Patented Nov.

6, 1945 ‘2,388,410

umrso STATES PATENT ‘OFFICE

I 2,388,410

,1, - . KETONE nnsms

‘ Vernon E. Haury, El 'Gerrlto, Calif” assliznor to

Shell Development Company, San Francisco,
Calif., a corporation of Delaware
No Drawing. Application March 3, 1944,
Serial No. 524,952
20 Claims. (01. 260-64)
This invention relates to ketone resins and to xylitones, other higher auto-condensation prod- .
-. a process for their manufacture. ‘ More particu . ucts of acetone are suitable, such as condensates
larly, the invention deals with a novel class of which are pentamers,- hexamers, heptamers, etc.
ketone resins prepared by reacting an aldehyde Furthermore, unsaturated ketones derived by
with unsaturated cyclic ketones of a particular auto-condensation of other lower aliphatic ke
type. - - tones which are at least tetramers of such ketones . .
It is an object of the present invention to pro are also used in obtaining the resinous products
vide a method for converting a class of higher by condensation with aldehydes. Such unsatu
ketones- into valuable resinous materials. - An rated ketones include what may be termed the
other object is to provide a method of reacting 10 homoxylitones of methyl ethyl ketone, the homo
these higher ketones with aldehydes in a manner zylitones of methyl propyl ketone, the homo
which permits high yields of thermoplastic ketone xylitones of diethyl ketone, etc., all of which are
resins with valuable and unusual properties not tetramer auto-condensates of the parent, lower
possessed by ketone resins prepared heretofore. ketones. If desired, the higher and more complex
I have discovered that these and other objects 15 auto-condensates can be employed such as the
of the invention. which will be apparent from pentamer, hexamer, heptamer, etc, These un
the following description, are accomplished by saturated ketones are crotonaldehyde-type» of
condensing a particular type of cyclic and unsat auto- or self-condensation products of lower ali
uated ketones with an aldehyde in the presence of phatic ketones and are products or by-products
a condensing catalyst and of a substance render 20 obtainable by certain methods of condensation
ing ‘the. reaction mixture homogeneous. Further, which are described in U. S. Patent 2,309,650 and
it was found that since the ketones are cyclic copending application, Serial No. 474,060, ?led
and contain at least two ole?nic double bonds per January 28, 1943. .
molecule, the resins which are obtained have the In this application, the terms “tetramer,”
property of changing their solubility character 26 “pentamer,” “hexamer," etc., refer to the num
istic upon being contacted with oxygen, which ber of molecules of a .lower ketone which have
property is particularly useful and valuable in a been combined to form a molecule of auto-con
resinous material. In general, the resins of the densate by crotonaldehyde-type of condensation.
invention are hard, reddish colored thermoplas Thus xylitone, .which is formed by condensation
tics which are soluble in common organic solvents. 30 of four molecules of acetone to form a molecule
The unsaturated cyclic ketones converted to of the product, is termed the tetramer auto
resins by the method 01’ the invention are substi condensate of acetone and, for convenience and
tuted cyclohexen-2-ones having at least one ole lack of a better name, the product obtainable by
?nic linkage present in a side chain or side chains combination of live molecules of acetone ‘is re
linked to the cyclohexenone ring. The exact 35 ferred to as the pentamer auto-condensate of
structure or chemical con?guration of these un acetone. Similarly, the auto-condensate from
saturated ketones is not known, although it is six molecules of other ketones than acetone such
recognized that they are unsaturated mono ke as methyl ethyl ketone is termed the hexamer
tones which are substituted cyclohexenones with auto-condensate of the parent ketone. , These
an ole?nic linkage present in the’ ring probably 40 terms are used to indicate the character of the
in the A2 position and with at least one ole?nic higher auto-condensation products wherein the
linkage contained in a side-chain or additional exact con?guration of the atoms or chemical
ring linked to the cyclohexenone ring. These un ' structure is unknown.
saturated cyclic ketones thus contain at least two The lower aliphatic ketones employed in form
ole?nic linkages and the presence in the com 45 ing the unsaturated ketones by crotonaldehyde
pounds of this unsaturation, coupled with their . type of auto-condensation include such repre
cyclic character, is responsible for the resins ob sentative compounds as acetone, methyl ethyl
tained by condensing the ketones with aldehydes ketone, methyl propyl ketone, methyl isopropyl
to absorb or combine with oxygen so as to cause ketone, diethyl ketone, methyl butyl ketone,
the valuable change in solubility. characteristics. 50 methyl isobutyl ketone, methyl pentyl ketone,
The simplest member of the class of unsatu dipropyl ketone, ethyl butyl ketone, and methyl
rated ketones are termed xylitones by the art. heptyl ketone. In addition, intermediate‘ auto
The xylitones, of which there are several isomeric condensates like mesityl oxide can be subjected .
compounds, are tetramer condensates of acetone to crotonaldehyde-type of condensation to yield
of the formula C12H1a0. In addition to the 65 ~12 carbon atom xylitone'aswell as higher multi
 2 2,388,410
pie-unsaturated products containing 18, 24 and quality than with other aldehydes. However,
30 carbon atoms which are substituted Az-cyclo other aldehydes may be used, if desired, such as
hexenones. Condensation of homomesityl oxides acetal'dehyde, propionaldehyde, butyraldehyde,
of the other lower aliphatic ketones are similarly isobutyraldehyde, valeric aldehyde, ethylhexanal.
suitable. By “crotonaldehyde-type” of condensa acrolein, crotonaldehyde, benzaldehyde, para
tion used in this speci?cation reference is made methylbenzaldehyde, ortho-tertiary butyl benzal
to that type of condensation which occurs when dehyde, and the like, together with their homo
two molecules of acetaldehyde couple with elimi logues, analogues'and suitable substitution prod
nation of a molecule of water forming a mole ucts. In general, the aldehyde reactant used
cule of crotonaldehyde as distinguished from in the process is an aldehyde wherein the alde
aldol-type of condensation which involves cou- 10 hyde group is linked directly to a member of the
pling of two molecules of acetaldehyde with no class consisting of the hydrogen atom and mono.
formation or elimination of a molecule of water valent hydrocarbon radicals. Besides the free
in the reaction which gives a molecule of aldol. uncombined aldehydes, polymers of the aide
The formation of the substituted Az-cyclohexei- 15 hydes, which are capable of giving free aldehydes
nones also involves cyclization as well as croton- under the resin-forming conditions, can be used
aldehyde-type of auto-condensation. such as para-formaldehyde, para-aldehyde.
While the resin treated according to the pres- meta-aldehyde, and the like.
ent invention has been described as being formed In order to effect the reaction between a higher
by reaction of an aldehyde with a single substi- 20 ketone and an aldehyde, it is necessary to place a
tuted Az-cyclohexenone of the indicated class, the mixture. of the reactants in contact with a con
resin can be formed from mixtures of the ketones densing agent or catalyst. For this purpose,
including structural isomers within the class as any condensing agent can be employed although
well as mixtures which contain different numbers some types are more preferable than others. An
of carbon atoms. 25 amount of from about, 0.5 to 5 per cent by weight
All of the Class Of unsaturated ketones which of the reactants is used. The preferred catalysts
are tetramer or higher auto-condensates of low- include strong basic condensing agents such as
er aliphatic ketones have in common the char- the hydroxides, oxides and a-lcoholates .of the
acteristic structure of being substituted az-cyclo- alkali metals as well as strong organic bases like
hexenones. While the higher compounds arenot 30 the quaternary ammonium bases. Other less
simply homologues of xylitone and homoxylitone, basic agents may be used if desired such as the
the class does possess an orderly regularity of alkaline earth hydroxides and oxides. In some
structure. This may be illustrated by consider- cases it may be advantageous to employ acidic
ation of the auto-condensates of acetone, methyl substances such as sulfuric acid, hydrochloric '
ethyl ketone and methyl propyl ketone given in 35 acid, phosphoric acid, telluric acid, tungstic acid
the following table together with the general for- and the like as well as acid salts such as sodium
mula for each series wherein m is an integer of 4 acid sulfate, etc. The catalysts may be employed
to 10 and n is related to m by the indicated equa- in the reaction mixture per se or, if desired, they
tion. 4 may be used as a solution with a solvent. Suit

Auto~condensate Acetone Meggggghyl Metgjygoggopyl

Tetramer ................ -- CHHIBO 015E150 CaoHnO
‘ H CmHnO CuHnO
CuHuO CaoHwO
CuHuO Etc.
Etc. .

Decamer ................. --- ‘030E410

_ Formula of the series ..... .. o.nm..+l>o ' Q.Hz(s-+1)O ouiuhmo

wherein m a an integer'oi 4 to 10 and

n=3m _ n=4m. n=5m

Preferably the unsaturated ketones contain, not able organic solvents may be employed for this
more than 30 carbon atoms and the most pre purpose. Particularly suited are aqueous solu
ferred compounds are the tetramers and penta tions of the alkali metal hydroxides, the quater
mers of lower aliphatic ketones. The unsatu nary ammonium _bases, the acids and the acid
rated ketones of the class are of the formula 60 salts.
CnHz(m(r¢-1)+1)O wherein m and k are each in The higher ketones employed as starting mate
tegers with m of 4 to 10 and k of 3 to 9 and rials in the process are substantially insoluble in
n=kX m. In this general formula, n is related to water and in aqueous solutions of the aldehydes
the number of carbon atoms in the ketone and is such as an aqueous solution of the most preferred
at least 12 while It represents the number of car 65 reactant, formaldehyde. In order that the re
bon atoms in the parent ketone from which the action between the ketones and aldehydes be ef
auto-condensate is derived. Further, m is the fected readily, it is desirable that the reaction
measure of degree of condensation (m equals mixture be in a homogeneous state, i. e., that the
4 with the tetramer, 5 with the pentamer, etc.). reactants and catalyst be in a solution compris
The substituted Az-cyclohexenones of the class 70 ing a single phase, at least at the start and early
indicated are converted into resinous materials part of the reaction. To this end, a homogeniz
by reaction with an aldehyde. For this purpose ing solvent is employed in the reaction mixture.
formaldehyde is a most preferred reactant in In the absence of a homogenizing solvent, the
that this substance is more reactive and gives yield of resin is very low. Many solvents are suit
higher yields while the products are of better 75 able for this purpose and the choice of a partic
 assauo' ‘ 3
ular solvent will depend upon the particular re homogenizing solvent, condensation catalyst and
actants employed, the catalyst used and the pres unreacted materials, and then subject the sep
ence or absence of water in the mixture. The ‘evarated resin to the action of heat under anhy
lower aliphatic alcohols such as methanol, eth drous conditions using a temperature of 150° C. to
anol, isopropanol, etc., are particularly suitable 5 250° C. whereby the softening point of the resin
homogenizing solvents. The amount. of these is increased by the treatment.’ This curing op
homogenizing solvents ’employed will depend eration does not in general cause the resins to
upon the character of the reaction mixture. In set to an insoluble and infusible state. In other
general, su?icient homogenizing solvent is used words, the resins of the invention prepared from
so that the reaction mixture is homogeneous at 10 saturated aldehydes are not thermo-setting, but
least when ?rst heated. , rather, are thermoplastic although they are sub
The homogenizing solvent may serve a two ject to curing by heat which causes their soften
fold purpose in the process. Besides rendering ing points to be raised. Although the softening
the reaction mixture homogeneous, it may also be point of the resins is increased by heating the
used to regulate the temperature of the reaction initial reaction mixture at the higher indicated
mixture during the heating thereof since ordi temperatures, this procedure is undesirable since
narily the reaction is e?ected at not overly high , the presence of the catalyst at the high temper
temperatures. By heating the reaction ‘mixture ature causes the resins to become more discolored
in a vessel ?tted with a re?ux condenser, the than when the heating is done after removal of
temperature may be made to reach and hold the the catalyst.
boiling temperature of the mixture and this will . The unique resins of the invention prepared
be largely’ dependent upon the re?uxing temper from higher ketones containing at least two ole
ature of the homogenizing solvent especially after?nic double bonds in the molecule combine with
the reaction has progressed to a considerable ex or absorb oxygen and may be converted to the
tent with substantially no other lower boiling 25 less-soluble form by contact with oxygen. A
constituents remaining in the mixture. To effect suitable method of converting the resins is to
the desired reaction, temperatures, in general, dissolve them in a suitable solvent and pass on
between about 50° C. and 150° C. are employed. oxygen-containing gas such "as air through the
While temperatures of from about 50° C. to 150° ' solution. The rate of absorption of oxygen by
C. are preferred for eifecting the condensation 30 the resins is increased in the presence of a sic
to form the resin, higher temperatures can be cative and heat and, if desired, the resins may be
used if desired. Thus, the reaction mixture con changed to the less-soluble form more rapidly
taining the reactants, catalyst solution and ho ' by incorporating in them driers such as lead.
mogenizer, can be heated in a closed pressure manganese and/or cobalt naphthenates, linol
vessel at a temperature between 150° C. and 300° eates, resinates and other like-acting substances.
C. in order to convert the ketones to resins. In The resins are very useful substances. They
general, however, temperatures within the pre may be employed in coating compositions, im
ferred range are most desirable since the resins pregnating compositions, ?lm-forming composi
obtained in this manner are lighter in’ color tions and the like as well as for electrical insu
than those prepared at thehigher temperatures. 40 lation, manufacturing molded articles and nu
Upon completion of the resin-forming conden- "merous other miscellaneous uses.
sation reactions between the ketones and alde The following examples are given for the pur
hydes, the resin may be recovered from the re pose of illustrating various details of the inven
action mixture by several suitable methods. A tion, but are not to be construed as limitative:
preferred procedure is' to wash the mixture with Example I
a catalyst solvent such as water so that the mix
ture will be substantially freed of the condensing About 1240 gms'or xyntone (01211180) and 565 >
agent. If desired, however, the catalyst may be gms. of ~3'7 % aqueous formaldehyde were homo
destroyed by neutralization with an appropriate genized with 1100 gms. of methanol to which was
acidic or basic substance‘. The mixture may 50 added sodium hydroxide (0.5% of total charge) in
then be distilled, ?rst at higher pressures such ‘the form of its 30% aqueous solution. The mix
as atmospheric to remove the homogenizing sol ture was warmed cautiously, an exothermic reac
vent, catalyst solvent, unreacted reactants and tion taking place, and ?nally re?uxed for a period
low-boilingproducts, and secondly at reduced. of three hours. The methanol was distilled from
pressures to remove higher-boiling products from the mixture and the residue washed with water
the ketone resin. By completing the distillation to remove caustic. Unreacted ketone was then
operation at very low pressures of 1 to 10 mm. of separated by vacuum distillation. The product
Hg and at temperatures between about ‘150° C. weighing about 850 gms. was obtained as the res
and 250° C., but below a temperature at which idue from this distillation and solidi?ed on cool
appreciable thermal decomposition of the resin 60 ing to a brittle resin. The physical properties
occurs, the resin is obtained in a hard, brittle, of a sample of the resin were as follows:
desirable form.v Besides the above-outlined Per cent-carbon ________________________ __ 79.5
scheme of recovery of the resin, other methods Per cent-hydrogen _____________ Q. ________ ....‘. 9.3
may be employed, if desired, such as fractional _ Mol. wt_r___; ______________________ __'_____ 600
precipitation, extraction and the like. ' M. P., °C. (Mercury) _____________________ __ 70
It has been found that subjecting the resinous Color______ _-Orange to red, E to H (rosin scale)
materials to the distillation operation serves _a
two-fold purpose; one, volatile materials asso , Example II
ciated with the resins are removed and two, the About 100 gms. of 'xylitone (B. R. 110-112.5° C.
subjecting of the resins to the action of heat after 70 at 10 mm.), 32 gms. of acrolein, and su?icient
removal of the condensation catalyst cures the methanol to render the mixture homogeneous,
resins, which eifect is manifested by an increase to gether with 0.5% sodium hydroxide‘as its 30%
in the softening point. In some cases it is de aqeous solution, were re?uxed for about 2 hours.
sirable to separate the resin from the other con The resin layer which formed during the heating
stituents of the reaction mixture suchas the 75 was separated and washed twice with water to
4 2,888,410
remove the basic catalyst. The washed resin Example V
layer .was then distilled under a pressure of 2 A mixture containing about 258 gms. of cylic
mm. Hg up to a temperature of 180° C. for re unsaturated ketones having the formula CraHaoO
moval of unreacted ketone. The resin obtained prepared by erotonaldehyde-type auto-conden
was a brittle, dark red solid having a softening sation of mesityl oxide, about 83 gms. of 36%
point on a hot plate of 46 to 60° C. and a molecu aqueous formaldehyde solution, and about 0.5%
lar weight of 510 by ebullioscopic determination of sodium hydroxide in the form of an aqueous
in benzene. ' ' solution was prepared. To this mixture was
. Example III added about 170 gms. of methanol to make it
A ketone resin was prepared from a mixture of 10 homogeneous and the mixture was then heated
isomeric substituted na-cyclohexenones of the for approximately three hours at a temperature
formula CmHazO having a boiling range of 142° of 65i5° C. The resin‘ formed was recovered
C. to 175° C. at 10 mm. pressure. The ketone mix- - in a similar manner to that described in Example
ture was obtained as a higher boiling by-product III. The resin had a color of E on the Rosin
from preparation of isophorone by crotonalde 15 scale and softened at 95° C.
hyde-type auto-condensation of acetone with Example VI
aqueous potassium hydroxide in liquid phase at
about 170° C.‘ r
' Approximately 169 gms. of substituted A’
A mixture of about 250 gms. of the ketone, 166 oyclohexenones of the formula 02411340 from con
gms. of 36% aqueous formaldehyde, and sum 20 densation of mesityl oxide, about 42 gms. of 36%
cient methanol (about 300 gms.) to render the aqueous formaldehyde solution, and 0.5% sodium
reaction mixture homogeneous, to which was hydroxide as aqueous solution together with
added sodium hydroxide in amount of 0.5% of about 325 gms. of methanol were heated at a tem
the total mixture, was heated at re?ux tempera perature of 65 15° C. for three hours. About 169
ture for about 3 hours. The reaction mixture 25 gms. of light red brittle resin was recovered from
was then cooled, the catalyst neutralized and the the reaction mixture which was slightly darker
resin layer separated. The separated layer was in color than that described in Example V.
washed several times with hot water and distilled Example VII
to 180° C. at 2 mm. pressure. About 80 gms. of
unreacted ketone was recovered by the distilla 30 A mixture of isomers of substituted Ail-cyclo
tion while about 193 gms. of‘ the thermoplastic hexenone of the formulas CizHuO (xylitone) and
ketone resin remained as residue. The resin had
C15H22O which had a boiling range of 110° C.
a color of D on the Rosin scale and a softening to 140° C. at 10 mm. was reacted with formalde
point of about 78° C. hyde to give a resin. About 100 gms. of the ke
35 tone, 82 gms. of 36% formalin, and su?lcient
Example 1V methanol to render the reaction mixture homo
About 178 gms. of xylitones (C12H1s0) obtained geneous when mixed together with 0.5% sodium
by crotonaldehyde-type auto-condensation of hydroxide as its 30% aqueous solution, were
mesityl oxide was mixed with 81 gms. of 37%‘ heated in a closed nickel bomb at 145° C. to 165°
aqueous formaldehyde solution. To this mixture 40 C. for 11/2 hours. The catalyst was then neutral
was added approximately 5 gms. of 30% aqueous ized, the resin .layer separated and distilled in
sodium hydroxide solution and about 95 gms. of vacuo whereupon about 9 gms. of unreacted ke
methanol which rendered the mixture homogene tone was discovered. The resin obtained
ous. The mixture was contained in a ?ask fitted amounted to about 86 gms. and was a brittle solid
with a re?ux condenser and upon heating the (5 which was black in color owing to the high tem
contents of the ?ask, the temperature of the mix perature employed and the presence of the cata
ture remained at about 76° C. owing to the re lyst at that temperature.
?uxing of the methanol therein. The mixture Example VIII
remained homogeneous for about 1/2 hour after
which two liquid phases separated. The heating 60 A mixture of about 100 gms. of rketone (the
was continued over a total period of about 3 same as that described in Example VII), 89 gms.
hours. The mixture was then cooled, brine added of 36% formalin, sufficient methanol to render
and the resin phase extracted with ether. The‘ the mixture homogeneous, and 0.5% sodium hy
ether was dried with anhydrous sodium sulphate droxide based on the total weight of the mixture,
and the ether distilled therefrom. The remain 55 was heated in a nickel bomb for 11/2 hours at
ing oil was then distilled in vacuo and after re 140° C. to 150° C. The catalyst was neutralized
moval of the distillable material, about 106 gms. and the resin layer separated. In order to deter
of a reddish, brittle, transparent resin was ob mine the effect of avoiding the high tempera
tained. This resin had a color corresponding to ture used in removing unreacted ketone which
E on the rosin color scale and was soluble in cures the resinyand increases its softening point, ,
alcohols, ketones, esters, aromatic hydrocarbons the separated layer was ‘steam distilled to remove
and paraiiinic hydrocarbons. A cryoscopic deter the unreacted ketone. In this manner, about 24
mination in glacial acetic acid indicated the mo gms. of ketone was recovered. The resin obtained
lecular weight was about 530. Exposure of the in an amount of about 64 gms. was dark red in
resin to the action of air increased its oxygen 65 color and soft and sticky in consistency. By sub
content and changed it to a form which was in jecting the resin to‘ temperatures of 160° C. to
soluble in para?inic hydrocarbons. 180° C. after its initial formation, it can be con
The presence of the homogenizer in the reac verted to a hard material of satisfactory soften
tion mixture is essential to obtaining a practical ing point.
rate of resin formation. With a reaction mixture 70 Example IX
containing the same amount of identical react
ants, but in the absence of the homogenizer, Tetra ethyl ammonium hydroxide was tested
methyl alcohol, which was treated under the as a polymerization catalyst by heating a mix
same conditions as in the preceding example, the ture consisting of about 178 gms. of xylitones de
quantity of resin amounted to less than one gram. scribed in Example I, 81 gms. of (37% aqueous
 . 5
11

formaldehyde solution, 120 gm. of methanol, and Examples XIV

20 ms. of 10% aqueous tetra ethyl ammonium
hydroxide. The mixture was re?uxed at about Samples of resin prepared from mesityl oxide
78° C. for three hours. The product was washed condensate and formaldehyde were given the
with water and distilled in vacuo. After removal 5 treatment indicated in the following table and
of unreacted unsaturated ketones and lower were analyzed thereafter:
boiling constituents, there remained about, 107
gins. of light-colored, hard, brittle resin having Tm?mm’
Per cent Per cent
o H ,
Per cent 0
(by am.)
.9
H
a color'oi' G on the rosin color scale.
Example X 10 None __________________ _. 79. 9 9. 3 10. 8 8. 60
Air blown in isododeeane
A. mixture containing about 178 gm. of at 90° 0. for 16 hours.-. 72. 7 8. 5 18.7 8. 56 >
Air blown in benzene at _
xylitones from condensation of mesityl oxide, 30 80° C for 30 hours-..-- 78. 0 8.8 13. 2 8. 87
gm. of formaldehyde in the form of a 37% aque Powder exposed to air at
25° 0. for 2 weeks .... -. 70.3 8.2 21.5 8. 67
ous solution, 5 gms. of 96% sulfuric acid, and suf 16
?cient methanol to homogenize the mixture was
heated at re?uxing temperature for approxi The results obtained from the experiments
mately three hours. The resin which was re demonstrate the ability of the resin to, absorb
covered was dark red in color. ‘ oxygen.- Furthermore, the fact that the ratio of
carbon to hydrogen
Example x1 -' 2"
» la
A crude mixture of cyclic unsaturated ketones (11)
was converted into a resin. The ketone mixture remains substantially constant indicates that the
boiled at 110° C. to 175° C. at 10 mm. pressure and oxygen combines with the resin with no ap
consisted 'of various isomeric compounds of the 25 preciable removal of carbon or hydrogen there-v
formula Cal-11.0 and 015K220 which were sub from. .
stituted n?-cyelohexenones. . This application is a co'ntinuation-in-part of
About 250 gms. oi’ the ketone, 186 gms. of 36% my copending application, Serial No. 337,686,
formalin, 35 ms. of 30% aqueous sodium hy-' ?led May 28, 1940.
droxide and su?icient methyl alcohol to homo 30 I claim as my invention: _
genize, were heated at re?ux temperature for 3 1. A process for the production of ketone resins
hours. The catalyst was neutralized, the resin which comprises heating a substituted Ail-cyclo
layer separated and then subjected to distillation hexenone with an aldehyde wherein the aldehyde
in vacuo for recovery of about 42 gms. of un group is linked directly to a member of the class
reacted ketone. About 250 gm. of resin was ob 35 consisting of the hydrogen atom and monovalent
tained whichwas of color F on the Rosin scale hydrocarbon radicals, said heating being effected
and had a softening point of 85° C. on a hot plate. with the reactants in the presence of a condensing
Example XII agent and suflicient organic homogenizing solvent
A mixture was prepared containing about 178 to render the reaction mixture homogeneous at
least when ?rst heated and said substituted A2
ms. of xylitones from condensation of mesityl 40 cyclohexenone being an auto-condensation prod
oxide, 200 gm. of methanol, and 5 gms. of 30% uct of an aliphatic ketone and of the formula
- aqueous sodium hydroxide solution. To this mix
ture there was added about 44 gms. of acetalde
CnHa(m(1_=-l)+1)O wherein m and k are integers with
m or 4 to 10 and 1c of 3 to 9 and n=k><m.
hyde in 100 gms. of methanol in the course of 15 45 2. A process for the production of ketone resins
minutes while maintaining the temperature at which comprises heating a substituted nz-cyclo
about 15° C. The entire mixture was then heated hexenone with formaldehyde in the presence of
for about 3 hours at a re?uxing temperature oi‘ a basic-acting condensing agent and su?icient
about 69° Q. The product'was water-washed and methyl alcohol to render the reaction mixture
distilled. The resin obtained amounted to about 50 homogeneous at least when first heated, said sub
38 gms. and was a dark red, brittle solid with the stituted na-cyclohexenorle being an auto-con
followlngisolubility characteristics: 7
densation product or‘ an aliphatic ketone and of
the formula CnH:(m(lé-l)+l)0 wnerem m and lo are
Solvent Cold Hot integers with ‘m of at least 4 and 1c of at least 3
65 and n=icxm but not more-than 30. .
-1> v thinner 801113100. ’
3. A process for the production of ketone resins
Slightly soluble. which comprises heating formaldehyde with a
oluble.
Do.
substituted Az-cyclonexenone auto-condensation
Do. product of acetone of the formula CnH2(2m+i)O
Do. 60 wherein m is an integer of 4 to 10 and n=3m, said
heating being effected with the reactants in the
Example XIII presence of an alkali metal hydroxide ‘and su?i
cient organic homogenizing solvent to render. the '
Approximately 178 ms. of xylitones from con reaction mixture homogeneous at least when ?rst
densation of mesityl oxide, 106 ms. of benzalde 65 heated. . , ‘

hyde, 4 gms. of 30% aqueous sodium hydroxide 4. A process for the production of ketone resins
solution, and 150 ms. of methanol were heated which comprises heating formaldehyde with a
at about 72° C. for 5 hours. ,1 The ‘reaction product substituted A‘i-cyclohexenone auto-condensation
was washed with water and distilled under sub product of acetone of the formula CnH2(2m+1)O
. ‘atmospheric pressure. The distillable material at 70 wherein 'm is an integer of at least 4 ‘and n=-3m
about 215° C. under 1 mm. pressure was removed but is not greater than 30, said heating being
and about 11 ms. of dark red resin remained. effected with the reactants in the presence of an
This resin was soluble in P and V thinner, ketones, alkali metal hydroxide and su?lcient methyl alco
alcohols higher than methanol and slightly sol hol to render the reaction mixture homogeneous
uble in methanol. 75 at least when ?rst heated.
6 2,888,410
5. A process for the production of ketone resins
which comprises heating formaldehyde with a
substituted AQ-cyclohexenone auto-condensation
product of acetone of the formula CnHll(2m+l)O
wherein m is an integer of at least 4 and n=3m
but is not greater than 30, said heating being ef-'
fected with the reactants in the presence of an
alkali metal hydroxide and sufficient methyl al
cohol to render the reaction mixture homoge
neous at least when ?rst heated. and subsequently 10 action
heating the formed resin which has been freed
of the condensing catalyst at a temperature of
150° C. to 250° C. whereby the softening point of
the resin is increased. ~ ,
6. A process for the production of ketone resins 15 substituted A'i-cyclohexenone auto-condensation
which comprises heating xylitone with formalde
hyde in the presence of sodium hydroxide. and
su?icient methyl alcohol to render the reaction
mixture homogeneous at least when ?rst heated.
7. A process for the production of ketone resins 20 of a condensing agent of formaldehyde with a
which comprises heating xylitone with formalde
hyde in the presence of sodium hydroxide and
sufficient methyl alcohol to render the reaction
mixture homogeneous at least when ?rst heated,
and subsequently heating the formed resin which 25
has been freed of the condensing agent at a tem
' perature of 150° C. to 250° C. whereby the soften
ing point is increased above that of the initially
formed resin. -
8. A process for the production of ketone resins 30 action at an elevated temperature in the presence
which comprises heating formaldehyde with a
substituted AQ-cyclohexenone auto-condensation
product of methyl ethyl ketone of the formula
C1|H2(3m+1)0 wherein m is an integer of 4 to 10
and n=4m.
9. A process for the production of ketone resins
which comprises heating a substituted ALcyclo
hexenone product of crotonaldehyde-type auto
condensation of mesityl oxide containing not
more than 30 carbon atoms with an aldehyde 40
wherein the aldehyde group is linked directly to
~a member of the class consisting of the hydrogen
atom and monovalent hydrocarbon radicals in
the presence of a basic-acting condensation agent
and su?lcient organic homogenizing solvent to
render the reaction mixture homogeneous at least
when ?rst heated.
10. A process for the production of ketone resins
which comprises heating a substituted iii-cyclo
hexenone product of crotonaldehyde-type auto
condensation of mesityl oxide with formaldehyde
in the presence of an alkali metal hydroxide and
su?lcient methanol to render the reaction mix
ture homogeneous at least when ?rst heated.
11. A thermoplastic ketone resin from the reac
tion at an elevated temperature in the presence
of a condensing agent of a substituted ALcyclo
hexenone with an aldehyde wherein the aldehyde
group is linked directly to a member of the class
consisting of the hydrogen atom and monovalent
hydrocarbon radicals, said substituted A=-cyclo
hexenone being an auto-condensation product
of ~- an aliphatic ketone and of the formula
Gamma-mp0 wherein m and k are integers with
mof4to 10 andkof3to9 andn=kxm.
12. A thermoplastic ketone resin from the re
action at an elevated temperature in the presence
of a condensing agent of a substituted iii-cyclo
hexenone with formaldehyde, said substituted
ni-cyclohexenone being an auto-condensation
product of an aliphatic ketone and of the formula
CnH2(m(k-l)+1o wherein m and k are integers with
m of at least 4 and k of at least 3v and n=-k><m
but not more than 30.
13. A thermoplastic ketone resin from the re
at an elevated temperature in the presence
of a condensing agent of an aldehyde wherein
the aldehyde group is linked directly to a mem
. ber of the class consisting of the hydrogen atom
and monovalent hydrocarbon radicals with a
product of acetone of the formula CnH2(2m+l)O
wherein m is an integer of 4 to 10 and n=3m.
14. A thermoplastic ketone resin from the re
action at an elevated temperature in the presence
substituted nz-cyclohexenone auto-condensation
product of acetone of the formula C1|H2(21n+l)0
wherein m is an integer of at least 4 and n=~3m
but is not greater than 30.
15. A thermoplastic ketone resin from the re
action at an elevated temperature in the pres
ence of a condensing agent of formaldehyde with
xylitone. "
16. A thermoplastic ketone resin from the re
of a condensing agent of formaldehyde with a
substituted nz-cyclohexenone auto-condensation
product of methyl ethyl ketone of the formula
C?HlG?H-DO wherein m is an integer of 4 to 10
35 and n=4m.'
17. A thermoplastic ketone resin from the re
action at an elevated temperature in the presence
of a condensing agent of formaldehyde with a
homoxylitone of methyl ethyl ketone.
18. A thermoplastic ketone resin from the re
‘ action at an elevated temperature in the presence
of a condensing agent of an aldehyde wherein the
aldehyde group is linked directly to a member of
the class consisting of the hydrogen atom and
45 monovalent hydrocarbon radicals with a substi
tuted ni-cyclohexenone containing at least two
_ ole?nic double bonds and not more than 30 car
bop; atoms per molecule obtained by crotonalde
hyde-type auto-condensation of mesityl oxide.
50 19. A thermoplastic ketone resin from the
reaction at an elevated temperature in the
presence of a condensing agent of a substi
tuted ni-cyclohexenone from crotonaldehyde
type auto-condensation of mesityl oxide contain
55 ing at least two ole?nic double bonds and not
more than 30 carbon atoms per molecule with a
lower aliphatic aldehyde. '
20. A thermoplastic ketone resin from the re
action at an elevated temperature in the pres
60 ence of a condensing agent of formaldehyde with
a crotonaldehyde-type auto-condensation product
of mesityl oxide containing at least two ole?nic
double bonds and not more than 30 carbon atoms
per molecule which is a substituted N-cyclo
hex'enone.
VERNON n mum.