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Патент USA US2404204

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2,404,204
Patented July 16, 1946
UNITED STATES PATENT OFFICE
DROXYLATED FATTY‘l OILS AND ALPHA
UNSATURATED POLYCARBOXYLIC ACIDS
Maynard ‘C. Agens and Birger W. Nordlander,
Schenectady, N. Y., assignors to General Elec
tric Company, a corporation of New York
. No Drawing. Application January 20, 1943,
Serial No. 472,988
19 Claims.
1
(c1. zsofzs)
2
,
The present invention relates to polymerizable
resinous compositions comprising decarboxylated
partial or half esters of hydroxylated fatty oils,
‘,Butyl methacrylate has been found to be an ideal 1
material for this purpose when elastic or ?exible
products are desired. Styrene gives a more rigid
copolymer which is elastic or ?exible at elevated
such as castor oil or hydrogenated castor oiLand
I an alpha unsaturated polycarboxylic acid.
temperatures. Another composition useful for
the production of heat-hardened cast bodies or
?lling compounds is a mixture of at least twenty
per cent by weight of the decarboxylation prod
It is
concerned particularly with compositions of this
type capable of being polymerized by application
of heat to a solid state.
In the copending patent application, Serial No.
not with raw castor oil. Such mixtures may be
422,905 (now Patent 2,373,527), ?led December 10 modi?ed by the addition of butyl methacrylate
13, 1941, in the name of Maynard C. Agens and
assigned to the same assignee as the present in
vention are disclosed and claimed synthetic res
The following examples will serve to illustrate
typical compositions falling within the scope of
inous compositions comprising decarboxylated
the present invention:
or the like.
partially esteri?ed alpha-unsaturated polycar 15
boxylic acids in which the ester group or groups
were derived from mono- or polyhydric alcohols.
The partial esters were generally prepared by re
acting an alpha unsaturated polycarboxylic acid,
such as maleic acid or its anhydride, with an al
cohol in proportions such that about one-half
of the carboxyl groups of the acid'remained un
"
.
Example 1
Castor oil ______________ __v___ 742.5 g. (0.8 mol)
Maleic anhydride __________ __ 157.5 g. (1.6 mols)
The above ingredients were heated together for
20 46 minutes, the temperature rising to 179° C.
The acid value dropped from an original .200 to
101 showing that the ,anhydride reaction result
esteri?ed in the reaction product. The partial
ing in the formation of a maleic ester had taken .
ester was heated with decarboxylating agents
place. About 10 g. (0.12 mol) pyridine was added »
such as pyridine, quinoline, nicotine, piperidine, 25 to 500 g‘. of the above reaction product and the
and their homologues capable of decarboxylating
heating continued at temperatures ranging from
the free carboxyl groups of the acid. The result
110° to 200° over a 2% hour period. During this
ing products were heat-polymerizable.
.
time another 10 g. of pyridine was added. Con
The present invention is concerned with poly
siderable carbon dioxide was evolved during the
merizable compounds of the above general type 80 reaction period. The ?nal product was a viscous
in which'the alcoholic radical is one derived from
resin having an acid value of 36.4. With a per
castor oil or an equivalent polyester of a long
oxide catalyst such as benzoyl peroxide this’resin
chain hydroxy fatty acid and a polyhydric a1
set to a solid, ?exible state when heated on a
cohol. The ‘free hydroxyl groups of the fatty acid
radicals are reacted with an alpha unsatu
rated polycarboxylic acid, speci?cally an alpha
unsaturated alpha, beta dicarboxylicacid such
as maleic acid or its anhydride, in proportions
such that the principal products are acid or half
esters of the polycarboxylic acid. Decarboxyla
tion of these half esters by heating with a decar
boxylating agent has been found to result in the
formation of oily or syrupy resinous compositions
steam bath. ,
35 _ A25 per centsolution of the resinous product i
in monomeric butyl methacrylate was used to gel,
a large quantity of raw castor oil in the following
manner:_
.
'
-
Parts by weight
40 25% solution of resin in butyl methacrylate__
25
Castor oil containing 11/2 % benzoyl peroxide_ 75
The above ingredients were thoroughly mixed
and the mixture heated in an 80° C. oven. An
which polymerize on heating to a solid, infusible,
and somewhat elastic or ?exible‘state and which 45 infusible, ?exible gel was formed in one-half hour.
The heat-gellable. mixture was particularly
are particularly useful for making castings, as
?lling compounds, etc.
-
Particularly useful compositions are obtained
adapted for use as a heat-hardenable ?lling com
pound for electrical apparatus.
‘
by copolymerizing the decarboxylated products
Example 2
with other compatible polymerizable compounds, 50
e. g. styrene and the higher methacrylic esters
Castor 011 ________________ __ 462 g. (.5 mon
such as butyl methacrylate, capable of polymer
Maleic anhydride _________ __ 73.5 g. (.75 mol)
izingby virtue of the polymerizable
'
i
'
The above were heated together for one-half
hour at 100° C. to 178° C. The product, consist
ing essentially of the half ester, was cooled to
I"
2,404,204
3
4
.
form at 150° C. Unlike polystyrene, the copoly
mer does not ?ow at elevated temperatures. At
150° C. the product had a power factor of 0.003
121° C. and about 15 g. (0.18 mol) pyridine added
and the resultant mixture heated for 2 hours at
121° to 228° C. to form a reddish, viscous resin
having an acid value of 39. The resin solidi?ed,
in bulk when heated witha polymerization cata-;
at 60 cycles.
The same, copolymer containing
7.5 per cent ?int ‘as a ?ller had a dielectric con
Ul
stant of' 3.8 and a power factor of 0.003 at 40
'
’
A gellable composition prepared from this resin n. . megacycles at room temperature.
lyst such as ben'zoyl peroxide.
Although maleic anhydride and pyridine have
had the following composition:
been used in illustrating the manner in which
the: present. invention may be carried into effect,
, Parts by weight
___- __________________ ___.-___~____1_»..__
25.
Butyl niethacrylate ______ __; _____ -a _____ __
Resin
25
Castor oil ________________ _____l__
v
-it is to be understood that other alpha unsatu
rated polycarboxylic‘ acids and other decarbox
_._ 50
Benzoyl peroxide _________ _.._’____.
ylating'a'gents may be substituted for thesespe- ,
a ' 0.51 -
cif?e materials asv is set forth more fully in the
This composition gelled to an elasti
heated for 80 minutes at 80°
above-mentioned patent application, Serial No,
_ 7,
¢'4é22,905.'~Examp1es-of other suitable alpha un
saturated polycarboxylic acids are fumaric acid,
itaconic, acid, and aconitic acid. The alpha un
saturated, alpha, beta dicarboxylic acids such as
Example 3
A heat-gellablecomposition consisting oficastor i
oil and the decarboxylated maleic anhydride
maleicand fumaric acids are preferred since the
castor :oil reaction product of Example 2 was 20
made as follows:
/
>
free carboxyl groups in the mono-esterification.
products of either of these acids are readily de-_'
carboxylated to form terminal CH2=CH< groups
irrespective of which carboxyl group of the. acid
reactant has become esteri?ed by reaction. with.
the hydroxyl groups on the fatty acidradicals.
Decarboxylati'ng agents found suitable for the
‘
' 'Pa'rts byweight,
Castor; oil containing
benzoyl peroxide_; 70
Resin. of Example 2__'____'__'__:__~_1 ________ -e. 30
This mixture could‘ be gene-<1 by heating to
80°C‘. for‘ 2 hours. ' The exact gel timej'depends '
on- the acid value of the decarboxylation product.
If the acid value does not substantially exceed
30', two hours heating at 80° C. is ample. With
higher acid value products, a somewhat'longe'r
curingtime may befound‘ necessary.
practice of the present invention are those se
lected from the group’ consisting of pyridine,
qui'noline, nicotine, .piperidine; and their homo
'
logues.
The hydroxylated
,
" ‘fatty
A
oil. half-esters
,
of the
" The‘heat-gellabl'e product of Example 3is par
ticularly useful as a ?lling compound‘for elec
trical apparatus where a ?exible or elastic, shock
alpha unsaturated acids or. their anhydrides may
theoretically be formed by'reacting the oil and
‘acid, in equimolecular proportions. However,
faster reaction rates-rand. better products are
absorbing .?ner posseslsipglg°9d§l€°t¥i®l Prop"
erties-is required. ‘Neither natural rubber nor
synthetic rubbers such as Hycar are swelled by '
obtained when the mol. ratio of polycarboxylic
acid to fatty oil. is somewhat greater than 1:1,
anyof these castor oil products. In some cases
for, example about 1.521.
the natural and’ synthetic rubbers exert ‘a slight
When 3 mols maleic ‘ '
40 anhydride were reacted with 1. mol castor oil
inhibiting effect on theigell‘ation of the portion
and. the resulting product decarboxylated by
of the ?lling compound in direct contact with
thefrubber but this effectmayv be overcome by‘
coating the surface of ‘the rubber prior to intro’
treatment with pyridine, a very viscous, reddish
resin having an acid value of 77 was obtained.
The product polymerized, quite rapidly on heat
I ducti'on of the ?lling compound with a'suitablel. 1' ing with. a'peroxide' catalyst. In general, we
lacquer. "
,
:
prefer to react at least' one and. not exceeding
Example 4*
approximately two mols. of alpha unsaturated
, This example illustrates the preparation of - a
flexible infusiblecopolym'er of the decarboxyl'ate'd- .
polycarboxylic acid with each mol of castor oil '
~ as the products so obtained arev most easily han
dled in the preparation of vcopolymers or gels,
castor oil-maleic anhydride. esterification product;
andibutyll' methacrylate.
’ .
need.’ not exceed the; minimum' quantity found
necessary to decarboxylate the‘ free carboxyl.
I A'solution‘of '75 g. of the liquid resin of Exam
ple 2 in 75 gr. butyl methacrylate was mixed‘ with
160g. additional butiyl meth-acrylate and 0.375 g.
benzoyl peroxide. The copolymer formed ‘by
heating the'mixture for 15 hours at 50° C., 8 hours
at 80° C., and 8 hours at 100° C. was an infusible,
?exible ‘solid which at elevated temperatures was
very rubbery and elastic. It had a dielectric‘ con
stant-of 6.4 at a frequency of 60 cycles and 3.6‘
, groups. In general, fromv 0.1 to 0.3 mol of decar~
boxylating agent per mol polycarboxylic acid
is sufficient.
~
Example 5
,
\
7
V
' this invention may be employed in applications
other than those’ which are. speci?cally men
tioned- hereinbefore.
Since they exhibit good
curing and air-drying properties, particularly in .
the presence of sicca-tives, they may be. used in
the preparation of coating compositions, impreg
1 nating compositions, insulating compositions, etc.
C.) if with or‘ without the addition: of ?llers,v such as
wood ?our, asbestos, glass ?ber, sand, paper, etc.
A styrene copolymer was prepared by heating
a mixture of 10 parts styrene and 1 part of the
decarboxylation product of Example 2 with 1 per
,
The oily resinous d-ecarboxylation. products of
at 1000cycles. It was found to be useful for the
samelapplications as the castor, oil vgels of the
previous ‘examples.
_
The amount of decarboxylating agent used
, What we claim as new and desire to secure
by‘Letters Patent of the. United, States, is:
~-
1;.A
polymerizable- decarboxylated
partial
cent by Weight of a peroxidencatalyst, speci?cally 70 esteri?cation product of a hydroxylated fattyIoi-l
tertiary ,butyl hydroperoxideh After '15, hours
and an alpha unsaturated ‘polycarboxylic acid
heating at 60° C. a ?exible gel ' was obtained.
obtained
Further heating for '8- hours at 80° C‘. and 15 hours,
product of a hydroxylated fatty oil and an alpha
at 1500* c. resulted‘in the 'formatinn‘lofwari‘gid
unsaturated polycarboxylic acid containing free '
product which ‘became fl'exible'but 'di'd'fn‘ot de
carboxyl groups with an amine selected from the
by heating,v a- - partial->-esteri?‘cation
2,404,204
6
5
‘11. A composition of matter comprising castor
group consisting of pyridine, quinoline, nicotine,
piperidine, and their homologues.
2. A heat-polymerizable composition of matter
oil and at least 20 per cent by weight of a poly
merizable composition comprising a decarboxy
comprising a resinous compound obtained by
heating a hydroxylated fatty oil half-acid ester
of an alpha unsaturated polycarboxylic acid with
a cyclic amine selected from the group consist
carboxylating agent selected from the group con
ing of pyridine, quinoline, nicotine, piperidine,
sisting of pyridine, nicotine, quinoline, piperidine,
and their homologues to effect decarboxylation
and their homologues.
lated acid ester of. an alpha unsaturated, alpha,
beta dicarboxylic acid and castor oil obtained by
heating said acid ester in the presence of a de
‘
12. A composition of matter comprising (1) a
of unesteri?ed carboxyl groups of said ester.
'10
resinous material obtained by heating a partial
3. A heat-curable composition of matter com
ester of castor oil and an alpha unsaturated
prising (1) a decarboxylated, hydroxylated fatty
alpha, beta polycarboxlic acid in the presence of
oil acid ester of an alpha unsaturated polycar- ~
a cyclic amine selected from the group consist
?cation product of a hydroxylated fatty oil and ' 15 ing of pyridine, quinoline, nicotine, piperidine,
~ boxylic acid obtained by heating apartial esteri
and their homologues to effect decarboxylation
of the unesteri?ed carboxyl groups of said ester
an alpha unsaturated polycarboxylic acid con
taining free carboxyl groups with an amine se
lected from the group consisting of pyridine,
and.‘ (2) a methacrylic ester of an aliphatic alco
hol compatible with (1) .
quinoline, nicotine, piperidine, and their homo
logues and (2) a methacrylic ester of an aliphatic
alcohol compatible with (1) .
13. A composition as in claim 12 wherein the
20 methacrylic ester is butyl methacrylate.
4. The heat-cured composition of claim 3.
5. A composition as in claim 3 wherein the
alpha unsaturated polycarboxylic acid is an
alpha unsaturated alpha, beta polycarboxylic
14. A heat-curable composition of matter com
prising (1) a polymerizable liquid obtained by '
heating a partial esteri?cation product of one
mol of castor oil and from 1 to 2 mols maleic
‘
anhydride with pyridine/to effect decarboxyla
6. A heat-curable composition of matter com
tion of unesteri?ed carboxyl groups in said par
acid.
tial esteri?cation product and (2) styrene.
prising (1) a polymerizable compound obtained
by heating (a) a partial esteri?cation product
.of poly ester of a long chain hydroxy fatty acid
and an alpha unsaturated dicarboxylic acid,
‘ ' 15. A heat-gellable composition of matter com- a
prising castor oil and a butyl methacrylate solu
tion of a polymerizable liquid Obtained by heat
ing a partial esteri?cation product of one mol of
castor oil and 1 to 2 mols maleic anhydride with
from 0.1 to 0.3 mol of pyridine per mol maleic
about one-half of the carboxyl groups of the
dicarboxylic acid component of said ester being
unesteri?ed, with (b) a cyclic amine selected
anhydride to effect decarboxylation of unesteri
from the group consisting of pyridine, nicotine,
quinoline, piperidine, and their homologues to 35 ?ed carboxyl groups in said partial esteri?cation
effect decarboxylation of unesteri?ed carboxyl
16. A process which comprises forming a par
groups of said alpha unsaturated dicarboxylic
tial ester of an alpha unsaturated polycarboxlic
acid and (2) castor oil.
7. A composition of matter capable of form 40 acid and a hydroxylated fatty oil and decarboxy
ing a stable gel on heating comprising a major
lating the free acid group by heating said partial
product.
»
'
'
portion of castor oh and a minor portion of a
ester in the presence of a decarboxylating agent
polymerizable resinous material obtained by
selected from the group consisting of pyridine,
quinoline, nicotine, piperidine, and their homo
heating a partial esteri?cation product of castor
oil and an alpha unsaturated dicarboxylic acid
with a cyclic amine selected from, the group con
.
logues.
17. A process Which comprises heat-reacting a
hydroxylated fatty acid oil with an alpha un
sisting of pyridine, nicotine, quinoline, piperidine,
saturated alpha, beta dicarboxylic acid to form
and their homologues to effect decarboxylation of
unesteri?ed carboxyl groups of said alpha unsat
urated dicarboxylic acid.
8. A composition of matter ‘capable of being
converted to a non-fusible stable gel on heating
comprising castor oil and at least 20 per cent by
weight‘ of a polymerizable resinous material ob
tained by decarboxylating a partial esteri?cation
an acid ester in which approximately half of
the acid groups of said dicarboxylic acid are un
esteri?ed and heating said acid ester in contact
with an agent selected from the group consist
ing of pyridine, quinoline, nicotine, piperidine,
and their homologues to decarboxylate the un- _
esteri?ed carboxyl group.
18. The process which comprises forming a
castor oil acid-ester of maleic acid and decar
boxylating the unesteri?ed carboxyl groups on
product of castor oil and maleic anhydride by .
heating said partial esteri?cation product with
a decarboxylating agent selected from the group
consisting of pyridine, nicotine, quinoline, piperi
dine and their homoloogues.
'
9. A heat-gellable composition of matter com
prising castor oil and at least 20 per cent by
60
, said acid-ester by heating said ester in the pres
ence of a decarboxylating agent selected from
weight of a decarboxylated partial ester obtained '
the group consisting of pyridine, quinoline, nico
tine, piperidine, and their homologues.
19. The process which comprises heating a
by heating together (1) the partial esteri?cation
hydroxylated fatty acid oil with maleic anhy
product of one mol castor oil with from 1 to 2 65 dride to form a half ester of maleic acid and
mols maleic anhydride and (2) from 0.1 to 0.3
heating said half ester with pyridine to decar
mol pyridine per mol maleic anhydride used in
boxylate the free carboxyl groups of said half »
preparing the partial esteri?cation product of
(1).
ester.
MAYNARD C. AGENS.
-
10. The heat-gelled product of claim 8.
70
BIRGER W. NORDLANDER,
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