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Патент USA US3072624

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United States Patent 0
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3,072,614
Patented Jan. 8, 1963
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from 1 hour to 12 hours are employed. The de?ned ester
and diisocyanate may be mixed at room temperature for
from 10 to 30 minutes and ‘then heated to complete the
reaction. This two step method of reaction is particular
3,072,614
_ POLYURETHANE COMPOSITIONS
Benjamin A. Bolton, Gary, Ind., assignor to Standard
011 Company, Chicago, Ill., a corporation of Indiana
No Drawing. Filed Jau. 29, 1960, Ser. No. 5,356
14 Claims. (Cl. 260—77.5)
ly advantageous when an amine catalyst is used; tertiary
amines are a preferred catalyst.
Many amines, particularly tertiary amines, are known
to be useful in reactions to form polyurethane. Suitable
This invention relates to polyurethane compositions.
and particularly it relates to polyurethane compositions
made from glycol triesters of benzene tricarboxylic acids
and organic diisocyanates.
amines include triethylamine, dimethylethanolamine, di
ethylcyclohexylamine, dimethylhexadecylamine, dimethyl
cetylamine, pyridine; substituted pyridines such as 2~(etha
nol) pyridine, 2-(propanol) pyridine, 2—(5~nonyl) pyri
The polyurethane compositions of the invention are
dine, Z-benzyl pyridine, 4-benzy1 pyridine, 2,6-butidine;
made by reacting a herein-after de?ned glycol triester of
quinoline and substituted quinoline such as 3-methyl iso
a benzene tricarboxylic acid with an organic diisocyanate.
The glycol triester used in the reaction has an acid num 15 quinoline; morpholine and substituted morpholines such
as N-methyl m-orpholine, N~et~hyl morpholine, and N-coco
ber from about 0 to not'more than 30.
morpholine. The catalyst is employed in an amount
A Wide variety of hereinafter de?ned glycol triesters
from 0.1 to 3.0 weight percent, preferably 0.5 to 2.0
of benzene tricarboxylic acids may be utilized in making
percent based on weight of the glycol triester.
the compositions of the invention. The acid portion of
The polyurethane compositions of the invention are
the triester may be derived from trimellitic acid, tnimesic 20
useful in coatings, foams, and adhesives. The composi
‘acid, and/ or hemimellitic ‘acid. The preferred esters are
tions may be used alone or in compositions with various
?llers and additives known in the polyurethane art; for
derived from trimellitic acid and trimesic acid.
The glycol portion of the 'triester of the benzene tri
carboxylic acid may be derived from ethylene glycol,
propylene glycol, diethylene glycol, triethylene glycol,
example carbon black.
25
butanediol, heptanediol, or poly-glycolethers such as poly
ethylene glycol and polypropylene glycol having an aver
Example I
19.2 grams of trimellitic anhydride (0.1 mole‘) and 45
grams of triethylene glycol (0.3 mole) were placed in a
?ask provided with agitation and a nitrogen atmosphere.
age molecular weight as high ‘as 4000. Advantageously,
the glycol constituent of ‘the triester is a glycol having
from 2 to 12 carbon atoms; preferred glycols are di 30 Provision was made for removal of water of reaction.
The contents of the ?ask were heated at a temperature
of from 420 to 440° F. for 21/2 hours. The acid number
The de?ned triesrter may be purchased as a true triester
of
the ester product was 25.
compound or it may be prepared by reacting the desired
21/2 grams of tolylene diisocyanate, a commercial mix
glycol and the desired benzene tricarboxylic acid or an
hydride. An “ester product” suitable ‘for use in the inven 35 ture containing 80% of the 2,4-isomer and 20% of the
ethylene glycol, triethylene glycol, and 1,4-butanediol.
tion may be prepared by reacting from 2.9 to 3.5 moles
of glycol per mol of acid; preferably from about 3.0-6.3
moles of glycol per mole of acid. Any of the benzene
tricarboxylic acids or anhydrides may be used: trimellitic
3,6-isomer (0.014 mole), and 10 grams of the triethylene
glycol ester product and 3 drops of an amine catalyst
(Selectofoam 6202 made by Pittsburgh Plate Glass Co.)
were mixed by simple stirring in a beaker. Considerable
acid, trimesic acid, hemimeliitic acid, trimellitic anhy 40 heat of reaction was evolved. After a few minutes re—
action time, a ?lm was coated on tin plate and a small
dride, hemimellitic anhydride.
quantity was poured into an aluminum dish. The ?lm
The temperature employed for preparing the de?ned
and the material in the dish were heated for 1/2 hour at
esters is from about 300° F. to about 550° F., preferably
260° F. The ?lm and the material in the dish were soft
from about 400° F. to about 500° F. The time required
for the reaction will vary depending upon the reactants; 45 and spongy.
Example 11
the time should be su?icient to yield a product having
the desired acid number in the range of from 0 to not
5 grams of tolylene diisocyanate (0.28 mole) and 10
more than 30.
v
grams of the triethylene glycol ester product prepared in
The preparation of the de?ned ester may be advan
Example I and 3 drops of an amine catalyst (Selecto
tageously carried out in an inert atmosphere. It is bene 50 foam 6202) were reacted and treated as in Example I.
?cial to provide for removal of water of reaction during
The cured ?lm was very hard and had excellent ?exibility.
the esteri?cation reaction.
The material cast in the aluminum dish foamed con
A wide variety of organic diisocyanate compounds may
siderably and was execeptionally tough and hard. When
be utilized in making the compositions of the invention.
struck by a sharp hammer blow the material compressed
The compound may be an aromatic diisocyanate such as 65 and did not shatter.
tolylene diisocyana-te, naphthalene diisocyanate, phenylene
diisocyanate, diphenyl methane diisocyanate; a substituted
aromatic diisocyanate such as methoxyphenylene diiso
Example III
50 grams of triethylene glycol (0.33 mole) and 19.2
cyan-ate, phenoxy phenylene diisocyanate, chlorophenyl
grams (0.1 mole) of trimellitic anhydride were placed in
60 a ?ask provided with agitation and a nitrogen atmosphere.
me'thylene diisocyanate, tetramethylene diisocyanate, cy
Provision was made for removal of water of reaction.
clohexylene diisocyanate. Advantageously, the diiso
The contents of the ?ask were heated at a temperature
cyanate is aromatic; a preferred diisocyanate is tolylene
of 415° F. for 21/2 hours. The acid number of the ester
diisocyanate.
product was 15.5.
ene diisocyan-ate; or an aliphatic compound such as hexa
In the preparation of the polyurethane compositions 65
5 grams of tolylene diisocyanate (0.028 mole) and 10
of the invention, the ratio of ‘the de?ned ester to the di
grams of the triethylene glycol ester product were reacted
isocyanate is usually from about 0.5 mole to about 1.5
and treated as inExample I.
moles; preferably from about 0.6 mole to about 1.2 moles.
The product was. similar to that of Example II but
The time and temperature required for the reaction of
slightly more brittle.
the de?ned ester ‘With the diisocyanate varies with the 70
Example IV
different compounds. In general, a temperature from
4 grams of tolylene diisocyanate (0.023 mole) and 10
about 150° F. to about 300° F. and a time of reaction
3,072,614
A.
3
grams of the triethylene glycol ester product prepared in
Example III were reacted and treated as in Example I.
The ?lm cast on tin plate had excellent ?exibility and
hardness.
,
Thus having described the invention what is claimed is:
1. A polyurethane composition consisting of the poly
urethane reaction product of (I) a triester of an un
a
an acid number of not more than 30, and (II) an organic
diisocyanate in an amount of from about 0.6 to about 1.2
moles of said triester produce per mole of said diisocyan
ate, at an elevated temperature for time su?icient to pro
duce a polyurethane reaction product.
10. The composition of claim 9 wherein said acid is
trimellitic anhydride.
substituted benzene tricarboxylic acid and a glycol, said
11. The composition of claim 9 wherein said acid is
glycol having a molecular weight of not more than about
trimesic acid.
12. The composition of claim 9 wherein said glycol
4,000, and (II) an organic diisocyanate, in an amount of 10
is triethylene glycol.
from about 0.5 to about 1.5 moles of said triester per
mole of said diisocyanate, at an elevated reaction tem
13. The composition of claim 9 wherein said glycol is
perature for time suf?cient to produce a polyurethane
1,4-butanediol.
reaction product.
14. A polyurethane composition consisting of the poly
2. The composition of claim 1 wherein said glycol is 15 urethane reaction product of (I) a triester product pre
ethylene glycol.
pared by reacting a benzene tricarboxylic acid selected
3. The composition of claim 1 wherein said glycol is
from the class consisting of trimellitic anhydride and
triethylene glycol.
trimellitic acid with triethylene glycol in the ratio of
4. The composition of claim 1 wherein said acid is
about 3.0~3.3 moles of said gylcol per mole of acid at a
trimellitic acid.
20 temperature of 400440“ F., said triester product having
5. The composition of claim 1 wherein said acid is
an acid number from about 10 to about 30, and (II) toly
trimesic acid.
lene diisocyanate in a ratio of from about 0.6 to about 1.2
6. The composition of claim 1 wherein said diisocyan
moles of said triester product per mole of said diisocyan
ate is an aromatic diisocyanate.
ate, said reactants being reacted at ordinary temperature
7. The composition of claim 1 wherein said ester is 25 for about 10 minutes and then for about one-half hour
the ethylene glycol triester of trimellitic acid.
at 260° F.
8. The composition of claim 1 wherein said ester is
the triethylene glycol triester of trimellitic acid.
9. A polyurethane composition consisting of the poly
urethane reaction product of (I) a triester product pre
pared by reacting a benzene tricarboxylic acid selected
from the class consisting of unsubstituted benzene tri
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,929,794
Simon et a1 ___________ __ Mar. 22, 1960
206,295
57,722
Australia ____________ __ Feb. 10, 1955
Netherlands __________ __ June 15, 1946
carboxylic acids and anhydrides thereof with a glycol hav
ing 2 to 12 carbon atoms, in the ratio of 2.90 to 3.5 moles
of glycol per mole of acid at a temperature from about 30
300° F. to about 550° F., said triester product having
FOREIGN PATENTS
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