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Patented‘ov. 5, i946
_'
5410,425 .
ST
*5.
~
2,410,425
ORGANIC POLYBASIC ACID POLYESTER/S
0F “HYDROIHYDRGNORPQLYCYCLOTENTADIENES
Herman A. Bruson, Philadelphia, Pa., assignor to
'
The Resinous Products & Chemical Company,
Philadelphia, Pa, a corporation of Delaware
No'Drawing. Application March 13, 1944,
Serial No. 526,313
6 Claims. (Cl. 260-475)
2
This invention relates to polyesters of organic '
mént products of a polycarboxylic acid and di
cyclopentadiene. They are esters of hydroxy
polycarboxylic acids and hydroxydihydronorpoly
cyclopentadienes. More speci?cally, this inven
dihydronordicyclopentadiene and a polycarbox- '
tion deals with polyesters of said acids and hy
ylic acid and have the general formula:
droxydihydronordicyclopentadiene.
6.
These new esters possess the unique property
of absorbing oxygen from the air to form prod
ucts which are insoluble in water and organic
solvents. They are particularly useful as coating
materials, serving in this respect as drying oils
which have been modi?ed with resins.
These esters may be- prepared in several dif
ferent ways. One method is to reactat least two
Coo; 0 H_\il_1
. Zion-l‘‘m
C
1
wherein, ‘as before, R is the organic residue of a
poiycarboxylic acid, 11. is a small integer of two
or more,‘ and Cal-I4 is a propylene group which
mols of dicyclopentadiene with one mol of an
‘organic poiycarboxylic acid, advantageously in 15 in conjunction with the adjoining carbon atoms
the presence of an acidic condensing agent such
as boron tri?uoride, as described, in copending
forms a cyclopenteno group.
The functional
carboxyl group is attached tothe dihydronordi
application ‘Serial No. 476,639, ?led February 20,
1943, of which the present application is a con- ‘
tinuation-in~part, whereby addition of each car
boxyl group to the endomethylene cycle of the
cyclodienyl ring system at a secondary carbon
atom ?anked by a methylene group and by a
20 tertiary carbon atom in an endoethylene cyclo
pentano group which carries the said propenylene
.group forming a cyclopenteno ring therewith.
neous molecular rearrangement of the latter to
Theaddition of a polycarboxylic acid to di
the nordicyclopentadienyl ring system, thus:
cyclopentadiene having'two double bonds and one
as endomethylene cycle per molecule voccurs readily
at temperatures from about 50° C. to about 145° C‘.,‘
a \ H
dicyclopentadiene is accompanied by a simulta- .
on
-
'
although temperatures both somewhat higher and -
mooon). +1»
51
lower may be used. It is sometimes desirable, but
not ‘essential, to use an organic solvent, such as
benzene, toluene, xylene; ethylene dichloride, or ”
other organic solvent, in which case the reaction
H
may be effected under re?ux.
_
Small amounts of acidic condensing agents
promote the formation of the desired polyesters.
The most e?'ective are boron tri?uoride and itsv
coordination complexes, such asv those formed
with boron’ trifluoride and oxygenated com-»
pounds, including aldehydes, ketones, ethers,
esters, alcohols, and carboxylic acids, typified by
BF3.2CH3CHO, BF‘3.C2I~I5OC2H5, BF: .CHaC‘OOCzI-Is,
BFs.CH3CQCH3, BFaCiI-l'sOH etc. The catalyst
or
CH
calms
CH
_
may be removed from the reaction mixture by
washing with water or mildly alkaline solutions,
‘such as aqueous sodium carbonate solutions.
db
wherein R is the organic residue of a polycar
boxylic acidnand n is an integer of at least two.
The ?rst formula given for the products is
more probable, di?ering from the second only in '
the position of the double bond of the terminal 50
cyclopenteno group relative to the position of the
functional substituent in the opposite terminal .
cycle, an endoethylene cyclopentano group.
The products as thus obtained may be regarded
from one point of view as addition-rearrange
The reaction product may be‘dried with-con
ventional drying agents, or water may be removed
therefrom by distillation of a solvent. The prod
uct may be further purified by treatment with
activated clays or charcoal and/or distillation
under reduced pressure in many cases.
The compounds formed are esters from one
molecule of an organic polycarboxylic acid and
at least two molecules of hydroxydihydronordi
cyclopentadiene.
Another method is to esterify one molecule of
2,410,425
with at least two molecules of hydroxydihydro
, nordicyclopentadiene, a new alcohol obtained by
the hydration-rearrangement reaction of dicyclo
pentadiene with water in the presence of sulfuric
acid, as described in copending application Serial
lead, cobalt, manganese, and other polyvalent
metals supplying siccative action, and of carbox
No. 476,645, filed February 20, 1943, the formation
' ylic acids imparting oil-solubility to the salt, in
' of which may be represented as follows: I
CH2"
.4
admixed with at least one oxidation catalyst.
The oxidation catalysts include peroxides, such
as benzoyl peroxide, tert. butyl hydroperoxide, or
lauroyl peroxide, and metallic driers, such as the
oil-soluble salts of heavy metals, typi?ed by
the organic polycarboxylic acid or its anhydride
eluding naphthenic acids, long-chained fatty
10 acids such as .linolelo and linolenic, and ether
acids, such as butoxyacetic or octyloxyacetlc acids.
Mixtures of peroxides and metallic driers are par
ticularly e?icacious.
When coating compositions comprising the
15 polyesters of this invention and an oxidation cat
alyst are applied to surfaces which are then ex
posed to air or preferably baked at 130° C. to 190°
(3., they are converted to hard, tough ?lms, which
are substantially insoluble in all common organic
20 solvents and are highly water-resistant and non
porous. When used in ?nishes on metal, excep
tional adhesion is obtained, and treated metal
sheets ?nished with a baked coating may be
?exed without cracking or breaking of the ?lm.
Since the new esters are compatible with nitro
25
cellulose as well as with the natural drying oils,
for example, linseed, tung, soyabean, oiticica, and
?sh oils, as well as with many natural and‘ syn
thetic resins, they may be used for the prepara
Hydroxydihydronordicyclopentadlene may thus
30 tion of a wide variety of coating and plastic com
positions.
be represented by the formula:
The following examples illustrate the prepara
tion and properties of these esters:
Example 1
Fifty-nine grams of diethyl carbonate was
mixed with 150 grams of hydroxydihydronorcy
,clopentadiene and one gram of sodium was added.
The resulting mixture was heated in a still under
wherein C3114 is a propenylene group which in
such conditions that the temperature of the va
conjunction with the adjoining carbon atoms 40 por did not exceed 90° C. About 33 grams of dis
forms a cyclopenteno group as oneiterminal cycle. '
Still another method for the preparation of the
esters of this invention is based upon trans‘esteri
tillate was taken off between 80° and 85° C. The
. pressure was then reduced and distillation con
tinues until no more ethyl alcohol was obtained.
iication or ester interchange. According to this
Thereupon, the still residue was distilled under
method, an ester :of a polycarboxylic acid and an 45 reduced pressure. The fraction boiling between
- alcohol of lower molecular weight than hydroxy
200° and 240° C. at 3 mm. was a pale yellow vis
dihydronordicyclopentadiene is heated with hy
droxydihydronordicyclopentadiene in the pres
cous oil, amounting to 61 grams, which upon re- .
ence of a catalyst, such as sodium ethylate or sul
analysis agreed with the formula for di-(dihy
distillation boiled at 217°~220° C./2.5 mm.
furic acid, and the alcohol of lower molecular 50
dronordicyclopentadienyl)
carbonate,
Its
‘
'
-
weight displaced. Thus, by displacing at least
two molecules of a lower molecular weight alcohol
It possessed the following constants: ND25 1.5288;
_ with hydroxydihydronordicyclopentadiene, there
may be prepared polyesters of said acid and said
compound which contain only these components
55
or which contain these components in addition to
_
Particularly useful polyesters are derived from
carbonic, oxalic, malonic, succinic, maleic, fu
‘
‘a
The above ester was mixed with such amounts
of lead, cobalt, and manganese naphthenates as
siccatives that 0.50% of lead, 0.02% of cobalt, and
0.02% of manganese by weight, respectively, were
present in the mixture. A ?lm of this composi
another alcoholic residue or other alcoholic resi
dues.
d4“ 1.0216.
60 tion was formed on a glass plate and allowed to
‘maric, chloromaleic, glutaric, e,a-diethy1 glutaric,
itaconic, adipic, pimelic, suberic, azelaic, sebacic,
dry in the air at room temperature. After forty
phthalic, 3,6 - endomethylene-1,2,3,6-tetrahydro
an oleoresinous varnish was obtained.
eight hours, a hard, dry, colorless film resembling
phthalic, A3-tetrahydrophthalic, tartaric, malic',
Example 2
be prepared from other polycarboxylic acids, such
A mixture of 36.5 grams of adipic acid, 90 grams
of hydroxydihydronordicyclopentadiene, 120
citric, and tricarballylic acids. Esters may also 65
as 'v-alkyl-v-carboxypimelic acids, delta-ketonic
tetracarboxylic acids (of. United States Patent _' grams of benzene, and 0.5 gram of sulfuric acid ,
(95%) was stirred and boiled under a're?ux con
2,329,432) , and the carbocyclic, compounds in
which two to six p-carboxyethyl groups are joined 70 denser attached to a water trap for six hours un
til no more water distilled over with the benzene.
, to unsaturated carbocycles (cf. United States Pat
The product was cooled, washed several times
ent No. 2,339,218) .
with cold water, then with dilute sodium carbon
The new esters are advantageously used as ve
ate solution, followed by a water wash. The ben- '
hicles in preparing paintsyvarnishes, and similar
coating materials. For this purpose, they may be 75 zone was evaporated ed and the excess hydroxy
2,410,425
dihydronordicyclopentadiene
vacuo.
,
distilled
oil
in
dronordicyclopentadiene, and 1.5 grams of con
centrated sulfuric acid was boiled under a re?ux
condenser attached to a water trap for three
1
The residual oil consisted essentially of di
(dihydronordicyclopentadienyl) adipate,
hours, during which time 8.5 grams of water was
collected in the trap. The reaction product was
C10H13—OCO—CH2CH2CH2CH2COO—C10H13
Upon distillation in high vacuo, it boiled between
cooled to room temperature ‘and stirred for sev
eral hours with ?ve grams of powdered calcium
‘250° and 270°C. at 3 mm. and formed a pale
hydroxide. Thev mixture was ?ltered and the
yellow oil which crystallized on standing. After
recrystallization from ethanol, it formed color
less crystals melting at.75°-77." C.
clear ?ltrate distilled at 3 mm. until the benzenev
and excess hydroxydihydronordicyclopentadiene
had been stripped oil‘.
A solution of the above ester in ‘benzene was
'
-
The residual product, consisting of di-(dihy
mixed with lead, cobalt, and manganese naphe
dronordicyclopentadienyl) maleate,‘was a thick
thenates to give a composition containing 0.25%
oil. When heated in the air at 190°-200° C., it
of lead, 0.02% of cobalt, and 0.02% of man 15 rapidly polymerizes to a hard re'sin.- Films of
ganese on the weight of the ester. A ?lm of this
the oil dry by oxidation in the air.
solution was baked on a steel panel for one hour
A solution of equal parts of the above ester
at 150° C. to yield a hard, varnish-like coating.
and linseed oil was mixed with 0.50% of lead,
0.02% of cobalt,‘ and 0.02% of manganese in the
Ewample 3
form of the corresponding naphthenate driers,
20
A mixture of 180 grams of hydroxydihydronor
and ?lms of this solution baked on steel plate
dicyclopentadiene, 59 grams ofsuccinic acid, 200
at 150° C. forone to two hours. Hard, adherent,
grams of benzene, and one gram of sulfuric acid
tough, mar-proof coatings were obtained.
'
(95%) was boiled under a re?ux condenser at
Example
6
tached to a water trap for six and one-half
hours, at which time 18 grams of water had been 25
A mixture of 178 grams of sebacic acid, 531
collected. The product was then cooled and
.grams of hydroxydihydronordicyclopentadiene,
mixed with ten. grams of calcium hydroxide.
110 grams of ethylene dichloride, and 1.5 grams
This mixture was stirred for several hours and
of concentrated sulfuric acid was boiled for two
?ltered. The ?ltrate was evaporated to dryness.
hoursunder a re?ux condenser attached to a
The product, consisting essentially of di-(dihy
water trap until 33 cc. of water had been col
dronordicyclopentadienyl) succinate crystallized
lected. The product was cooled, stirred for two
on standing. After recrystallization from meth
hours with ?ve grams of powdered lime, ?ltered,
anol, it formed colorless crystals melting at
' and the clear ?ltrate evaporated to dryness. The
100° C.
.
.\
35 ' residual oil was heated in vacuo to strip off the
Example 4;‘
excess of the alcohol used. The ?nal product
(a) A mixture of 66 grams oi dicyclopenta
diene, 22.5 grams of anhydrous oxalic acid, and
was a thick oil consisting essentially of di-(dihy-
dronordicyclopentadieneyl) -sebacate.
A solution was prepared by ,mixing this ester
75 grams of tetrachlorethane was stirred and
boiled under re?ux at 135°~140° C. for ?ve hours. 40 with driers to give a composition containing 0.5%
The product was cooled, washed with water, with
dilute soda solution until free from acidity, and
again with water. The liquid was dried and
then evaporated under reduced pressure to re
of lead, 0.03% of cobalt, and 0.03% of manga
nese in the form of their naphthenates. A ?lm
of this solution was formed on a steel plate and
baked for two hours at 135°-150° C. A hard,
move the tetrachlorethane. The residual dark, 45 tough, adherent, mar-proof ?lm of excellent
quality was thus obtained.
viscous product consisted essentially of crude
di-(dihydronordicyclopentadienyl) oxalate. The
In the same manner as described in Example -
6. the phthalic acid ester of dihydronordicyclo
_ yield was '75 grams.
(b) A mixture of 126 grams of oxalic acid
pentadienyl phthalate is obtained as a thick oil
dihydrate, 380 grams of hydroxydihydronordi 50 by using 150 grams of phthalic anhydride in place
of the sebacic acid. When mixed with driers as
cyclopentadiene, 200 grams of benzene, and one
described above, it gives a hard ?lm when baked
gram of 98% sulfuric acid was stirred and boiled
for two hours at 150° C.
under a re?ux condenser attached to a water The corresponding tartaric acid, tricarballylic
trap. At the end of three and one-half hours
of boiling, '74 cc. of water had been separated in 55 acid, citric acid, 3,6-endomethylene-1,2,3,6-tet
the trap, indicating that the esteri?cation was
rahyd'rophthalic acid polyesters of hydroxydihy
complete. The product was cooled to room tem
perature and stirred for a half hour with ten
grams of powdered calcium hydroxide and ?ve
pared. They are thick, autoxidizable, polymer
grams of water to destroy free acidity. The 60
precipitate which was formed was ?ltered off
and the filtrate heated in vacuo up to a vapor _
temperature of 200° C./2 mm. to distill there
from the excess of alcohol. The residue, con
sisting of a black thick syrup, was mixed with an 65
dronordicyclopentadiene can be similarly pre
izable oils useful for the preparation of coatings.
The po1y-dihydronorpolycyclopentadienyl es~
ters of a polycarboxylic acid may be represented
by the general formula:
a melting point of 83°-85° C.
'
.4.»
l CHzl if
C i
R 000- n_'_-
A mixture of 49 grams of maleic anhydride, 70
grams of benzene, 302 grams of hydroxydihy 75
3
' ls.
_l
-C:
'
v Example 5
‘
OH
equal volume of petroleum ether and chilled,
whereupon the crude oxalate crystallized out and
was ‘?ltered, off. After recrystallization from
petroleum ether, the di-dihydronordicyclopenta
dienyl oxalate formed colorless crystals having
_
wherein R. and n have the same signi?cance as
above and m is a number from zero to three, in
clusive.
'
.
2,410,425
7
dicyclopentadiene or the alcohol derived there
from by addition of water and rearrangement to
the norcyclopentadienyl system is used, there
being further'characterized by having the car
boxylic ester groups attached to a terminal cycle
from the rearranged dicyclopentadiene at a sec
' may be used with similar results higher polycy
' clopentadienes or mixtures of dicyclopentadiene
ondary carbon atom thereof, the opposite termi
nal cycle thereofv being a flve-membered ring
and higher crystalline polycyclopentadienes hav
containing one ole?nic linkage.
3. As a new compound, a di-(dihydronordicy
clopentadienyl) ester of a dicarboxylic organic
acid, said ester being the acid-catalyzed addition
rearrangement product of a dicarboxylic acid and
ing two double bonds per molecule. There may
be prepared mixtures of crystalline di-, tri-, tet~
ra-, and penta-cyclopentadiene having two dou
ble bonds and one to four endomethylene cycles
per molecule. These undergo the same esterify
ing reactions as pure dicyclopentadiene. Further
details of the behavior of these polycyclopenta
dienes are given in the patent application. The
polyesters of the various hydroxydihydronorpoly
cyclopentadienes of the type aforesaid all have
the drying properties above described and are
useful in coating compositions.
F'rom'the foregoing, it can beseen that the
dihydronordicyclopentadienyl polyesters of or
ganic polycarboxylic acids are unique and valu
able materials. They are particularly useful as
dicyclopentadiene, said ester being further char
acterized by having each carboxylic ester group
attached to a terminal cycle from the rearranged
dicyclopentadiene at a secondary carbon atom
thereof, the opposite terminal cycle thereof be
ing a five-membered ring containing one ole?nic
linkage.
4. As a new compound, the di-(dihydronordi
cyclopentadienyl) ester of maleic acid, said ester
being the acid-catalyzed addition-rearrangement
product of maleic acid and dicyclopentadiene.
said ester being characterized by having each
carboxylic ester group attached to a terminal cy
varnishes or lacquers, either alone or with sic
catives. They may be mixed in compositions
with drying or semi-drying oils, alkyd resins, and
other ?lmeforming materials. They may be
blown and bodied to a viscous state. They may
be mixed with other autoxidizable derivatives
from pol'ycyclopentadiene, including the esters of
hydroxydihydronordicyclopentadiene and unsat
urated higher aliphatic acids which are claimed
in copending application Serial No. 526,312, ?led
on even date.
I claim:
1
.
1. As a new compound, a polydihydronor
cle from the rearranged dicyclopentadiene at a
secondary carbon atom thereof, the opposite ter
minal cycle thereof being a five-membered ring
, containing one ole?nic linkage.
30
35 carboxylic ester group attached .to a, terminal
cycle from the rearranged dicyclopentadiene at a -
' lyzed addition-rearrangement product of a poly
basic carboxylic acid and a crystalline polycyclo
pentadiene having two double bonds and one to
four endomethylene cycles per molecule, said es“
ter being further characterized by having each
carboxylic ester group attached to a terminal cy
cle from the rearranged polycyclopentadiene at
a secondary carbon atom thereof, the opposite
terminal cycle thereof being a ?ve-membered
‘
5. As a new compound, the di-(dihydronordi
- cyclopentadienyl) ester of sebacic acid,.said ester
being the acid-catalyzed addition-rearrangement
product of sebacic acid and dicyclopentadiene,
said ester being characterized by having each
polycyclopentadienyl ester of a polybasic organic
carboxylic acid, said ester being the acid-cata
ring containing one ole?nic linkage.
8
addition-rearrangement product of a polybasic,
carboxylic acid and dicyclopentadiene, said ester
While in the above examples essentially pure
.
2. Asa new compound, a polydihydronordicyg
clopentadienyl ester of a polybasic organiccar
boxylic acid, said ester being the acid-catalyzed 50.
secondary carbon atom thereof, the opposite ter
minal cycle thereof being a ?ve-membered ring
containing one ole?nic linkage.
6. As a new compound, the di-(dihydronordi
cyciopentadienyl) ester of phthalic acid, said es
ter being the acid-catalyzed addition-rearrange
_ment product of phthalic acid and dicyclopenta
diene, said ester being characterized by having ,
each carboxylic ester group attached to a termi
nal cycle from the rearranged dicyclopentadiene
at a secondary carbon atom thereof, the oppo
site terminal cycle thereoi’ being a ?ve-membered
ring containing one ole?nlc linkage.
A. ‘BRUISON.
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