarbons thus obtained are
so far more costly than petroleum hydrocarbons.
16
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
But could not these multiphase proces~es be replaced by a reaction of
carbon with water, without participat~on of hydrogen, to obtain hydro- .
carbons and C02 directly: 2C + 2H2O ~ CH4 + C02? Thermodynamic cal-
culations have shown that even for graphite at temperatures 400-500� C
_ the reaction is sufficiently shifted to have in equilibrium 25~a methane,
25% C02 and 50% water. If the calculation is done for au:orphous carbon,
which is less stable than graphite and closer to mineral o~l, this
reaction turns out to be possible even at 400-500� C. The thermodynamic
feasibility of such a reaction may be qualitatively explained by noting
that we convert carbon into very low-energy carbon dioxide and very high-
_ energy methane which carries the aain part of the whole calorific power
" of coal.
The thermodynamics of this reaction varies little with temperature. But
other reactions, accessory in this case (formation of CO and H2), shift
with temperature very abruptly. Consequently, for the reaction to proceed
selectively, it has to be carried out at comparatively low temperatures,
up to 400-500� C at most. However, complete destruction of the graphite
fragmeats in coal can hardly be expected at such temperatures. Thus the
_ problem of catalytic decomposition of the carbon lattice cf gr3phitF arises
again, and here an i.mportant part may be played by compounds of transition
metals, among them complexes of graphite ~aith transition metals,
The work reported here was initiated at the Institute of Organoelemental
Compounds and at present many organizations and institutions participate
in it. Synthesis of tiew compounds and investigation of their catalytic
properties is conducted at the Institute of Organoelemental Compounds
by the group of Yu. N. Novikov. At the Institute of Physical Chemistry
of the USSR Academy of Sciznces investigations of graphite complexes are
conducted by magnetic and Mossbauer methods. At the Institute of Organic -
Chemistry imeni N, D. Zelinskiy and at the Institute of Petrochemical
Synthesis imeni A. V. Topchiyev of the USSR Academy of Sciences some
interesting reactions of these complexes have been studied. Investigations
of X-ray spectra are conducted at the University of Rostov and work on
diamond synthesis under pressure at the University of Moscow., Also
industrial institutes participate in the study of catalytic properties.
~ ~ ~
The communication of M. Ye. Vol'pin was received with great interest, ,
Academician G. A. Razuvayev stressed in his statement that the theoretical
significance of the work communicated by the speaker is not inferior to
its obvious practical importance. In particular, one may expect the
discovery of many interesting directed reactions in the "corridors"
between the carbon layers where atoms of one or several metals penetrate.
Academician N. M. Emanuel' pointed out that M. Ye. Vol'pin, after brilliant
work on chemical fixation of nitrogen, displayed a whole spectrum of new
amazing possibilities of the metal complexes of graphite synthesized
17
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ~NLY
by himself. Special attention should be paid to catalytic properties -
of the new compounds which may allow, in particular, to carry out an
extremely important process - the direct oxidation of propylene. N. M.
Emanuel' offered the use of installations of the Institute of Physical
Chemistry for the study of such possibilities. He also expressed the
wish to enlist the cooperation of othei institutions with the work already
- being conducted in order to elucidate more quickly the practical prospects
of utilization of the metal complexes of graphite.
The president of the USSR Aca3emy of Sciences, academician A. P. Aleksandrov,
assess�:d the work on the synthesis and study of the new compounds as very
i.mportant and promising. This is true above all for such applied trends
as fixation of nitrogen, obtaining artificial diamonds, and new ways of '
coal processing: they must be expanded, advocated and supported by all
means. A. P. Aleksandrov offered help from the Institute of Atomic
Energy in arranging large-scale experiments and in investigations by the
method of Mossbauer spectroscopy: he also asked the lecturer to formulate
suggestions about other meauures which could be helpful in the conduct
of further experiments.
The president backed up the opinion of N. M. Emanuel' on the necessity
to accelerate this extremely promising work and the need of participation
of a greater number of institutes of various fields.
In conclusion A. P. Aleksandrov congratulated M. Ye. Vol'pin on his
great scientific achievements.
- COPYRIGHT: Izdatel'stvo "Nauka", "Vestnik Akademii Nauk SSSR" 1980
[152-12157]
12157
CSO: 1841
18
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2047102108: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
POLYMERS AND POLYMERIZATION
UDC 541.64
,
~ ON THE MECHANISM OF LOW TEMPERATURE SOLID PHASE POLYMERIZATION
Moscow DOKLADY AKADEMII NAUK SSSR in Russian Vol 244, No 6, 1979 pp 1379-
- 1383
[Article by G. N. Gerasimov, M. V. Bazilivskiy, V. A. Tikhomirov, and
A. D. Abkin, Scientific Research Physical Chemical Institute imeni
L. Ya. Karpova, MoscowJ
[Text] Solid phase polymerization reactions initiated by ultra-viol e t
or ior.izing radiation are currently attracting great attmetion. The
effe;;t of temperature on the rate of such reactions is often not desc ribed
~y the simple Arnc~~ius equation. Over a ce~tain interval of temper~:tures
this effect markedly ~~.iminishes, and with further cooling of the sol id
monomer, the rate app~oacnes a final limit, so that formation of polymer
chains is observed even at 4.2 K. Various hypotheses on the mechanism
of low temperature solid phase polymerization have been proposed whic h
are not dependent on thermal activation. According to one of these hypo-
theses this athermal reaction depends on quantum-mechanica.l tunneling
of the reacting molecules through a potential barrier of the reaction (1).
However, the probability of such a process for heavy monomer molecule s
is very low. It was also proposed that the reaction is controlled by
d:Cffusion and that low temperature growth of the chain takes place as a
result of diffusion of the monomer caused by irradiation (2, 3). However,
athermal polymerization of the solid monomer at low temperature also takes
place in the case where the initiating irradiation is not absorbed by
, the monomer, and acts only on a certain sensibilizing reaction to form
active sites (4). For low temperature reactions such sites are eithe r
ions or excited molecules (5, 6). Here we will examine a new mechanism
describing the most diverse process of this type: ionic polymeriza t ion
of monomers with Pi-electron bonds.
The attachment of an isolated monomer molecule to a growing ion in a
gas most probably takes place without a barrier (7). The barrier in solid
phase addition is conditioned by the interaction of reacting particles
with the lattice and therefore depends strongly on the position of th e
particles in the lattice. The polymer chain in a solid monomer forms .
from the ordered monomeric precursors (5, 8) after irradiation create d
19
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
a primary monomeric ion. Part of the energy expended on ionization of '
the system is converted into local energy of yibration of the precursor
molecules in the vicinity of the excited ion. The barrier of the initial
reaction of the monomer ion with the molecule may be overcome as a result -
of these vibrations, in which case the rate of transition through this
barrier does not depend on temperature, The mechanism of the initiating
reaction leading to the appearance of precursors of the polymer chain -
is considered in works (5, 6). In this article is described a model of
the development of such a precursor. It is esser.tial that the precursor
of a growing chain arises in a metastable position in respect to its
surrounding part of the crystal lattice, the status of which ceases to
be in equilibrium owing to the nearness of a growing defect. The basis .
. of the proposed scheme rests on two assumptions: first, in a metastable
position of the growing chain, the barrier to the chain growth disappears
entirely, and second, in the corresponding ordered monomeric system this
position of the chain is preserved during the process of its growth, since
the reaction deveiops faster than the diffusion process of relaxation,
thereby "confusing" the polymer chain and the solid body lattice to each
- other. The latter is confirmed by experimental data according to which
the structure and conformation of molecules growing in a solid monomeric
matrix, as well as the sub-molecular structure of the formed polymer phase
are not in equilibrium (5). If our assumptions are correct, during
athermal generation of chains under the action of irradiation the overall
rate of polymerization will not depend on temper~ture, and the polymeriza-
tion may take place even in the vicinity of absolute zero.
The cationic polymerization of ethylene was selected as a model. This
is a hy~othetical reaction, since crystalline ethylene hardly polymerizes
at all, most probably due to the unfavorable positioning of the molecules
(9). The lattice being examined here differs from a real crystal of
ethylene and contains the molecule precursors needed for reaction
(Figure 1), analogous to typical monomt~ic precursers in polymerizing
molecular crystals (5, 10). The lattice is constructed according to
- general principles determining the structure of crystals: the molecules
, in the lattice are densely packed and the distance between adjacent
atoms of neighboring molecules is approximately equal to the sum of the
van der Waals radius of these atoms.
For the sake of definition the act of the formation of a cationic site
is considered to be the addition of a proton: a molecule of ethylene I
(Figure 1) is converted to an ethyl cation C2H5+. The initial reaction
of this cation with a molecule of II leads to the formation of a dimer
precursor of the growing chain of the butyl cation C4H5+. (This reaction,
as stated above, takes place probably as a result of the energy which
is reLeased locally during the formation of the ethyl cation). We are
interested in the next act of chain growth - the interaction of cation
C4H9+ with Molecule III of the monomer precursor (Figure 2).
20
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007/02108: CIA-RDP82-00850R000300010006-1
- FOR OFFICIAL USE ONLY
Let us select a subsystem of reactants in the crystal, At a given stage -
_ it will be entered by a C4H9~' Cati.on and an ethylene molecule III. The
other molecules in the system we consider as an immc,bile crystal background.
In this case, the energy of the reactants U consists of the energy of
_ reaction among themselves - chemical energy Uchem and the energy or
reaction between them and the background - crystal?ine energy Ucryst~
U = Uchem + Ucryst
In a gaseous reaction chemical energy is the only component. The specifics _
of the solid phase reaction is determined by the addition of an additional
me~nber Ucryst� Optimization of Ucryst in a harmonic approximation leads
to an important conclusion: a minimum of energy corresponds to the '
position of a precursor mid-way between the molecule layers of the crystal
_ (Figure 2). This conculsion is also justified in the case of anharmonism
if the width of the crystalline potential holes is sufficiently large
in comparison with the distance between the layers: the crystalline
potentials for molecules I and II, forming the dimer precursor, must
effectively cover each other,
The initial stage of addition of III to the dimer precursor is shown
in Figure 2. The slight shift of the monomer molecule - the horizontal
shift of 0.7 A and the rotation of 20� - leads to configuration 2b, for
which it is a simple matter to evaluate the chemical potential energy.
Calculating Ucryst by an atom-atom scheme with parameters foom work (11)
and by utilizing quantum-chemical calculations of Uchem for a gas phase
reaction (7), it is possible to show that the reaction in configuration
2b takes place without a barrier: the corresponding route of addition
although different from the optimal route of a gas phase reaction (7),
never-the-less facilitates a sufficiently rapid decrease in Uchem� To
evaluate the change in Uchgm in the transition from 2a to 2b, the work
method used in (7) is unsuitable. Such an evaluation requires additional
research. Preliminary calculations by ppdg and mChpdp methods showed
the Uchem at this stage of the reaction changes insignificantly; lattice
resistance is also low; Ucryst increases only by 1-2 kcal/mole. As a
whole, hypothesis (1) appears ~ustified.
To check proposition (2) we computed Ucryst on the atom-atom scheme for
various fragments of the polymer chain CnH2n+1� 1'he structure of the _
precursor is such that the growing chain takes on the cis-configuration,
in which the carbon atoms are located in a single plane and is unstable
_ in the gaseous phase, but in the lattice corresponds to the metastable -
state of the chain. During the process of growth, the chain holds its
position in the center between the layers of the crystal. According to
our esti.mates, inside the hollow of the crystal arising during polymeriza-
tion, the polymer fragment may freely transfer to the horizontal direction,
if the lattice surrounding the hollow is ordered: in a lattice which is
incoherent to the chain, stresses arise which at a definite length of the
polymer fragment overcome the barrier for such a displacement. Therefore,
21
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2047102108: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
hypothesis (2) is also justified, In general, non-barrier growth of a
chain may be viewed as movement of the chain into the metastable state
between the layers of the lattice, in connection with subsequent "stringing-
on" of new monomer molecules to the chain.
Termination of the reaction depends on relaxation processes related to
disruption of order in those parts ot the crystal associated with the
growing chain, Thus, confrontation of a growing chain with a defect -
causes its deactivation. For example, on collision with a vacancy it
is possible for the chain links to transfer from the flat cis- to the
non-flat hom-conformation, so that the chain becomes entrapped in the
lattice and thereby loses the mobility necessary for reaction, If such -
_ a transfer takes place in a terminal link containing a cationic site, �
then this site breaks off from the monomer precursor and becomes unreac- _
tive. However, at higher temperatures conformational changes halting chain
growth, may take place in the absence of defects, so that the probability
of chain rupture at conformational entrapments increases. On the other _
hand, chain generation processes related to thermal activation begin to
play a role, as we11 as thermal reactivation from conformational traps.
In this case one may expect transition to conventional Arrhenius kinetics,
as indeed observed experimentally.
The main conclusion coming from the present work is that in order to
understand the mechanism of solid phase reactions, it is absolutely
necessary to have the effects of the crystal field clearly in view.
The proposed concrete mechanism rests on a number of model assumptions.
We sutmit that in general outline it correctly describes the character
of the actual polymerization process, although many details undoubtedly
_ require clarification.
'C~Si.np
U O C
1 ~ ~ "
~ 4
' \O`
aR ~ yo
,o \
I
~ ~
Q
Figure 1. Scheme of monomer precursor in a model ethylene crystal.
The cry~stal is o~ tricliniG modif ication with the parameters:
' a=5.0 A; b=4,36 A; c=4.07 A; alpha=5~+�; beta=56�; gamma=73�,
Plane of projection ac.
22
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFIrI~t, USE ONLY
C Sin b
1 ~
0
'~,.^o
\ N
. \ 9 ~
- ~ C J~~I ~3
i-
~
a �
~
~Ja ,
~ ~
I
~ ~
L------------ - -#-a
Figure 2. Reaction scheme of a dimeric precursor of a growing
chain in model crystal of ethylene; a- initial
configuration; b- intermediate configuration. Only
the carbon atoms are shown. Crystal layers are desig-
nated by dashed lines.
BIBLIOGRAPHY
1. Gol'danskiy V. I. USP. KHIM, Vol 44, p 2121, 1975. '
2. Finkel'shteyn Ye. I. ; Abkin A. D. DAN, Vol 174, p 837, 1967.
3. Finkel'shteyn Ye. I. VYSOKOMOLEK. SOYELI. , Vol B11, p 399, 1969.
4. Dolotov S. M.; Gerasimov G. N.; Abkin A. D. ibid., Vol B20, p 331,
19 78.
5. Ahkin A. D. ; Sheynker A. P. ; Gerasimov G. N. RADIATSIONNAYA KHIMIYA
POLIMEROV, Nbscow, "Nauka", 1973.
6. Gerasimov G. M. ; Mikova 0. B. ; et al. DAN, Vol 216 , p 1051., 1974.
7. Bazilevskiy M. V. ; Z`ikhomirov V. A. TEORETICH. I EKSP. KHIM., Vol 8,
p 728, 1972.
8. Kargin V. A. ; Kabanov V. A. ZHURTT, VSESOYUZ. KHIM. ~SH(~I-VA L~f.
D. I. MENDELEYEVA, Vol 9, p 602, 1964.
z3
- FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
9. Elliott G. R. ; Leroi A. J. J. QiEM. PHYS. , Vol 59, p 1271, 1973~
10. Letort M. ; Richard A. J. J. CHIM. tHYS. ET PHYS.-(~iIi~. BIOL. Vol 57,
p 752, 1960.
11. Mirsky K.; Cohen M. D. J. QiEM., SOC., Farad. Trans. II, Vol 72,
p 2155, 1976.
COPYRIQiT: Izdatel'stvo Nauka DOKLADY AKADEMII NAUK SSSR, 1980
[8144/13Q4-P]
CSO: 8144/1304-P
24
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
UDC 541(64+14)
SOLID PHASE PHOTOSENSITIZED P(?LYMERIZATION OF ACRYLONITRILE AT CRYOGENIC
TEMPERATURES '
Moscow DOKLADY AKADEMII NAUK SSSR in Russian Vol 250, No 2, 1980
pp 384-387
' [Article by S. M. Dolotov, G. N. Gerasimov, and A. D. Abkin, Scientific-
Research Physical~Chemical Institute im. L. Ya. Karpov, Moscow] _
[Text] During solid phase polymerization, initiated by irradiation, the
influence of temperature on the reaction rate (W) is in many cases not
described by the simple Arrhenius equation. At a certain temperature
interval this influence markedly diminishes and with further cooling
of the monomer jJ approaches a limit, so that polymerization is observed
even in the vicinity of 4.2� K(1-4). Various possible explanations
- of athermal polymerization at extremely 1ow temperatures have been pro-
posed (5, 6). However, to establish a true mechanism for this unusual
_ reaction, experimental data are lacking. The processes of cr~yogenic chain
polymerization known so far have very low yields (less than 15), which
present great difficulties in the theoretical analysis of the results.
Furthermore, these processes were initiated with high energy ionizing
radiation which is absorbed by the monomer lattice and creates pertur-
bations which are difficult to predict.
In the present article we describe a new effective process of photo-
sensitized chain polymerization of a solid monomer at cryogenic tempera-
tures. This process takes place without the direct action of irradiation
on the monomer: light is absorbed only by the sensitizer which leads
to the formation of active sites which initiate polymerization of the
solid monomer. The process describ~d is unique i:~ having a high velocity -
and a high conversion of monomer to polymer.
Acrylonitrile (AN) and N, N'-tetramethyl-p-phenylene diamine (TMPhD)
were chosen as monomer and sensitizer, respectively. After careful -
purification, the AN and the TMPhD were condensed under vacuum onto a
, cooled ~bstrate of CaF2 which o~as fixed in a cryostat holder for
spectroscopic investigation. The samples were irradiated with light
- from a high pressure mercury vapor lamp DRSh-500 through a UFS-2 filter, -
25
FOR OFFICIAL USE ONLY '
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
separating out the 260-400 nm region. Conversion of the monomer and a
accumulation of the polymer were determined by infra-red spectroscopy
at the irradiation temperature. The IR spectra were measured on a
"Perkin Elmer-580" instrument. Ultra-violet spectra of the irradiated
samples were recorded on a"Beckman Acta II" spectrophotometer,
Condensation of AN vapors at 80� K leads to the formation of a glassy
monomer (according to calorimetric data, the glassification temperature
(Tg1) of AN is 115 K(7); on deposition of AN on a substrate, cooled to
140 K, crystals of the metastable modification AN-AN I are formed (7). `
The various phase states of solid AN are readily distinguished by the
position and width of the bands of valence vibrations of C=N and C-N
in the IR spectra of_ AN. Condensation, both at 80 and at 140 K yields '
a glassy TMPhD which is stable at up to 150 K and crystallizes at 150-160 K.
Experiments were conducted at 20-150 K in binary systems; TMPhD (glass) -
AN (glass) and TMPhD (glass) - AN (crystals of AN I).
The photosensitized reaction in the system AN-TM}.'hD is conditioned by
the electron donor properties of TMPhD and is the result of the photo
transfer of an electron from the TMPhD to AN. It is characteristic that
in the presence of electron acceptor benzophenone, photosensitizing the -
formation of excited AN molecules, no low temperature changes in AN ~
_ were observed. Phototransfer of an electron initiates the anionic poly-
merization of AN at cryogenic temperatures. The formation of ionic sites
is manifested by the appearance in the ultraviolet spectra of the irradiated
systems of absorption bands characteristic of the TMPhD cation-radical
at 590 and 620 nm. The number of cation-radicals is equal to the number
of electrons "captured" in the AN, since, as the experiments showed, the _
charged are not stabilized in the TMPhD.
Figure 1 shows a kinetic curve for the polymerization and a curve for -
the accumulation of ions for glassy AN at 20 K. The reaction takes place _
without an induction period, although the number of ions in the initial -
stage gradually increases reaching a constant number after about 30 min.
Apparently, the time required for the development of the chain is sig-
- nificantly less than the life-time of the ions in the system. The ratio
of the overall polymerization rate (Wpol) to the rate of ion formation
~ion~ ' specific rate (WgP) of polymerization as computed for 1 ion - _
is equal to the product vf, where z3 is the average chain length, and f
is the probability of conversion of the primary ionic site to a growing _
carbion (chain generation). Judging by the data obtained, WSp comprised
about 100 at 20 K. This quantity is the lower limit of v under the
given conditions. Therefore, the active site formed in solid AN, causes
the conversion of a large number of molecules at cryogenic temperatures.
Cooling of glassy AN results in a step-like drop in W ol at 50 K, condi-
- tioned by a corresponding drop in Wion ~Figure 2). A~ter heating, Wion
increases anew to its previous value. The observed changes in Wion
are probably related to the change in interaction between the glassy
26
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFI~IAL USE ONLY
particles of AN and TMPhD. I.*. may be proposed that elastic deformations,
conditioned by cooling of the system, leads to a marked increase in the
barrier, thereby inhibiting electron transfer from donor to acceptor.
Elastic deformations are reversible, and after reheating of the system,
the barrier again decreases. It should be noted that under the action
- of gamma-radiation on single-component homogeneous glasses, the probability
of formation of stabilized charges is the same both at 4.2 and at 77 K
(9, 10). The initial value of WS~ -(Wsp)0 remains constant in the interval
20-50 K. In the interval SO-70 K(WSp)0 increases by 1.5-2 times, and with
further heating of the system to 110 K there is practically no change
(Figure 3).
- Crystalline AN at cryogenic temperatures polymerizes only to a slight '
degree (about 10%), after which the reaction terminates (Figure 4), For
crystalline AN the rate of formation and the stationary concentration
of stabilized ions are lower than in the glassy state. Furthermere, in
systems containing crystalline Aiti no step-like changes in Wion are observed
at low temperatures: throughout the entire interval of temperatures under
study Wion Was practically independent of temperature. The value of
(WSp)~ of crystalline AN remains practically constant on heating the
crystals from 20 to 80 K(Figure 3): the reaction takes place athermally,
At sbout 85 K this value increases by about 2 times. C~t the same time
the character of the kinetic curves changes: polymerization at temperatures
above 85 K proceeds to extensive conversions of the monomer, In the
interval 90-110 K(WSp)~ increases insignificantly: the effective activation
energy of the process (Eeff~ comprises approximately 0.3 kcal/mole, With
further heating Eff increases to 2 kcal/mole (Figure 3).
Solid phase polymerization is conditioned by an ordered structure in the
lattice of the solid monomer: the reacting molecules form "precursors"
of future polymer chains (11, 12). Such aggregates exist not only in -
crystals, but also in g1as~~s consi~~~~.o ~L a5yuu~~etric molecules bound
strongly together; such an association is characteristic particularly
for nitriles (13). The primary site in our case is apparently the anion- _
radical (AN):. Conversion of (AN)~ to a growing carbion - chain generation -
takes place apparently as a result of the addition of (AN)~ to the monomer
(14). It may be supposed that this addition takes place at cryogenic
temperatures as the result of local lattice vibrations arising at the
moment of formation of (AN)~ (4); the energy of such vibrations consists
partly of the irradiation energy expended on rupture of an electron from
the sensitizer. A probable scheme for the further growth of an ionic
chain precursor is considered in work (15): the position of the formed
precursor in the lattice is metastable, and deformations arise around it
which overcome the barrier to ionic growth of the chain. In an ordered -
configuration of molecules, the activated metastable state of the growing
chain is maintained regardless of its length; in this way, athermal
cryogenic polymerization becomes possible. Chains are torn off during �
collision with defects, and for further growth of these chains thermal
activation is required, which takes place, apparently, at higher tempera-
tures (Figure 3); the reactivation energy depends on the depth of the
traps into which the chains fall.
27
_ FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
Chain development is facilitated wherever the monomeric "precursors" are
weakly bound to the surrounding lattice. Glassy AN, apparently, consists
of just such labile precursors. It may be assumed that in AN crystals
at cryogenic temperatures, only those precursors near certain extended
defects are labile, while extension of the reaction throughout the entire
bulk of the crystal during heating takes place in connection with thermal
disintegration of the lattice of crystalline AN. Supplementary kinetic
investigations now under way will more definitely characterize the reaction.
9 .
~.r ~:111'~ l(OM~C?G(It, ~i ~ W ~N ~
E: ~ JO
, ~ .
0 10 ?,J
~ Z ~ � a � � � -
0
1.V o
. JO
~,0 �
J
~ ~ ~ ~ ~~-1 r , ,
4 JO 60 90t,MUM 9 ~1 /3 10 ~0 t,,~r
T
Figure 1. Relationship of monomer conversion (1) and ion
yield (2) on irradiation time during polymerization
of glassy AN; at 20 K.
Figure 2. Relationship of rate of formation of ion to tem-
perature for glassy AN; rate expressed in mole/l.s
28
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
ly~~v 1
'D o IfvN~epcup,'/.
~.d � f
� O Z 'JZ ~ f ~ ~
o ~ a 1
� ?u n J
� � ~ � Q
- o o � ~ �
lA � o~ 1~ -r= !6 c
. .
n o 0 0 .
;,6 r B o ~ ~
~ i ~ ~ ~ i i
1 9 /1 J3 r JO 30 0 JO 60 90 !ZO
T �!0~ t,ruN
Figure 3. Relationship of initial specific rate of
polymerization of glassy (1) and crystalline
(2) AN to temperature. _
Figuxe 4. Kinetic curves for polymerization of crys-
talline AN at 20 (1) , 82~ (2) , 90 (3) and
103 K (4) .
BIBLIOGRAPHY
1. Finkel'shteyn Ye. I. ; Gorbatov E. Ya. ; et al. VYSOKOI~LEK. SOYED. ,
Vol B10, p 398, 1968.
2. Bruk M.A. ; Chuyko K. K. ; et al. ibid, Vol A14, p 794, 1972.
3. Kiryukhin D. P. ; Kaplan A. M. ; et al. ibid, p 2115.
4. Gerasimov G. N. ; Mikova 0. B.; et al. DAN Vol 216, p 1Q51, 1974.
5. Finkel'shteyn Ye. I. VOYSOKOI~LEK. SOYED, Vol B11, p 399, 1969.
6. Gol'danskiy V. I.; Frank-Kamenetskiy M. D.; Barkalov I. M. DAN,
Vol 2ll, p 133, 1973.
7. Barkalov I. M. "Dokl. na mezhdunarodn. simp. po mikromolekulyarnoy
khimii", Budapest, 1969.
8. Lin R. S. H. ; Gale D. M. J. AM. QiEM. SOC. , Vol 90, p 1897, 1968.
9. Hase H. ; Noda M. ; Higashimura T. J. ~iEM PHYS. , Vol 54, p 2975, 1971.
10. Higashimura T. INTERN. J. RADIAT. PHYS. QiEM., Vol 6, p 393, 1974.
11. Semenov N. N. J. POLYMER SG'I. , Vol S5, p 563, 1961.
29
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1

APPROVED FOR RELEASE: 2007102/08: CIA-RDP82-00850R000300010006-1
FOR OFFICIAL USE ONLY
12. Abkin A. D. , Sheynker A. P. ; Gerasimov G. N. RA.DIATSIONNAYA KHIMIYA
POLYMEROV, "Nauka", p 51, 1973.
13. Kratochwill A. ; Weidner J. U. ; Ziffinerman H. "Ber. Bunsenges.", B77,
p 408, 1973.
14. Szwarz M. CARBANIONS, LIVING POLYMERS AND ELECTRON TRANSFER PROCESSES,
1968.
15 . Gerasimov G. N. ; Bazilevskiy M. V. ; et al. DAN, Vol 244, p 1379, 1979.
COPYRIC~iT: Izdatel'stvo Nauka DOKIADY AKADEMII NAUK SSSR, 1980 �
[ 8144/ 130 4-P ]
CSO: 8144/1304-P
CSO: 1841 END
30
FOR OFFICIAL USE ONLY
APPROVED FOR RELEASE: 2007/02/08: CIA-RDP82-00850R000300010006-1