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Патент USA US2122089

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Patented I‘ June28, 1938
UNITED STATES PATENT ‘OFFICE >
>
_.
2.122.089
PnocEss For. THE MANUFACTURE‘ or
.
ARTIFICIAL nnsms
Werner Conrad, Cologne, Germany, assignor to
the firm Her-big: Haarhaus Aktiengesellschaft,
Cologne-Bickendorf, Germany
w,
.
' No Drawing. Application November 2'1, 1935,
Serlal No. 51,965. In Germany November 30,
10 Claims. (Cl. 260-—'8)
and unsaturated and/or saturated higher fatty
This invention relates to a process for the acids and also polybasic acids or their derivatives.
.1934
manufacture of arti?cial resins.
Various proposals have already been made for
the manufacture of‘ arti?cial resins from poly
hydric alcohols, higher unsaturated or saturated
fatty acids and polybasic acids or their‘ deriva
tives.
_
_
'_
According to an earlier process the acid of a
drying-oil or the oil itself is added'to the mixture
of glycerine and phthalic anhydride during the
condensation process, which takes place in the
10
presence of sulphuric acid.
_
'
~
In another, publication it has been proposed
to employ the phthalic anhydride prior to the
The process of the invention consists in that
esters from polyhydric alcohols and polybasic“
acids, which esters still possess free hydroxyl 5
groups, are brought into reaction with esters
from polyhydric alcohols and higher fatty acids,’
which esters also still contain free hydroxyl
groups the fatty acid esters employed preferably
having an acidv number of about 2, and the poly- 10
basic acid esters employed preferably an acid
number of about 20., The etheri?cation may take
place in accordance with the following scheme
of formulae:--
.
15 resin formation for the solution of the drying
oil and then to carry out the condensation with
glycerine.
“
J
H
I
A third process consists in that theoil and the
ester from poly-basic acid and polyhydric alcohol
20 are boiled in a high boiling solvent whereby the
oil becomes distributed in the resin.
Then it has been proposed initially to esterify
the glycerine only partly with phthalic anhydride
and then to carry out an esteri?cation of the still
free hydroxyl groups with a mono-basic acid.
A further proposal consists in converting
glycerine or other polyhydric alcohols. with mono
free
R indicates fatty acid residue.
hydroxyl groups,‘ which in a second stage are
R’ residue of-a diebasic acid.v
' basic acids into
esters still containing
substituted with polybasic acids such ‘as phthalic
acid.
.
In accordance with, a recent proposal mono
esters which are prepared from at least trihydric
polyhydric alcohols and conjugated unsaturated
higher fatty acids are only treated with such
quantities of a polybasic acid or. its anhydride
that only a second hydroxyl group of the glyc
erine residue for example is substituted so that
the third .hydroxyl group still present remains
40 available for‘ etherlike condensations.
"
All known processes depend in principle upon -
a linking of the individual alcohol molecules by
45
esteri?cationwith ‘the carboxyl groups of the
polybasic acids, the‘ introduction of the fatty acid
components, which impart to the resin drying
'
The reaction takes place exclusively between 30
the free hydroxyl groups of incompletely esteri
?ed polyhydric alcohols. In ‘an astonishing mane
ner the linking of the components has therefore
been successfully effected by etheriflcation only.
The importance of this reaction for the manu- 35
facturev of arti?cial [resins from polyhydric
alcohols, higher monobasic fatty acids and poly
basic acids or their derivatives is shown by the
following characteristics of the reactions for the
combination of the above mentioned constituents. 40'
The introduction of a fatty acid into an already .
produced condensation product does not allow of
the production of uniform products; the pro
posed application for this type of process of high
boiling solvents renders the end products useless 45 I
energy, cohesion, elasticity and resistance to for many purposes. The application of an agent,
weather, taking place either before, during or, promoting the condensation, such as sulphuric acid, renders the resins produced unsuitable for
' after the condensation process between the poly
use in coating materials owing to the discolora
hydric alcohol and‘ the polybasic acid.
tion occurring. ,
' .
.
.
50
In accordance with the present invention new
arti?cial resins which are particularly suited on
account of their valuable properties for applica
tion as a basis for lacquers, as impregnating,
?lling and sizing agents and also for molded
55
articles, are produced from polyhydric alcohols
y
The hitherto known processes for the linking
of an ester from a polyhydric alcohol and a higher
unsaturated fatty acid with a polybasic acidhave
the great disadvantage that for the condensation
,a long boiling process is necessary which in- '55
_
teaose
jm'lously in?uences the colour of the products
obtained. The long boiling process is, however,
The following ‘examples illustrate the invené
tion.
unavoidable in order to obtain at all uniform,
Example .1
neutral, utilizableproducts. On the other hand,
it is discovered that in the manufacture of a con- ‘
densation product from a polyhydric alcohol, for
example of ,“Glyptal”, from glycerine and
phthalic anhydride, even in along boiling process
the quality of the resin is in no way injured and
10 products can be produced in which practically no
free carboxyl groups are still present.
Two mols of glycerine and 2 mols of phthalic
anhydride are esteri?ed at 190° C. to an acid
number of 20. This ester, which 'still contains 2
freehydroxyl groups, is etheriiied with 1 mol.
of a mono-ester which has been produced in the
known manner by alcoholysis of one mol. of 10
linseed oil with two mols of glycerlne at about
'275“ C. For etheri?cation the temperature of
The etherl?cation of the free hydroxyl groups
still contained in such products with the hydroxyl - the mixture is increased to about 290° C. By
groups of an ester of a polyhydric alcohol and a this means with foaming the etheri?cation sets
15 fatty acid takes place extraordinarily rapidly at - in. after a short time and the reaction product 15
elevated temperature. Since, as is known, the becomes clear. The resin produced is, in the cold,
manufacture of the esters of the latter type offers hard and very light coloured. It has the acid '
no di?culties, the new process allows of the number 4 and is easily soluble in aromatic hy
manufacture of light coloured arti?cial resins of drocarbons, alcohols and the nitrocellulose sol
20 completely neutral nature, which is shown for vents. It is compatible with basic pigments and 20
example by the ‘fact that the new products can after treatment with drying substances dries
be worked up with basic pigments such as zinc in 8 hours. It is furthermore suitable for oven
white without thickening.
drying.
-
The new process o?ers the further possibility oi
the production of arti?cial resins in which, ac
cording to the requirements whichthe resin is
intended to ful?l, the individual constituents can
be varied in quantity to a far-reaching extent.
Thus for example both a mono-acid ester and
30 also a di-acid ester of a polyhydric alcohol can
be etheri?ed with a condensation product from
a polybasic acid and a polyhydric alcohol. As
cs
regards the constituents of the components of
the condensation product, for example Glyptal,
care need only be taken that over and above the
hydroxyl groups necessary for complete satura
tion of the carboxyl groups further hydroxyl
groups remain free for etheri?cation. Within
Example 2'
Three mols of glycerine and two mols of;
phthalic anhydride are esteri?ed at 190° C. as
'in Example 1 and etheri?ed with three mols of
a (ii-ester which has been produced in the known
manner by alcoholysis of two mols of rape oil
with one moi. of glycerine at 275° C. For etheri
?catlon the mixture is heated to about 290° C.
vfor half an hour, if ‘desired until the foaming
is complete. The very light resin produced is
viscous and is soluble in aliphatic and/or aro
25
matic hydrocarbons, alcohols, esters and ethers,
It has the acid number 2 and is compatible with
basic pigments. It is excellently suited as resin
constituent in nitrocellulose lacquers.
these limits the individual constituents can be
varied corresponding to practical requirements.
Example 3
Obviously it is not necessary that in the two es
ters to be etheri?ed equivalent quantities of un
40
One vmol. of glycerine and one mol. of octode
cadiene carboxylic acid are esteri?ed at about
esteri?ed hydroxyl groups should always be pres
ent; in the one or in the other constituent hy
275° C. to an acid number 1. Two mols of glyc
erine and two mols of phthalic anhydride are
esteri?ed at 190° C. to an acid number of about
20, in a separate batch. The two esters are now
etheri?ed at about 290° C. The resin is similar
droxyl groups can be in excess, being then free
for further etheri?cation. In addition it is possible to add during or after the ether formation
drying and/or non-drying oils.
in its properties to that obtained in Example 1.
Example 4
a far-reaching extent by, subsequent treatment
One
incl.
of
erythrite
is esteri?ed with two
with air orsulphuror by another known process '
for coating materials. They can likewise be mols of tall oil distillate up to an acid number
mixed with natural resins such as. colophony, 2 and etheri?ed with an ester from two mols
copal or their esters or arti?cial resins, such as of methyladipic acid and two mols of glycerine.
phenol-formaldehyde condensation products, The temperature is maintained at 220° C. until 55
formaldehyde-urea condensation Products .or the etherification is complete. The resin is suit
vinyl resins, pigments, ?lling materials and the able for the manufacture of molded articles and
The properties of the arti?cial resins produced
according to the new process can be improved to
like.
.
.
impregnating agents.
.
' It has already been proposed to convert glyc
erlne and resins ?rst into mono- or di-glycerldes,
which are then converted among themselves into
tion and properties:---
ether-like complexes by subsequent condensation.
The present invention is fundamentally distin
Acid number____ __ 181.8
Moisture content__
3.7%
:-.w1;-'.
Resin acids_-______
Total acids _____ __
32.2%
93.7%
therefrom in that no etheri?cation be
tween similar esters takes place but, for
pie,
Iodine number____ 115.0
,
of glycerine-mono-oleic acid ester with, for ex- , ‘
ample,v glycerine dl-succinic acid ester. The
small addition of phthalic acid provided in the
'30 mown process has only the importance of a
agent which in addition is in-=
tended to accelerate the etheri?cation, whereby
' however the dibasic acid is esteri?ed with the
glycerine mono-acid ester, which does not
75 place in the present case.
e
.
The tall oil distillate employed according to
the ‘present example has the following composi 60
'
Saggni?cation num
r __________ __ 190.3
Speci?c g r a v i t y
0.920 at _____ __ 20°
Unsaponi?able____
6.3%
atty acids _____ __
______ __c._..__
61.5%
0%
Example 5
Two mols of glycerine areesteri?ed with two
mols of phthalic anhydride at 190° C. to an acid 7.0
number of about 20. One mol. of mono-ester
from two mole of glycerine and one mol. of lin
seed oil stand oil is then added. There is fur
ther added one third mol. of linseed oil and the
three components areheated to 290° C. until any 75
s
3
‘ ' 2,122,089
turbidity has disappeared.v The resin produced‘
is very light coloured and solublein aliphatic and
aromatic hydrocarbons, alcohols, esters, ethers
hols partly esteri?ed with fatty acids selected
from the group of saturatedand unsaturated
15 drocarbons, alcohols and esters.
- I wish it to beunderstood that I do not desire
to be limited to the exact details of the process
polyhydric alcohol partly esteri?ed witha poly
basic organic‘carboxylic acideach of the esteri
?ed products being produced with polyhydric al
cohol exceeding in substantial amount the molec
ular equivalent necessary for complete reaction
higher fatty acids with polyhydric alcohols partly
esteri?ed by a .polybasic ‘organic carboxylic acid
and drying and/or non-drying oils.
‘ each
of the esteri?ed products being produced with
Example 6
' polyhydric alcohol exceeding‘ in‘ substantial
One mol. of glycerine and one mol. of stearic amount the molecular equivalent necessary for
acid ~are esteri?ed at about 275° C. to an acid complete reaction with the carboxyl groups of
number 1. Two mols of glycerine are esteri?ed "the acids and incorporating a glyceride oil into
10
vwith
two mols of phthalic anhydride' at 190° C. ‘the ether complex.v
10
6. A composition containing the reaction prod
to an acid number of about 20 in aseparate
batch. The two esters are now etheri?ed at 290° uct of a polyhydric alcohol partly esteri?ed with
C. The very light resin produced is similar to a fatty acid selected from the group of saturated
and unsaturated higher fatty acids, with the
wax and dissolves in aliphatic and aromatic hy
described, for obvious chemical equivalents there
of will occur to a person skilled in the art.
I claim:
15‘
' with the carboxyl groups of the acids.
1 '
20
'7. A composition containing the reaction‘com
resins in which polyhydric alcohols partly ester "plex of a glyceride oil with the reaction product
iiied with fatty acids selected from the‘ group of of a'polyhydric alcohol partly esteri?ed by a fatty
saturated-and unsaturated higher fatty acids are acid selected from the group of saturated and un
~ reacted with polyhydric alcohols partly esteri?ed saturated higher, fatty acids, with a polyhydric 25
by a polybasic organic 'carboxylic acid each of alcohol partly esteri?ed by a polybasic organic
the esteri?ed‘ products being produced with poly. carboxylic acid each "of the esteri?ed products be
hydric alcohol exceeding in substantial amount ing produced with polyhydric alcohol exceeding '
the‘ molecular equivalent necessary for complete in substantial. amount the molecular equivalent
1. The . process 'of manufacturing arti?cial
- necessary for complete reaction with the carboxyl 30
reaction with the carboxyl groups of the acids.
groups of the acids.
2. The process of manufacturing arti?cial
8.'A light colored, substantially neutral resin
resins in which polyhydric alcohols partly esteri-‘ comprising
the reaction product resulting from
?ed with a fatty acid selected from the group
the reaction of two esters still containing free
hydroxyl groups obtained by the esteri?cation of 35
glycerine with linseed oil stand oil’ and glycerine
- of saturated andunsaturated higher fatty acids
are reacted with polyhydric alcohols partly ester;
l?ed by a polybasic organic carboxylic acid at
elevated temperatures, each of the esteri?ed prod
ucts being produced with polyhydric alcohol ex
with phthalic anhydride, respectively each of
the esteri?ed products being produced with
glycerine exceeding in substantial amount, the
ceeding in substantial amount - the molecular
molecular ~ equivalent necessary for complete 40
equivalent necessary for complete reaction with
reaction with the carboxyl groups of the acids.
‘the carboxyl groups of the acids.
.
3. The process of manufacturing arti?cial
’9. The process of manufacturingv arti?cial
resins which comprises reacting polyhydric alco—‘ resins-in which esters from polyhydric alcohols I‘
hols partly esteri?ed with fatty acids selected from and fatty acids selected from the-group of satu
rated and unsaturated higher fatty acids are re-‘ 45
the group of saturated and unsaturated higher
fatty acids with polyhydric alcohols partly esteri (‘acted with esters from polyhydric alcohols and
?ed by a-polybasic organic carboxyiic acid each polybasic acids each of the esteri?ed products be
of the esteri?ed products being produced with ing produced with polyhydric alcohol exceeding
polyhydric alcohol exceeding in _ substantial in‘ substantial amount the molecular equivalent
amount the molecular equivalent necessary for necessary for completevreaction with the car 50
groups of the acids, the esters employed
complete reaction with the carboxyl groups of the boxyl
acids and'then subsequently treating the prod-‘ being practically neutral and containing at least
ucts with a modifying agent selected from air and one free hydroxyl group each.
10. The process of manufacturing arti?cial
sulphur.
'
v
'
resins in which esters from polyhydric alcohols 55
and fatty acids selected from the group of satu
rated and unsaturated higher fatty acids are
. 4. The process of manufacturing arti?cial
‘ 5‘ resins which comprises reacting polyhydric alco
hols partly esteri?ed with fatty acids selected
from the. group of saturated and unsaturated heated to a temperature of about 290° C. with
‘higher fatty acids with polyhydric alcohols partly esters from polyhydric alcohols and polybasic
esteri?ed by a polybasic organic carboxylic‘acid acids each of the esteri?ed products being pro 60
duced with‘ polyhydric ‘alcohol exceeding in sub
inthe presence of a glyceride oil each‘of the esteri
stantial amount the molecular equivalent neces
?ed products being produced with polyhydric al
cohol exceeding in substantial amount the molec- _ sary for complete reaction "with the carboxyl
ular equivalent necessary for complete-reaction groups of the acids, the esters employed being
_ with the carboxyl groups of the acids.
-
practically neutral and containing at least one
5. The process _' of manufacturing arti?cial ' free hydroxyl group each.
resins which comprises reacting polyhydric alco
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