close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2130740

код для вставки
'
Patented Sept. 20, 1938
2,130,140 i -.
UNITED? STATES PATENT OFFICE
2,130,740
mm ‘AL
HYDBOGENATEDrnonuomo
ss'rsas 0FAND
METHOD
OF
oonor.
Del., assignor
'
‘
Humphrey, Wilmington,
Irvin W.
to Hercules Powder Company, Wilmington,
DeL, a oorporation‘o! Delaware
No Drawing. Application August so, 1933, '
Serial No. some; .
.
46 Claims- (CL 280-400)‘
Thus. for example, a rosin ester, as ethyl abie- ‘
Thislinventi'on relates to esters of hydrogenat
ed abietyl alcohol and method of producing. -
The esters contemplated by this invention will
be produced from fully or partially hydrogenated
tate, in solution in ethyl alcohol is heated with
metallic sodium and the abietyl alcohol formed
is recovered. The abietyl alcohol is then treat
ed with hydrogen at elevated temperature and, 5
abietyl ‘alcohol, as, for example, dihydro and ' pressure in the presence of a base metal hy'dro- ‘
5 tetrahydro abietyl alcohol or their mixtures, by
genation catalyst as nickel, cobalt, copper chro- f
reaction with an organic acid or, an equivalent mite, etc., or at lower temperatures in the pres- “
therefor according to the method contemplated ‘ ence of a noble metal catalyst as platinum, pal
ladium, etc. ' For example,the abietyl alcohol 10
by this invention.
=
More speci?cally in producing esters in ac-‘ may be hydrogenated by treatment with hydro
cordance with this invention abietyl alcohol may gen ata temperature of 125-225’ .C., and under
be first hydrogenated to the desired degree and ' a hydrogen pressure of about 5-400, atmospheres,
then esteri?ed with an organioacid or equiv
in the‘ presence of a nickelhydrogenation cata
. alent by heating with or without the use of‘ an
esteri?'cation- catalyst. >Or' the abietyl alcohol
15
may first be esteri?ed with the organic acid,
and the abietyl ester so formed hydrogenated to
tion of a mixture oi dihydro- and tet'rahydro
abietyl alcohol by addition of hydrogen to the
abietyl alcohol. The
the desired degree. The hydrogenated abietyl
proportion
alcohol may also be prepared directly by the
hydrogenation and reduction 0! the abietyl
20'
-group to the-alcohol group of abietic acid or its
r
,
lyst. Such procedure will result in the produc
esters.
is
}
increased with'increase oi the pressure used 50.
above about 100 atmospheres.
- '
.
Alternatively, for example, the‘ hydrogenated‘
abietyl alcohol may be produced by reducing
.
In proceeding to the practical-adaptation oi , the. ester group of, for example, hydrogenated '
this invention theabietyl alcohol may. be pro- ' ethyl butyl or methyl abietate to the alcohol 35 '
as for example group with ‘hydrogen, ata temperature of about .
ducedby any suitable method,
225-325° C., under-pressure of 80-1000 atmos
ple, ethyl or methyl abietate, in amonohydric pheres and in the presence of, a conversion cata
\
nickel chromite.
aliphatic alcohol, for example, ethyl or butyl ‘lyst such as copper-chromite,
alcohol, heating the solution with metallic so‘ etc. If desired hydrogenated rosin, dihydro
dium, diluting the solution with water, distilling . abietic acid, tetrahydroabietic acid, or- their mix
of the low boiling alcohol, and ?nally extracting -; tureamay be converted into dihydro- or tetra
the abietyl alcohol iormed by means of a water hydro-abietyl alcohol or mixtures ‘thereof simi
immiscible solvent, as benzene." Hydrogenationn larly. The rosin ester, rosin, or abietic ‘acid
may‘ be ?rst hydrogenated by contacting with a=
of the abietyl-alcohol so produced ‘may be ‘ac
complished .byany oi the well known methods ' base metalI hydrogenation catalyst as nickel, cop- ‘
‘for the’ hydrogenation of unsaturated com per-chromite, cobalt, etc., at a temperature of
about 150-225“ C. and under about 10-500 at- ”
Hydrogenated abietyl alcohol may also be ob- .mospheres hydrogen pressure, yielding ' either
tained by reducing the carboxyl group of hydro
dlhYdI'O-r and tetrahydro-abietate esters or di
genated abietic acid to a primary‘ alcohol group hydro- and~tetrahydro-abietic acid.
' .
> _ ‘
by dissolving an ester of abietic acid, for exam-.
pounds.
,
,
,
_
,
e
.
4.0. ‘by
treatment oi hydrogenated abietic‘ acid, or’ ~ The esters contempla ‘ by this invention may
rosin, or anester of hydrogenated abietic acid vhe formed by‘ reacting partially or fully hydroe
genated abietyl alcohol with an ‘organic acid,
with hydrogen ‘under pressure of say about 70
‘ ‘at anjelevated temperature of
' 1000 atmospheres
say about 225-350’ C., in the presence or ‘a’ cata
' lyst, such
as, , for.‘ ‘ example,
copper; chromite,
to. . all
as is more fully dis
nickel chromite, e,
_
or equivalently with an organic anhydride, or
certain organic acid compounds, as organic, acid
chlorides, acid esters, etc. The organic acid or
equivalent. may ,be- aromatic, hydroaromatic,'
closed in my application vfor United ‘States Let- " he'terooyclic, or aliphatic. and may :be monobasio -
'
ters Patent, Serial Number 004,859. ?led April.
this application is a continuaé
12, 1932,
of which
tion
in part;
The hydrogenated abietyl alcohol‘ '
oi dihydroe or tetrahy
so'produced will consist
droabietyl alcohol-or a mixture thereof depend
ing upon the exact conditions ‘of temperature
andpressure employed.
or polybasic. As illustrative, the organic acid 501
or equivalent may, for example, be acetic, butyric,
propionic, valeric, iuroic, benzoic, cinnamic,
oleic, palmitic, stearic, lauri ,
linoleic; linolenic, abietic, dihydro abietic, tetra- ‘
- salicylic, lactic,
hydro 1abietic, pimaric, \ricinoleic, 'dihydroxy 5s
2
, 2,130,740
stearic', glycollic, formic, naphthenic. anisic,
at any operable temperature and pressure. Any
.capric, tetrahydro-furoic acid, caprylic, cerotic,
pyruvic, naphthoic,'sorbic, hydrosorbic, carnau
temperature, including room temperature, which
‘ bio, mellissic, margaric, toluic, erucic, levulinic,
myristic?monylic, sativic, undecylenic, alpha or
beta-elaeostearic,
10
etc.,~ or
'mixtures
I
" thereof; -
adipic, citric, citraconic, maleic, malic,» tartaric,
sebacic, succinic, terep thalic, phthalic, itaconic, sirably at temperatures say within about the
malonic, oxalic, glutaric, suberic, camphoronic, ' range
150°-300° C., and generally fairly rapidly
methyl succinic, terephthalic, azelaic, ~aconitic,
tricarballylic, diphenic, fumaric, naphthalic,
acids present in copal and kauri, and pyromel
erally be completed, when using the temperatures
indicated, within about 2-15 hours depending
upon the temperature, catalyst, reactivity of the
acidic groups in acid esters as mono-methyl suc
acid, and proportion of reagents.
cinate, alpha-terpinene monobutyl maleate, the
The reagents may be heated in any desired pro
monoethyl maleate of methyl abietate, the'di
methyl maleate of abietic acid, the monomethyl
20 ester of alpha-pinene-maleic anhydride, mono
ethyl phthalate, etc., may be esteri?ed with hy
" drogenated abietyl alcohol.
at 175-225” C., under atmospheric pressure,
while, desirably, permitting the water produced
in the reaction to escape. The reaction will gen
litic, etc., or mixtures thereof. Substituted. or
ganic acids as monochlor acetic, dichlor acetic,
15 nitrobenzoic, etc., may be used.. likewise the
25
will not decompose the reagents or the product,
under the pressure conditions prevailing and at
which the reaction will proceed, in other words,
various reaction temperatures may be used.
Generally speaking, the reaction will proceed de
portion, but usually itwill be found e?icient to
react the hydrogenated abietyl alcohol and an
organic acid or equivalent in about the desired 20
chemically equivalent reacting proportions form
As indicated, or
ing neutral or acid esters from polybasic acids.
ganic anhydrides, as acetic, phthalic, maleic, suc
cinic, etc. anhydrides, or addition products of
maleic anhydride to unsaturated compounds, as
As speci?cally illustrative of the _ practical
adaptation of the method in accordance with this
invention for the production of the product con 25
templated, for example, 9 parts by weight of hy
terpinene-maleic anhydride, dipentene-maleic
anhydride, abietic-acid-maleic anhydride, abie drogenated abietyl alcohol, say comprising a mix
tyl-alcohol maleic anhydride, 'butadiene-maleic ture of dihydro and tetrahydro abietyl alcohol,
30
anhydride, pinene-m leic anhydride etc. may be
Since hydrogenated abietyl alcohol is high
used.
-
'
is heated at about 200° C., for about 8 hours with
-
1.8 parts of succinic acid, using an air condenser 30
hydrogenated abietyl alcohol will be converted
to permit the removal of water of reaction. The
boiling, the esters may generally be produced
without the useof acatalyst, especially when
the organic acid is also comparably non-volatile, ’
as is the case, for example, with abietic, hydro
genated abietic, succinic, stearic, palmitic, etc.,
acids. However, it is frequently desirable to em
ploy‘ a catalyst- and when such is used, for ex
~ample, 1-8% byI weight of dry hydrogen chloride
40 or concentrated hydrochloric acid, less than 1%
of concentrated sulphuric acid, anhydrous zinc
chloride, small amounts of phosphoric acid, or a
small percentage of paratoluene sulphonic acid,
benzene sulphonic acid, acid sodium sulphate,
45 boric anhydride, etc., or mixtures thereof will be
found satisfactory.
into an ester of low acidity.
v
As a further illustration, v21 parts of hydro
genated abietyl alcohol is allowed to react with 35
80 parts of acetic anhydride, containing 4 parts
of sulphuric acid as a catalyst, at room tempera
ture, for three days. The resultant ester will
show only a few‘ percent of unreacted alcohol.
As a further illustration‘, 10 parts of hydro 40
genated abietyl alcohol are-heated with» 10 parts
_ of hydrogenated rosin for 5 hours at 250°-260°
C., and then for 5 more hours at 260°-280° C.
The resultant ester is a hydrogenated abietyl hy
droabietate.
.
The esters in accordance with this invention
If desired in carrying out the method conteme‘
plated a relatively low boiling water irmniscible are usually amorphous compounds. Sometimes
solvent for the ester product, as benzene, toluene, they are'very viscous liquids but are more gen
50 carbon tetrachloride, etc., may be used to assist erally solids with melting points varying from
about 50 to 100". C. (dro-pmethod). When con
in the removalof the water of reaction.
ditions are such as to effect a high degree of 50
In the practical adaptation of the method em
v bodying this
invention for production of the es
_
ters contemplated, generally speaking the hydro
genated abietyl alcohol, as dihydro or tetrahydro
abietyl alcohol,’ or a mixture thereof, will be
reacted by heating with an organic acid, ‘or
equivalently an organic anhydride, or acid com
pound of an organic acid, as an acid ester, with
60 or without-use of a catalyst and/or a low boil
ing water immiscible solvent to facilitate the
removal of water of reaction. On completion of
esteri?cation the acid number varies from 5 to 25. .
They are in general more readily saponi?ed thanv
esters of abietic acid. Esters of hydrogenated
abietyl alcohol are more resistant to discolora 55
tion on aging than esters of non-hydrogenated
abietyl alcohol. They have thiocyanate values
Oif from 0 to about 40 depending upon the de
gree of hydrogenation of the unsaturated bonds
of the abietyl alcohol, and exhibit much lower.
iodin . values than those of the corresponding
non-hydrogenated abietyl esters. Their proper
ties also depend upon the purity of the hydro
vent, as benzene, toluene; etc., and the solution
washed with aqueous alkali, to remove excess
acid with ?nal evaporation of the solvent.
If a ‘volatile organic acid, ‘such ‘as, for exam
ple, acetic acid, etc., be used the esteri?cation
.may be ‘carried out bypassing an excess of the
vvolatile acid into the heated hydrogenated abietyl
alcohol. The excess acid may be removed along
with the water‘ of reaction by distillation.
75
In proceeding, the reaction may be carriedv out
genated abietyl alcohol used.
'
The prbducts in accordance with this invention 65'.
will be found variously adaptable for use in the
commercial arts as, for example, ingredients in
coating compositions, as lacquer, varnishes, etc.,
or‘ in plastic compositions. The products in ac
cordance with this invention may be advanta-' 70
geously used in such compositions to replace in
whole or in part other resins heretofore used for
such purposes.
‘This application is~?1ed as a continuation in 75
.
.
3
1 2,180,740
a resin acid in the presence or heat at a reaction
part of an application for United States patent
for method of producing abietyl alcohol and
product, ?led by me April 12, 1932, Serial Num
ber 604,859.
'
temperature.
'
~
which in- ‘
25. The method of forming an ester
_
cludes reacting hydrogenated abietyl alcohol with
a fatty acid in the presence of heat at a reaction
'
What I claim and desire to protect by Letters
Patent
1. Anis:organic carboxylic acid ester of hydro
genated abietyl alcohol. I '
cludes reacting hydrogenated abietyl alcohol ‘
with phthalic acid in the presence of heat at a
- reaction temperature.
10'
27. The method of forming an ester'which in
genated abietyl alcohol.
3. A dibasic carboxylic acid ester of hydrogen
ated abietyl alcohol. '
.
4. An aromatic carboxylic acid ester of hydro
cludes reacting hydrogenated abietyl alcohol with‘
hydrogenated abietic acid in the presence of heat
at a reaction temperature.
“
‘
‘
28. A carboxylic acid ester of hydro-abietyl 15
genated abietyl alcohol. '
5. An aliphatic carboxylic acid ester of hydro
15
'
26. The method of forming an ester which in
’
2. A monobasic carboxylic acid ester of hydro
10
temperature.
alcohol.
.
I
29. A compound _ oi the
genated abietyl alcohol.
H
general
formula
hydrogenated‘ abietyl Ab-eCI-I
O-—R, where Ab stands for the.
6. A resin acid esterof
hydrocarbon
nucleus
of ,hydroabietic acid, whilev
alcohol.
'
7. A fatty acid ester of hydrogenated abietyl _ R stands for an organic radical of the alkyl,
‘alcohol.
'
aralkyl, cycloalkyl or aryl series.
’
30. The ester of hydroabietyl alcohol and an '
“a. The method of forming an ester which in
cludes reacting hydrogenated abietyl alcohol with
an organic carboxylic acid.
acetic acid. 4
31. Hydroabietyl acetate.
‘
25
32.. Hydroabletyl-hydroabietate.
9. The method of forming an ester which in
33. An ester of a polycarboxylic acid wherein
the hydrogen of at least one carboxyl group is
cludes reacting hydrogenated abietyl alcohol with
25 an acid organic carboxylic acid compound.
10. The method of forming .an ester which in
'replaced by the radical'of a hydroabietyl alcohol: a
34. A hydroabietyl phthalate.
35. The method which includes reacting in the 30
an organic carboxylic acid in the presence of
cludes reacting hydrogenated abietyl alcohol with
presence of heat a hydroxyl group of a hydro- .
heat at a reaction temperature.
_
o 11. The method of forming an ester which in
genated abietyl alcohol with a carboxyl group
derived from a carboxylic acid.
36..The method of producing an ester which
cludes reacting hydrogenated abietyl alcohol with
an organic carboxylic acid at a temperature of
includes reacting in the presence of heat a hy 35
12. The method of forming an ester which in- _ droxyl group of a hydrogenated abietyl alcohol
cludes reacting hydrogenated abietyl alcohol with a carboxyl group of a polycarboxylic acid.
37. The method of producing an ester which
with an organic carboxylic acid-in the presence
'
includes reacting in the presence of heat and in 40
of an esterification catalyst.
the
presence
of
a
volatile
water-immiscible
sol
13. The method of forming an. ester which in
cludes reacting
abietyl alcohol vent for the ester product a hydroxyl group of
with an organic carboxylic acid in the presence or hydrogenated abietyl alcohol with a carboxyl
heat at a reaction temperature and in the pres
group of a polycarboxylic acid.
. about 150 to about 300° C.
ence of an esteri?cation- catalyst.
'38. Hydroabietyl phthalate.
_
_ 39. The method of forming an ester which in 45
14. The method of forming an ester which in
cludes reacting hydrogenated abietyl alcohol with
cludes reacting hydrogenated abietyl alcohol
with an organic carboxylic acid at a tempera
150 to about 300° C. and in the
' ture of about
presence of an esteri?cation catalyst.
15. A polybasic carboxylic acid ester of hydro
genated abietyl alcohol.
"
16. A hydroxy carboxylic acid ester of hydro
gena'ted abietyl alcohol.
>
-
'
1
19. A saturated‘carboxylicacid ester of hydro
genated abietyl alcohol.
20. A su
reacting hydroabietyl alcohol with a carboxylic
acid compound under anhydrous conditions.
.41. The method of forming an ester which in
a carboxylic acid in the presence oi a dehydrating
'
-
‘
cludes reacting a hydroxyl group of hydrogenated
ylic acid. .4
_
‘
_
I
43. The method of forming an ester which in 60'
cludes reacting hydrogenated abietyl alcoholwith
hydrogenated abietyl alcohol. .
21. A phthalic acid ‘ester of hydrogenated
an organic polycarboxylic acid.
'44.‘ An unsaturated. polycarboxylic acid .ester
'
22. A hydrogenated abietic acid ester of hydro‘
-_. of hydrogenated abietyl alcohol.
genated abietyl alcohol.
65
o
_
,
45. The method of forming an ester which in_- =65
23. The method oi‘forming an ester which in
cludes reacting hydrogenated abietyl alcohol with
cludes reacting hydrogenated abietyl alcohol
an organic polycarboxylic acid.
.'
' 46‘. A hydroxy ipolycarboxylic acid’ ester or
with an organic carboxylic acid at a temperature
of about 175° C. to about 225° C.‘
. -
24. The method‘ of forming an ester which in
cludes reacting hydrogenated abietyl
10
a
42. The method of forming an ester which in
. abietyl alcohol with a carboxyl group of va carbox- -
'stituted. carbonylic acid ester . ofv
abietyl alcohol.‘
ester of hydroabietyl alcohol, which comprises
agent.
18. An unsaturated carboxylic acid ester of
hydrogenated abietyl alcohol.
_
40. The process of preparing a carboxylic acid
cludes reacting hydrogenated abietyl alcohol with
1'7. A cyclic carboxylic acid ester of hydro?‘
genated abietyl alcohol.
a carboxylic acid anhydride.
alcohol with
hydrogenated abietyl alcohol.
‘
_,
IRVIN
'
Документ
Категория
Без категории
Просмотров
0
Размер файла
515 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа