These masterbatches of treated resin were blended with un- posure of the agent and plastic a t temperatures above

eratures above 400’ F.

treated resin to prepare polyethylene containing Catanac SN
in concentrations ranging from 0.25 to 5%. Four-inch disks
were made by compression molding and tested for antistatic
activity. Results are shown in Figure 8 (tested within a week
after molding).
Catanac SN antistatic agent is equally effective on low den-
sity and other types of polyethylene.
should be avoided. I n the case of the polyolefins, powder or
flake forms of the polymer should be used in preference to the
pelletized form. Only small amounts of the agent are required
to produce moldings which remain static-free for long periods of
time.
Acknowledgment

T h e authors gratefully acknowledge the assistance of Ralph

Polypropylene
I n a similar fashion polypropylene flakes or powder were
treated to make a masterbatch containing 10 to 5001, Catanac
SN antistatic agent.
When treated polypropylene was blended with untreated
material and 4-inch disks were subsequently molded, again
excellent static control was obtained, as shown in Figure 9
(test made a week after molding).
Extruded polyethylene or polypropylene pellets cannot be
readily treated with high levels of antistatic agent to make
“masterbatches,” as can the powder or flake forms.
Conclusions
Catanac SN antistatic agent, a cationic quaternary am-
monium compound, can be successfully combined in the
laboratory with many thermoplastic materials under carefully
controlled processing conditions. For example, prolonged ex-
J. Chamberlain and Lyle Andrew, who performed many of the
experiments; Richard Anderson and Michael Sabia, who pre-
pared the Catanac SN in nonaqueous solvents; J. J. Robinson,
G. A. Clarke, and their staffs for the analyses of samples; and
Donald L. Swanson and Theresa F. Ziegler for the preparation
and study of Catanac SN containing tritium.
literature Cited
(1) American Cyanamid Co., Intermediates Dept., Data Sheet on
Catanac SN Antistatic Agent, 1961.
(2) American Cvanamid Co.. unDublished results.
(3’ Carnes, J. J.: U. S. Patents 2,&626,876,2,626,877(1953).
4) Chamberlain, R. J., Zbid., 2,891,878 (1959).
(5) Gruber, A. H., van Loo, LV. J., Zbid., 2,836,517 (1958).
( 6 ) Humfeld, G. P., RCA Eneineer 6, 18-20 (November 1960).
(7) Lee, E. LV., Lambert, F. P.,Brit. Patent 815,662 (1959). ’
RECEIVED
for review October 26, 1962
ACCEPTED January 18, 1963
Division of Organic Coatings and Plastics Chemistry, 142nd
Meeting, ACS, Atlantic City, N.J., September 1962.

INHIBITORS FOR UNSATURATED

POLYESTER RESINS
E A R L E. P A R K E R , Pittsburgh Plate Glass Co., Springdale, Pa.

The inhibitor system for an unsaturated polyester resin is expected to provide long storage life, fast cure, a
minimum of catalyzed or uncatalyzed drift, and mechanically sound parts without any undesirable colors,
odors, or side effects. A large number of compounds were screened in order to determine which would
best meet these requirements. Hydroquinone, 4,4-dihydroxybiphenyI, and catechols with 3-n-alkyl,
3-isopropy1, 3-pheny1, 4-n-alky1, 4-isopropy1, 3,5-dialkyl, and 3,6-dialkyl substitutions were found to have
considerable merit as inhibitors.

HE inhibitor system for an unsaturated polyester resin is
Trequired to meet a number of rather difficult requirements,
which vary depending on the particular application that is
intended. For example, a resin to be used in matched metal
molding must meet the following requirements :
I t should gel and cure as rapidly as possible without cracking,
blistering, or crazing.
Gelling and curing characteristics should change (drift) as
little as possible as the catalyzed resin ages.
T h e storage life (tank life) of the catalyzed resin should be as
long as possible a t ambient temperatures.
T h e storage life of the uncatalyzed resin should be as long as
possible.
Gelling and curing characteristics of the uncatalyzed resin
should not change on long storage.
T h e inhibitor should not impart color or odor to the resin,
either cured or uncured.
Since very little has been published on this subject outside
of the patent literature (7-73), a screening program was under-
taken to establish which of the known types of effective in-
hibiting compounds would provide the most desirable proper-
ties in a polyester resin.
Experimental
Two polyesters were used in this work. Polyester A was
prepared from 10 moles (980 grams) of maleic anhydride, 10
moles (1480 grams) of phthalic anhydride, and 22 moles
(1672 grams) of propylene glycol. Polyester B contained 9
moles (882 grams) of maleic anhydride, 11 moles (1628 grams)
of phthalic anhydride, and 22 moles (1672 grams) of propylene
glycol. Both polyesters were prepared in a 5-liter 3-necked
flask equipped with a thermometer, an inlet tube for inert gas,
and a device for the azeotropic removal of water. T h e in-
gredients were refluxed with xylene as a solvent at 195’ C. until
the acid number was reduced to approximately 50. At this point
a vigorous stream of inert gas was introduced to remove the
xylene and to increase the molecular weight of the polyester
until a 60y0 solution by weight in ethylene glycol monoethyl
ether (Cellosolve) had a viscosity of approximately I on the

102 l & E C P R O D U C T RESEARCH A N D D E V E L O P M E N T

 Table I . Results Obtained on Polyester Resin A Catalyzed with 1.5% Benzoyl Peroxide
L.P.E., Minutes Tank Lqe, Hours
Inhibitora Ob 24 48 100' F. 77' F. I d IiP
Catechols Substituted in 3-Position
0.025 yo 3-methyl catechol 3.9 144 6.4 36.9
0 . 025y0 3-ethyl catechol 4.1 87 5.4 21.2
0.025 yo 3-n-propyl catechol 4.0 77 6.0 19.3
0 . 025y0 3-n-butyl catechol 3.2 52 4.4 16.3
0.05% 3-n-butyl catechol 4.1 58 5.1 14.2
0.08 yo 3-phenyl catechol 4.05 3.7 3.6 15 216 3.7 53.4
0 . 0 5yo pyrocatechuic acid 2.9 ... ... 4 23 1.4 7.9
0 . 1 yo 3-methoxy catechol 5,s 4.2 3.9 37 ... 6.4 ...
0 . 1 % catechol (control) J.J 4.9 ... 54 ... 9.8 ...
Nonee (control) 2.5 ... ... 2 21 0.8 8.4
Catechols Substituted in 4-Position
0,025y0 4-methyl catechol 5.3 3.8 3.4 32 104 6.0 19.7
0 . O25yO4-ethyl catechol 4.5 3.8 3.1 25 91 5.6 20.2
0 . 025y0 4-n-propyl catechol 3.5 3.3 2.9 24 86 7.1 24.6
0,0570 4-n-propyl catechol 6.5 ... 6.6 ...
0,025y0 4-n-butyl catechol 3.4 72 5.9 21.2
0,059/, 4-n-butyl catechol 5.0 102 5.8 20.4
0 . 025y0 4-isopropyl catechol 4.3 115 8.6 26.8
0.0570 4-propionyl catechol 2.75 ... ... 8 20 2.9 7.3
0.0470 4-phenyl catechol 5.8 4.9 4.0 25 154 4.3 26.6
0 . 1 1% 4-chloro catechol 4.5 3.8 3.5 22 151 4.9 33.6
0.025% 4-tert-butyl catechol 4.6 5.3 4.5 37 125 8.0 27.2
0.025'% 4-n-butyryl catechol 2.9 ... ... 8 20 2.9 7.3
Disubstituted Catechols
0.017% 3,6-diallyl catechol 4.35 ... ... 16 77 3.8 17.7
0.01 5% 3,5-di-sec-butyl catechol 4.8 5.5 5.5 37 206 7.8 43.0
0.02570 4,5-dichlorocatechol 3.15 3.0 2.8 4 44 1.3 14.4
0 . 0 1 yo 1,2-dihydroxynaphthalene 6.75 6.0 5.2 23 266 3.4 33.5
0 . 0 5 ~ nordihydroguaiaretic
0 acid 7.6 6.7 4.8 33 180 4.3 23.7
0 . 04y0 4-methyl esculetin 3.1 2.7 ... 4 28 1.3 9.0
Quinones and Hydroquinones
0.01 257, p-benzoquinone 6.0 5.3 5.0 33 168 5.5 28
0.025 yop-benzoquinone 10.1 9.4 8.9 84 ... 8.3 ...
0.05 yo dichlorobenzoquinone 10.2 9.6 8.5 68 336 6.7 32.9
0.025'% dichlorobenzoquinone 6.1 5.2 4.8 35 26.9
0 . 1 yochloranil 9.8 8.4 8.4 37 21 . 7
0 . 1yodi-tert-butyl-@-benzoquinone 7.6 8.1 7.9 21 14.4
0.0270 1,2-naphthaquinone 7.5 7.0 6.2 92 47.0
0 . 02y0 tetrahydroxyquinone 1.5 2.8 ... 0-4 0-4 ... ...
O.OZyo hydroquinone 3.8 5.0 5.3 30 ... 7.9 ...
0.04y0 tetrachlorohydroquinone 3.7 4.5 3.8 18 106 4.8 28.7
0 . 025y0 ethylhydroquinone 4.75 6.25 5,s 44 ...
0.025'% propylhydroquinone 2.85 2.16 ... 6 14.0
0.0250/, n-butylhydroquinone 3.25 3.25 3.05 14 19.0
Miscellaneous Compounds
0 .05% n-propyl gallate 3.3 ... ... 1.5 13 0.5 3.9
0.050/, Tenox BHA (butylated
hydroxyanisole) 4.5 5.0 5.2 27 >508 6.0 >113
0.02'% lapacholf 2.7 ... ... 2 21 0.7 7.8
0.02% lawsone+ 3.9 3.6 3.3 5 73 1.3 18.7
0.05% Ionol (2,6-di-tert-butyl-p-
cresol) 2.9 2.75 ... 4 27 1.14 9.3
0 . o5y0 8-quinolinol 3.05 3.35 3.3 6 51 2.0 16.7
0.275 resorcinol 2.4 2 10 0.8 4.4
0 . 1yo 4-benzylresorcinol 2.6 10 13 3.6 5.1
0 . 1yo 4-tert-butylresorcinol 2.8 ... ... 10 13 3.4 4.6
tank life at 700" F,
a Percentages of inhibitor based on uieight of polyester. Hours of storage at 77a F. of catalyzed resin before test mas run. c Ilw =
L.P.E. at zero hours
tank life at 77' F.
d I;, = e Styrene used contained 50 p.p.m. p-tert-butyl catechol. f 2-Hydroxy-7,Cnaphthoquinonc. a 2-Hydroxy-3-(3-methyl-
L.P.E. at zero hours
2-butenyl- 7,4-naphthoquinone.

Gardner-Holdt scale. This process gives of polyester with a
molecular weight in the 1000 to 1500 range.
Polyester A was cooled to approximately 125' C., a t which
temperature 2 parts of polyester were mixed with 1 part of
styrene (inhibited with 50 p.p.m. of p-tert-butyl catechol)
containing the inhibitor to be tested. If the inhibitor did not
dissolve in the styrene readily, it was dissolved in the polyester
a t 150' C. After the polyester was dissolved in the styrene,
the mixture was cooled to room temperature in a cold water
bath. T h e L.P.E. a n d the tank life tests were run on mixtures
containing polyester A with 1.5y0benzoyl peroxide as the
catalyst. [The L.P.E. test was developed in the laboratories of
the Pittsburgh Plate Glass Co. before the SPI gel test was
accepted by the industry. T h e procedure is identical with the
SPI gel test, except that a smaller test tube is used a n d only the
value corresponding to the SPI total time is reported.]

VOL. 2 NO. 2 JUNE 1 9 6 3 103

 Polyester B was mixed with styrene i n the same manner as
polyester A. except that these mixtures contained 29y' styrene
by weight. T h e L.P.E. and the tank life tests lvere r u n on
mixtures containing polyester B with 1% of benzoyl peroxide
as the catalyst.
For the L.P.E. test, resin was placed in a 16 X 130 mm.
borosilicate glass test tube to a depth of 3 inches. A needle-
type thermocouple attached to a Brown recording potentiom-
eter was centered in this resin mass. This assembly !cas
placed in a constant temperature water bath held a t 180' F.
T h e L.P.E. value was taken as the time in minutes required for
the resin to go from 150' F. to its peak temperature. This
test was run on freshly catalyzed resin and on catalyzed resin
that had been stored for 24 or 48 hcurs a t 77' F.
For the tank life tests, samples of catalyzed resin Lvere placed
in 2-ounce glass bottles, stored a t 77' and 100' F., and checked
every 4 hours for signs of gelation. When a sample had nor
started to gel a t one check time a n d was completely gelled a t
the next, it was arbitrarily considered to have gelled 2 hours
after the last check when it was still liquid.
The value was calculated by dividing the tank life a t
100' F. by the L.P.E. value obtained on freshly catalyzed resin.
T h e Iii value was similarly obtained from the tank life a t 77' F.
These terms were used as a measure of the effectiveness of
inhibitors when the L.P.E. values were not comparable. Since
fast cures a n d long tank lives are usually desired simultaneously,
inhibitors that have large 1100 a n d values are likely to provide
more desirable characteristics in the resin. I100 and I,i were
fairly constant for the same inhibitor over a narrow range of
inhibitor concentrations.
Discussion
Tables I a n d I1 show the results that were obtained on
catechols substituted in the 3 a n d 4 positions. T h e substitution
of a normal alkyl group in either the 3 or the 4 position on the
catechol nucleus increases the effectiveness of the compound as
a n inhibitor. T h e 3-substituted compounds seem to be some-
what more effective than the corresponding 4-substituted
compounds. T h e L.P.E. values drift "down" or shorter in
both cases, but the degree of drift is less with the 3-compound
than with the 4-compound. \%'hen the alkyl group is branched
on the a-carbon atom, the L.P.E. values tend to drift '.up"

Table II. Results Obtained on Polyester Resin B Catalyzed with 1.0% Benzoyl Peroxide
L. P.E., Minutes Tank Life, Hours
Inhibitora 0 24 48 100' F. 77" F. IlW 17:
Catechols Substituted in 3-Position
0.015% 3-methyl catechol 3.45 3.1 2.95 19 120 5.5 34.8
0.020'7 3-methyl catechol 3.8 3.7 3.1 21 130 5.5 34.2
0.025% 3-methyl catechol 3.9 3.85 3.45 25 144 6.4 36.7
0.02% 3-ethyl catechol 4.95 4.6 ... 30 168 6.1 34.0
0.0370 3-ethyl catechol 5.75 5,15 5.0 59 >336 10.2 >57.5
0 .02y03-n-propyl catechol 3.25 3.15 3.0 28 132 8.6 40.5
0 . 0 3 % 3-n-propyl catechol 8.9 44.5
0 . O4y0 3-n-propyl catechol 8.6 54.0
0.02'7, 3-isopropyl catechol 8.6 58.8
0 . o3Y0 3-isopropyl catechol 9.1 59.0
0.04% 3-isopropyl catechol 7.1 7.05 6.5 84 420 11.8 59.3
0 . 02y03-isobutyl catechol 4.75 4.4 4.15 17 113 3.6 23.8
0,047, 3-isobutyl catechol 5.35 5.0 4.65 29 192 5.4 35.9
0.03% 3-n-amyl catechol 5.0 4.7 4.3 34 170 6.8 34.0
0.047, 3-a-phenylethyl catechol 5.7 5.45 4.65 40 192 7.1 33.7
0.03yG 3-a-phenylethyl catechol 5.6 5.1 ... 51 >168 9.1 >30.0
0.04% 3-a-phenylethyl catechol 6.65 6.1 5.5 54 336 8.0 52.0
0.010% 3,6-di-n-propyl catechol 6.5 6.2 ... 21 ... 3.3 ...
None (control)* 3.4 ... ... 3 23 0.9 6.8
Catechols Substituted in 4-Position
0,0157, 4-methyl catechol 5.55 5.25 4.6 29 156 5.2 28.2
0,0207, 4-methyl catechol 6.6 6.15 5.3 33 170 5.0 30.2
0.025% 4-methyl catechol 8.2 7.4 5.9 50 228 6.1 30.8
0 .OS% 4-ethyl catechol 5.6 5.2 4.6 43 192 7.7 34.3
0.02% 4-propyl catechol 6.4 6 6 5 - 48 192 8.0 32.0
0 . O3y0 4-propyl catechol 6.9 6 6 6 0 56 192 8.1 27.8
0.04'70 4-propyl catechol 11 . o 10.0 9.1 80 240 7.3 21.8
0 . 0 2 % 4-isopropyl catechol 5.7 6.4 5.5 36 192 6.3 33.7
0.03Oj, 4-isopropyl catechol 6.8 7.9 6.7 52 288 7,: 42.4
0.04'% 4-isopropyl catechol 8.65 9.4 8.15 67 360 7 . )I 41.7
0.02?ZG 4-n-amyl catechol 6.0 5.75 5.1 48 192 8.0 32.0
0 . 03y0 4-n-amyl catechol 7.15 7.0 5.8 60 240 8.4 33.6
0.04% 4-n-amyl catechol 8.9 8.3 6.45 91 300 10.2 33.6
0.047, 4-a-phenylethyl catechol 6.5 '.3 6.- 52 336 8.0 52.0
0 . 05 yo O-( 3,4-dihydroxyphenyl)alanine 3.65 3.6 ... 4 31 1.1 8.5
Miscellaneous Compounds
0.04% 4,4'-dihydroxybiphenyl 4.2 4.8 4.6 3' >168 8.8 >40
0.0570 phenolphthalein 3.8 3,4 ... 6 28 1.6 7.4
0.0570 diethylstilbesterol 3.9 3.75 ... 6 45 1.5 11.5
0.05% 4,4 '-dihydroxybenzophenone 3.65 4 8 1. I 2.2
0.05% 2,4 '-dihydroxybenzophenone 3.85 4 11 1.o 2.9
0.05% 2,4,6-tribromophenol 3.85 3.75 ... 4 28 1. o 7.3
0.05y0 pentabromophenol 3.6 3,6 ... 4 28 1.1 7.8
0.05% phenothioxin (phenoxathiin) 4.0 3.75 ... 4 28 1 .o 7.3
0 .OS% phenothioxin-10-oxide 3.7 3.55 ... 4 28 1.1 7.6
0.05 '7 5 7-dihydroxy-4-methylcoumarin 3.7 ... ... 2 10 0.5 2.6
2
0.05 phloroglucide
0.05 Yobenzyl-P-methylumbelliferone
3.7
3.7
...
...
...
...
2
5
10
8
0.5
1.4
2.6
2.2
0.050/, 2,6-dihydroxyquinone 5.6 5.2 4.6 4 . 3 192 7.7 54.3
a Percentages of inhibitor based on weight of polyester. b Styrene used contained 5 0 p . p . m . p-tert-butyl catechol.

104 I & E C P R O D U C T RESEARCH A N D D E V E L O P M E N T

or longer. This upward drift is greater with 4-substitution
than kvith 3-substitution. Since a minimum amount of drift
in either direction is very desirable, 3-isopropyl catechol is
believed to have a very desirable combination of properties.
An excellent combination of properties was also obtained with
3-n-propyl catechol. Branching on the @-carbon,as shown by
the results with 3-isobutyl catechol, is less effective for pre-
vention of downward drift than branching on the a-carbon.
Compounds having oxygenated side chains are, in general.
much less effective than those containing hydrocarbon side
chains. This may be seen by comparing the properties of 4-
propionyl catechol with 4-n-propyl catechol and 4-n-butyryl
catechol with 4-n-butyl catechol. Unsaturation in the side
chain also appears to reduce the effectiveness of the compounds
as inhibitors (note the weak activity of 3,6-diallyl catechol).
T h e tables also show the results obtained with a variety of
disubstituted catechols and of quinones and hydroquinones.
I n general, p-benzoquinone and hydroquinone are very effec-
tive inhibitors and chemical modification of the structure
tends to reduce the effectiveness of the parent compound.
Hydroquinone derivatives are characterized by their rather
strong upward drifts. T h e results of Table I were obtained
Lvith 1.5% benzoyl peroxide, which tends to minimize the
up\vard drift. LYhen similar values are obtained with lower
amounts of catalyst, the upward drift is considerably greater.
Quinones are more effective than the corresponding hydro-
quinones from which they might be obtained by oxidation.
Quinones normally show a downward drift.
T h e last section of Table I s h o w the results obtained with a
variety of miscellaneous compounds. Derivatives of phenol
are normally rather weak inhibitors, as is shown by the results
with Ionol. Derivatives of resorcinol and pyrogallol are also
rather ineffective inhibitors.
ENDENE AND CENTRENE POLYESTERS
A NT0 N I SZ A Y NA
Unsaturated polyesters having the double bonds located toward the ends of the chain have physical proper-
ties superior to those of the isomers in which the double bonds are located toward the center of the chain.
Three pairs of such isomers were synthesized, cured, and tested.
HE importance of placing double bonds in polymeric
Tn~aterials at the ends of the chain has been recognized
theoretically for some time ( 3 ) , but no experimental proof
has been given. T h e present work shows that in the case of
polyesters the materials with double bonds located toward
the ends of the chain (Endenes) exhibit, upon curing, physical
properties substantially improved over those of the isomers
having the double bonds in the center (Centrenes). Three
pairs of isomeric polyesters have been prepared and tested;
in all cases the Endene structures had superior physical prop-
erties.
I n one set (Table I) the Endene A isomer was prepared by
first esterifying 2 moles of succinic anhydride with 3 moles of
diethylene glycol and then adding to the saturated spine un-
saturated terminals in the form of 2 moles of maleic anhydride.
T h e corresponding Centrene B isomer was prepared by first
The last section of Table I1 shows the results obtained with
a variety of miscellaneous compounds using polyester B. The
most effective compound in this group was 4,4-dihydroxy-
biphenyl. Most of the other compounds showed very little
activity and were not studied further.
Literature Cited
(1) Abrams, I. M., et al. (to Diamond Alkali Co.), U. S. Patent
3,028,361 (April 3, 1962).
.,
(2) Anderson, T. F. (to Libbv-Owens-Ford Glass Co.). Zbid.,
2,559,837, 2,559,838' (July io, 1951) ; 2,607,756 (Xug. 19;
1952) ; 2,610,168 (Sept. 9, 1952); 2,632,751,2,632,753 (March
24, 1953); 2,635,089 (April 14, 1953); 2,679,493 (May 25,
1954).
(3) Andrews, R. C., Peterson, N. G. (to Glidden Co.), Zbid.,
2,777,829 (Jan. 15, 1957).
(4) Bjorksten, J., "Polyesters and Their Applications," pp. 288-95,
418-21, Reinhold, New York, 1956.
(5) Brooks. M. C.. Praper. I. A. (to United States Rubber Co.).
\-, ~~~~~~ , I
U. S. Paient 3;028,366(April 3, i962).
(6) Cass, 1". E., Burnett, R. E., Ind. Eng.Chem. 46, 1619 (1954).
(7) Ellis, C. (to Ellis-Foster Co.), U. S. Patent 2,255,313 (Sept. 9,
1041)
- '' - 1 .
(8) Fraser, G. L. (to Monsanto Chemical Co.), Ibid., 2,516,309
(July 25, 1950).
(9) Gerhart, H. L. (to Pittsburgh Plate Glass Co.), Ibid.. 2,493,343
(Jan. 3. 1950).
\----- ---~, - I
(10) Gerhart, H. L., M o d . Plastics 25, NO. 6, 86 (1947).
(11) Meyer, I:. \V., Klein, J. G. (to Glidden Co.), U. S. Patent
' 2,846,411 (Xug. 5, 1958).
(12) Noller, D. G., M o d . Plastics 39, No. 12, 147 (August 1962).
(13) Parker. 15. E. (to Pittsburgh Plate Glass Co.). U. S. Patents
' 2,570,269'(0ct. 9,'1951) ; 2,533,787 (April 12, 1952) ; 2,627,510
(Frh. 3. 1~ 9 5 3-I )' : 2.643.985
\---- - 2 - ~ (June 30. 1953): 2.646.416 (Julv 21.
- > - - - I - - -
1953) ; 2,664,413 (Dec. 29; 19j3) ; '2,676,9477(Ap'ril 2?, 1954) ;
2,698,312 (Dec. 28, 1954) ; 2,740,765 (April 3, 1956) ; 2,829,120
(kpril 1, 1958); 2,844,559 (July 22, 1958).
RECEIVED
for review November 19, 1962
ACCEPTEDMarch 11, 1963
, Research Center, United States Rubber Go., Wayne, A'. J .
reacting maleic anhydride with diethylene glycol and then
adding the succinic anhydride to that unsaturated spine,
forming saturated terminals.
I n the above syntheses there is little likelihood of skeletal
isomerization (change of relative position of building blocks
in the chain), since in the formation of the spine only one kind
of acid and glycol is used and the terminal acid anhydride
is added to the spine under very mild conditions (120' to
130' C . for 30 minutes) without water formation. No catalysts
are used in the procedure.
I n the case of both Endene A and Centrene B, use of iden-
tical components and proportions as well as identical esteri-
fication procedures will result in essentially identical molecular
weight distributions ( Z ) , thus eliminating this latter factor
from affecting the differentiation of properties of the two
isomeric forms. Therefore, we ascribe the differences in phys-
VOL. 2 NO. 2 JUNE 1 9 6 3 105