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Патент USA US3038892

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1C@
' 3,®38,88Z
Patented June 12, 1962
2
3,038,882
METHOD OF PREPG CHLORINATED
PHENOLHC - FQRMALDEHYLE CONDENSA~
a novolak which would not have the desired chlorination.
Accordingly, one of the main objects of this invention
is to eliminate the foregoing disadvantages and to pro
vide a new and improved method of preparing chlorinated
TlON PRODUCTS
Gilbert Gavlin, Lincolnwood, and William M. Boyer, 5 novolaks.
Another object is to provide a process for obtaining
Park Forest, iiL, assignors to The Richardson Com
pany, Melrose Park, 111., a corporation of Ohio
No Drawing. Filed Dec. 24, 1956, Ser. No. 630,054
1 Claim. (Cl. 260—59)
chlorinated novolaks wherein the degree of chlorination
can be predetermined and controlled.
A further object is to provide novolak type compounds
10 which have improved compatibility with other substances
This invention relates to new and improved resinous
such as non-polar solvents, resins and rubbers.
compositions of the novolak type and more particularly
A further object is to provide a process for making
to chlorinated novolaks.
normally fusible chlorianted resins having branch chains.
Novolaks and their preparation have been known for
A still further object is the provision of chlorinated
some time, as is evidenced by numerous references in the
novolaks which may be reacted with other compounds to
available literature. Processes for forming novolaks are,
produce new products having enhanced properties.
at this date, fairly well standardized and comprise, in
Other objects of the invention and advantages thereof
general, the reaction of a phenol with an aldehyde in the
will appear in the more detailed disclosure set forth here
presence of an acid catalyst with the molar ratio of phenol
inafter.
to aldehyde usually being about 1:1 or ‘slightly higher. 20 The present invention, in one of its aspects, is directed
Novolaks produced in the foregoing manner are soluble
to obtaining ‘a chlorinated novolak wherein the novolak is
in numerous organic solvents and permanently fusible, and
?rst formed from a phenol, unmodi?ed by a halogen, and
thus, cannot be cured upon subsequent heating. Such
an aldehyde using an acid catalyst, followed by introduc
resins ‘are to be distinguished from somewhat similar res
ing chlorine into the previously prepared novolak. The
inous compounds normally referred to as resoles, which 25 chlorine, normally as a gas, is preferably introduced under
are capable of being permanently cured to a hardened
the surface of a solution of the novolak in a solvent for
condition by continued application of heat. Resoles are,
a required period of time and at any one of a number of
in general, also formed by reacting phenols and aldehydes
in desired proportions, but in the presence of a basic cata
lyst rather than an acid catalyst. It is possible, of course,
to cure novolaks to a final hard non-fusible product by
adding to the novolak a compound which is methylene
donating, such as hexamethylene tetramine, ‘and subject
ing the composition to heat.
Certain limited reports have (been published with re
spect to chlorinated novolaks, however, as far as can be
determined, these reports propose to form a ‘chlorinated
novolak by starting with a chlorophenol, in particular,
para chlorophenol and reacting the same with formalde
hyde in the presence of an acid catalyst. While such a
process may yield a speci?c type of chlorinated compound,
it has certain inherent disadvantages, and also lacks the
temperature levels, either above or below zero degrees
centigrade. It has been found that chlorine is readily
accepted by novolaks and in fact chlorination of a novo<
lak to any desired degree can be easily controlled without
using a catalyst. Various temperatures have been em
ployed for chlorination extending from minus 70° C. up
to well above room temperature without appreciably af—
' fecting the rapidity of the reaction or the acceptability
of the chlorine by the novolak.
As is to be expected during the chlorination of a novo~
lak, hydrogen chloride will Ibe formed and, depending on
the temperature employed, will usually either be retained
in the solution or evolved therefrom as a gas.
However,
certain solvents tend to retain the hydrogen chloride more
readily than others.
Various solvents have been used, in which the novolak
structures, as well as disadvantages in not being capable
45 is dissolved during the chlorination, such as methanol,
of producing highly chlorinated novolaks.
acetic acid, chloroform and l-nitroprop‘ane. The latter
For example, when a novolak is to ‘be made from a
solvent, that is l-nitropropane, is preferred, for the reason
phenol which has been chlorinated, such as para chloro
that it has less a?inity for the hydrogen chloride produced
phenol, the desired reaction is relatively sluggish and
and, therefore, permits ready separation of the same
slow, due to the presence of chlorine in the phenol ring
from the solution at lower temperatures of reaction. The
or nucleus and, ‘accordingly, relatively high molecular
chlorinated novolak formed when, for example, using a
weight products are di?icult to achieve. As will be ap
solvent may be isolated by simply stripping the solvent
preciated .by those familiar with the art of forming such
under vacuum or by drowning the reaction mixture in
resins, the presence of an element in the phenol ring such
water and separating the resin, the latter process being
?exibility of obtaining resins with desirable branch-chain
as chlorine has a de?nite tendency to deactivate the ring
preferred.
relative to reaction with formaldehyde. If it is desired to 55
While in some instances it is preferable to chlorinate
form a resinous product using a phenol which has more
a novolak in solvent solutions of the aforementioned type,
than one chlorine in the ring, it will be found even more
chlorination can also take place when the novolak is
dif?cult to achieve any real degree of polymerization,
merely heated to a ?uid condition without a solvent.
for the reason that the chlorine will make the phenolic
In forming a novolak by reacting a phenol and an alde
60
ring highly inactive.
hyde under acid conditions, it can be expected that both
Additionally, to make a partially chlorinated novolak
straight chain reactions and branch-chain reactions will
the normal course of action taken would be to initially
occur. However, if the phenol ring contains chlorinated
form a mixture of a chlorinated phenol and a non-chlo
rinated phenol and react the same with an aldehyde under
positions there will be little opportunity for branch-chain
reactions to take place, which for some purposes would
appropriate conditions, the mixture of chlorinated phenol 65 be desirable. Thus, chlorinated novolaks can be formed,
and non-chlorinated being made in approximately the
in accordance with the teachings of the present invention,
having a relatively high degree of branch-chain struc
partially chlorinated novolak desired. However, due to
tures which would not be the case if a chlorinated novolak
the relative inactive chlorinated phenol in the initial mix
were to be formed from, for example, a para chloro
ture, the tendency would be for the aldehyde to react with 70 phenol as a starting ingredient.
all of the non-chlorinated phenol and to only a limited
At this point it is advisable to set forth certain theo
extent with the chlorinated phenol, thereby resulting in
retical considerations which are believed involved in the
proportions which would be ‘estimated to give a resultant
3,038,882
3
4
Upon chlorination of a novolak, as indicated above,
the chlorine enters the phenol ring or nucleus replacing
hydrogen and is thereby added to the ring, at a position
2070 grams (22 moles) of phenol were melted and
poured into a 3 liter resin ?ask equipped with a glass
fabric heating mantle, an internal thermometer, a reflux
condenser, a paddle stirrer and a stoppered opening
through which solid materials or liquids may be added.
Twenty-nine grams of oxalic acid dihydrate were dis
solved in 290 grams of ethyl alcohol and this solution
either ortho or para, or both, to the hydroxyl group,
when such positions are open and depending on the ex
tent of treatment with chlorine. As more and more
stirred and heated to 110° C. Through the stoppered
opening ?ve portions of 90.6 grams each of paraform
chlorination of novolaks in accordance with the pro
cedures set forth herein, although it is not intended that
the invention be necessarily limited by such considera
trons.
was added to the melted phenol.
This mixture was
chlorine enters the molecule, selectivity tends to disappear
were added in 15 minute intervals. Thus a total of 45 3.0
and the chlorine will be added at almost any available
position on the ring. In some instances it has been indi
cated that chlorine, to a very minor extent, has entered
were added in 60 minutes.
grams (13.75 equivalents of 91% active formaldehyde)
After the last addition of
paraform the reaction mixture was re?uxed gently for
the methylene groups of the resin, but this is quite in 15 two hours during which time the internal temperature
fell slowly from 1l0.5° to 100.8° C. The re?ux con
denser was removed and arranged for distillation. In 2
hours 7 minutes 595 ml. of distillate were removed and
the internal temperature rose to 151° C. The mixture
ring until other non-chlorine containing rings have been
was
heated electrically while steam was passed into the
reacted. Once all of the phenolic rings in the resin mole 20
stirred mixture. In 5 hours 45 minutes of steam dis
cule contain a chlorine atom, subsequent addition of
tillation, the internal temperature rose to 164° C. and 9
chlorine will cause other chlorine atoms to enter previ
liters
of distillate were collected. Toward the end of
ously chlorinated rings, where positions are available to
steam distillation the distillate was found to be nearly
them.
In view of the foregoing theories of reaction it has been 25 free of phenol. Electrical heating was continued and
steam was replaced by a slow stream of carbon dioxide to
found, as previously indicated, that the degree of chlori
remove
small amounts of Water. In the next hour and
nation can be readily controlled and a novolak can be
45 minutes the temperature in the resin kettle rose to
chlorinated to any extent desired by controlling the
183° C. The yield of ?nished novolak was 1830 grams.
amount of chlorine introduced into the resin. The chlori
nation of novolaks does not affect their subsequent reac 30
Example 11
tion with certain modifying agents and such a novolak
The following procedure was employed to produce a
frequent. Further, when a chlorine atom is attached to
one phenolic ring or nucleus of a novolak resin, at second
chlorine atom will not normally attach itself to the same
can, for example, be readily epoxylated by reaction with
epichlorohydrin.
Chlorinated novolaks of this invention can be used as
chlorinated novolak resulting in an addition of chlorine
to the resin in an amount equal to about one chlorine
casting resins and surface coatings. They also have been 35 atom per phenolic ring.
Eight hundred and forty-eight grams of a phenol form
found to be readily compatible with a variety of other
aldehyde novolak were ground up in a mortar. The
types of resins, especially hydrocarbon resins, and rub
ground novolak was placed in a 5' liter four necked
bers such as GRS to form new compositions having
?ask ?tted with a paddle stirrer, then 858 grams of
improved properties. Laminates having increased ?ame
retardance have been made using a mixture of a chlori 40 l-nitropropane was added and the novolak dissolved by
slow stirring overnight. A few small pieces of resin re
nated novolak and a cresylic resole, as well as a chlori
mained so that 100 grams more l-nitropropane was added
nated novolak with a standard phenolic resole.
in the morning. An internal thermometer, a re?ux con
It has also been discovered that chlorinated novolaks
denser and a fritted glass gas inlet tube were added to
of the type contemplated by this invention have marked
the
?ask and the mixture was heated to 49° C. on a
45
fungicidal and bactericidal properties and, hence may be
steam bath. Chlorine from a weighed cylinder was then
employed with carriers or added to paints for this pur
introduced through the gas inlet tube into the rapidly
pose. The use of chlorinated novolaks as fungicidal
agents is more fully disclosed and claimed in the co
pending application of William M. Boyer, S.N. 674,019,
?led July 25, 1957.
While the foregoing disclosure has centered around
novolaks produced from unsubstituted phenol, it should
stirred mixture and in 7 hours a total of 605 grams (8.5
moles) of chlorine gas was passed into the resin solu
tion. During the chlorination the temperature ranged
from 47° to 62° but was close to 50° most of the time.
The mixture was stirred slowly overnight and then
drowned by pouring into ?ve gallons of vigorously stirred
be emphasized that alkylated phenols can be used to
cool water. The resin was allowed to settle and then
form the novolaks without encountering certain of the
di?iculties found with chlorophenols. In fact, certain 55 Washed with three five gallon portions of cool water.
After separation of the third wash water, the cherry red
alkylated phenols enhance the formation of novolaks.
resin was dissolved in 3 liters of methyl ethyl ketone by
Thus, a meta cresol will tend to be more reactive in the
vigorous stirring. This solution was transferred to a
formation of a novolak than will normal phenol. Like
large separatory funnel, one more liter of methyl ethyl
wise para cresol and 3,5-xylenol may also be used in
forming novolaks for subsequent chlorination. Accord 60 ketone was added and the water layer drawn off. The
ingly, when the term “novola ” is used herein its is in
tended to mean a fusible, organic solvent-soluble con
densation product of an aldehyde with a phenol such as
normal phenol, meta or para cresol and 3,5-xylenol or
solvent was removed from the ?ltered resin by vacuum
stripping at 45° to 60° with a water aspirator and ?nally
at 105° C. with a high vacuum pump.
catalyst.
cent by weight volatiles and 0.3 percent by weight water.
The yield of resin was 1035 grams. Analysis showed
mixtures thereof and wherein the condensation reaction 65 23.66 percent by weight chlorine, 0.287 percent by weight
chlorine reactive with silver nitrate at 150° F., 0.85‘ per
is normally performed in the presence of an acid
Certain examples are set forth hereinafter for purposes
Example 111
of illustrating the concepts of the invention without in
70 This example illustrates the production of a chlorinated
tending to thereby limit the same.
resin having approximately two chlorine atoms per phe
Example 1
nol ring. One thousand and sixty grams of a phenol
formaldehyde novolak were ground in a mortar. Using
This example illustrates the formation of a typical
the same apparatus as described in Example II, the resin
novolak which may be subsequently chlorinated as de
was dissolved in 1615 grams of l-nitropropane. Chlo
75
scribed herein.
5
3,038,882
rination was carried out in 12 hours 30 minutes (2 hours
rst day, 8 hours second day and 2% hours the third
day) at temperatures of 26° to 68° but mostly near 45°
C. In this time a total of 1400 grams (19.7 moles) of
chlorine gas was run into the resin solution.
The resin
was drowned in water, washed, dissolved in methylethyl
ketone, ?ltered and stripped of solvent essentially as de
scribed previously, except that a higher temperature,
6
this invention may be subjected to reaction with many
curing and modifying agents to give an end product hav
ing desired properties. Thus, they can be cured by react
ing with hexamethylene tetramine or modi?ed by reacting
with epichlorohydrin. An example of an epoxylation of
a chlorinated novolak is as follows:
Example VII
170° C. was used in the ?nal stripping.
The yield of resin was 1940 grams.
Six hundred thirty two grams of chlorinated novolak
Analysis showed 10 (containing 35.58 percent by weight chlorine) were dis
38.03 percent by Weight chlorine, 3.57 percent by weight
solved in a mixture of 740 grams (8 moles) of epi
chlorine reactive with silver nitrate at 150° F., 5.34 per
chloro'hydrin and 500 ml. of ethyl alcohol in a 5 liter
cent by weight voltalies and 0.30 percent by weight water.
four necked ?ask ?tted with a heating mantle, a pad
die stirrer, an internal thermometer, a re?ux condenser
Example IV
and an addition funnel. A solution of 160 grams (4
Two hundred and twelve grams of a phenol formalde
moles) of sodium hydroxide in 207 ml. of water was
hyde novolak were dissolved in 800 ml. of methanol in
prepared and placed in the addition funnel. The resin
a three liter four necked flask ?tted with an internal
solution was heated to 63° C. and slow addition of the
thermometer, a fritted glass gas inlet tube, a paddle
sodium hydroxide solution was begun. Eighty-three
stirrer and a re?ux condenser. When solution was com 20 minutes were required to add all of the sodium hy
plete, the resin solution was cooled to minus 66° C. in
droxide solution and occasional immersion of the ?ask
a Dowanol 33B-Dry Ice bath and chlorine was led
in Water was necessary to moderate the reaction. The
through the fritted glass inlet tube from a weighed cylin
internal temperature remained at 75 to 82° during the
der. In 3 hours and 42 minutes at minus 63° to minus
reaction and was accompanied by vigorous re?uxing.
68", 284 grams (4 moles) of chlorine gas were passed 25 In ?fteen minutes the addition of sodium hydroxide was
into the mixture. No hydrogen chloride was evolved
completed and the reaction considered ?nished. ‘Three
from the mixture until after chlorination when the solu
liters of warm distilled water were added and stirred
tion was allowed to warm up to 5° C. The reaction
well. The resin was allowed to separate and the water
mixture was drowned in 6 liters of cold water by pour—
was sucked out. This washing was repeated again.
ing ‘a thin stream of the reaction mixture into the vigor 30 After removal of the second wash water, 2 liters of
ously agitated water. The precipitated resin was washed
methyl ethyl ketone were used to dissolve the resin.
with cold water six times and the resin separated by
Water was separated from this solution. It was ?ltered
decantation. The solid resin was ?ltered off and oven
and the solvent removed under water pump vacuum to a
dried at 80° C. The yield of resin was 307 grams.
?nal resin temperature of 147° C. The yield of resin
Analysis showed 40.15 percent by weight chlorine, 5.17 35 was 840 grams. Analysis showed that this resin con
percent by weight volatiles and 0.6 percent by weight
tained 0.342 mole of epoxy groups per 100 grams of
water.
resin, 25.43 percent by weight chlorine and 8.80 per
cent by weight volatiles.
Six hundred thirty-six grams of a phenol-formaldehyde
Having disclosed and described the invention and
novolak were dissolved in 424 grams of methanol. The 40 certain exemplary embodiments therefor, it is intended
Example V
resin was dissolved in the methanol in the usual 5' liter
that the same be limited only by the scope of the fol
chlorination apparatus by gentle warming. The ?ask
lowing claim.
We claim:
was then cooled in a running water bath, and in three
hours 37 minutes at 9 to 15° C. a total of 213 grams (3
A method of preparing a chlorinated resinous com
moles) of chlorine gas was led into the mixture. After 45 position of matter which comprises the steps of dis
solving in l-nitropropane a permanently fusible acid
chlorine addition was completed to the desired level, the
reaction mixture was stripped of solvent and hydrogen
catalyzed resinous condensation product of formalde
chloride by heating under aspirator vacuum to a ?nal
hyde and a chlorine-free member of the class consisting
of phenols, cresols and xylenols, and introducing chlo—
temperature of 170° C. Seven hundred twenty-nine
grams of resin were obtained which showed by analysis
rine gas into the solution in an amount which will per
to contain 13.80 percent by weight chlorine and 3.19 per- 1 mit that minimum addition of chlorine to said conden
cent by weight volatiles.
sation product which is equivalent to at least one chlo
rine atom for at least one phenolic nucleus, said ch‘lo
Example VI
rination being conducted at a temperature which is suf
Two hundred and twelve grams of a phenol-formalde 55 ?cient to permit simultaneous evolution from the solu
hyde novolak of the type prepared in Example I was dis
solved in 1415 ml. of chloroform in the usual 5 liter
tion of the gaseous hydrogen chloride formed as a
by-product.
chlorination apparatus by stirring and gentle warming
overnight. Chlorine gas was led into the mixture for
References Cited in the ?le of this patent
61/2 hours at 45° to 62° C. When 285 grams (4 moles) 60
UNITED STATES PATENTS
of chlorine had been run in, the chlorine gas was shut
2,027,988
Landt ______________ __ Jan. 14, 1936
off. During this reaction, some hydrogen chloride was
2,475,587
Bender et al. ________ __ July 12, 1949
observed escaping from the exit of the re?ux condenser.
2,658,884
D’Alelio __________ __ Nov. 10, 1953
The chloroform solution was washed with ten equal vol
umes of cold water in a separatory funnel, the chloro 65
form layer drawn oil, ?ltered and the solvent removed
under the water pump. Finally, the high vacuum pump
was employed to remove the last traces of solvent, using
a maximum temperature of 78° C. 342 grams of resin
FOREIGN PATENTS
429,377
Italy ______________ __ Jan. 24, 1948
OTHER REFERENCES
was obtained, analyzing 43.3 percent by weight chlorine, 70 Bakeland: Iour. of Industrial Engineering Chemis
5.67 percent by weight chlorine reactive with silver nitrate
try. March 1909, page 155.
at 150° F., 6.54 percent by weight volatiles and 0.25 per
Carswell: “Phenoplasts” High Polymer Series, vol.
cent by weight water.
VII; Interscience Publishers, N.Y. (1947), pages 9 and
As previously indicated, the chlorinated novolaks of
35. (CopyinDiv. 60.)
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