124
722

__THS

 

2222222 22%.: 42.2; 222' 222.3222 2422244222222
24:22 2:42-24 1: 4 222.22. :22;
2242324 2024 2222 42:222—222. 222 4 a.
24 22:24 222422 $2422 220222442
04422‘.434402524

1941.

 

 

 

C
“In-1

LII-313A R Y

r I u f‘ . ‘( ‘ A '1‘
'\ ,/‘ ‘ P ..1LII{53?1 5) $1.; 3
I "'2‘

 

2,...“ University j

.45.:

hammfiunsx-nJhm I.

 

SOME STUDIES OF RESIN FORMATION
FROM CASHEW NUT SHELL OIL

by
CARL WALTER 3022220312223

I

A THESIS
Submitted to the Graduate School of lichigan
State College of Agriculture and Applied

Science in partial fulfilment of the
requirements for the degree of

MASTER OF SCIENCE

Department of Chemistry
September, 1941

(Na.
\.

\$>K‘

SOME STUDIES OF RESIN FORMATION

FROM CASHEW NUT SHELL OIL

331-6633

ACKHOWLEDGMENT

To Dr. R. C. Huston, the writer wishes
to acknowledge his appreciation for the guid-
ance and helpful suggestions which have made
possible the completion of this work.

The writer also wishes to thank General
FDods, Inc.. for furnishing the cashew nut
shell oil. and for the method used in the
separating and decarboxylating of anacardic
acid found in eectione V-B - l and 3, and

V-B - 4 respectively.

I.
II.
III.
IV.

VI.

TABLE OF CONTENTS

Introduction . . . . . . . . . .

Historical . . . . . . . . . . .

Theoretical o o o e e e e o o 0

Technique of Handling the Oil .

Experimental 0 o e e e o o e o o

A.
B.

D.
E.

materials 0 o o e I o e o e 0

Separation of Component Parts

1. Preparation of Calcium Anacardate

2. Preparation of Cardanol .

Separation of Components by Steam
DIStillation o e o o o o o o o

Polymerization Reactions . .

Stabilization Of COlor o o 0

Special Treatment of the Cashew

Nut Shell Oil
Use of Inhibitors
Dry Hydrogen Chloride
Hydrogeneration

Preparation of the Platinum

Catalyst

Procedure for Use of Apparatus

Used

5. Regeneration of Anacardic Acid .
4. Preparation of Anacardol . . .

Physical Properties of Resins Obtained .

A.

B.

Observations . . . . . . . .

10 TIMO
2. Color
5. Color Stability

Testings . . . . . . . . . .

l. Softening Point
2. Melting Point

Page

15
16
16
18
18
2O
21

24

28

52
52

52

Table of Contents (cont'd)

5. Flow under Pressure
4. Specific Gravity

VII. COHClUSionSeooeoo-ooooe I
VIIIQSWaI‘yooocoooe-oso...

IX. Bibliography c o o o e o o o o o o

I. INTRODUCTION

Since the discovery of Bakelite a great deal of
research has been done on the polymerization of syn-
thetic and naturally occurring substituted phenols
with formaldehyde to obtain.modified phenol-formaldehyde
resins. Coming under the latter category is the oil of
the cashew shell. formerly a waste by product, which is
made up essentially of cardanol (see page 10) and ana-
cardic acid (see page 10). This paper will deal with
further studies of cashew nut shell oil and formaldehyde

especially in the presence of certain modifiers.

II. HISTORICAL

The cashew nut made its first appearance in the lit-
erature in 1911 when Schenk (1) reported it as a new
confection. From.then until 1922 the kernel of the nut
was studied and the husk was given no attention at all.
In 1923 however J.J. Sudborough (2) found that the husk
contained 39.8% oil with d261.0151. acid value 107.
saponification equivalent 119, iodine number 296 n.fi%§
1.5158. and was made up essentially of anacardic acid
(022H3205) and cardol ' (032H5204), both being substi~
tuted phenols with unsaturated side chains.

These facts point to resins of both "A“ and "C"
type. but the problem remained untouched until 1927 when
Harvey (3) obtained a patent for the treatment of the
oil with nitric acid. etc., or formaldehyde which yieldei
a product suitable for molding or lacquers. From then
on much work has been done on the problem.with H.T. Har-
vey doing the major portion. In the same year he (4)
patented the polymerization of cashew nut shell oil and
glycerol induced by heat and catalyst. In 1928 another
patent was issued to Harvey (5) covering the drying of
cashew nut shell oil with a metal such as Cu. Al. or Pb.
In 1928 he (6) also received a patent for the treatment
of cashew nut shell oil with ammonia. smmonium.hydroxide.

etc. to produce compounds that varied in color from red

to violet useful as coloring agents. A product useful
for paints and varnishes was made by headhg the oil with
nitric acid and patented by Harvey (7) in 1929. In the
same year he (8) patented an insulator made from cashew
nut shell oil and formaldehyde with hmirochleric acid as
the catalyst.

A process for extracting the oil from the shell was
devised and patented by Hughes (9) in 1951. The nuts
are subjected to a sudden change in temperature from nor-
mal to charring, bursting the cellular structure of the
shell and allowing the liquid to run out. A compound
suitable for insulation was prepared in 1931 by Harvey
(10) by vulcanizing cashew nut shell oil with rubber.
Also in 1951 Harvey (11) patented a product prepared
from cashew nut shell oil and fonmaldehyde.

A.J. Haagen Smit (12) in 1931 proved the structure
of snacardic acid to be 2-03. l-COOH 5-n015327 benzene.

Harvey again in 1932 patented a great deal of work
including, (13) cashew nut shell oil used as a plasti-
cizer with cellulose esters such.as cellulose acetate.
(14) an insulator from.cashew nut shell oil and a drier
such as manganese. (15) a water-proofing material from
the oil for waterproofing of concrete surfaces, etc..
(16) a red to violet coloring material from the oil and
‘ ammonia and formaldehyde. (17) a resin obtained by treat-
ing cashew nut shell oil with an acid and oxidising with
nitric acid. (18) a varnish containing a modifier of

China wood oil. (19) a varnish for inside of iron food
containers.

Ryan in 1932 also patented a varnish (20) made from
cashew nut shell oil. a congealed vegetable oxidation
product such as copal gum. and a suitable catalyst.

In 1933 Harvey (21) prepared a compound consisting
of the oil. stearin pitch and hexamethalene tetramine.

In 1934 a product from.cashew nut shell oil and
casein with an alkaline catalyst was prepared by Harvey
(22).

The first mention of distillation was noted in 1934
when Harvey (23) reported and patented a method for the
distillation of cashew nut shell oil at a temperature of
300° to 400° C. at atmospheric pressure which yielded a
product of germicidal phenolic character.

Damitz (24) in 1935 reported a brittle fusible resin
from cashew nut shell oil and ester gum heated together
at a temperature of 315° C.

‘ Dickey (25) also in 1935 polymerized cashew nut
shell oil with rubber to give a material suitable for
typewriter platens, etc.

Harvey (26) obtained a product suitable for water~
proofing walls by reacting the oil with barium hydroxide
and then a glyerride.

Pillay (27) in 1935 found the formula of anacardic
acid to be 022H5203 M.P.22.5° C. It contained two active

hydrogens one of which was phenolic. Pyrolysis of the

acid yielded anacardol 0213520 B.R.215.2°. a§8.9399
n§9.1.5107. Two double bonds were shown in both com-
pounds, but were not located. The side chain however
was straight.

The formula.

CODE
OH OH
015327 15H27
Anacardic acid Anacardol

Rector (28) developed a new process for*extracting
the oil from the shell in 1936. The nuts were immersed
in a bath of cashew nut shell oil at a temperature and
for a time adjusted to effect the discharge of a major
portion of the oil without scorching the kernels.

Patel (29) in 1937 studied the effects of decarbaxyr
lation. The saponification number (117) and acid value
(109) of the oil decreased on heating until they became
almost zero. The rate of decrease was higher at higher
temperatures. This decrease was due mainly to decarboxy-
lation. 0n heating the iodine value (266) increased
initially owing to the splitting off of carbon dioxide
and the decomposition of the oil into unsaturated sub.
stituents. A subsequent decrease was thought to be due
to polymerization of the unsaturates. The specific grav-
ity (.996) of the oil decreased and then increased

slightly on further heating. The mean molecular weight

decreased to a minimum and then gradually increased.

Hughes (30) modified his previous method for the exe
traction of the oil by first causing the nut to absorb
water and then immersing it in a hot bath of the shell
oil. Harvey and Benita (31) in.1937 patented a procesl
for effecting the polymerization of the oil by using sale
furie acid. In 1938 Harvey and Damitz (32) devised a
method of driving off the sulfur existing in the oil and
then effecting polymerization.

In 1938 we found the first mention of cardanol (33)
being used with formaldehyde. It was obtained by either
steam distillation or distillation at atmospheric prose
sure.

Gardner (34) in 1938 reported the use of cashew nut
shell oil as a drying agent in points.

Jeffries (35) also in 1938 reported another method
for the extraction of the oil. A column of nuts and
broken shells was subjected to a downward stream of super-
heated steam, the water and oil being collected at the
bottom. In the same year Jeffries and Pierce (36) de~
vised a special pretreatment of the nuts before extrac‘
tion of the oil.

A patent issued to the Harvol Corporation (37) in
1938 described a process for the polymerization of cashew
nut shell oil by using 1 - 6% by volume of concentrated
sulfuric acid or with zinc chloride or tein tetrachloride.

The product obtained was used in paints. varnishes and

impregnsnts.

Wats and Bherscha (38) used the oil as a mosquito
larvicide in 1958. Five parts of cashew nut shell oil
and 95 parts of kerosene were used. In 1958 Pierce and
Jeffries (39) added another revision to their apparatus
for the extraction of the oil. This consisted in appe‘
retus for effecting rapid cooling and draining of the
shells that had been extracted.

Harvey (40) in 1959 showed the formula of cardsnol

H H
(CH2)5- c . 0(CH2)5 - CH3

K

~\

and used it with formaldehyde to make costings. molded
products. etc.

Hughes (41) in the same year polymerized cashew nut
shell oil with glycerol phtholic unhydride condensation
products to obtain materials suitable for shooting and
molding, Kiezmick (42) polymerized the oil with sul-
furic acid to a flowable state and then completed poly-
merization to a rubbery state with hexamethalene tetra~
mine.

Patel and Patel (43) reported that the roasted
shells contained 18 - 20% oil with a saponificetion
number of 4.5. iodine number of 294, dgg .9578 and mean
molecular weight of 540. ‘

Caplsn (44) in 1940 used diethyl sulphate dissolved

in the oil and heat to effect reaction of the solution

with the metals naturally present in the 011. These
precipitated metals sere then removed and the product
polymerized to yield resins suitable for paints. var—
nishes, etc.

Downing (45) showed that dermatitis from cashew
nut shell oil is not caused by ingestion of the cooked
nuts, but only by contact with the oil of the shells
and reported that ointments and pastes should be avoided
but hot wet dressing applied.

Cayo (46) decreased the poison ivy effect by treat-
ing the oil with protein such as egg or blood albumin or
heating with acetamide, benzamido, etc.

Harvey and Caplan (47) published a paper on cashew
nut shell oil describing the manufacturing processes,
polymerization utilizing both the unsaturated nature of
the oil and the phenolic group. Upon distillation the
distillate consisting largely of anacardic acid polymer-
ized slowly. The residue showed both phenolic and an-
saturated preperties and also reacted slowly with alde-

hydes.

III. THEORETICAL

From the graphic formula on the following page it
is evident that the components or cashew nut shell oil
(cardanol and anacardic acid) and their synthetic deriv-
atives (dihydrocardanol, anacardol and tetrahydroana-
cardic acid) are all substituted phenols and should
therefore react as such in the presence of formaldehyde.
According to Baekeland one mole of formaldehyde reacts
with one mole of phenol or its derivatives to yield

benzyl alcohols as follows:-

 

H H
HO cos t s so tugs
4-— ‘ —'
as car" He " (:1 HO c-c-OH
I a
H H

The benzyl alcohols formed will then. by the elimination
of water. combine to give a straight chained, thermoset-

ting resin

 

 

 

 

H H
as 6-03 HG 6-01!
B 4' H
so c-G—OH so 0-0-0}!
3 H
. c
H a

If however more formaldehyde is used, a thermosetting
resin will be obtained due to the formation of cross

linkages. All reactions carried out for this paper were

10

 

 

 

 

 

 

.BE n\ommH bmmmao
0E5 ¢\OMON
OE ¢H\DHN I mo HOUH002<
anamao
Uflod
I m.mm mo eavesomn<
moo cheeseMpea
bummdo
0 .mm we
on 1 uao<
moo advances<
mmmva
.5 OH 0* HOCQEmO
\o m m.on cheeses
..,3...Sna§hcmu .08..” o 2 .
nmonammovo a oeammov
. a m m
55 oH\ommm acnechao
useom.mnnnaom peace meapaos massage ease

m92<ewzoo Q<0Hmwmm ho mqm<fi

mole per mole.

The speed of the reaction of the substituted phenolfl
and formaldehyde varies with the position of the alkyl
group in respect to the hydroxyl group. For instance.
the reaction of meta xylene and formaldehyde is faster
than phenol and formaldehyde and yields a thermosetting
resin providing enough formaldehyde is present. This is
due to the fact that both the hydroxyl and alkyl groups
are ortho-para directing and consequently direct to the
some positions on the ring.

With ortho and para xylenes the reaction is slower
than phenol formaldehyde and only thermoplastic resins
can be obtained because one position either ortho or
para to the hydroxyl is blocked leaving two open.

In the case where an alky is substituted on both
ortho positions or on one ortho and the para position
the reaction is much slower than either or the above be-
cause only one position remains open. Only thermOplastic
resins can be obtained from this type of phenol due to
the fact that no cross linkages whatever can be formed.

Applying the above generalisations to the constitu~
ents of cashew nut shell oil. we should expect that car-
danol, which is a meta substituted phenol.should react
the fastest, anacardol (ortho substituted phenol) next
and anacardic acid (di ortho substituted phenol) the
slowest. The raw oil which is predominantly cardanol

should probably react between anacardol and anacardic

acid. By glancing at the time of reaction for each of
the above on Tables I, II. III, and IV we find these

expectations correct.

13

IV. TECKEIEUH 0F HAEELIEG THE OIL

The first and foremost consideration in handling the
oil is scrupulous cleanliness. The 011 should be stored
in a place where miscellaneous contact is not apt to ac.
cur. Persons handling the oil should deveIOp a technique
toward it which may be described as similar in thorough
cleanliness to that used in handling virile bacteria.
This does not mean, however, that the Operator need be
afraid of the material or should hesitate to get it on
his hands, because only those who are not allergic should
work with the oil. The point to emphasize is that minute
traces of the oil, spread through careless handling, can
cause very unpleasant effects to peeple unaware of its
presence. To be specific, traces of the oil left on door
knobs or table tape can poison individuals who have nothing
to do with the problem. The essential thing is for the
Operator to wash his hands very frequently, and at the
slightest provocation, with plenty of mild soap and luke~
warm water. A generous supply of paper towels should be
near at hand, not only to wipe the hands but also to wipe
containers and benches when the oil is transferred or
spilled. The used towels shoald be deposited in paper
sacks and burned, helping to prevent the spread of the
oil.

Apparatus heavily contaminated should be first

l4

soaked in a suitable solvent such as ethylene dichloride.
Ethyl acetate can also be used satisfactorily. Beyond
this, washing or scrubbing with soapy water is generally
sufficient to clean up the apparatus and make it fit for
future use.

During the previous eleven months only one case of
poisoning has occurred. This was traced to the common
sink used by every one in the laboratory. The only way
to eliminate poisoning from this source, if the pre-
ceeding precautions have been carried out, is to have a
separate sink for washing contaminated dishes. If this
is impossible, the sink should be used as infrequently
as possible and should be scrubbed thoroughly with soap
and lukewarm water after washing dishes containing the
oil. A private stock of brushes and soap powder is 31.0
recommended. The trouble seems to be worse in hot
weather when the pores of the skin are naturally Open.
Contaminated clothing should be sponged with solvent
and the garment thoroughly washed or dry cleaned before
being worn again.

There appears to be some justification for the be.
lief that the use of grease or oil on the hands moderates
the toxicity of the oil. The action seems to be purely
one of delaying adsorption into the lower layers of the
skin and facilitating the washing off of the contamina-
tion. An individual doing much dishwashing should prev

tect the skin by use of some ointment or vanishing cream.

H
U!

The better the condition of th sP:in ti1e loss lilcoly the
chance for irritatioo. In acute cases "Calamine Lotion,”
freely applied, is a good remedy. This laboratorm how-
ever, has found that "Bwrrow's ”11*1'1 " is moc.h 31jerior
to "Calamine Lotion." Eurrow's solution 13 made by dis-
solviz1g 150 Prar.s of 111d acete.ta and 85 grams of aluminum
3 lphato in one lite r of water. The effiectcd area should
be Popt moist with tho solution by a‘pl"i*g d1?essin:3
saturated with the solution.

Iocause of t21o fact that cashew nut 33.1911 oil has
such a serious affect upon some individuals only hose
porso :.s wn.o are not alle1'gic shozld work w ’th it. A very
simple way to determine ”16131r or not an inzivi hzal is
allorprio is to place a small drOp of the oil (so more t11an
the amount that will ajhore to the point of a pin) on the
wrist. After a mimuto the excess is wiped off and a
bandage applied. If .he patient is allergic the spot
will begin to itch within 2 to 13 hoxrs and a large red
blotch.will appear. is soon as the pesitive signs «on
pear apply Burrow's Solution or Calamino Lotion as
directed above. If nothing devoloos within two days the

test is taken as nogativo.

16

A. hiat 61" 181 3
Cashew nut shell oil was furnished by the General

Foods Inc. and used as such without further purification.

Calcium anacardate was prepared by adding a solution
of cashew nut shell oil in iSOpTOpyl alcohol to a water

susp naion of slaked limo.

Isopropyl alcohol (practical B.P. 82-8300) was

purchased from Eastman Kodak Co.

Slaked lime (commorcial) was obtained from Carrior

Stephens Co.

Cardanol was obtained by evaporation of the solvent
from which calcium anacardato had been precipitated anfi

removed.

‘

Anacardio acid was pro; red by a fiirg sulf"rio acid

(1-8 solution) to a suspension of calciz- anaoarfiate in

S

hexane.

Roxane (practical B.P. 68-7000) was purchased from

Eastman Kodak Co.

Anacardol was obtainofi by the doourboxylation or

auaourdio acid.

l7

Formalin (40% commercial) was the source of

\

formaldenyde.

Acctaldehydc, a Central Scientific product, was

used after distillation at 25°C.

Chlor acetone, a Commercial Solvents product, was

used after distillation at 119°C.

Phenol (U.S.P.) was obtained from Carrier Stephens

and used after distillation at 184°C.

Linseed oil (Commercial, boiled) was obtained from

Carrier Stephens.

18

5. Separation of the Component Parts.
1. Preparation of Calcium Anacardate

Five hundred grams of centrifuged cashew out shell
oil were dissolved in three liters of isotropyl alcohol,
shaken at regular intervals and allowed to atanfi over-
night. The precir'tete formed was removed by centri-
fusing.

One hundred and eight grams or slaked lime were
trituratea to a thin paste with a sufficient quantity of
water added in small quantities.

The lime paste was then transferred to a five liter,
three neck, round bottom flask fitted with an efficient
stirrer, reflux condenser and dropping funoel and sus-
pended in 1000 c.c. of isoprooyl alcohol. To this sus-
pension the centrifuged oil was added in a small stream
from the drapping. inc mixture was stirred until the
reaction appeared to be complete and then for an addition
hour. The completion of the reaction was indicated by
the refiuction in the color of the solution from dark
brown to a light reddish brown and by the formation of a

1

rather voluminous 111’

    

t red colored, finely divided pron
cipitate.

At the completion of the adfiitional stirring, the
mixture was filtered by suction, washed with fresh
solvent, pressed dry, and then allowed to dry in the air.

The yield of solvent free salt was approximately EDS of

the wei~ht of the cashe w nut shell oil Daed. According to
this, disrefarming the origizal preci; 21tat3 f11tm3re$ off,
thure 333 ag2pr3} :imately L43 acid and 283 cardaxzol in the
cashew nut 33311 011.

The time of reacticn varied from one hSHr aid forty
3:133t9 3 to twe tv-fonr hours, the naval time b313g about
feur to five hours 3. 126 time of reacticm a3peared to be
depe3den t, to a Considerable extent, 3303 the amgnnt of
water 13 the system. More water seemed to favnr the re-
act} on 31 11133 adry solvent flacelerated it. The reaction

was 3130 303313 ated by hoa.ting t1-e mixture on a water

03.3, using the reflzr x concfiensor to Linifl no salvent loss.
2. Isolation of Cardauol

The preparation of cardanol, due to tile i‘act that it
is soluble 13 130pr0p31 alcohol, simnly involved tha
13olation of it from the filtrate obtained 13 the pre-
pgration of calcium aaacardata

The filtrate o3tainad from the preparation of cal-
cium agacardate was centrif 3g ed to mags sure all tLe Ca.
anacardtte was removea. I13 30 ution was then placed in
a 033 liter claigen £1333 33d tne isopror yl alcohol ra-
moved over a water bath. When m33t of the alcohol was
removed, the re 913323 was taken from the flask, a new
portion addad and the distillation repeatefl. All the
residues were then 913333 back in tha flask and the

r,“aluiuu 3103301 removed by heat from the water bath

and gentle auction. This procedure was found to he faster
and more efficim at then afifiinf more solution to the flask
as the solvent was rerioved. fihen foaming beran, which was
n indication tha.t 0317 tra cos of solvent remaineé,the
residue was placed in an 80°C oven to remove the last
traces of solvert. The cardanol was used in tr A13 form

nd also in the purified form. The pure product boils

at 2r:5°c/10 m.
3. Regeneration of Anacardic Acid

Four hundred grams of air dr7 calcium anacardete
fiere placed in a five liter t3ree neck round bottom flask
eq ipped with a mechanical stirrer, reflux condenser and
firepfing funnel. Three liter 3 of hexane were a: lded and
the suspension stirred vigorously. The quaotity of
eilforic aclfi equivalent to the calcium present as deter-
mined b7 ash .1al7eis we 3 diluted va'it1161‘
water and edoei elou17 but continmzozsly from t

futeel. The amount of wlfur 1

0
l-b
0...
£1
53
o
{In
(I:
L 3
e
r .J

1

to aboot 90 c.c. epecific rrnvity 1.84. The etirrine
was continued for two hours efte r the lost of th e sul-
furic acid had been edied. The sL creatout liquid was
h n decanted as cevplcte17 as possilsle and the reeidue
washed with hexane to remove an7 ask erin: macardic acid,
the weenie? being combined with that obtained by de-

antatlo The calcium sulfate was centrifuged. The

liq7m1 137 or (hexane containinq sulfuric acid was placed

21

with the previousl7 obtained liquid and the remainoer
was dis corded. ihe hexasc lo; er of th reaction was also
ent.rifug ed to remove any calcimm sulfate present, and
then 7cched with.water until the latter was Acwtwo to
litmus paper. It was foufld aJ'oou- cone to be very careu
fol and shake the bozo mac-7oter mi nxtnro go: t17 io orfier
to avoid the formation of emulsions which were fiifficult
to break. Those emulsions when once formed ooImli 0317 be
broken by outriluginfi.

The washed hexane solution was transferred to a
distilling flask provided with a concenoor and aotometic
separator 7hereb7 the water was removed from the s7etem
and the hexane recycled. This cpo 1°ation was continued
until the anacaru ie acid was free from water and then
recovered by distill 13g off the hexane. The last portion
of solvent 7a a removed unc:er a ql’oot vacuum 71th a stream
of air bubbles passing through the liquid. This was tried
on c ardanol out Violicu a o017m rizeé product so the al»
teroete method as provioiel7 described 733 coo ptcd. Anna
cardic acid in the {acre for13 is a sol
Purification co ld not be carriol out by dici illotion even
at reduced pro esure *ocauee it is so easily decerboxylatod.
The acid used for making resins was that obtained in the

crofie state after all hexane had been removed.

4. Preparation of Anecerdol

Anacordol was pooo°7ed b7 th e decarbox:wl tion of

2:73

anacardlc acid. The decarhox717tinn was carried (at by
mixing one percent of £13017 divided slaked lime wit

any 6esL ed qaarw ity of acid. Usually 200 jvarzs of acid
and 20 grams of 317796 lime were need. The 3 73777 was
heated to a temperature of 195—1500 G,nre erebly 150~140°,
until the evolution of carbon 51 371.8 had s”b7tantially
ceased. The heatin7 time 7 rL Od between two and four
hnure 697936133 7707 tfie rate of heating and other
machanical circumctances. The reactinfi was carrleé out
in a round bottom 31377 or a distilllnv flask. When the
former was 3773 it 7a: fitted 71tha still head for vacumm
distillatien of the reaction product. This 093773103 was
canducted unfler 7 770377 of 10 mm. or 1677. Th? still
head ha: to he insulated ayainst heat less and amper-
henting kegzt at a mi 1333. The chief difficfllt7 was
foaming 7hich been 7.e trc 169770 at the time tie 733773
was applied or as the temperature was raiseé above the
initial to effect distilletlcn. The focmigg was due to
836693 evolfitinfi f cavhe 13n73 that 737 J ld in the
011, or tb3t was liter“fcc es the Paaction reaches comm
pletieu. The s3ebiilt7 of t‘: 13 £03313 largely cexditiGua
ed by impurities in th7 aracerdic as 3 erried over tram

the casaew xzut shell 03L. finacerd)l 50113 at 195-18700

at 5 mm. and nég a 1.5C93.
Another grocedure for de oer MYJXWletion was develonedo
1 J ..
T7) “3.37:3 77773 of the acid and twenty 77733 of slaked

lime wer. placed in a two liter, three neck, 33333 bottom

flask fitted with a condenser, thermometer and stirrer.
The temperature was held between.130-14000 for six hours
while the mixture was stirred to help liberate the carbon
dioxide without causing too much foaming. T.e temperature
was then raised to 170° for an hour, the mixture cooled,
centrifuged and used either in this form or after further
purification by distillation. U33 of the cardaflol in

this crude state was justified by the fact that neither
the raw oil nor the acid were used in the pure state.

The pure anacardol was a yellow liquid boiling at 185.

137° at 3 mm.

C. Separation of the Components by Distillation.

Harvey (25} in 1954 reported a method for the dis~
tillation of cashew nut shell oil at atmaepherio oressure
which yielded a product boiling between the temperatures
of SQO~4OGOC. In 1933 steam éietillation wee eleo mention,
ed as well as vacuum distillation. All three processes
were covered by patents, however, so no defirite in—
formation or procedure was obtainefi. fie a reenlt die-
tillatina at attonpheric, in vacuum, or with steam enfied
in this laboratory in failtre. The main diffieoltg'wes
the large amount of foaming at high temperature due un~
don tedly to docarboxrlation of the acid and imgurities.
Several anti foam afiente were need but none were found
that would boil hitter than the oil. Kot much time was
spent on this because the main object of the Lroblem was

formation of resin and also because the separation

described in SBCtiOL G was very excellent.

D. Polymerization Reactions

V,“ ha» n. -. ,v -- ' -_. " . , '---_ -. . , -, F s . g - Q- - _..‘ ’3' h! -
Ego gulffiefithlfix rvaotLoLs Haze divia3u iuud four
(\ '1 . 1" C. ‘1‘ “H- -v\ -. «an a 9. In
grLisa V1232u~ LoldLLrizati 33 of (3) £33 wgolo oil,
n ;\ "'3": I, .. 73;: "9. '\ r". 4 r: ”C \ ‘ f: \1 r 9 ‘ Q y‘. n "r" “ J": (N 1: “
(I: aliubc‘ll 'u..LL1 ab .LKi’ v ; C 9.1 91511301 -31 \ “J1 , .1...;_:.8.L_.U..- Q 4 J— . ’-’ i; C6
all LJLLLLO'S W618 C1 Pi d out in Lsouiiillv tho 333
..‘, t. '1 ‘-. a , 0-, n
m unor, 0313 one lei 33 dosuribod 36T2.
Una-oifihti mole of “013“‘fiir1513 SQTmftm133 (eiLL or

the whole oil ox a 63*woL\3t) was olchoeii - 3503 cc

' .q. ‘- ‘ ‘2 :'L- .-- . ‘U ' "' "\ J', .3» s. *14‘."’" -.
flLox equLwtoa WLLL a m- urn MiC'll :tirrnr, Luosxnuctor 33d

553
H.)
L?
a
" 1
'"f‘
9
2.4
n!-
{D
u)
i
L')
L.»
«9
‘

reflax coidon-or 331 sieroi for
eighth mole of formalfiofiyfio (13 co formalin) and 1 co of
1% sodium hyflroxifie were azdofi a:;d the t3593fiaturo raised
to 83-920 until tl;o reaction :33 caovlLto. Rho; no
modLifior was used the ol,uorizaolo substance 3: the
formaldehyde Lore equivol cola. r in qkoztitv. The sodizm
hydroxide catalyst was a l} 3 Jlntion and the volxmo afiood
eqLailed 11: of tb e VOI’L‘TLB of formalin use-fl. 13138:; the

rEactio; mixture ageimefi a taffy~liko apvoat use and ad-
hered to the rototiufi siirring Too 731‘3r tha; the
of th3 flank gentle suction was applied to remo'o any ex-
cess water. Ehe deb d prodtrot 333 then poured into
time and baked at 500 for 56 hours. all hoot was finolied
by an oil bath rai} Ler {Len a blrzzor to prevent sectional
overheating and scorching.

In cases 3b. ere pizonol was used as the re »odif ier the

amount of fornalfobyro 33333 was HQWLl to iho total

26

I

number of melee of the polymorizable substance and the
phenol. For instance 1/4 mole of formaldehyde was added
to a mixture of l/B mole of oil and 1/8 mole of phenol.
The catalyst as mentioned above would be 10% of the volume
of formalin or 2 e.o.

This policy differed, however, when linseed oil was
used as the modifier in that the amount of formaldehyde
used was equivalent only to the molecular quantity of
‘he polymerizable substance regardless of the qwantity
of the linseed oil added.

The end point of the cardanol, formaldehyde reaction
differed from the one described above in that instead of
becoming taffy-llke, it became solid and asanmed the ap-
pearance of curd.

The following reactions were carried out with all
four groups. The quantity of the polymerizable sob-
eiance was kept constant (1/8 mole) while the modifiers,
polymerizing agents, catalysts and conditions were varied.
he quantities will be given but they are taboleted in

the tables, pages 35-38.

Q Q,flO

:vO": ' 3: 1935‘s

‘ . ‘ I
14.1.);338u ‘Jil
'j’) ‘,l 3. .f .. 1‘ -.. .i.
Joiymorizine Awente
T‘ .9 .31: ”Y“ -1
3.e;ot~ltJ3Lwfiio

. 3-. ... c" .. ‘ . .. ‘ .
£5.00 n 211! m; 137033

V
ASCWJ‘"”

27

Chloracetone
Catalysts
Exodi1m,Hydro ide (1?? )
Hydrochloric Acid (1%)
Acetic Acid (1”)

Tie only reaction carried out differently from the
above procedure was 1hat of anacardic acid, urea and
fozfldlethyde.

ere-1iuntn hole of anneareic acid add on»~eig?th
mole of urea were placed in a flask similar to ”he above.
inc mixture was stirred and heated for 91 hours. One-
quarter role (19 cc} of formalinnvde and the proper

on; it of caialret were added and the reaction firefight
to the usual end point. The dehydrated product nee al-
lowed to bake at 50' for the usual 36 hours.: 1116 rec

‘

action was 1130 carzi1d Cit wiil one-1* lid mole of

h- A. .«.~

‘

ea 13, one—e ixtecz 1t?; 1:2: 3 of urea and threeaeixieothc mole

of 1orra aldehyde.

28

E. Stabilization of Color.

The resins formed from the whole oil, anacardio acid
and anacardol turned black on standing in air while those
from cardanol turned from red to black and back to red.
It was thought at first that this was due to 1rpnxities
in the oil. %sins, however, obtairod from purifio d 011
turned black also, so another solution such as 01139 ti on
of the unpolymerized double bonds was turned to. An at-
tortt t3 iflhitit this oxifiatlou was mafia by aduixf an

.. . . . 01 .0 . . ' 1-"?! -1. 2-1!- " ., (*1, .0 -
avfi-ou1mlut W luLLn1Lor 1mm; as LzquvliflJuuo 1h1s did

not prevent the blackening, but stimzleted it and the
resin; obtained cgrkerod Hora q ickly 11am thorn with no

hyfivoquirono in them.

f‘t'ill urq-n‘r-t .g (\r‘t 413‘. 1'}

r3?

'1 ’ 1A, - ‘ 9 “Us ‘1
Mm! t.-.nt time do 1.113 Quads

were 1~eg'_-2o:2.’::1h11 for {3:112 2."1:317:12.foray, afid.:?_tio...:o 11.221 and

- 2‘ f“ '-‘¢ “ ' ‘9 ‘ 2' “ TN. *2 71",” “law <v ' r ' ' a- n. 7 ‘1’ -¢. ‘
hjnrobo; 193 111ec per». wry :u 1.3 an; 11110“ 1110 an
“.1", ,2 s r u 't- 1‘ , " ‘8 v' .‘ ". “‘ 1 " ' fi‘. . g g 1 '9 q l. ,
an yjfic a 101,11»1 on Cmfinég “Ll $1111 011 1a *FOQ?OPy1
1— c .. .. .4. .14 ’2» , :2 ‘-- .. can -
alcouol. Tie graducc op 11Hoo 111 r C1161 l cantoration

L. ’ . 1.”. -- 8 1 .. -- .,- a 1 a .
of tga sclvent oc111211zod mar; ra,1dly alo tua r12-n

, I " w ., 1,. .~ FTP” . '9 , :9. ., p. .1

nbfgxnod 3139 11110101. 4m" uguxumoo cgloriuo 1210 iact
.,. . ., . . 11..., :3”. M. .M "..,1 ,2 '3 UL

123m; 6.13.313 1.33.9.1 gave: 23.; 1.5.0111; 0,11011113 a,» a low

1.4
{‘1
‘- o
’3;
.I-t
a
(It
29
{“4
C 1
pi.
0
,4-
p

0'
(D

tsmp¢ratur9 shoring 1bat the KC
muble bond 1: 1;; probuhly only dissolved 1; the oil.
V7111“ forati 1:, 2111:: (32111111211 0 at in the apparatus
0:1 ya; 9 31 w:;L xvlccular hyjrogon in the yr,: 9136 of

,.._ ,...‘. ,‘3 , , x. 4 a
groicnuteu Cr wluc%;s #013 octalned.

t"

T“IgltW'H‘”? C: Cfdzfi . :0 h

This failvre 119 h°r% 3-y due to tact fact that no heat

621

could be applied to the apparatus and only very little

pressure.

Preparation of the Platinum Catalyst.

Three and one-half grams of platinum chloride were
placed in a porcelain casserole and 10 cc. of water and
35 g. of C. P. sodium nitrate were added. The mixture
was evaporated to dryness over a Bunsen burner and stir-
red continuously. The temperature was raised to 350°~
570°C in about ten minutes. Fusion took place and brown
fumes were evolved while the precipitation or brown
platinum.oxide gradually took place. During this Opera-
tion foaming occurred, which.was controlled by more vig-
orous stirring and an additional burner directed at the
tap of the casserole. At the end of 15 minutes, when the
temperature had reached 400°C, the evolution of gas
greatly decreased. The temperature was held at this
point until the evolution of gas had ceased and then
heated for thirty minutes longer. he mass was allowed
to cool and was then washed uith.water. The washings
were stepped as soon as the precipitated began to become

colloidal.
Procedure for Use of Apparatus Used.

Ten grams of oil, .2 g. of platinum oxide and 200 c.c.
of 95% ethyl alcohol were placed in the reaction bottle.

The mercury bulb was placed at position A with.st0pcock D

$0

‘

closed and E Oped to cvacvate i
ogeaod add an eves flow of hrfiroyen obteiaefi throw)? the

hcakor of water. 3 and C were oaosod and E Opened to al-
low the R?i?0f€fl to fill the Staten. after the evacuatioo

I.

‘ . .133 ., . N A 4 g ~ 3 o:- .. _ b ‘ Q :1... — '- -~ ._. . fi ‘ a... . 7'.-
aid c argllg was rcgaaced several tide to lMS~P9 a agateo

‘0 ”W

'. "" P'\ . O. i'? “ $"'. A' ’5‘. :‘fl 5'. ’
reads a id D were closed, the hydrogen

.‘

I

.- . .,. .8 a, up
free fro: ELF, SL3:

_ u a w e - .a a “a a a
source amnt ofi a.d tno norcwry reservoir place. Ev Loci-

.3

.2 1': .3 “.1 *4... . ‘3' tar...= -... - ,.;'_ 3
tlfil m tfi €2Vfi a 31;“.u §T9333V90 #399 “IV!” E‘ L43 *lrou

a‘

. (‘1.

.72.. P“" I A!— ,-\_I.4~ + up v ,' __ fls- ‘- “1“.‘1 (x 5. ‘15 ‘1 I v". ‘u‘ g"? x ,- ‘3 ,‘ /'_ .1 t I 9 ‘
to tr? 9,3 m. at .relcs L i tyrraze ezm noC¢9t* e ace

}Jo
! 4.

a qwantitetivc oddities conld be made.

i.

“I '3 . . R, 1 -. \ u ‘.‘ o .7. .- 7 a . .mq- _- - . - ... . ' ‘ -‘ i
colors Ck&Tflu: 1’0 reactwr txo a stun cad Looted for

"- v. 2- -~. .* -. 'z r -- .3 M in... ' “a ' .--r i' '5 ’ ...-..'. M. w...- «m ' " .1
"UCJ "L “8 1-7 31' fl .1.- L Li; f", “I a. '3. '.' a} 3. fl "3'1 .- 5:, a m.) A" M." "u 7‘ I ’i-f' -7~ a: <5» ’51-‘15
' t' \u. t: ... s.- L
up". LI” .- ,u. .~- -, ? .‘VI- (3., :1 (a; ’-j~u‘ ‘ «-' :\0,0”> (9-, 1 ‘Q‘W‘I‘I,
.3- }? L‘ -’-‘ H‘. a: 2F (3.57;.- o,‘ Q -- ‘ -- .i ‘ O : £31."; 1- t. L, a (a ‘1: ,‘r. CL ’
m __ A ” — —v-
J.) 1 M'J. ‘ AL‘x i i j 3 .1

 

 

 

 

 

 

 

 

ix [‘1']

 

 

1

73.2? ‘v
3'2) 1":er l
‘ 2 1.1.7277
+11 Tv‘m':
1

If].

 

 

 

 

 

 

 

' ) ‘YI'I‘I-l

l._J
K.)
-—+
- 4

\J
1"]

 

 

\J

—1

4
\4

us, .-
}r1~__

"1
'4

 

 

 

 

 

 

 

 

_. +
: 1 t:
E :- L21
E -7“ D AC

 

 

 

.‘llmu'lflll'lllll'lll'l'l UUII'HHLULIH'Il'H'Irr'IW

>
I I I I
Will:

 

 

 

DJ. 7 7 13.7.“; 1'! . PL J'ETACTC'R

9“
70

“2: 19:3.

3' ‘
at. .\

””3 c

k

4
II in

t on
B1.) 'A.’

r's'.
u

3‘.

3r

itiena

mar—'10???
OJ ‘f- '

I
u.’

1". .
=;_-{’ O

O
.
o

:e fellow

r._ a.

resins ’

.9
"V

I

~
.A .

I t
1" U‘

out 0'

1

r'tk”. {‘
_ u _ _ 1.;

1" 1‘“
(5:

"fl
..

0.
1
u-

2 ,

a...”
P
3
I...
) ..
.,....
a f.
o\| p

“I
;'§ 3
. n—

l

‘1
r
A.

l

..
X
A~K4~

' v

&

~acad

'7

"\M 1)..

)“VT‘F'
Ln”

ta

.‘1 A.
.3 t0 LC

u; .
6‘ ‘

1‘
p

'\

raw-1 ‘7‘ r?

war-r

‘r‘i'ffl
a a" E \J 0

0 a...

‘1
.54-

.- d h—O’-<‘} '

va

1

Q

S

vation

“11cm
'5‘.‘

' a

‘ '7

'1 'v ..
1.1.2111. 13.1.

3.:

(7' v ‘
’3 ~ 7.

I

'.‘\ '1”;
32%.? a :i‘

u
‘ \
a

- C117 8

1
pa.-

1

3.3»

v.

.u...-! «us-«L

“a "1

v3
-J ’

at

.v *- 'A 1
“mag-Q}?

.ect of c

3,.(‘0
.1

r
‘
‘
up

4 :75?
i'r-DU. ‘2...

”at.“
_.

orfiafiian TR.

..-‘ .C;
.a a.)

1.

H‘

17.7 'i 7. + '

\ )t. ..- '..’ -1

a .

i- ‘3‘,
. HI

. a ~ '3 -3 ..
‘f' . '. a In
{3,4 I I J :D-J.‘ M ; (I? '3! .5..-

'3’)
;- O

.3

“'1‘
C
u.-

CO

.

emeral brow.

{0

g .

I
I'

~‘ 1
J {un-

—.-.. :
{.L'ul.

".2" '20
.. "-

- J

\v k» -

7..

._--., 73 ‘
u - h.“

‘3
7!

10‘
l 3-.”

n
u

n N"
If}.

,5

0 .~. ‘
I L], E": L. 3 v I :'
.u- u. «at. a- . 4- . a»

.
.40 ." .

¢.

.3
J'

34v.
&.v ’0-

'1
I

«1 naw
“‘5 \ ‘;.v.1..-

u-

pOTSuW-

~

' I

r-

a

“-1.3"
. u < l,-I
;,\ u

_'
~ud

.5.

In
t
1

I.»

fish
<3

1‘6; .

4

I.

0‘7
‘d

M‘ i",
'_.L~'-..—a

'.
x,

I

t

. ‘ L03?

.1. 7
‘
L

3"
huh

3:)

Ta

5.

.“fl‘i
v- ‘7. ' -

3
t

fiotm+
V.-H-

37-13

if

p.

r)

A,
. .. ~..- «A

gun“

S

afifiavafv

‘n
«an,
‘4‘ -b at

E

(I.

A-
t \f

I“!
s.
‘

'7. f".

q
I

fie I

I

9 at

R V’

1‘1 ' 'f
‘.

was cut from a p

., +3. 1...»... 4~r~s°~ pm.» “1+
03 “He MUEUVu 33.0r P 333

1

,n

Txfiflfi .1.

.‘l .‘.
:3.uxt waifink o 7 “r:3
m.

:9 .
=—’O':."-4

33

- "I...”
£;\'-.'. ate: *‘m“"' l."C.L;-t ‘57.

-
Iv S v", 1".
- .

31333 of tie p“:3:

O TCA”t‘“-ar- 17"." .231:
1... inf-5.1. ~. ”g: 1. .33.. .
{4 fiwr‘-~1 .1 I." O .f. ”a a ‘1 .5.
"£- 1.;5 win-.i—u 5.. J. \9" 1.;- 553..

”*1

(A)

I.“ -‘ F 1
‘ m ~. r11- r‘.'-.~~;-rw—.-~; a" v- w. 1. t- - ,
I .5... -3“; g9...) 43 v ‘u‘ \- 3.‘ “3L3. N .3.- v-4» :1 Kati .3'

. . 71 7.. ' .. . _ .' * -€ "1'.
'b ‘- f r . Ff. , QC ' _. v.4 .' x I I n
-s 333 3323 31331j 33Vi333. 146
'1". .‘ Q.»’u-.--—. .‘W '- 0; :4 .1... -~ ‘I... ..
at 133 Lb 53:32.39 3» 3,353 tie

J's-«a 1“"

Min \
(I “9" or“

s)

857”" an“
'W-fi b.)\l

-3
8-; .‘u.

"- . ' ‘ . ’3 h V
" ’“ "P " 3 "t’ ”‘2 WP'J' "3Q Wr’flfi') "R': 4’. Km '\ r " ‘ - “ ' “"o- -L 3 3 '~: 1!,
s", In: 1'.” L.~:).u. .1 ‘0' £113 ‘0' '~. .‘ 1:» ‘.;a - a j— .. .‘ -.}‘ 5 ifflk'fli k5 -.' -1. la-‘ .~~h—- - ~ '1‘ J 7. I k» .LJ..’-30
-- ». I" ., 's
‘ ”3‘.“ . r. .3 ".~‘;“ , :17 . . 7" ,,. A. . ‘11.,» --. 4“ -..;.. .3 i -9" yrv‘r , -..,,‘
13‘. K..- "- _: I 4.1.5: 5‘ :13 l ‘v- s ‘ \1 :31, ”£3. 1. -KJ 9"}.1. .. t. Om . it? r ~ '9“ an. '? «1.: U:
. n w .. - -' 3- £3 . n. 3 ‘ m "7 .' .3 '2'. A n 3" 't , .“""".- ’7 W‘ '. "- “ F "'1" A it
t7 ' L'1 -\l L‘?)C ‘s—U-sl3 O‘- I- -~"~’ .‘of s~;.a1v‘l‘;;.v ‘4: .10 t} 11-. -. ’vu'i’LI} b.-.u I x . . 0 1"")
‘ '- ‘ 1' 5' ‘5 ' '.'
q -' u y w w. 4- ~.“ y‘. r \ ..‘ .1 I.- 44“" I}. r) :x, a. - ~ 1 11‘. '- ~o~~ \ 3-. ”s. p’ “0-9 ;¢~_._-‘1
"o” ‘ w 11 1,1,} t} 3’1.‘ q S 5.51")...» 1 ’1‘ .‘1 ‘EO. 4:— “7r . 7.: A3$51 K'l‘~»:.§.i b'b L7; I. 'w W».- 0"
~ g u. ’ y‘ a . n 3.. y. . Cu‘ a 4.
9" - ~ I .5”) _ 1' "'1" ° " « nwv- “\ " ’3 ' ‘_ " " -. 5'.) >35“ "it .' '.'!.o ‘ r: ""1 . I 9'“!
\dibol Z.‘.*..‘.~_ awra, a L...'.1..'. u. \ehl-n'y? .LuLSJJ. L: 'K). 8....4 Aau...v $4.'..“_..L¢_\.)Ld0
"‘1 .. -' J- a. . . 1.. u . .- .-. 9 .2. 4.. ..‘ J 7 -4 ~ .. :2 .. -
2' ¥ ‘3 :' r. r‘ , "H ‘ - ' .w- .- . 4:1 4 3" '3 "a 5'3, * ,1 - 1 ‘5 ~ ..
.4 _.‘\,I A: 1.: .ngfo ‘1 .' .L,‘.. ‘n u (L x.‘ i.- -$‘t 1.! -’ L. '. ‘J In. 9.: W-..L.L!\ - 1’2. 14 .IU .1. an .32 ”.3- 1 {n C” G
\—
4- ,. 3', \ a .1 3 ‘1’” 4'3“ f5 _ 7" ~;- 7" ;’} ‘ 3 ~ 0 J" .1 - .5. I. = «E '- ~ . I" '3 t a C7 3 «a V.
L .1 vi}. 3 .1} :4"; (State C3 a» ‘. . ..-.. -33}. 1.1.0.» ...- J. .s 3“; . :J .z 3.-.. ;.'~ 1..- ~..=.. w 3 0"
v” .7. «3- r. ~ 3 ' { '3 l (‘07:... w: 7 "*7 5‘ :1 i F-g‘n .ez- ‘7 m w: as”: v“. 37313 "‘ "-5“ . ‘ ‘ 1n»?
1" ‘ig; (117' . {5' ‘\)J-. C‘: .I‘s ~ 4'. 3 he ‘- I JrL-b-‘A 7' In» to: ".\J ,u'b I“-'S "(-'.- U U-J kit-A- - ‘4‘“.
Q 9133
f. O 'r 3
... . - 6
-, Q . '1‘”. T" '3- ": 4 “a 4‘." y " ‘-«‘- 0"“. f5 '7 ”'7. 1".“ t ." “~ 11’3”: . " T V 1‘ {in} .9 " ‘LY-‘rfi
l J.- :« I: .l j. . 9L ( (I ' L I ‘1: .- ‘ - 3 K "5‘. ' K . ~ ' . -7 \ C "I. 3/ \. n. .. -4 Vl‘ “ I d .V J‘ WI! ‘. .- — . . 1- ‘ I l--‘ 'M
'1 w ‘1. .. .... .. 3 1 1‘. . . ; 9‘ "i" l
l -. v ‘ ..'~ 3 '- . v -1 ' - ‘0 ‘W ‘ I " . , n r 4" ‘ I“. . ',‘
C . ‘ a. C‘ f 1'5. .'.(3 4?: ‘1: lg. “.1 i)" ‘(‘ 5‘ . a. 3—}- ...‘o 7 ..‘.7_ [(3 3 l o ,, ~ '1; i. "3.2". \i J.- in. . ‘ :.;:.3 u.
_ q " I) . *- ..... .n. .. '7 u a, a ' - ‘ w .7». 1 ‘ n '. r; .7 u nL . ' any . -..-- lha"
~~ . ~, 1w. . ,. , .. .1_-; n . ., 1"! '3‘ .fl ,y‘t‘IN “"53
t)‘ :»J i I'ahfw‘.’ 12;: ii inn-A {4 a ‘L H-v‘ 1L. ‘- .L - :- ~’ I . at" A ..-C ¢IO( '7 .1-.. )vdhi 3:" sh. ~ 3." t. .1 V uA «1 f V
q ._ un-Q
r.'} m 4- ‘ ,«. 1.... in ' * "1 -. 2‘5 Vat-w} e.- c; n , 'r'g‘. -{'1 2:: 1 *7373“ ('1 “-"V' 1 '1 .‘.- -- H " n
il’fii‘a‘e-vg 0 £-.? {5‘ l _....n‘-' L ‘ ’ Lt 3‘v ‘7‘“ lg! - V" .r‘-’ '- ' . ‘ III/'- ’1 '5. '5' ‘7‘"
“ 3' " ‘ .“ .1 .~ ~‘ ‘7 3 ‘ '3: .v- ‘3 A , - a" Q! . ’-
. -H . , -., ., .. _\ Lt~r~x v . .3 3. J. . yum
FYIi‘) {3 1‘2. 3‘53? :31 '1'. 11'! A '.J.( . ; t ‘a I 3 \ .7 .3..’ a Ly r .- ‘ ‘ .. X 5 .3 ~./ .; 3. .' .-' 1.1:. (. sa-u- 0;:
A: - ‘ f~~‘~~ . . 6.7-” I—‘I ~.~.. 7'
-19--" $;’?\g 35:.- l,:— d"; L-. J-Il'fif-PI 1:..- I ‘2‘; C.
I . “ f .
~ . Ir-e' “Ha." (‘1 ‘ 4 "“ ~ Rk ’4 :2 - f! ""3 a" ‘E‘ ' "I ”V ’ '5" .’.‘.« “ 4’ A " "‘\ \ 'ét
11:1 c a f: 5 S u! Kkfl _ . -4. 4""? .v 1I" ;~b-I 9 1 c -. .. An '..1- ~4' 3."an ‘1. 14 ‘-‘ h J. ‘3 \l (III. a‘
_ '9 . , . ,. .~ :“ 4-_ I .- - , p .9 - rv‘ .0 1 , 7‘ '0 .7 I. 7| . [fl ‘~ t x,
“TCH s t .. :f.‘ I; €18q5:—-4‘5 ' ”3'; ‘ £- '2‘ I LC ‘L‘ ‘ .1.» Iv 1; . «kl. I§J kn) .24,- 4' m ' ‘ ’ I'd‘L-L 'u’L‘ I In}. ‘ ‘ . ‘~' -'- 1.9
_- _. .- I _ .t .q 5 7"," $ .- “a .1 Try) ‘ h" ‘ 7‘ -: T. 3.). 1.2.. “x; {7"‘Tfldzb (\«1. §.1‘13 $5251....
. . '$ ). J T? v‘ T“! I L ‘A_\’ t‘ ‘...' . ;.‘ ., ‘..‘« \(l .' " 1 ' 9. \- J K, \ .' 1 ,. M. n . I}! J u
5 1| .1
an.»~a 1v» 3* wvah33‘WT3‘v ‘ EerL._;.
‘ ' . v! LLL-‘J‘J c a... I. 4 t ' L‘ 9 j; k ’3‘ V 5 " “ ‘.‘ f‘

‘0" "

1 '11_F.- .‘w #fl.‘

’1 <‘ “"1". ’4

1“ n4‘1fi7fl
I} C .1 9-“ .L\’_\

1510

r" '-'3 v . .3 ? n a"! 13> c- 3 *-
\—tw-‘5‘-' abALKunl‘I'A. ‘. .5. 1 '31 ‘f ~:—:-v
. 4 . r -$ ~~ 1.", ‘-
T‘ V‘ . - fl - I “P ‘1‘"
3..» km: 4.33: \ 4-3..\.v

‘
9 3’ W
‘5'

f: «w; ‘3 .,, A. f ‘ .. .. 7 . , ,3. n .3 1- «a». » m g

. «L—o-uu I ‘u ‘J » 1 - D c'v- u - y: :u L) c ' K L, 7..- a 1' ‘» DK :7 '
_ '5‘ —‘ ‘ \ '3 "3» - I. was 9 -1 y; w ‘. 3 F V.

a. \hi ‘5" .1 L __L‘.‘ a" ‘ ;-_,.‘ ‘3 A. _', . #3.. A-‘ $3.. . 3 if .. L. J

.‘ .9
.1 .‘.
.... .... r-
«‘L- y—d

u; '-- .

u.
3-_'-~-r’.-v

é‘ ._ s. .r- a ‘--

{

 

r' s. '-
33s; *

.
j a . .
-. ’ . uJa;¢. -.- o \ ...~. IV‘- 7 ~ ,~‘- u. \'..n‘- .4

. F.‘
(:3 7‘25" a, g 1‘ W, A r “£va W1 7 v? 2:" a -_-:. n1 3"" ‘ r.
0-! ' 5' u.~. twice: ‘3. . ‘. ‘¢-.' $ b n . - ‘-

t? to

i; 3 11:16.9

rd).
U3
7'1
, ,:

fifiAfiT 1. - haaotien a: (m whfiw fiflt4$h®31 Liquid

w _ - w .. .A... . A. ._
"“ J- “ 4.

¢ 4 T Y "W“; .ammunt ' “W019. —
Wrama ‘ WPfiWfi! ”GIVm. 3 fifinfit

5 -
§

1 “4"} "$."1 $43~gf~fiza§ ‘CM-f' ..L 3.4; ‘r ”a
g “9...“... ..:m:m~mw~ pWWW .‘ " ' . ’
f .

1

1

   

  

 

 

 
 

Whym we

g
F

 

 

h
~

A i
.,‘~a

1“ M“

 

I- -,,7._.,«..,_._,.«, A A- . _... A.‘

 

' 1. 520?: ' “ " ‘
5-1/3 “ganja A $5 $1 2 a E?§fi ..3.143

w.— ‘

i .
t . ,, L .

3- i 5'33} figzifi‘ , .. aim Sit-9w“ _ m. a- a-
1

‘V
,.
o
J
L
and
u”?
.M’V
i
3

~
5
1
i
.Vu““"l -.w~d}L‘v ' now-«qua 45‘ -
I

I‘,"

l
J
1
Q
1
F
ll
I
p
b

 

 

 

 

2‘ .- 7— "cm-ran...qu
‘2’
3‘

no-avw‘ .hr )1 u “0“» Mia-n+mu- 'W" y‘firum‘..w; h. n- ...¢,..,r.,gg...“,g WM mea.‘luuu¢o4-.
’

 

i “W H”. _ , , 1 fififigaat Lanai
m“, LN ,£_h . i : ~ in .w~: : 3—1/& 71 v: wr~w a
u» _ ,, "a.“ murun.me-m«q}ptunmwm Mm“. L.,,,“.m,- __ __ “.1.W . . ' ' 'I “it! ”POW“ 4 gang? {31"} .3 . 14k?
* 1 4A+emVlw
- - 5 fiubtast ~nat 1 -
1

i
3
i
I
i
i
3
a) 1" 4k~ «‘4
E
‘J
7
3
3
F
M
l’
. i .
1 Q
a:
L,
{K
x
p
k
g
a»
5“)
C!
{J
haul
.
g.»
H
Le

- ~-\, .cn - ' aim“ may 4- .v» .u-n‘ A

 

 

4...,w‘ ‘F‘ur—V‘o \
l

 

 

i
1
i

 

"I 04 - . ' 0 '
.M. . , ~~ ~~ n: ‘~wwwr ~ 5/ ‘wx - , ,
. m... '2 at: ‘J’Amw "; “““‘“ {a ‘ 1‘ A“ T i m... - - _ ..' ' v‘ ‘— M J? - “E. E: .L 4.". fl _ _ '3‘; '7 3 ‘3 “1)er 1 d 1 3):”: .1 . 134%

 

 

 

 

 

4
u ‘. mv-‘3'&AW~:.A Pu...
. _ i
‘ "I ‘

 

 

 

 

 

 

 

 

 
 
 
 
   
 
   
 
 

 

 

 

 

7 1 1
I: ‘d . , .. _ ‘3' .5 133”!)‘1; 5: $3!
«- I~ r:~¢.n #0 a» an i: I." (l I? it A: I: {’2 1 1" b ‘1'”) f j ‘1 3- . ’7‘ I g 11"; 1‘ ) 1 I‘H. Lit; - {0/4 ‘ 1”)“ ‘ 4p r " ‘ ' a. Q t I? ' ‘ ~,
*1 0: u ”MT Man-J v m- ‘O-wfivénn w '.*<- ‘ n ib—b- ~~M¢oww~qv~wlww ':%~M.V.<‘:l 1"}, 3w--. «.vr.’ w. 4‘5"- -w- v - _,-.-_- -- , _, ,hwflr“.,.;.,~..fl, H. . i W . I t) . I _‘ M {I k 5:) IQ; (3? Wk; 5 ‘5' :‘j bikrty 1 . l. 5‘0: 5
; 't‘ j _ b 1 WV "‘ W .. w. mu..-vmu.wf.w.*..wu.,ww.. .‘hw.m "W'M '
I, .‘ _ 1‘. ' \j 1 Q . K
w ~ ,, ,- “mea M_ A _ “.3 1% H x m A/4 } 2“ .. L. “N .w
M»- I J § 3 In . - m». , H»- w w ‘ 4. ¢ , A - - A . $3324 w..... .. . ’ , '__'.m.~“w\ 3.- . ’Vg 1.9 J...“l 0w ._ wngwjmu.‘ MM ‘m‘;:é w..- “a“? ‘374 ~. 2 __ 4:] “‘43:: Q3.) ‘1 ~. 1 $3.9
] . ? i g p , v W W i -, { - 1 firrtg t ' " '~“w-*
. . . » * . ?3 ? r * wuswr - ‘ ~ , m g _ _ w Mm '8 ,
i '_‘j1';;;mqmgmqg*bgm~md*mwlmmwww .. 5:131"; u o -w W __ w A ‘ _. m 4 n] O I w; i 0 ‘fi‘ #2 i)‘ 5/ 4 $33- 3322 1‘31".ij 1 l‘, 3!.“ , . g 1 Hg}? P

 

 

 

 

fi—‘v- n.

 

«n I}: raga qfl$>ii ' ~\:‘ .‘ . - . ' L ‘ .. , _ Wm”

" 5'.
{q.* ‘ , té_ ‘ _ 911 iWar est

flufij. L 4w , 38 orawn 5

5-;14; 44 85 A 2
‘ Eightast

 

1
1

1.151

A

 

 

L IBVJ

Mn «1, vwwmflk‘h

A ».Mm.*-..‘ D444”. .f.'i’.;l,i .u - mutt: ‘ ..- ‘vmr‘ ‘hflt LO-Ifi-wrwn» mw- \ ‘1, ~ - unwanww

 

~+Pmn< “9-4 -..w .;

 

 

  

 

 

 

 

 
 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

\
I
m Juv- raga-«w kw» Lh¢w \ ”'W‘ ”-0 4.. fikO“. yaw t” w
”'4“ A H." up ‘mmm in- m' 1mwugf4fvm (’M W r (W
'i V .
{ fl 3 a 3 t
w. " . :- . 7“ .
i 3 V ? fl q a . , L War K 1
,ug M L L”. j , n g 1* *1g 1H ‘ v n W
M. . w v a .- ’ . ' Kym-m“ ‘ --‘-- ~ I. I, ' I. ' H I ‘. ~~
1; ; I; I? v “A , J 3 no no , firm ‘ - w an o In no
5 I‘ ’ V ‘ ...
Vf :- Z '1 ' N, ' ,A $ t I
a L. 1 J a x ,t . ' W a
. lav-r1 ‘- r - 3... ~ ‘ Q} «4-... . . -~ “ w '.-.'., . MM gy-ur q-V ins-urn .IW‘HW 4&1» 4..“ch “mg-musfiypu—J‘ ”WW um; . - ‘. n - ‘
l ‘ J k A“ m-w— A ~ - u ‘ w -
g i y "-..- w. - "' ‘ “ ‘5—
_ A" . ‘
, z i“ '5 5‘ fl“) § ‘3 l V
.- I -' I. ‘H
no rugw L Jaw-1n -------- m. vat—M \ . M | aw _ ‘ ‘ 1 x M
3‘ Wm- vm- ...._ w. 1?. «4n»- wan-awn... ...\ '____ . Lu.“ W _ (“Kl ..-—— ~. ~ ‘ . *’ L -- ' *~
V _Y ' W W rw "NLMI
9-. g ‘
“' i "” ~~ . xV;xw $.E~ { ‘ q» ’ -
‘ nan 4v \fl'O‘-“ sum-mu» 9n“ AN w“ '— ~11» ..“ - am -A' W t ‘. "I * l. ”u ‘3 V ‘ 3 W '
M“ m ‘M P” ' '4’ ”"" ww-dr'we-o- "' ““3“ -‘ k w A.w~:.m; ‘J .I - ~ - - . ~ - v ‘ ‘fi .-
m, 1 ,_.
'. V ‘ r q i
.‘ m «u I m an 5. f5 :5 t ‘1" ’ 3 3 ""5 ' 7.
("aw-n v.4, 4—4 Run-m.- m-Muw.1¢wowa V‘M" I‘ -' :&¢.A.v~qc*-. .. :\ ,Ar—u MD “Hakka-«Anal who ‘ k m - ‘1‘: OJ . H ‘ h" . “3 (if) Q ‘
‘ 7 yr" _ ‘ .. ._. __ an d- a- - w n 10 H
WY ~13? ‘ - “”“w‘” ~- ‘
\..~ a.” a . .: m. ~o’v- A
g ‘‘‘‘ ”4.. *T‘Wmvhdmg m". ‘1fo f"; ...,... m A r ..- A.» l :- cn i no u u:- up 0 u
. w V ‘I -
”and a «1.» «we- ”07‘- jnb .m .- .- . ... -- r- \- ‘ - . ‘~ ' “ ' ' ' ’
n- '9- ‘v' My.» .3an .. I'IA-‘W‘ -- «flirflflt n -yd_~.u...v-*n.w UM“ '».,{.4 rum-w.-. .'"“ 4"».- -<‘\‘-.- a. - , m-w‘fiyu- ‘ 1.35:6... Huh-4s. “.04 - "3.: 7 «mm- a, .- m,.'1 duh—v 'w-"v
. z = ”aft ' ' X
‘ r Wark 3

v-

I

_ 4 mnlifi 5a fifi brawn , finch 3750 1.178 }
1 iiuht 'd 1

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

_. g Yne“. Fri'Ti .C} i * ' M > -
ammwmmwmwwmwijww , y . éfifipd 3,10LAM WW , V A 1 3 . @9116 ue , 120 brgwn Rattle 3250_ A 1.150

 

 

 

 

 

  
        

     
 
   
     
        

 
  
   
    
     

   
  
       
        

! A 7"! mm.
c

0

      
    
     
     

   
     
    

  
   
      
    

  
     
          

  
   
   
 
 
   
        
 

   
  
 
    
      
  
  

     
  
   

  
     
  

   
    

I .
‘ Hrnmg Gramm. “olym. A amt Cat. Time Phyaical fixida~ Flow
Acid moflifier Tofi. Acemt cc. ”atal at we. hrs atate Color tion 230 C.

 

      
       
  

  
   

  

 
 
  

   
  

 

Moat

 
 

 
  

 
 

 
  

    

     

   

  
 

L. A N30}! 420 m 3.1m Brown 11 mm
L 40 9’ fl 2

  
  
 

 
 

n

 

5

 
  

fl

 
 
  
 

   
 

Moat
rubbe

  

filack 3

  
  
  
 

2

 
   
  

  
  
 
 
 

 

as
ru bar

rown
b we

 
  
 

1

  
    
   
  

  
 
  
  

'i'immwd

  

L1 uid

Sandy
solid
wan y
011d
4!}
mare
0 M
less 1

Brown

Dark
tan

 
 
 
  

moat
solid
#33
80

    
   
 
  
   

 
  
    
   
    

T?
~rfia

   
  
   

  
 
  
    

    

tan d

   
 
  

    

  
    

   

  
  

  
   

  
  

Elack 11 t 1160

 

     

  
 
 

      

Tan liwht 41000

  
 

 
 
  

 
  

wast
I1 aid aolid 3

       

flpctflfifi

.. L-
Ju'AYEpCHNE:

 

 

 

 

 

.' _ . . 4..
- - W . v w n—rw

S

§ ,
f a» ‘l .
‘ P 33. 17-: :7‘.‘

 
   
   
   
  
  
  
    

  
 
  
 
  
    
 

    
  
    
  
 

   
  
  

A $10.31???
f-‘f :5"! n t
”"5 0 ¢

   
 
 
   
  
  

  
  
 
 
   

   
   
 

@rfiwa
fiarfisnfial

‘O‘M .h;

View

1693-.

prm‘irqi 4,331 I
t. i 031

Santa

  

“*1 A:
'2 (\H’J .

    

C”; "‘ ‘3 f” 3'. ~71?!"

    

 
 

£1 mid light

  
  

..

   
   

Granular

 
   

H ‘3 :‘(I 'a.
istJx)
m

         

Granular 33D0* 8300

   

   

Fla u?&0

 

  

filafi

 
  
 
 

    

W m

firsnmlnr

 
  

Urannlmr

 
  
    

Granular

 
 

floft

 
   
   

z u .
:Emwamm my

 
   
 

 
  
 

 
  

{jg fffirj; L1 1;. {i

L .
Tao-want“. u—c‘ rmw‘www~

 
  
 
 

   

  
 

 

yeatmma L1 uifl

    
   
 

  

 

 

.- , ., . .._v_ ‘ ‘
.. ‘3»-......-,... “u y 2"! 34.312: in

'1 0* M
.... ‘.~.-" muvm‘uIOJ-‘W-VIM'IHTWLy

L1 mid

 
 

 

 

 

 

 

 

.1A?? 1%. - waaatiana a? Aaacfiraol

 

 

ffimgfirfiml ifiifi?

I i

5f

 

    

 

 

 

'3" hunt-PM-Ma-om-MWIN’Q-m~-I«l.\»¢'a-\ , _ ‘ .,

 

 
 
 

?hysieal

Eiquid

 

3t3t1\

 

axifia-

tian
. m

0-

 

 

 

$11ab1e
meta 3

‘

#11. .11
1»? 3. 1 M at
. . .- A _

 

 

 

 

 

 

 

 

‘filififiiéw'
lans

. . 11. ,r'xjht

MW”-

Havgess ‘

 

 

fiaqdang

 

 

 

 

 

 

' r '1 A F
' wardens
. w. 1 wv‘v- - A "’4,-)‘€~{“_19‘¢,A‘~,J- _. y In a

1,

 

<lQQQ ‘_

 

 

 

 

 

 

 

 

 

 

 

 

L-w- an 4»
'3
1.1

 

A ._1_A
w _ 1" __.._...
\
.
1!
k __ _
.w w fl
1
i

fitwn- Er,
._ a. M.

 

 

ficfitana

‘ fiiquid

fl.-

 

.._1

"5T _

1, C G? t 053$
___ M‘. w A“

 

 

 

 

 

 

 

 

{igugg

 

 

 

 

- w—v-v

 

 

 

 

 

 

.1
“1- fl-
’1.

 

 

 

 

 

 

1?}1gbla

sag-

 

 

VII. C NCLUSIOHS

A. Cashew Nut Shell Oil

1. C.H.S.O. will polymerize with formaldehyde alone,
but a catalyst speede the reaction considerably.

2. acreasing the amount of phenol slows the rea-
ction, causes a decrease in softening point and flow pl
prescnre but increases the melting point and improves
color stability.

5. Increasing the amount of linseed oil also slows

‘I‘L .

 

the reaction and causes a decrease in soften ng point, t
melting point, flow pressure and improves color stability.
4. C.N.S.O. will not polymerize with acetaldehyde,

acetone or chloracetonc.

B. Anacardic Acid

1. Anacardic acid cannot be polymerized with formal-
dehyde, acetaldehyde, acetone or chloracetone even in the
presence of a catalyst.

2. Addition of phenol gives a solid resin. Increas-
ing the amount of phenol increases the speed of reaction,
melting point, softening point and flow pressure. It
imparts a rubberyness to the product.

5. Addition of linseed oil has no effect.

4. Addition of urea gives a tacky resin. Increasing
amount of urea yields a resin lees tacky with an increased

melting point. softening point and flow pressure.

[IT-
\- 4’

C. C351: sLHL-‘Jl.

~11. 11v1' ;-‘ Ii. 0"" '- 9 1‘: . - "" ""r‘. r! :1 ‘1“ ,1’.
1. C" V 7 f7 ”J's. “fl“ "fivfi‘fi' 1’5“” 1'7 Wit“ P'.J?t..-i.L.1C.-."\,le

i .
Vs: 544.5... «‘4‘ co uu « ,_~ -- -- - p..- -1»! . -1.- .—-.~. ;‘

r.r~’4{4.‘~i-.V‘~+;I~p mhfira -.. ‘.'\'\ rgfibi:nt.r.

' 1 .. .
.L 4c. ...-._ dogs.) ,A‘.--'-- -.,1_ L c;

F T v .- - v {-“x - v .r f .- .0 ‘ ‘..‘~
'u c- A.‘ .'\ Pfi‘fisfi I‘ .- . a: . "we! 1‘ . '5 '3.
I... 8—..a1‘rT‘W k}... ~h... I I v'-~.‘-~l (J‘- . \' - ~.—t . n -n ~O~£II {.113 o u.) t! ’2 :- n-

. - 1!- 1~ . “3.. 1 1': -. 1.- 1‘1“-
c. I area" .“ t1“ a'o rt 0 lipeceq oil ;icae tie --
. : °,- - A . 1 4" .- 4-1:. - 4.4? 1- . '1 1 ..
3 V1150 u .'-='-.".'rT 3.1.51 \ 90%;?” 333 .I‘? S3) 3.. U3 liiaé‘: EVIL -‘1.:3 :— ‘1 J. . i

3 .. . :1 ‘17;- . -
:fif‘ . 1*; a 11.1 9 * 1")"
..' ’ l55.1”: :5“. o‘ { ’ I ‘:’o- C.) M _. .ml. .. .
Iv

 

I. I“; ‘1 1'3-" ‘ “ .. 7. l 'W . 9 1 - L p ‘: f1
. . means. a. - \ ---r§':1-.~1.1\1~;-:'\ 11 1.x- '1'! 1 1* 1 z :5.
‘4. V1-.." ..-:.c.:~ .1 .w ‘m’ i. . .L_. w» .L... 4.1.! L1.1._ x «L .LJ 4: .i. J.” '..i .11..- .‘s- ¢
1
F
O Q n A
r*“v~ .‘ ‘4' ~'--" *1 ‘51" ‘ \ ‘1‘ “ V‘ "\" c‘ #3 :‘1 114.1 " ‘1‘: K 5
O) u I Aa‘a )— LL-~< ‘ C 5' ‘3 3"“ we I.WH‘. ‘1'. P
T . . .. l ,- - 5 . .. 1 , ”- ? '1 , .-
1,. .fi‘ '30.. -.1--11.1v ,1,- .1 rs .rN’zfl.\~ q - “'14 ’1" 4' "- ‘3 ""'
t... . .A.,.5g .Lv‘c;:-\C.v‘u~a‘ ‘1 W- 1! .a‘. .C" ~’ ‘1 I. T”; 0". - n , .. .', ‘3. ..’_' .‘u,.1'_,' -‘3-

.I .I.— "‘0: .. ‘.?I 1 % ,.‘I.~.t.<-. q C; “1.9 (‘1‘). C “AI-.1 A“ C." . ‘. ? .1 ! I.- '90 I? '3 P911‘11-1
. — ~-A» vow-J» -.~ 5 an... -1 \. '--\

0'. _ '
.A‘J’. la» v’1\'~(LfixQC

1' h__ '1 o. g 1 v Q
g: - ’ 1.3.? '|1 . ne“ -. +1 t9\.\{'s_-'1 --. 1_ 3 3 .'\ ‘1 '0“ -. .‘N '
3- . COL- fsAad-u . Q3 ‘. ' S u‘ . 1..".4'. ._. {.4 iJU 1.; u. L-.— » 1 ah.— 1." .- LJ .' . o

0
+4
6
H
.0
3
r
‘1
id
'1-
I
,4
,1
\4
J
C
q
C
P:
”I.
~.‘
1.,
i
“I
»
.-
i
f}
f
I
. i
.‘4
L‘.‘
f -
’5
'3
1.;1
I

Q ~ 9.

_ 1w ”>1 111 u, )4 ..."\:-" :1." n ' 7 .‘1. 1.1-“: ' * "". "1 l i- " 1 f 1‘ . - 13;...‘1

‘- ti-LiJé {-19 Li! L4(.1K,J 54‘1145‘11" s.) ia.L\.- 1 1.).6 Lt'5cblhua ‘ LJ5J.L.;.-‘4 xgny‘g (max-.1; .1 A, x.‘ '4'.-
.4 ‘ ‘

«f- 54“ at . a g A ‘ - j A I I
' '_-’ a “CI. :3. 31: fl 4' fl"? '.‘ i) »‘r\ ‘1." I . 5 (g ,- - 1'3 '2. I3” ,‘ I, .,!’-‘.
3. 1%..--4 .‘D I .1 O.‘ :3.-- s- '-.' s ck." .1. g «4.. in! I \«g..t1.- Y. Li. k)‘..‘. 11...... kg») 1.....5 L. 1'5.) ~.- 3
.I.I ’1‘ Q 9 .' 5 9’“! e
I? A v. . '9 . AI, . ‘. | J" '. Ir) . 54’ '
1.: .. $531.2J0LL .-: .J\/J-J-..:J '£-5\.i Luvs/3.1 3 {If}; “no
‘ II.— v
I \ \ 1’ I. g , o _ c f. v 1 g - 1 I -
.1 I .... , '3i'."‘1‘—:‘, .3 1 ' ._ .4. ‘. «'1' ~J I..— .p... ‘ 5. .-a ..‘
‘I . JEN! dab 3A..)- kn~3m ." Id. .-0 -. £3.34 ~ .J.’t.41~.~ b) t. A. in... “V UL 4.8.uy- . Ir. ,A .l 9
nn04.'11') p31: p'1’ip-w 1 11L31n
a. l L m- uh I... a“; ux‘... 81.5... ‘w u .. ~u I
.- . n g . 5 . ‘
\II ‘ ._ y' ~ ‘ ‘ "I Ix" f‘ r. - q I, a. i 1" -I\ :\ -\ A..- [‘31-'- J P :9 t ',"‘ ‘O
"£JL- .4.» . «Lo-a J pne- fi‘.».& ‘21-. t.-..,'-J\. -4 ‘1' 1‘: U. . I ‘1‘ . v--- 4-. ~oq. -J IL‘J'.
‘ A . , .‘ r . .. a1 .\ O. a v :u
«1’1 ‘1 a" c {r ‘ 1., «wt . 1. 3 i 1’ '.‘ ' ‘x . v- 11) .P. ’~ F- '1‘) - i
‘1‘.» 1 ...,£. 5- x.‘ \1~{-'~n ~'t\. £'(. t’n « 1. t‘r j— \ ..‘. '1‘ ‘ v I r“ . ’ d n w | |L If; l.)

3 "i w '
‘ '5‘ Nu.- “Ci 3‘ . i --‘I ’
. ‘1 h.“ Q ~ \, V... ‘r .1

11-1-11
EAR;

I“:

,.
.d-.-

A

0
La.

C‘ 3
1.1.3.0

gear

111‘.

4.

:1

.9
.=;

rs
"—u 5: . 55

Q
n ”'9113 '1 vs
V '.&'...'—- h... “Lu”

k- -3 EL".

3qu 4“

" 5.’C1

Q, ”#1 '. A.
I; Q’ ['7

.m n
.- .0 VJ.

s

O
T‘ Q a. ‘3'} r.
41-- .5'... ‘--‘ a .'.

f):

d.||

#4:! lo, II V.

. X
r .. Fl.
3
h. 3.
.31
.1. 1 1 a.
C 1 w
\u. n \. a
l. 5 .1: _
a _
CV...“ W...“
a. k
’
1L .. w
n”. .3
u .. at.”
\ I
(.5 l..\
.0 a h
.5.
W n I;
5 .
0H.” m... x
. t
f... I

.‘ A
‘ .. \J

J— ”
[4.

a... 3
-. 4,. ..
fl.“ 1.
2.... n;
1%!» .7 b
n... S
a
w .L
r

. 5.. \.
5... /
3.1%.. A w
P
3 a u
n...“ ~ ,
‘l 5. ..
C s. _..
1..” v. .N

. h 1.,
‘21.
a? W
p...
.1... C
\4 5 .‘
I5 A o.
.1 o

b
.1131 n 1.1.. 51...];

'ontg,

1"
J..~€

A U!
. : 'u- ,.;, .‘"
I‘h‘ L . 5’ :-

w i“, "f '2‘:
,. \J .4. '
‘ g1 ,

, ’3.
7 . “A ‘- .-
‘ t x. u

l in {F L; Q.
.
, ‘W Q
. 5’. 3..
.) Ly ‘-

v‘ a“
a

Our
“v...

3 "a

‘ntha 1“

x,
\J

+3.

fi‘?—‘P'3O \ «raj?
'._/ ‘J- :.;;.;;.‘ . J

& C11 was

7' JR .1 .1 u ,3.)
.. . a m . m, , .
-..4 J. ’v Ely . LL u.“ 3.x“.

« w
y?, a . 'A,‘ n f. 2" . . “X af.‘,~-‘
‘E - - L . L! Li. a. a r H. . r

""(W "'Zf')
Q; Eda. 0-:

. F‘ 4 fi '.
3 . ' . . " . - ~ -A -
;‘ LA“- “' S L! .) 9 :-—‘-.’h ‘n. u:- L
L-
‘I r- 5
":4“. "‘éi T; 3 '1"“' i:

o
1" . . J) ‘u! or. .1 . - ,
~ . ..

:5 Va “~Vool‘ ‘1.

li‘gf} . Etna
J. g. \A a t‘.

“':.'"“" Vfl“.
L;-\\‘..-}. ‘1J-’

fl, ,
L I

. ..v‘ - .'.. 4. -
Sepasuzei Eggs 1

r:
‘ .
trn .y .
w u. v5 .4. .-
”,~
a\.L " ‘V’a
"‘.‘“"“ “! .\ @-
'--‘ ‘J . s a
‘f . “
- -- ,
U §
_-‘.‘J J_ . }

I
:

J

 

M

l.

C

m
9

.
8

C3

'I.

-L‘ ’

> g.-
"\
u

p:
f '4‘.
O

Cffi‘“?‘:\,~i~v(~1y.v

~ ‘. ‘ ' \“IT‘
is": ‘ i :3 3 ,

t—n
m"
I". v

1'1. #1: .--r (>81:
”'01”; 1' u- r

”A

i‘r'

I'-
m

H

3"}

.1 'Q
J

T ‘4 .“l "1?.- 4‘3 r-‘r
.9 .'..*s '3 \a '3!" ’

C3

7

'0 q ‘3‘

...o .,, a

T1!
4..

.4

".1‘:T"‘." 1' 8.

.' _
,,. ...,..1 .. . -/

S (31,121,831

>..

{'0 o

T

n.1-

. , .
")2 . ’4
p- - .. t. a

7 ’7
I ~.
‘- Os D
.. ,

(1

__. 9 Ln

"'1‘ ‘3" v5 \'

my" a

:A .A\.

Z

.‘
Wf‘ '

(‘3
0‘4.

"x
f.
it
a .
J
1‘. r
L' K, ,
‘3

~-

73? ’V

- .3.

HI
‘

_ m. .
I. ‘-. -
‘wl‘uu' «.1,
~\ - r—
{:13 . 5
.1': "g (“1

9".

1

7: 007030313:

0‘ ll

2'\
rm!-
I

:- 1':-

fit

I
9

C".
i...a

A F! 9.

a . " ~

,V9 -\ an“ I -
.‘- .‘Vg '

g g - » ,‘a
" 3‘?

a
535

s.‘
....

06
t
O
’\
5.
~51.
f.
., .
52

(I {b.1503
l/ l .‘ -1
M

. c
v‘
n .
.- ‘ j . .
. '1 wu-
. : I a)
, . ‘
.. -, ,II
n 8..
8 a
.' l
‘5 s’ 4’ via
1“ -- 0 .'
.' ' J J i -‘
.‘ 9
V . J . -
1.4 do
.- ,
. ‘ 1
5- F .o
I
, .
no D ‘ , | j
. ‘ -
- . .
._ -~-.'b

‘\ -’
f
. _ ;’
#Kflf ‘
u -’ :
0-.

4‘. “

‘ I
O ' 1
‘ .
r :-
. V. 5
{iv 0
“-...

. 3
a ‘. D
- ...
.'..". u
f. .‘
f: . “I D
II! ‘1‘

(\fl ‘
“ ..
',‘. ~‘
61.24;),
a
I: -. . 4
u) -" I:
QC: 1':
‘l

'l ..
Jug

“oz-"c;
,. 1 .1
x: ' :‘I‘tr
m-'*.:.|' ‘J
(“(172
.44.!

a". -
‘ {V ‘s
- ..-l‘.
. ,—~.
' :
,.
._‘
.A-v

‘ "a
t.
.1 a
("s
1 0,. a»)
'._" 3
v‘.’
W“
,A
1“: .‘~«'~J
1}“ '~.-'

" 7‘,"
v 8
u. g n n1 2
n' . 4 {.8
km" ‘J-
-. .-..I~
-‘ [[5 :.
Java/.61.;
fl
-\ 9a.. a, '-
' -
L ‘ZUk;
‘1 "a"?
J...
r:
4- 8r~.m. ,
T I'"l"’; ‘9")
L 4 5 -\,,/
.‘I l‘ 'l
. .\
Jn‘ “9‘4.
.‘9
"1 r. c -,..:_;‘~-.)
-‘— ' c $.95."
1 ”2"."
4 v.‘
n
-f-. ~,,.
‘7' -. t.’ .‘J
.. , "2 ~11
.3. v-\.I°"\)..) «LQ'U

’P" ‘
e E '.>" b
4-.“ V-
«, UH
"i 1:
- I
-4.‘4,.~‘.J.o
.— .
I I

ar-o-\
1 L”1 I“:
.u~ -".r-'|
F'-
8,83
'z ‘10“,

17.

18.

19.

20.

21.

22.

23.

29.

50.

31.

32.

35.

Harvey,

Harvey,

Harvey,

Ayan.

Harvey,

Harvey,

Harvey,

Damitz,

Dickey,

Harvey,

Pillay,

Rector,

M.T.

M.T.

E.T.

2.1.

M.T.

Fred M.

Charla s

2.5.”!

i; J.

P.P.

T.M.

T.

Patel, Mg... 86 HOMO

{13.5218 8 ,

EOR.

Harvey & Damitz, F.fi.

Harvey & Damitz, F.M.

Harvey,

M.T.

0.1. 26; P 25544
Ger. P 558, 748 Oct. 15, 1926

C.A. §§= P 14598'9
U.S. 1, 838, 076 Dec. 22, 1952

0.2.‘28: P 14598,9
U.S. 1, 858, 075 Dec. 22, 1952

0.1. 22: P 14598:9
U.S. 1, 858, 072 Lee. 22, 1952

0.1. 21; P 52055
U08. 1. 921, 292 Aug. 8, 1955

C.A. 28; P 55416
U.S. 1, 952, 515 Mar. 27, 1954

0.1. 225 P 51887
U.S. 1, 950, 085 Mar. 6, 1954

0.2. 29; P 75293
U.S. 2, 014, 570 Sept. 17, 1954

C.A. 29: P 81024
0.5. 2, 008, 458 July 18, 1954

C.A. 29: 2585
0.5. 1, 977, 826 Oct. 23; 1955

0.4. 29: 68886
J. Ind. Chem. 500. $2} 226-51 (1955)

0.1. 53: P 5185
0.8. 2, 018, 091 Oct. 22, 1956

C.A. 51: P 55139
J. Univ. Bombay g; Pt. 27.114-51 (1936)

0.1. 51; P 9845
U.S. 2, 058, 456 Oct. 27, 1957

0.1. 51: P 1522’5
U... 2, 067, 919 Jan. ., 1957

0.1. 51: P 88125
U.S. 2, 128, 247 Aug. 30, 1937

0.1. 52. P 2741
U.S. 2, 098, 824 Nov. 9:"1958

34.

35.
56.
37.

38.
40.

41.

42.

47.

Gardner, H o A 0
Oil, Paint & Drug

Jeffries, Wm.
Brit. P 486, 169

Jeffries, Wm. & Pierce
brit. P 480, 981

Harvey, 1LT.
Brit. P 481, 960

Wats, B.C. & Bharaeha, K.H.
J. Malaria Inst.

Jeffries, Wm. & Pierce
Brit. P 480, 468

Harvey, M.T.
U.S. 2, 157, 126

H‘uléfile 3 , 13:31. A o
U.S. 2, 145, 880

Kuzmick, J.N.
U.S. 2, 156, 451

Patel, Mus. & H.111.
.In . & News Ed. of J. o
1: 83-90 (1938)
Caplan, S.
U08. 2, 176, 059
Dawning, J.G.

C.A. 32:

P
march $, 19

C.A. 32: P 6500

March”21, 1958

0.1. 52: 6248
India 1, 21’

0.1. 52: P .
Feb. 25, 1958
5 P

C.A. 5-

0.1. 55: 50274
Jan. 17, 1959

0.1. 55: P 68548
May 2, 1959
0.1. 55: 8887

m

0.1. 54: P 12027
Oct. 17, 1940

0.1. 54: 42954

J. Ind. Hygene Toxical.Ӥg: 169 (1940)

Cave, Martha B.
U03. 2, 183' 957

Harvey, M.T. & Caplan, S.

0.1. 54: 25021
Dec. 1 1940

9:
0.1. 54: 76571

u..-

Ind. Eng. Chem. 52:1506-10 (1940)

Ind. Chem.Soc.

 

3 1293 02808 0673

> ||”WWII“1||H||W|l|l|lliIlHllUIHIHIWIHIIIHW\I