SCIENTIFIC ABSTRACT RADO, J. - RADO, S.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001343920012-6
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: January 3, 2017
• Document Release Date: August 1, 2000
• Sequence Number: 12
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

RADD, Janos. dr.: FRANK, Magda, dr.; FENYES, Imre, dr.; Technikai
"Mwars: Fulop, Belane, assiaztang
Kidney function in diabetic coma. Orv. hmtil. 98 no.24:
650-651 16 June 57.
1. A Janos Korhaz Rendelointezet (Igazgato-foorvog:
Baknes, Tibor, dr.) II. sz. Rmlosztalyanak (foorv(%s:
BmncRath, AladeLr. dr.) ProsecturaJanak (foorvos:
Kallo, Antal, dr., az orvostudomarxvok doktora) e9
Kozpontl Lahorstoriumanak (foorvos: Hammer, Sarolta, dr.)
kozlemmnye.
(DIABEMS KELLITUS, compl.
coma, kidney funct., prognostic significance (Hun))
(KIDNEYS, In various die.
diabetic coma, prognostic significance of funct. (Hun))

RADO, Janos, Dr.; ABIURAM, Karola, Dr.; ESZEKI, iozsef, Dr.
Simultaneous occurrence of congenital septal defect and cardiac
in.farct in old age. Orv. hetil. 98 no-39:1079-1081 29 Sept 57.
1. A Tauos Korhaz-Rendelointezet (igazgato: Bakaes Tibor dr. ) II.
sz. Belosztalyanak (foorvos: Bencsath Aladar dr.) es Prosecturajanak
(foorvos: Kallo Antal dr., az orvostudomanyok doktora) kozlemenys.
(CARDIAC SEPTUM, abnorm.
interventric. septal defect with mYocardial infarct
in aged, case report (Hun))
(MYOCARDIAL INFARCT, case reports
with interventric. septal defect in aged (Hun))

EXCERPTA YEDICA Sec 18 Vol 3/4 Cardiovascular Dis. Apr 59
1 (163 .The clinical and pathological aspects of interventricular septal perforation in
the light of the literature and personal cases Dw k-Iiiii-when und pathologischen Pro-
bletue der ~,vptutnperioratiou im Lichtv dt:r Lortatur un(l unemr
eigvw-n F.Jlr. Rmlt) J., KiNt A. and F(wi)R 1. 2. Inn. Aht., ldno~-Krankenh_
Bullap"'t /. 'Y; . . Ird. 13 7 (227 Graphs2"Fable,.~ I illo,:t
[it onr of thv.twn casus of pt-t-foration of the intervviariculm- st-ptutu diagnost-d in
vivo awl confirmed at autopsy, double heart ropturt, was prv~vnt: rupture of the
right ventricular hatt joint(I thv 1wi-foration of tht, inter-,untricular septum.
fit fhe other ca,v the rour,;c of the di-wase w;1, fill- mflv sign of Neptilln
pt-rforation was fit(- su(Men appearance of a chararteri-tic systolic murniur. wherms
stvnorardia and dilatation were ah,-ent. A survey k presented of the literature on
thc pcrforation of fit(, septurn. The authors. on the basis of 2 cases in which the
genital -eptum defect was associated with car(liac infarction, add the former to
cong
the list of conditions that play a role in differential diagnosis. According to the
statistiral analysis septum perforation, but particular]%- ruptore of the heart, is
more frequent in aged individuals with cardiac infarction. Perforation of the septum
is more common in females with cardiac: infarction and the majority of the patients
alsosuffer from hypertension. In thegenesisof the perforation of t1winterventricular
~;vptlun the alithors attribute great significance to a difference in intco-ventricular
prc~survs. Although infarction spreads most frequently also to the septum, perfora-
tion of the latter is a most uncommon occurrence. Rupture of the heart is much more
common and often takes place transseptally or paraseptaliv. (XV I I 1, 6, 9)

EXURPTA See 18. Vol- 31/_~_ Cardlo. Dis. Feb 59
- ----- ------- -
if 7 71C r0le' (ij VOWICS t ons1rid t, m i it cin ul(th tr I- ill
n BuoLq,,,l 1?7,t7.-77Te-,iPt
a
f IKf)v.ics E. Dupt. of .11rd. If.
(:19!1 :1116)
The 4-fft-vt of Sodium nitritv oil x-o-now; prv,;snrv was examint-d in conge,46%o hrart
failurv, in disea,;v without heart faiinre, and in control ~;ubjvct-~ with a
normal circulation, The invv'figations wvrv rclivatud in thv course of the tri-atinent
(if licart failure and also when reaching the optimal compensation. It was foinid that
(1) in ever 'v phase of heart failure, (2.) in patients reaching tile optimal coml),- -tisation,
and (3) in hYpertensix-v diseast- without heart failure, the venous pressure fell under
tile influence of sodium nitrite more than in control subject,;. Ill tile 3 following
groups: (1) control subjects, (2) hypertensive patiunts without heart failure or thow
with previous heart failure that has become compensated by treatment, and (3)
patients with heart failure, the fail of venous pressure of tile cases with equal venous
pressure was lowest in the I st group, highest in tile .1rd group, and interniciliate in
the 2,nd group. The fall of venous pressure induced by sodium nitfite did not correlate
with the decrease of arterial pressure. The fall of venous pressure induced by sodium

nitrite results from a suppression of venoconstriction, by decreasing tile increased
venonlotor tone. These investigations suggest that tile increase of venomotor tolle in
cardiacdecompensation isanearly and common phenomenon. Tile effect of sodium
nitrite can be used also as a test to decide whether tile increased venoconstriction
plays a role in tile venous pressure beyond or within the normal range. With its
help tile improvement of heart failure call be followed. (XVIII, 6.)
: ~tf
.4
"A

RADO, Janos, dr.; BLUMMII), Gj~ula, dr.; MUM, Sarolta,dr.
Prednisone therapy of novurite-induced refractory cardiac
edem. III. Significance of tubular mechanisms in the reversal
of mercurial sensitivity. Magy.belorv.arch. 12 no.6:183-188
D 159.
1. A Janos Korhaz-Readelointezet (igazgato foorvos; Tako Jozsef dr.)
Izotop V.. Beloaztalyanak (foorvos: Tako Jozsef dr.), Il. sz.
Beloaztalyanak (foorvos: Goth Xndre dr.) es Kozponti laboratoriumanak
(foorvos: Hamner Sarolta dr.) kozlemenye.
(PREDNISONE phar,nacol)
(1WT FAILURE CONGES'LIVE exper)

RADO, Janos., dr.; UaIVAS, Jozsef, BIKICH, Georgy, dr.
Role of various factors in the pathoevenesis of skin hemorrhage
(steroid ecchymosis) due to ne-,.r gluccorticoids. Magy belorv. arch.
14 no. 3:107-11.8 J1 161.
1. A Janos Korhaz-Rendeloin'Lezet (Igazgato-foorvos*. Tako Jozsef dr.)
(Izotop osztalyanak (Foorvos: Tako -Tozeef dr.) es Anyagcsereszakrende-
lesenek (Foorvos: Bikich Gyorgy dr.) kozlemenye.
(ADRENAL CORTEK HORMONES toxicol)
(SKIN dis) (HEMORRHAGE etiol)

RADOY Janos, dr.; HA10ER, Sarolta, dr.; SZILAGYI, Laszlo, dr.; technikai
assistens., HIDEG, Katalin
Effect of new synthetic glucocorticoids (dex&-jethasone and medrol)
on mercurial diuresis in liver cirrhosis. IV. Experimental studies
on the renal and extrarenal effect of steroids with special reference
to the concentrating capacity of the kidney. Magy. Belorv. arch. 15
no.1:16-29 Fe 162.
1. A Janos Korhaz Rendelointezet Izotop (V.bel) osztalyanak,
Anyagesereszakrendelese'nek es Kozpont* Laboratoriiimanak kozlemenye.
(DEXAMETHASONE ther) (PIEDNISOLONE rel cpds)
(LIVER CIRRHOSIS ther) (DIURETICS14 MERCUMAL.ther)

RADO, Janos, dr.; W11ER, Sarolta, dr.; SZ1LAGY1, Laszlo, dr.; technikal
aseziqztens: CZIBULA, Etelka; HIDEG, Katalin
Effective treatment of decompensated liver cirrhosis with new
synthethic glucocorticoids (6 methylpredriisolone, OradexonR) and
thiazide compounds (dihydrochlorothiazide, chlorthalidone-HygrotoneR
bendroflumethiazide) combined with mercurial diuretics. Magy. belorv.
ardh. 15 no.4:1"-156 Ag 162.
1. A Janos Korhaz Rendelointezet Izotop Osztalyanak es Kozponti
Laboratoriumanak kozlemenye.
(LIVER CIRRHOSIS) (CUSHINGIS SYNDROME) (METHYLPREDNISOLONE)
(DEM4ETHAZONE) (HYDROCHLORTHIAZIDE) (CHLORTHIAZIDE)
(DIURETICS, MERCURIAL) (FETATITIS) (ALKOHOLISM)
(CHOLELITHIASIS) (COLLAGEN DISEASES)

- RADO, J#os, dr.; TAKO, Jozsef, dr.; GEDER, Iaszlo, dr.; JENEY, Eniko, dr.;
Munkatars: GOSChl, Irma.
Group occurance of herpes zoster in patients treated with
corticosteroids. Qrv. hetil. 105 no.27:1266-1270 5 J1164
1. Budapesti Janos Korhaz,, Izolop (V.Bel.) Osztaly es Debreceni
Orvostudomany:L Egyetem, Mikrobiologiai Intemat.

TAKO, Jozsef, dr.;_ ROO, Janos, dr.
Generalized herpes zoster complicated by meningitis in a
patient treated with corticosteroids. Orv. hetil. 105
no.2711271-1273 5 J1164
1. Budapesti Janos Korhazp Izotop (7. Be!.) Osztaly.

r C, E e

TAKO, ir.; i-JiLIO, janos, r1r., munkatars; SZANTO, Ervirine, dr.
in the "functional- reserve capacity" of the pituitary
glmvi and the adrenal cortEx under the effect of antithyroid
therapy. Orv. betil. ID6 no.35:1646-1650 29 Ag 165.
1. Fovarosi Janos Korhaz, Izotop (V. Bel.) rjsztaly.

94
KOMAR%ff, Jozsef, dr; TjAGS-NAGY, Lorand. dr; RADO, Yaroly, dr
Case of renal osteodystrophy. Magy belorv. arch. 7 no-3:94-96
June 54.
1. Budapesti Orvostudomanyi XUetem III. oz. Belk.11nikajanak
(igazgatoi dr Gomori Pal egyetemi tanar) es a III. oz. Sebeezati
Klinika (igazgato.- dr Rubanyi Pal egyetemi tanar) Prosecturajanak
kozlemenye.
(RICKETS, RENAL)

RADO Karoly, dr., RADNAI, Bela, dr.; TAKACS-NAGY, Lorand, dr.
Case of metastasis of sarcoma to kidneys with unusual symptoms.
sebeBzet 7 no.1:73-76 Fab 54.
1. A Budapesti Orvostudomanyi M~7,etem 111. sz. Sebeezati Klinika-
janak kozlemenye. Igazgato: Ruban3ri Pal dr. eg3ret. tanar.
(SARCOkA
leg, metastasis to kidneys, surg.)
(KIDNEYS, neoplasms
sarcoma, metastatic from leg. surg.)
(LZ
G, neoplasms
sarcoma, metastasis to kidneys, surg.)

- - - - - - -TZ

P'The kingtic -relations of the, without
lei 'OV', 1~ h
ressure of trifluorachloroet x2 h
h
1
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, VOOZ-
y
p
dona,
'Cal 60-%v Ov. It
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In v C h z-,, t - 10 1 to),( 110)(Gertnall
-~U-Mal zec - ;e kincti-c releastalwts e-r f,,r tile
Mary).--n '.n, "s

po ymerization (initiated by Bz,O:) !it a solu. of C.-FaCl in
C
0.. The method 6 bmed on the weasurement-4 of de,
crease of concn. of CzFaCl during the palymer"tion. reac-
tion. The exponent of the dependence of the pulymeriza-
tion speed on the concn. of the initiator is 0.3 at 7tHW,
-whichagTees with thefindingsof Thomas and O'Shauglincisy
(C-4. 48, 3771a). The total active energy of the polymeri-
zation is 26 kcat./mol., and the active energy of the initiation
process is 30.5 :J= 1.5 kcal./mol. The initiation process is
caused by the radicals from the soln., formed during the
polymerization, and th
olyth of the polymer chain is as
usual. The ending of ei growth of the chain causes 2 re-
U
actions simultaneously, oactwhig by the termination of
retardation and by the termination of recombination.

The
klutka Oolii~eiizauou of
mutuallga M- -La2Ar -d W.
)v lwlaujw.Br%EFS9VA,,L EClrr. Chan. Westi
All 383z:9(1957)(Guman4ummary).~-B -det ' th oly-

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An p -2,.6 mol./kg.) st,70.3, 80.
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ind! OQX.aud. by. ouw~~g the vclodty'cousU. of the
.1 the

f--d
hildatibu ~nd the unimol. de&wiptl. of BZA, it id
that the velocity.of the polymedzation lucreues
M

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the relatiou w" the c6ncn. of thi monamer. - TI
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spontaneous
'd the Initiition el the
-4 ddd. czciudv V bk
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mol.Ag. and at BOX that 15- a sqixv~root tetaflam of the
c6u
Yin Odty to the in.
itlation rmctim there~js IL PaTtIcipati

M
o
'

CZECHOSLOVPKIA/Chemist--y of High Molecular Substances.
Abs Jour: Referat. Zt=nal Khimiya, No 10, 1953, 34981-
Author : Rudoir Ra~:.o, Milan Lazar.
Inst :Not 1~f--,ren.
Title :Thermal Degradation of Polytrichlorofluoroetbylene.
Orig Pub: Cher-,-. prUMY31., 1957, 7, h1o 8, 457-459.
Abstract: The thermal dissociation of polytrifluorochloroethy-
lene at 3400 under atmospheric pressure was studied
by the method of weight losses and change of charac-
teristical viscosity dependent of the destruction
durat-ion. A mechanism of chain degradation based
on the assunTtion of random initiation by C-C bond
scission is suggested. '11he chain development cou-
sists in splitting off of monomer molecules. The
Card 1/2

CZEC1[CSLOVAKIA/Ch1!mical Technology - Chemical Products and H-29
Application. Synthetic Polymers. Plastics.
Abe Jour : Ref Zhur - Khimiya, No 8, 1958, 2&)99
Author : Lazar Milan, Rado Rudolf
Inst
Title Fluorinated Hydrocarbons and Their Derivatives as
Thermostable Insulating Materials.
Orig Pub Strojnoelektrotechn. casop., 1957, 8, No 1, 54-66
Abstract A review article concerning current comcepts of the
causes which bring about chemical inertness and thermal
stability of polymeric fluorohydrocarbons and their deri-
vatives. It is noted that the most promising course of
development of new thermostable insulating fluoro-poly-
mers is one of the following: copolymerization of tetra-
fluorethylene and hexafluoropropylene, synthesis of sili-
cones in which organic radicals are substituted by
Card 1/2
- 83 -

CZECHOSLOI[AICIA/Chemistry of High Molecular Substances. I
Ab s Jo, 1r: Z2yarnal 1,,iimiya, No 10, 1953, 34964.
Autlaor LA. Iazar, P. Rado.
11,-St Not
Title t.--.2 C, .,F!-4;i(,n of Trifluorochloroethylene Fo1ymeriz-=-t,1cn
in loroe~'iane-
Orig Pub: Cbtera- zveb'L-.i., 1957., 11., No 7., 383-369-
Abstract: The -noly=rization kinetics of trifluorochloroethy-
lenc in p~~ntachioroethane solution at -(0 to 900 was
studied: beinzoyl peroxide was the initiator. It is
shawn that the reaction rate rises linearly together
with the !iicuamer concentration. The initiation rate
(fc=d by the inhibition method) is determined by
the monomolecular decomposition of the initiator.
It is assumed that the solvent participates in the
initiation reaction.
Card Vi

'incl.

PHASE I BUOK EIPLOITATION
International symposium ou mAcramolecular chemistry. Moscow,
ig6o.
Mezhdunarodnyy simpozium po makromolekulya.-noY kh1=11 SSSH,
Moskva, 14- IS Iyunya 1960 g.; doklidy I avtoreferaty.
Saktalya. III. (International Symposium an Klcromol~cular
Chemistry Held In Moscow, June 14-18, 1960; F,tpers and
Summaries) Section Ill. [Moscow, Izd-vo AN SSSR' litc)
469 P. 55,000 copies printed.
Tech. Ed.: P. S. Kashina.
Sponsoring Agency: The International Union of Pure and Applied
Chemistry. Commission an Macromolecular Chemistry.
PURPOSE: This book is Intendbd for chemists interested in poly-
merization reactions and the synthesis of high molecular
compounds.
COVERAGE.- 71310 In Section Ill of a multivolume work contain-
Ing Papers on macrossolecular chemistry. The articles In
general deal with the kinetics of polymerization reactions,
the myntheaLs of special-purpose polymerc;, e.g., !on ex-
change resIna, semiconductor materials. ate., methods of cat-
alyzing Polymerization reactions* properties and cho=Ical
Interactions of high molecular materials, and tte effe:ts or
various factors on polymerization and tne deg7adaticn of
high.molocular compounds. No personalities are =entloned.
References given follow the articles.
No ~Ptusa`- v, and R. S. Ti_j1_LxA2_ ~LSZR),
~Acrylcnl tZ,
Polystyrene and ParchlorovInyl ..3.70
Raf1kov. S. B., a ' ~,nvi 1. V. Zhuravlevi, and P. N.
SR). Oxyethylatl _'9F__Rete
GrIbkown (US on or U-arkwchain d -o- 184
Chain PolyamIdes
Santo I , '4nd X. Gal (Hungary). Grafting Ileth I Methicr7l4t
MEO MN Of P_QlY_V_l_nyl Alcohol Under the Actjoyn or x-F."s ~07
Laz ar X ' R R ~ do - A d Y (Czechoslovixia).
nj*j.~~:%_ft nry_~u. ?'LvI1-ts
tf_
c lite Onto Polypropylene and Poly-
ethylene 214
a I " I. A., Z__L-S. =&2r4, and Y. (USSR).
;N - N. Yr
t03 -u-n-or Carboxyl-ContAlning 1!utadlene-Styrene
Rubbers With Polynxides and E-Ciprolactan, 224
n q., and Ts'eng Han-ming (USSR). 3ynthea!.s
Hado =H- and1M. Lazar (Czechoalovzkia). 7h* Role of the
a Free RsdIcals on Cron3linking In Polyetn7lena 2aCj_
Mladenov I 'I. A. Tutorakly, and B. A. Dogidkin (USSR).
W the TMI -formations of Carboxyl-Co-n-E-471-n-ng lKitauene-
Styrene Rubbers and Their Mixtures With E-caprolactam
Under the Action or oa== Radiation 29.3
Rogovi V. A. Darevitqkq&_ Sun Tlung, Chang d.1-
4.0-n
Synthesis c.' New
Cellulose kir-N. Lvas and-Other Polyeaccharlde3 302
Y~;~rmoQ__J_Y_ and F. N. Kaputs MI(USSR). :nit_'.tIon
a t 0 cc -1 -or-)4Bar is Cellulo3as With
ntrollad Synth0B B
Ox1dea or Nitrogen 310
JAn2Y__Y__L, W. Ya. Lenahins, Y__3_1vangXa (USSR).
OxIdatIonal Tr4n_8_r0_rXaf1_0r;i_Tn Chains or ceiluiose_moascules 3,~l
B!etrn1jLS,_&,_A_ Ye. A. Panak4ya, and 0. 1. Volkov,-1 (USSR).
lUec"nicachemloa-r-rrnlr6i'r64T'-'Vns anZ_ffra_&_CcpoIY=eriza_
tion During the Freezing of Starch Solutions 334
I~ Aykk0d;t1.jZry. and U-AZJZQy _
&;R
_(U
=Hfl'..t~l.nol th7e ropertlea of Cellulose by Grafting 344

f
z/ooq/6o/ooo/oo9/OO4/OO5
E112/E453
AUTHOR~ Rudolf Rado
TITLE8 Polyethylenes,lCross-Linked by Means of Peroxides and
their Physical Characteristics
PERIODICAL. Chemicky' pruoraysl, 1960, No.9, pp.496-499
TEXT-. Attempts to improve the thermal characteristics of
polyethylene are outlined. Cross-linking by free-radicall
mechanism initiated by peroxide breakdown is considered to be the
most suitable and economical method. Cross-linking by means of
irradiation is considered too expensive. The suitability of
different peroxides as cross-linking agents will be governed by
the rate of their breakdown at temperatures of compounding. The
conventional source of free radicalsq namely benzoyl peroxide,
has been found unsuitable by the author owing to its high rate of
decomposition at the temperatures of the reaction. A study of
t-butyl-perbenzoate as cross-linking agent for polyethylene is now
submitted and it is held by the authors that this compound has
better stability characteristics within the range of cross-linking
temperatures. The present paper sets out to investigate3
1. Effect of peroxide concentration on degree and content of
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z/oog/6o/oOO/009/004/005
E112/E453
Polyethylenes, Cross-Lxnked by Means of Peroxides and their
Physical Characteristics
cross-linking. II. Thermomechanical characteristics,.
III, Dielectric constants. Comparisons with the linear and an
irradiation cross-linked polyethylene are submitted. Two different
types of polyethylene are used as startipg material; high-pressure
polyethylene Q-f.W. 23000, Alkathene 2011D a d low-pressure
polyethylene (M.W. 80000~ Hostalen UF 2).7 Experimental details
of the cross-linking technique are outlined. The high-pressure
polyethylene is compounded for 10 min on a two-roll mill with
t-butylperbenzoate at 125cC. The low-pressure polyethylene, on the
other hand, is impregnated in the cold with a chloroform solution
of the peroxide and excess solvent is then removed by vacuum
distillation. Castings are prepared from each mixture at 1600C
and a pressure of 200 kg/ cm2. Cross-linking is completed by
extending treating time under pressure to 10 min. Rate of cross-
ILnking was determined by a) measuring the solubility of the
material in boiling carbon tetrachloride and b) by evaluating
elastic deformation curves at 150'C under load, (2800 g/cm),
For both types of polyethylene (high and low-pressure) the effect
Card 2/c

z/ooq/6o/ooo/ooq/oo4/005
E112/E453
I-olyethylenes, Cross-Linked by Means of Peroxides and their
Physical Characteristics
of peroxide concentration upon the efficiency of cross-linking
was determined, It is shown that the efficiency of cross-linking
decreases as peroxide concentration is increased.. 2 to 3% peroxide
being the optimal concentration. Effects of peroxide
concentration are summarized in a graph, Both methods of cross-
linking measurements (solubility and elastic deformation) provided
analogous results, The loss of cross-linking efficiency with
increased peroxide concentration is explained by peroxide breakdown.
The high-pressure polyethylene gave somewhat lower yields of cross--
linked material than the low-pressure material. It is suggested
that this may be caused by the presence of branched-off chains
and tertiary carbons in the high-pressure material, facilitating
chain rupture of the -C-C bonds of the principal chain. The
concentration of polymer free radicals. capable of producing cross-
linkages through recombination is, therefcre, decreased. The
effects of temperature on the elastic deformation characteristics
of polyethylenes with varying proportions of cross-linkages are
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Z/009/60/000/009/004/005
E112/E453
Polyethyl.enes, Cross-Linked by Means of Peroxides and their
Physical Characteristics
plotted in a graph which., in addition, shows also the behaviour
of linear high- and low-pressure polyethylene, polypropylenE: and
vulcanized silicone rubber0respectively. It is shown that Ir-ross-
linked polyW-t'hylenereta:Lns its elastic properties above its
first-order transition temperature, similar to vulcanized rubber.
Resistance to elastic deformation decreases in the following order2
polypropylene > cross-linked low-pressure polyethylene N cross-linked
high-pressure polyethylene. Cross-linked polyethylene with a cross-
linking rate ' I 'retains its resistance to elastic deformation under
load even at temperatures above the melting point of polypropylene.
Tested under identical conditions, however, the low-pressure polymer
showed better thermomechanical characteristics than the high-pressure
material. Cross-linking also causes a slight improvement of tensile
strength and reduction of elongation. D�electric constants, on
the other hand, are deteriorated not only in comparison with the
linear polymer but also a cross-linked polyethylene produced by
means of irradiation. The deterioration of these characteristics
is explained by the presence in the peroxide cvoss-linked material
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z/ooq/6o/ooo/ooq/oo4/005
E112/E453
Polyethylenes, Cross-Linked by Means of Peroxides and their
Physical Characteristics
of peroxide breakdown by-products. Electrical properties are
tabulated, There are 5 figures (I sketch showing heat
resistance of cross-linked polyethylenes), 1 table and
15 referen-~es3 9 English, 3 German, 2 Soviet and 1 French,
ASSOCIATIONSi V;Skumn~ ustav kAblov a izolantov, Bratislava
(Research Institute for Cables and Insulating
Materials, Bratislava)
Chemicky ustav Slovenskej akaddfmie vied, Bratislava
(Chemical Institute of the Slovak Academy of Sciences,
Bra tis lava F-- ---
SUBMITTED~ March 26, 1960
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23679
z/o43/61/000/003/001/001
D222/D305
AUTHORS: Rado, Rudolf, and Lazar, Milan, Engineers
TITLE: Cross-linking of polyethylene initiated by
benzoylperoxide (III) - Formation of cross links
PERIODICAL: Chemick4 zvesti, no. 3, 1961~ 191 - 197
TEXT: This is a continuation of previous studies on cross-linking
of polyethylene initiated by free radicals originating during
thermal decomposition of benzoylperoxide (R. Rado, M. Lazar, Ref".
1: Chem. zvesti 15, 63 (1961); R. Rado, M. Lazar, Ref. 2: Chem.
zvesti 15, a/5 (1961) ). This paper evaluatEs the chemism of
polyethylene cross linking and expresses, in terms of formal
kinetics, whose relations confirm the observed regularities. The
decomposition mechanism of benzoylperoxide JAbstractor's note:
In the following referred to as Bp~,7 is listed in the above ref-
erences and the limited solubility in organic solvents of cross-
linked polyetbylene Z_Abstractor's note: In the following refer-
red to as PE 7-was used for quantitative determination of0the
Card 1/ 5

2367 9
Z/043/61/000/003/001/001
Cross-linking of polyethylene... D222/D305
cross-linking proomss. The degree of cross-linking and the
quantity of cross-1-inks, obtained at various BP concentrations,
after various periods, and at different temperatures, are tab-
ulated, in analo,,-y i-.rith Polymer cross-linking initiated bY. ion-
izing and ultraviolet radiation, it is assumed that BP-initiated
cross-link 1 also occurs by recombination of polymer radicals:
PEO + PEI ~J'T_PE-PE. However, as distinct from the radiation-init-
iated cross-iihking, there is -no linear relation between the cross-
link formation and the concentration of the initiator (BP). This
is attributable to reactions which reduce the efficiency of the
BP, i.e. induced decomposition and termination (recombination)
between the BP ral'_Iical and the polymer radical, thus competing
with 'the cross-linking reaction itself, These inhibiting reactions
0
have inverted temperature dependence: the non-effective BP con-
sumption caused by induced decomposition drops, that caused by
RO + PEI recombination rises with increasing temperature. The kin-
etic equation for the cross-linking process can be derived as
-Lollows: The total amount of radicals (PEI and R*), originating
Card 2/5

23679
z/o43/61/000/003/001/001
Cross-linking of polyethylene... D222/D305
during a certain period is 2k, CBP-7,6t; the a-mount of PE* radicals
is given by the amount of liberated benzoic acid (ALM); the
amount of RG radicals is given ~y the difference of these two
values. Since each primary radical which is not transferred to a
polymer radical consumes an equivalent amount of polymer radicals
for its termination, the total amount of radicals lost by this
termination is 2(2kj CBP-7&t -,aRH), and only the remaining amount
of PEo radicals 2(,bRH - k, [BP3 At) recombines and serves the
formation cross-linIcs. Since always two PE* radicals are required
to form each cross-link 2 the total amount of originated cross-
links is given by the difference.& RH - k1F_BPJA t. kfter substi-
tution of the expression given for&RH in equation 7 (Ref. 2),
'the equation reads
d C PE - PE]
de prk i -k1 ) E BPJ-6
in which [PE - PEJ is the concentration of produced cross-links,
Card 3/5)

23679
Z/043/61/000/003/001/001
Cross-linking of polyethylene ... D222/D305
and EBP]t is the concentration of BP at the timet . which can be
calculated by a similar formular as valid for sponianeous decom-
L'
position:
C
[BO d-6 = 1
BP 0A(a-+l a ki ~2-303 log EA(a +- 1 a.3 - kitl
in which (ko-rki - kj) is the portion of effective(spontaneous)
peroxide decomposition, directly initidting the cross-link-ing.
In the two most extreme cases, the velocity of cross-link forr-qa-
tion will be either zero (k ki = k1) or equal to the spontaneous
_ ~~r-j .
BP decomposition (k k - 1 After subs-titut-ion for 'the expres-k
and adi ~e -7
sion CBPlt usE At results an equation
~PE - PE] = ,, , - ic-, ) ~2. -10-1 log ~~(a + 1a] -kjt~
( pr ki
Card 4./ 5

23679
Z/043/61/000/001/001/001
Cross-linking of polyethylene ... D222/D305
which contains 3 known kinetic constants and expresses -he
quantity of cross-link formation depending on the initial BP con-
centration and the reaction t
-ime. The calculated values coincide
well with exi)erimental results. There are 2 fiF-.ures, 2 tables and
12 references: 2 Soviet-bloc, and 10 non-Soviet-bloc. The ref-
erences to -he four most recent English-language publications
read as follows: L.D. 11-'oore: J. Polymer. Sci 20, c-41 137-l"3
(1056); A. Charlesby: Radiation Research 2, 9~_97 d055); E.S.
Lai.-.,top, J.S. Ealwit, E.S. Powell: j. Polymer. Sci, 32, 125, 257-
275 (1958); An. Drit. Plast (1958
31, 399, 8)
ASSOCIATION: Vyz_kumny ustav kablov a izolantov-v Bratislave
L,
(Research Inst~~ute for Cables ai>d InsulatvS,
Bratislava): stav dreva celUlozV
I . a umelych
vla'kien Slovenskej akadb'mie vied v 3ratislave
(Institute for 'Uood, Cellulose and Arti-[icial
Fibers, Slovak AS, Erati_-lava).
SUE.'ITTED: V:arci-i 1-960
Card

Z/009/61/000/004/003/002-
B112/E253
!MHOPS Rado, Rudolf and s4imLcova, Dagmar
TITLE: Stability of Peroxide Cross-linked Polyethylene
Against Thermo-Oxidative Degradation
a
PERIODICAL: Chemicky" prumysl, 1961, No. 4, pp. 209-211
TEXT: The present paper follows on a previous study,
describing the preparation and thermo-mechanical properties of a
peroxide-crosslinked polyethylene. Attention now is paid to the
latter's oxidative degradation under the influence of heat.
Crosslinking with peroxides will produce in the parent hydrocarbon
a number of tertiary carbon atoms which, it was thought, may have
an effect upon the resistance to scission-type reactions. To
elucidate this point, the rate of oxidation of three types of poly-
ethylenes was compared: (1) Polyethylene, cross-linked with
benzoyl peroxide; (2) polyethylene, also cross-linked with
benzoyl peroxide, but with all traces of .de or its decompo-
sition products carefully removed, and (3 linear, not cross-
linked polyethylene. The rate of oxidation (thermo-oxidative
degradation) was established by measuring the rate of oxyEen
Card 1/3

Z/009/61/000/004/003/005
E112/E253
Stability of Peroxide Gross-linked Polyethylene Against Thermo-
Oxidative Degradation
absorption and duration of the induction period for a temperature
range of 135-185*C. Preparation of samples and experimental
details are given. A commercial brand of high-pressure polyethy-
lene, "Telcothene" was used. Cross-linking was accomplished by
treating powdered "Telcothene" with a solution of benzoyl peroxide
in chloroform, evaporating the solvent in t~e cold and cross-
linking by heating 5 hours at 90'C in an atmosphere of nitrogen.
Removal of traces of peroxide or its decomposition products was
achieved by repeated washing with carbon tetrachloride. Samples of
the polymers in powder form were mixed with fine-grained silica
(aerosil), placed in a rlass-tube and connected through a gas-
burette to an oxygen cylinder. The apparatus was thermostatted.
Results are summarized in graphs, plotting volume of absorbed
oxygen versus time at different temperatures. It is clearly seen
that: (a) Decomposition products of benzoyl peroxide are without
effect upon the thermo-oxidative stability of polyethylene; (b)
decrease in stability is caused by structural changes resulting
Card 213

Z/009/61/000/004/003/005
E112/E253
Stability of Peroxide Cross-linked Polyethylene Against Thermo-
Oxidative Degradation
from cross-linkages. This is, however, considered insignificant
(in the order of 5*C) in view of other advantages which the cross-
linked polyethylene offers. There are 6 figures, 2 tables and 8
references: 2 Czech, 1 Soviet and 5 non-Czech.
ASSOCIATION: Vyskumny ustav k6blov a izolantov, Bratislava
(Research Institute for Cables and Insulating
Materials, Bratislava)
SUBMITTED: June 1, 1960
Card 3/3

31751
1 1
Z/0,J911 /6 1/0,." "--"1 .0121003100 5
E112/E)53
u,-1 o iand Tj a f-r ma j,
ccnditions-for -ci,-e cross-lu",.,`.nEr. of
uni
Lylcne with dicuinere perox-~do
:-l, 6~,7-
-1 fea-cures and advanta-e,, o'
~Cc -o~~,ica chemically
-,,,Iene and the use of dicumzem~ ce--oxide as
crosS-lin-'1-1in,r a--eru a--e discussed. The latters' ra-~e and temuera-
C, Cj -
ture of decomoosi,;ion correlate well with -orocessin.- temperatures
of polyethylene, -nd .! hi--h degree of cross-linking can be
~ic.'ileved. '-Phe of dicumene oeroxide nroceeds
evor !In solvents, by a ronomolecular, non-c,1--ain mechnism, and tii,
e tic a]. 1y im poor tt r~d i v idi,,,-.l reaction. steps of 4.- ~1 r ci s s -
.A-rlkinf~, ',rocess can ot-, e:,,--,ressed as:

31751
,q ond i t i o ris i'o - P-1 1 AD 0/0.
ki
R -�-> R R
k,
')>
PE, +
P, cun!~-ne
au t`
L o f Lime, temep--l-outure ~;~nd ~-P-
01! -,,-,s of evoss-link foraa---,tion. They r-av-- aiso
cou~jt
vm, c
Ol T I . D. -'e-r 0 -u
~rd

31751
the -_-;/00"
0.5
k4
nart~ High-
PE -
ren t
3thy-' w:.i -ofl 3e-di ort a roll m-i-il
late a un -D P z3amples were pla--.
-:~-en a--: W!Ach were sealed and
"D C. ad P- J. na :;n-rmo~;tat. Degree of

r)or t 4
s o flo -1 ~on of the macer-'al
zj orid~. -ts -centration from degrec of
I nv --
v-, ;-~ular ~
-:ven a
pproxi, mate ly as
000), s u ,
-
,
-:7.(J~ effcct on rale
c whicirrl -,_-.-actically constanT a-r
Cf-.'CC4- on
_.t affects, hovever. the speid of thc:

r~ c-_,timum vulcanisation 4~ I
me for eaer:,
]!:',--~ly _U:r' i,hf' 7i[M' 85--,'6 Of T)F'

c.once?;,..,aT;aon- of -.,%&-re abz)u
t
;
v P_ thy' e i; h 13) 1S
,
C 7'; 10 m~
!-ase

31751
-ad
-c- io a
ati on
i r E., a ~J
i . Fri.,
42,
)rg C~
12
av K..
istit
Brat
at
19 6- 1

89592
S/190/61/003/002/010/012
B101/B215
AUTHORS: Rado, R., LaAr, M.
TITLE: Process of cross linking in polyeth3lene caused by peroxide
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 3, no. 2, 1961,
310-318
TEXT: The authors studied the process of structurization of polyethylene
(PE) by cross linking due to benzoyl peroxide (BP). PE samples containing
BP were produced. Undecomposed BP was iodometrically determined after
heating in an inert atmosphere; benzoic acid formed by decomposition
was alkalimetrically determined; liberated CO 2 was gravimetrically deter-
mined. Cross links were calculated on the basis of A. Charlesbyfs(Ref. 10,
see below) ratio between solubility and degree of cross linking. Table 1
gives the data of the BP decomposition in PE. Table 2 those on the forma-
tion of cross links. It was concluded that the decomposition of BP is a)
continuous (rate constant k 1), and b) induced after reaction of the
second order (rate constant k i). The following equation holds for the
Card 1/ 8

89592
Process of cross linking... S/190/61/003/002/010/012
B101/B215
total decomposition: -d [BP] /dt= ki EBPJ + k , [BP] 2(1). Solution of this
equation and transformation give [BPJ t . [BP]. /[A(a+l) - a~ (2), where
A = exp k1t: a k,/kl. k, and ki, and the constant k t were calculated.
The equation X1 (k1 /ki )f2-303 log [A(a+l) - a] - k1t] (3) holds for
continuous decomposition, X2 = (kl/k,) f( a+1) - -*(a+l)/LA(a+l)- 'i
- 2.303 log[A(a+l) - a]/A] (4) for induced decomposition; and for kt:
kt =A RH/f2.303 log[A(a+l) - a] - k1tj (8). The constants obtained by
calculation are given in Table 4. The calculation of the reaction is
ki k k
such: BP )o 2R' ; R* + BP -::-,> R- + CO2+ RX; R*+ PH -14 P*+RH;
k
P, + P*
k products of deactivation; breaking off of the chain re-
P' + R'
Card 2/

89592
Process of cross linking... 5/19 61/003/002/010/012
B101YB215
action. (PH = polyethylene, RH - benzoic acid). The efficiency of
cross linking depends on the ratio of the reactions P* + R' and P' + P*;
in the first case, it is zero, in the second case k, LBP]t . The rate
of structurization is such: d[P-Pj/dt = (kikt - ki- )EBa (9). By
substituting [BPJt in Eq. (2), the following expression is obtained:
[P - Pj- (kt - kl/k,) f2-303 109EA(a + 1) - j - k1tj (10). The data
calculated and thoseobtained are compared in Fig. 3. Hence, the follow-
ing conclusions are drawn: 1) at low temperatures only a breaking off of
the reaction occurs due to cross linkage among the polymer radicals;
2) the reaction mechanism changes at higher temperatures. Interaction
among primary radicals and the polymer takes place; 3) if the tempera-
tures are still higher, the latter reaction prevails. This is explained
by the considerable difference between the activation energy of the in-
dependent BP decomposition and that of the transfer, and also by different
changes in the reaction rates. BP, which did not decompose monomolecular-
ly, is ineffectively lost. The process of transfer determining the
Card 3/8

89592
Process of cross linking...
S/19 61/0031/002/0110/012
B101YB215
number of cross links among the polymer radicals, plays an important
role. The reaction rate also depends on the difficult diffusion of
substances in PE. There are 4 figures, 5 tables, and 19 references:
7 Soviet-bloc and 11 non-Soviet-bloc. The 3 references to English
language publications read as follows: A. Charlesby, Atomics, L,12,1954;
H. C. Haas, J.Polymer Sci.,12, 493, 1959; R. Rado, M. Lazalry J.Polymer Sci.,
45, 257, 1960.
ASSOCIATION: Scientific Research Institute
Material; Chemical Institute
Sciences, Bratislava
for Cable and Isolation
of the Slovakian Academy of
SUBMITTED: October 26, 1960
Card 4/8

Process of-cross linking...
Legend to Fig- 3:
Content of,cross links in dependence
on time and initial concentration of
3P. 1) 70.3'C; 2) 80.10C; 3) 89.40C;
solid-line: calculated data; dots:
experimental data; a) moles/kg.
.ard 5/8
0~592
S/190/61/003/002/010/012
BIOI/B215
0
0.05 0.10
p
5 103 ce., 01
J~ 75
0.04
40.:,2
oi5 [n',11, Afoflbljrzo

Process of cross linking...
'remnepary-
Pa. *c

4)
r Bpem%
cem-10-

1
. 01) RommegTpaann.
aepenuca (Jenson
i1a, UOAb/Na PAC-Xo:X.ne%HI[Cff
Ceu on
AWI~bXl 0023082nOCU
FIeR3OREoa KD=O-
Tw. *"a-/"
1 WOPa3GAaAOCb
YOHXCX yr-lepO-
Aa. MQAa'1.Cz
ME
-
70,3 8.46 0,0164 0,0044 0,0047 0,0020
0,0203 0,0063 0,005t 0,0038
0,0284 0,0082 0,0072 0,0062
0,0368 0,0153 0,0037 O,OtO3
- 0,0586 0,0272 0,0116 0,0188
80,1 1,44 0, 02V, 0,0083 0,0079 0,0026
0,0360 0,0124 0,0086 0,0073
0,0586 0,0296 0,0184 0,0114
0,103 0,0555 0,0240 0,0230
0,116 0,0645 0,0274 0,0364
89,4 0,42 0,0368 O,OM 0,0208 0,0045
0,0586 0,0324 0,0330 O'Otoi
0,103 0,0555 0,0394 0,0276
0,116 0,0724 0,0529 0,0323

0,198
'0.1145
0,0675 S1190161100310021---,01012
0,06/,6
Table 1. DecOMDOsition of benzoyl peroxide in polyethylene. Legend:1)
0- 4 0 /kg;
temperature, Ci 2) time, sec*10- ; 3) concentration of BP, moles
4) consumption of BP, moles/kg; 5) formation of benzoic acid, moles/kg;
6) 00 2 formed, mole8/kg.
89592
Card 06/B

Procoss of cross linking...
S/1 90/8e170203/002/010/012
B101/B215

TemuepaTy.

a,

(4)
13pexin.

ell-to-, Horracn-
TPUUM

epelfull
11
Gewonna, COACPHIM11118
non
=evtr
3(!,

stmb/ril

emnep3.

rypa. ,c

MMI

cett-10

a) "Offne",

ellooll.,12.

fj-y-,.IKA GoAcpMaNve
-Muz
nonepe
cansen,
70,3 1,728 0,116 0,0152 89,4 0,108 0,041 0,0139
2,t60 O,Ot84 0,058 0,0150
2,592 0,0213 0,061 0,0182
3,564 0,0246 0,082 0,0191
4,464 0,0289 0,103 0,0208
5,184 0,0260 0,116 0,0230

l
SO
216
0
116
0 2 0,123 0,0220
' ,
0 288 ,
0130
0 0,144
1 0,0273

0:504 ,
0214
0 ,
0,16 0,0252

0 , 864 ,
OtO260 OJ77 0,0268
296 0 0274

728 0 0296
Table 2. Formation of cross links in polyethylene.
C; 2) time, see-lo-5; 3) concent--ratioA of BP; 4)
Moles/kg.
Card 7/8
t
Legend: 1) temperature,
content of cross links,

89592
Process of cross linking... S/190/61/003/002/010/012
B101/B215
Ta6anna 4
Ititne,ril.iecunexoHcTairrbipacaaAaaeper.nust Gefr3offaa a
noastarrunetic
Temnep-Tyl'~-. k'. cex-I k1t. k11
-C -1 -1 xs--
KS-AIOA? -CCK
n., 1 (1) S)
70,3.41OAb ~ t:92- 10-6 1 200-1 0,0296
80, 1 1 83-10-15 4:30 10-4 0,0657
89,4 1,20A0-4 1,20-10-3 0, t 330
-r, xxaAl 50,5 n'5 17,3
Table 4- Kinetic constants of decomposition of benzoyl peroxidi~ in p?ly-
ethylene. Legend: 1) temperature, 0 C; 2) kly.see-I 3) ki (k in the.
I - I U7
original) kg-mole- see ; 4) kt (kr' in the original), moles-kg
5) E, kcal/mole.
Card 8/8

~0-
S~11~~0161 03/008'019/019
8 06 2,, B1 1 O/B215
AUTHORS: Rado, R., Simunkova, D.
TITLE: Radical reactions in polyisobutylene initiated by peroxides
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 3, no. 8, 1961, 1277-1283
TEXT: The authors dedicated this paper to the effect of the chemical
structure of polyolefins on the course of the reaction of macroradicals,
and to the possibility of controlling the reaction for the desired polymer
transformations. The authors studied radical processes initiated by 99-5~4
benzoy~ peroxide (BP) on amorphous polyisobutylene (FIB) (molecular weight:
1-3~10 ). PIB samples were synthesized by BP and heated in an inert
atmosphere at constant temperature. The following factors were determined:
1) BP consumption; 2) formation of benzoic acid by titration of a M 4
solution with 0.01 N reagenti 3) molecular weight of PIB in the course of
destruction on the basis of the intrinsic viscosity at 300C by meang of
Ubbelohde~3 viscosimeter according to the equation [-yj - 2.9-10-4-MO- 8;
4) The number of double bonds by measuring the iodine number of 1 ~
solutions in M 4' The results obtained at 4 different temperatures are
Card 1/6

Radical reactions ...
-26304
S/190/6)-/d'63/008/019/019
B11O/B215
given in Table 1. The constants K of spontaneous decomposition and K ch
of chain destruction are given in Table 2. In accordance with the experi-
mental data the authors found that: 1) the following eq ation holds for
the transfer constant: k (A[RH] j/2-303109(exp(k t)u /kj) EBP] 0 +
tr ~ 1 '[(kch
- k h/k,[B~ 01- k1t, where A~H] stands for the amount of benzoic acid;
2) the amount of benzoic acid is approximately equal to the theoretical
amount of consumed BP due to spontaneous decomposition to X, ~ (kl/k ch)
t2-303 109[exp (k 1t)-(k ch /kl) [BP] 0 + 1) - (k ch /kj)[B~ o]- kltj- 3) The
redu ction of the molecular weight follows the equation M t = 1000 X0
Bp] 0-514 + 100-1- k = destruction constant. The con entration of the
/~J c o 7 d c
double bonds formed is obtained from the equation [=]t - (k chktr /2) [Bj c
+ k d M C' On the basis of the data, the authors concluded that: 1) the
decomposition of BP, like that of polyethylene, is an induced decomposition
of the second order. Benzoate radicals formed by spontaneous decomposition
initiate the further decomposition of BP and form polymer radicals; 2) the
Card 2/ 6

ww~
2b304
S11901611003100810191019
Radical reactions... B110/B215
transfer reaction is'due to the interaction with the methylene groupa..16f
the polymer chain and with the substituting methyl groups; 3) part of'the
polymer radicals with an unpaired electron in the substituent is isomerized
due to intramolecular transfer. This causes the destruction of the pcl~mer
chain. One of the resulting fragments forms a new polymer.radical, and
the other is stabilized by the formation of a double bond; The macro-
radicals, of PIB do not add d,4e to steric inhibitibh-..,. Thii.7 causes the
formation of'double bonds. There are 4 figures, 3 ttLblesand 8 referencess
6 Soviet-bloc and 2 non-Soviet-bloc. The references to English-language
publications read as fol;oWq: Ref- 4: T. G. Foxp P. J. Floryl.J. Phys.
Colloid. Chem., ~J, 197, 1949. Ref- 5: G. Harvey, L. Klee, J. Amer. Oil
Chem. Soc., 11, 127, 1950.
ASSOCIATION: Scientific Research Institute of Cables and Insulating
Materialq Bratislava
SUBMITTED: Februaty 28, 1961
Card 3/6,

(A
2_'W7
Z/O _'-_3'i6 I,/,-.;'_'0"/C-OG/0O2/0O2
D229/1)302
AUTHORS: Lazar, Milan, Engineer, Candidate of Sciences and Rado,
Rudolf, Engineer
TITLE: Cross-linkage of saturated polymers by grafting
4$--
PERIODICAL: Chemickt zvesti, no. 6, 1961, 435-440
TEXT: One of the possibilities for cross-linking polymers is grafting
with a monomer. Cross-links produced by grafting have a different
chemical composition from the linear chain. This paper deals with the
theory and calculation of the polymerization degree of grafting, es-
pecially in view of transfer reactions. The expression for the ratio
of cross-linked graft polymer to the total amount of grafted polymer
can be derived from the reaction scheme for grafting, listed by
M. Laz&r (Ref. 2: Chem. zvesti 15, 327 (1961)). According to this re-
action scheme, the growth of the branch chains is initiated by transfer
reactions from both the growing macroradical (P.)and initiator radicals
to the basic polymer (Po). To simplify the calculation, it is assumed
Card 1/7

21a77
Z/043/61/000/006/002/002
Cross-linkage of saturated... D229/D302
that the first addition of the monomer to the polymer radical (Po.),
the second addition, etc, have the same velocity constants. Cross-
-linkage by grafting occurs in the termination reactiong but only by
recombination. Disproportionation and transfer reactions compete with
the cross-linkage. The derivation of the proportion of crosswlinked
polymer (fz) is also based on the assumption that the state of free-
radical concentration in the system is stationary. (The concentration
of radicals can be derived from the concentration of reacting components
and the velocity constants of the pertinent reactions). The expression
reads then: /Z rL-'P0-I
k.Po-Po + k,mPo-Af + ksPo-I + 2rk.Pa-P- + d&'.2P0_P_
in which r is the proportion of recombination; and d is the proportion
of disproportionation in the terminationi-Abstracter's note: Other
symbols not explained ]. After introducing radical concentrations and
adjustment, the function reads:
fz r(1 - K)--k , in which the auxiliary
+ r v- K
Card 2/7

21877
Z/043/61/000/006/002/01)2
Cross-linkage of' saturated... D229/D302
r (CPO + CO) +CO(l +
symbol K (I + "I-) (l + (CPO + C M ; rA is the ratio of extinction
C+1
NI
velocity of polymer radicals (PO. and P.) reacting with each other,-
to the velocity of polymer radicals reacting with the basic polymer
(Po) and the monomer; C and C M are transfer constants. Solved for CL,
the equation reads: vp k0.5
2' in which r = 3 ; C = k
M -*+ C M
CPO%
C', = k k2 k2
01; v P is the total velocity for monomer consumption; and ~_ is
2
the ratio of the velocity for initiator radicals reacting with the basic
polymer to that for initiator radicals added to the monomer. The
portion of the cross-linked graft polymer increases at higher ratios
of recombination velocity to total termination velocity and lower
values for K. Cross-linkage reaches a maximum at K = 0 and is zero
at K = 1. The value for f z also strongly depends on the value for c~:,,
since the cross-linkage requires the transfer which enables the origin
Card 3/7

21877
Cross.linkage of saturated...
Z/043/61/000/006/002/002
D229/D302
of polymer radicals Po,; however, the transfer reaction itself com-
petes with the recombination reaction, during which the cross-linkage
takes place. The optimum value forq, corresponds exactly to the
maximum for fZ9 The dependence of the f value on values forcLand
z f
is shown in Fig. 1.
According to the
Fig. 1
Card4/7
2
2
ad -
0,4 - 3
7

L12 4
5
2 4 6
present know-
ledge it can be
expected that r6
values for most
polymers will
be rather low
when initiated
by low-molecular,
initiators. Iligher
jovalues can be
obtained when the
grafting is

Z/043/61/000/006/002/002
Cross-linkage of saturated... D229/D302
performed with the aid of polymer hydroperoxides. Under the supposition
that hydroperoxide groups are bound to the polymer to be grafted, that
they are subject to monomoleculax- decomposition and that the HO- radi-
cal initiates homopolymerization, while the macroradical initiates
directly the grafting of the branch chain, a value of P= I is obtained.
Fig. 1. Course of the dependence of Considering a different de-
f onOL under the assumption that composition mechanism where no
z monomolecular radicals origin-
the transfer to the monomer is ate, obtained valueg will be
negligible and that the recombina- very high. As Cn example for
tion prevails in the termination crosg-linkage, the authors
reactions (r = 1, or 0.8 respective- quote the grafting of a hydro-
ly), at13 = 100 (lines I and 2); carbon polymer with styrene.
P = I (lines 3 and 4); and (3= 0 In respect to the prevailing
(lines 5 and 6). recombination in the termina-
tion reaction, the cross-
linkage of this monomer seems
possible. However, when 0, cross-linkage will not take place,
because for most grafted polymers, the