United States Patent Office .

2
is
terminal epoxide groups. A further variation is possible
2,830,038 by reacting a molar excess of a polyalkyleneether glycol
POLY (POLYALKYLENE ETHER URETHANE) with an organic diisocyanate so as to form a polyurethane
containing terminal hydroxyl groups. This may then
SMSSENTAINING TERMINAL EP- 5 be reacted with two mols of an organic diisocyanate so
as to form an isocyanate-terminated polyurethane, fol
Dexter B. Pattison, Wilmington, Del, assignor to E. I. lowed by the reaction with two mols of a hydroxy epox
du Pont de Nemours and Company, Wilmington, Del, ide. In addition, it is possible to prepare polyurethane
a corporation of Delaware polyepoxides within the scope of the present invention
No Drawing. Application May 7, 1957 l0 by reacting one mol of an organic diisocyanate with one
Serial No. 657,504 - mol of a hydroxy epoxide to form an intermediate con
- taining terminal epoxy and isocyanate groups and then
10 Claims. (C. 260-77.5) reacting two mols of this intermediate with one mol of
a polyalkyleneether glycol so as to provide a polyure
This invention relates to novel polyurethane poly- 15 thane containing terminal epoxide groups. It is quite
epoxides and more particularly to polyurethane poly- obvious that various modifications of these procedures
epoxides which are prepared from polyalkyleneether may be used without departing from the spirit and scope
glycols and which may be cured to form highly useful of the present invention.
elastomers. The polyalkyleneether glycols which are used in the
Heretofore polyalkyleneether glycol/polyurethane 20 present invention may be represented by the formula
polymers have been found to possess several properties HO(GO)H, wherein G is an alkylene radical and m
which make them uniquely useful in a number of applica- is an integer. It is desired that m should be sufficiently
tions. It has not been possible, however, to use these large so that the glycol has a molecular weight of from
polymers with advantage as liquid polymers which could about 750 to 3500. These polyalkyleneether glycols
be mixed with a curing agent, poured into place, and 25 may be prepared by the polymerization of cyclic ethers,
then cured to form an elastomer in situ. The difficulty such as alkylene oxides or dioxolanes, or from the con
usually encountered is the fact that the polymers are densation of glycols. It is to be understood that in any
extremely reactive with the curing agents and, therefore, given glycol, the alkylene radicals represented by G need
become too viscous before the mixtures can be used as not necessarily be the same, as, for example, in poly
practical curable liquids. 30 tetramethylene formal glycol. Representative glycols in
It is an object of the present invention to provide novel clude polyethyleneether glycol, polypropyleneether gly
polyurethane polyepoxides. Another object is to provide col, polytetramethyleneether glycol, etc. For purposes
a process for the preparation of these novel polyurethane of the present invention, polytetramethyleneether glycol is
polyepoxides from polyalkyleneether glycols. A still preferred. Instead of using a polyalkyleneether glycol,
further object is to provide novel polyurethane poly- 35 othriglycols such as polyalkyleneether-thioether glycols.
epoxides which are prepared from polyalkyleneether gly- or polyalkylene-aryleneether glycols may be used.
cols and which may be mixed with curing agents to form Any of a wide variety of organic diisocyanates may
relatively stable curable liquids. A still further object be used to prepare the polyepoxides of the present in
is to provide a process for obtaining cured elastomers vention, including aromatic, aliphatic, and cycloaliphatic
from these novel polyurethane polyepoxides. Other ob- 40 diisocyanates, and combinations of these types. Mix
jects will appear hereinafter. tures of two or more organic diisocyanates may be used.
These and other objects of the present invention are Representative compounds include toluene-2,4-diiso
accomplished by a novel polyurethane polymer having cyanate, m-phenylene diisocyanate, 4-chloro-1,3-phenyl
a molecular weight of from about 1000 to 11,000 and ene diisocyanate, 4,4'-biphenylene diisocyanate, diphenyl
being characterized by the formula 45 methane-4,4'-diisocyanate, 1,5-naphthylene diisocyanate,
O O -'
of Si-OH,-O-(-NH-B-ENE-3-O-g-o--N-BNH-8-0-CH-4 Sch,
R in R
wherein O-G-O is a bivalent radical resulting from 50 1,4-tetramethylene diisocyanate, 1,6-hexamethylene di
removal of the terminal hydrogen atoms from a poly- isocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclo
alkyleneether glycol having a molecular weight of from hexylene diisocyanate, 4,4'-methylene-bis(cyclohexyliso
about 750 to 3500; B is a bivalent organic radical, said, cyanate), and 1,5-tetrahydronaphthalene diisocyanate.
radical being inert to isocyanate groups; n is an integer Arylene diisocyanates, such as toluene-2,4-diisocyanate,
ranging from about 1 to 11; and R is selected from the 55 are preferred.
group consisting of hydrogen and a methyl radical. The hydroxy epoxide compounds which are used to
These polyurethane polymers may be converted to cura- prepare the polyepoxides of the present invention are
ble liquid polymers by incorporating them with a com- compounds wherein the epoxide portion and the hy
pound such as a polyamine having at least two nitrogen droxyl portion are linked by a methylene radical. Rep
atoms with hydrogen attached thereto, or a polycarboxylic 60 resentative compounds include glycidol and 2-methyl
acid anhydride. They may then be cured by the applica- : glycidol. The preferred compound is glycidol.
tion of heat to form highly useful elastomers. . As mentioned above, the novel polyurethane polyepox
The polyurethane polyepoxides of the present inven- ides of the present invention may be prepared by several
tion may be prepared by several general procedures in- general procedures. In one typical method, a molar excess
volving the reaction of an organic diisocyanate with a of an organic diisocyanate is reacted with a polyalkylene
polyalkyleneether glycol and a compound containing one "ether glycol so as to form an isocyanate-terminated poly
hydroxyl and one epoxide group. Thus one mol of a urethane. Molar ratios of diisocyanate to glycol may
polyalkyleneether glycol may be reacted with two mols of range from about 12:11 to 2:1. The reaction between
an organic diisocyanate to form an isocyanate-terminated an organic diisocyanate and a polyalkyleneether glycol,
polyurethane which may then be reacted with two mols to San be accomplished by heating from 1 to 5 hours at 100
of a hydroxy epoxide to form a polyurethane containing, 'C., or by heating for longer times at lower temperature,
 2,830,038
... 3 . - - 4
wide variety of aliphatic or aromatic polycarboxylic acid
e.g., 10 hours at 60° C., with agitation and preferably anhydrides,
under an inert atmosphere such as a blanket of nitrogen. such as glutaric anhydride, phthalic anhydride,
The resulting isocyanate-terminated polyurethane may pyromellitic dianhydride may be used. Additional com
then be reacted with the hydroxy epoxy compound in pounds which may be used are succinic anhydride, maleic
molar ratios of polyurethane to the hydroxy epoxy con anhydride, phthalic anhydride substituted in the nucleus,
pound of about 1:2. The resulting polymer will be a hydrogenated phthalic anhydride, and polymerized acid
polyurethane containing terminal epoxide groups and anhydrides such as polyadipic and polysebacic acid anhy
having the general formula recited above. These poly drides. The amount of organic polycarboxylic acid anhy
urethane polyepoxides may be described as being rela dride which is necessary to effectively cure the polyure
tively stable, viscous liquids or solids melting below 10 thane polyepoxides must be selected so as to provide one,
mol of anhydride for each epoxide group. This is the
100° C.
As described above, the polyurethane polyepoxides of theoretical amount. The amount of anhydride may be
the present invention may be converted to curable liquid as high as 80 to 110% of this theoretical amount. The
polymers by incorporating therewith a liquid organic poly reaction mechanism involves conversion of the anhydride
amine or polycarboxylic acid anhydride. These curable 5 groups and epoxide groups to ester linkages.
liquid polymers can be cured to produce highly useful The following examples will better illustrate the nature
elastomers by pouring them into molds and heating at of the present invention; however, the invention is not
temperatures of about 80 to 160° C. If desired, some intended to be limited to these examples. Parts are by
of these liquid polymers can be cured by allowing them to 20 weight unless otherwise indicated.
stand at room temperature for longer periods of time. Example 1 -
It is preferred that these liquid polymers be cured by the
application of heat since the reaction of the polyamine or 37.4 parts of toluene-2,4-diisocyanate is added to a
the polycarboxylic acid anhydride is relatively slow at Stirred mixture of 333 parts of polytetramethyleneether
room temperature. In view of this fact, these curable glycol of 3100 molecular weight and 15.9 parts of glycidol
liquid polymers have sufficient pot life and stability which 25 kept under nitrogen. The mixture is stirred for 20 hours
enables them to be used as practical curable liquid poly at 80° C. to give a polyurethane of about 3600 molecular
S. Weight with an epoxide group at each end of the chain.
The organic liquid polyamines which are added to the The very viscous solution is cooled below 50° C. and 208
polyurethane polyepoxides of the present invention so as parts of chloroform is added to make a solution contain
to form curable liquid polymers may be any of a wide 30 ing 65% polyurethane polyepoxide.
variety of aromatic or aliphatic polyamines. These poly The polyurethane polyepoxide is cured by mixing 15.4,
amines must contain at least two primary or secondary parts of the 65% solution with 0.17 part of ethylene di
amine groups, i. e., at least two amino nitrogen atoms amine. The liquid is poured into a mold and is heated
which have hydrogen attached thereto. It is to be under 4 hours at 80 C., during which time the chloroform
stood that these polyamines may contain other substitu 35 evaporates. After this treatment, the product is a
ents; however, if these other substituents are functional thoroughly cured elastomer of light color with good re
groups, i.e., groups containing active hydrogen, they are silience and fair tensile strength.
to be less reactive with epoxides than are the amine Increasing the amount of ethylene diamine to 0.20 part
groups. For purposes of the present invention, the pre or decreasing the amount of ethylene diamine to 0.134
ferred polyamines are the aromatic diamines such as 40 part affects only slightly the properties of the resultant
m - phenylenediamine, 2,4-diaminocumene, or mixtures elastomer. The addition of high abrasion furnace black
thereof. Other representative diamines which may be (3.0 parts of black for 15.4 parts of the 65% polyurethane
used include aliphatic compounds such as ethylene di polyepoxide solution) results in an elastomer with a much
amine, 1,3-diaminopropanol-2, and hydroxyethylethylene higher modulus and a lower elongation at break.
diamine; aryl-alkyl compounds such as 4,4'-methylene 45 To obtain quantitative data, 62 parts of the 65%
bis-(2-chloroaniline); and polyalkylene polyamines, such polyurethane polyepoxide solution is mixed with 1.37 parts
as 2,2'-diamino-1,1-dimethyldiethylamine, 3,3'-diamino of 3,3'-diaminodipropylamine. The liquid is put on a
dipropylamine, and triethylene tetramine. Polymeric rubber roll mill and is mixed for 30 minutes at 80-90° C.
polyamines may also be used. Representative polymeric to remove solvent. Williams rings and Yerzley resilience
polyamine may be obtained by reacting one mol of the pellets are made by curing in molds for 30 minutes at
bischloroformate of polytetramethyleneether glycol with 120° C. Properties measured at 25° C. are:
two mols of a diamine, such as m-phenylenedianine or Modulus at 300% elongation.------------------ 350
4,4'-methylene-bis-(N-methylaniline). The amount of Tensile strength at break, p. s. i.---------------- 2200
organic polyamine which is necessary to effectively cure Elongation at break, percent.------------------- 580
the polyurethane polyepoxides must be selected so as to 55
provide at least one hydrogen-bearing amino nitrogen Yerzley resilience---------------------------- 62 50
atom for each epoxide group. This is the theoretical Shore hardness ------------------------------
amount. The amount of polyamine may be as high as Example 2.
about 80 to 200% of this theoretical amount, with the
preferred range being from about 100 to 140%. 60 A mixture of 293 parts of polytetramethyleneether
The organic polyamine functions as a curing agent for glycol of 977 molecular, weight, containing 1% phenyl
the polyurethane polyepoxides. The active hydrogen on B-naphthylamine as an antioxidant, and 34.8 parts of
the amino nitrogen atoms reacts with the terminal epoxide toluene-2,4-diisocyanate is heated with stirring for 3 hours
groups as follows: - at 100° C. under nitrogen. After cooling to 70° C., 34.8
OE 65 parts of-toluene-2,4-diisocyanate is added dropwise over
% hour, and the mixture is heated 2 hours at 70-75 C.
catch-R- - HN-R'- - -R-CH-CH-NH-R'- Then 16.3 parts of glycidol (110% of the theoretical
O - amount) is added. The mixture is stirred a few minutes,
In the instances where a polyamine containing more than poured into a polyethylene bag, and heated 3 days at
two active hydrogen atoms attached to nitrogen atoms is 70 80° C. in an oven. The resultant polyurethane polyep
used, the resulting cured polyurethane polyepoxide will oxide is a very viscous liquid of about 3780 molecular
weight.
be a cross-linked structure. 100 parts of the polyurethane polyepoxide is dissolved
Another curing agent which may be incorporated with in 200 parts of boiling chloroform and is mixed with 1.7
the polyurethane polyepoxides of the present invention is
an organic polycarboxylic acid anhydride. . . Any of a 75 parts of 1,2-diaminopropanol-2. After heating 3 hours
 5 2,830,088
6
in an oven at 80°C, the product is a well-cured elastomer
with good tensile strength and resilience. - antioxidant and 48.7 parts of toluene-2,4-diisocyanate is
heated under nitrogen at 70-75° C. for 3 hours. Then
Example 3 20.7 parts of glycidol is added and the mixture is heated
Starting with a polytetramethyleneether glycol of 1074 a 70-80° C. for 22 hours. The polyurethane polyepoxide
molecular weight, a polyurethane polyepoxide having a is a viscous, almost colorless liquid having a molecular
weight of about 1474.
molecular weight of about 2820 is prepared by the method (B) A mixture of 29.4 parts of the polyurethane poly
described in Example 2. epoxide of (A) above and 1.19 parts of m-phenylenedi
100 parts of this polyurethane polyepoxide, dissolved in amine is heated for 5 minutes at 80° C. and 2 minutes
50 parts of tetrahydrofuran and 50 parts of chloroform, 10 at 100° C. The liquid is poured into a mold and heated
is mixed with 1.57 parts of triethylene tetramine. After for 24 hours at 80 C. The product is a brown elastomer
standing 2 days at room temperature and 3 hours at 80° with moderate tensile strength and resilience, both at
C., the product is a resilient elastomer with good tensile room temperature and at 80° C.
strength. The properties of the elastomer appear un (C) A mixture of 29.4 parts of polyurethane poly
changed after heating for 6 hours at 100 C. and then 5 epoxide of (A) above and 1.61 parts of a liquid diamine
for 5 hours at 120° C. :
The polyurethane polyepoxide can also be cured to an consisting of equal parts of m-phenylenediamine and 2,4-
elastomer using 2.5% hydroxyethylethylene diamine. diaminocumene is mixed at 100° C. and poured into a
mold. After curing 24 hours at 80 C., the product is a
Example 4.
20 well-cured brown elastomer with moderate tensile strength
With stirring under nitrogen, 34.8 parts of toluene-2,4- and(D) resilience, both at room temperature and at 80 C.
A mixture of 29.4 parts of the polyurethane poly
diisocyanate is added to 293 parts of polytetramethylene
ether glycol having a molecular weight of 977 and con epoxide of (A) above and 3.36 parts of 4,4'-methylene
taining 1% phenyl-8-naphthylamine. The liquid is heated bis-(2-chloroaniline) is heated at 100 C. and poured into
to 100 C. and is maintained at 100° C. for 3 hours. 25 a mold. After curing 3 days at 100 C., the product is a
After cooling to 70. C., 37.7 parts of diphenylmethane cured but slightly tacky elastomer with moderate tensile
4,4'-diisocyanate and 7.4 parts of glycidol are added. strength and resilience.
The mixture is stirred rapidly for 5 minutes, poured into (E) A mixture of 14.7 parts of the polyurethane poly
a polyethylene bag, and heated at 80 C. for 3 days. epoxide of (A) above and 7.7 parts of a polymeric pri
The resulting polyurethane polyepoxide is a very viscous 30 mary diamine having a molecular weight of 1278 is stirred
liquid having a molecular weight of about 7450. at 80-100 C., poured into a mold and cured for 24 hours
100 parts of this polyurethane polyepoxide is dissolved at 100° C. The product is a cured elastomer with mod
in about 300 parts of boiling chloroform. This solution erate tensile strength and resilience. The polymeric pri
is thoroughly mixed with 1.84 parts of 3,3'-diaminodi mary diamine used above is prepared by first mixing 1200
propylamine and poured into a mold. After keeping 35 parts of benzene, 175 parts of calcium hydroxide, and 32.6
overnight at room temperature - and 4 hours at 80° C., parts of m-phenylene-diamine and then a solution of 171.4
the product is a cured elastoner with good tensile parts of the bischloroformate of polytetramethyleneether
strength and high elongation at the break. glycol, having a molecular weight of 1135, in 500 parts of
Example 5 benzene, is added dropwise to the stirred mixture over a
40 1% hour period. The mixture is stirred at room temper
With stirring under nitrogen, 41.8 parts of toluene-2,4- ature overnight and then filtered. The benzene is removed
diisocyanate is added to 352 parts of polytetramethylene at reduced pressure. The resulting polyurethanediamine
ether glycol having a molecular weight of 977 and con is a viscous oil.
taining 1% phenyl-3-maphthylamine. The liquid is (F) A mixture of 14.7 parts of the polyurethane poly
heated to 100° C. and maintained at 100° C. for 3 hours. epoxide of (A) above, 3.2 parts of the polymeric primary
After cooling to 70° C., there is added 40.2 parts of 45
diphenylmethane-4,4'-diisocyanate and 5.9-parts of glyci meric diamine described in (E) above, and 4.5 parts of a poly
secondary amine having a molecular weight of 1514
dol. The mixture is stirred rapidly for 5 minutes, poured is heated at 80-100° C. for 10 minutes, poured into a
into a polyethylene bag, and heated at 80 C. for 3 days.
The polyurethane polyepoxide is an extremely viscous 50 amold, and heated for 3 days at 100° C. The product is
soft cured elastomer with low modulus, high break
liquid having a molecular weight of about 11,000.
100 parts of this polyurethane polyepoxide is cured by elongation,
polymeric
and good tensile strength and resilience. The
secondary diamine used above is prepared by
the method of Example 4 except that 1.24 parts of 3,3'- first mixing 1200 parts of benzene, 175 parts of calcium
diaminodipropylamine is used. A soft, tacky elastomer hydroxide, and 67.9 parts of 4,4'- methylene - bis - (N-
is obtained. 55 methylaniline) and then adding dropwise to the stirred
Example 6 mixture, over a 1/2 hour period, a solution of 170.3 parts
A mixture of 149.3 parts of dry, polytetramethylene of the bischloroformate of polytetramethyleneether glycol,
ether glycol of 977 molecular weight. containing 1% having a molecular weight of 1135, in 500 parts of ben
phenyl-6-naphthylamine as an antioxidant and 52.2 parts zene. The mixture is stirred at room temperature over
of toluene-2,4-diisocyanate is stirred in a nitrogen atmos 60 night and then filtered. The benzene is removed at re
phere for 2 hours at 70-75 C. 26.7 parts of 2-methyl duced pressure. The resulting polyurethane secondary
glycidol is added dropwise over 10-15 minutes. The mix diamine is a viscous oil.
ture is held at 70-75 C. for 2 hours. The product is, (G). A mixture of 14.7 parts of the polyurethane poly
a viscous liquid having a molecular weight of about 1501. epoxide of (A) above, 2.66 parts of pthalic anhydride,
with an epoxide group on each end of the chain. and 0.15 part of 4,4'-methylene-bis-(N,N-dimethylaniline)
30 parts of this polyurethane polyepoxide is mixed with is stirred at 100° C. and the liquid is poured into a mold.
1.2 parts of ethylene diamine at room temperature. After After curing in an oven for 2% hours at 100° C., the
thorough mixing, the material is allowed to age 2 days at product is a well-cured elastomer with moderate tensile
room temperature, thereby yielding a cured elastomer strength and resilience.
with good tensile strength and good resilience. 70 Example 8
Example 7
(A) A mixture of 135.8 parts of polytetramethylene A mixture of 25 parts of high abrasion furnace black
and 75 parts of the polyurethane polyepoxide of Example
ether glycol having a molecular weight of 970 and con 7(A) is passed several times through a 3-roll ink mill in
taining 0.2% 2,6-ditertiary butyl-4-methylphenol as an 75 order to disperse the carbon black in the liquid. Then
 K. 2,880,038
-- - m 8

19.6 parts of this mixture and 6.4 parts of the polymeric and 0.4 part of p-toluenesulfonic acid under a nitrogen
primary diamine described in Example 7(E) are mixed atmosphere for 6 hours at 120-125 C. with rapid re
thoroughly and poured into a pan. After curing for 48 fluxing. After cooling and stirring for 2 hours with 1
hours at 100°C., the product is an elastomer with very part of decolorizing carbon, 4 parts of calcium hydroxide,
good tensile strength and resilience. This elastomer 5 and 1 part of an antioxidant, 4-methyl-2,6-ditertiary butyl
which contains 23 parts of carbon black per 100 parts of phenol, the liquid portion is separated by filtration and the
polymer is stronger and has a higher modulus than a cake is washed with benzene. Volatile material is re
similar sample containing no carbon black. , ... moved by drying in a rotating flask, finishing at 100-115
Example 9 C. for 2 hours at 2 mm. pressure. The polyformal gly
s. . . . - 10 col, which is solid at room temperature, has a hydroxyl
(A). A mixture of 14.7 parts of the polyurethane poly- number of 48.5 and a molecular weight of 2315.
epoxide of Example 7(A), 6.0 parts of a commerical (B) 231.5 parts of the polyformal glycol prepared in A
epoxy resin having the formula above and 34.8 parts of toluene-2,4-diisocyanate is heated
CHOR for 2 hours at 70-75° C. Then 14.8 parts of glycidol is
bHor 15 added, and the mixture is heated for 2 hours at 70° C. and
. for 16 hours at 80° C. to form a polyurethane polyepox
&H, or ide. Curing is effected by mixing at 80 C., 22.5 parts of
where 73% of the R's are this polyurethane polyepoxide with 0.48 part of m-phenyl
O . .. . . - enediamine and heating the liquid for 24 hours at 100
/ N. 20 C. in an oven. The product is a cured, slightly tacky
-. . -CH,CH-CH, - -- elastomer with good tensile strength and resilience.
and 27% of the R's are hydrogen, and 1.80 parts of It is apparent from the foregoing examples that the
ethylene diamine is stirred at room temperature and polyurethane epoxides of the present invention may be
poured into a mold. After curing for 2 hours at 60° C., cured by means of polyamines or polycarboxylic acid an
the product is a thoroughly cured, tough plastic. 25 hydrides to form highly useful elastomers. These elasto
(B) A mixture of 14.7 parts of the polyurethane poly- mers may be employed in the preparation of a wide
epoxide of Example 7(A), 5.3 parts of a commercial variety of articles, such as belts, hose and tubing, wire
epoxy resin having the formula and cable jackets, footwear, coated fabrics, etc. When

eyenon-O- KC-on-on-o-O-K)-on-ten
O
SH,

&H,
-

OH
-

n
where the average value for n=0.4, and 2.16 parts of 35 these polyurethane polyepoxides are used as curable liquid
Cs

CH O

m-phenylenediamine is heated at 80-100° C. for 10 min- polymers, they may be used advantageously to form intri
utes and poured into a mold. After curing for 5 hours at cate shaped articles since they may be poured into molds
80 C., the product is a thoroughly cured, tough plastic and cured in situ. The polyurethane polyepoxides may
with good strength at 80 C. and at room, temperature. also be used in combination with commercially available
(C) A mixture of 75 parts of the polyurethane poly- to epoxy resins to obtain plastics which have better proper
epoxide of Example 7(A), 25-parts of a commercial epoxy ties than do plastics obtained from the commercial epoxy
resin having the formula resins alone. Thus the combination of these polyurethane
CH polyepoxides with commercial epoxy resins produces plas
- - tics having a resilient nature with high thermal stability,
ce-chohio-(
O
)--K CH
X-0
-
chic Otoil, 45 good electrical properties, and resistance to moisture.
The properties of the cured elastomers which are ob
and 7.5 parts of a liquid diamine, which consists of equal tained from the polyurethane polyepoxides of the present
parts of m-phenylenediamine and 2,4-diaminocumene, is invention may be varied by suitable compounding ingredi.
stirred at 100° C., poured into molds, and cured for 2 ents, such as carbon black, silica, calcium carbonate, and
hours at 100° C. The product is a tough plastic with a 50 other fillers. Generally, these compounding ingredients
tensile strength of 4500 p.s. i. at 25° C. and an elonga- are incorporated with the polyurethane polyepoxide prior
tion at break of 250%. It has excellent impact strength to Curing.
and good tear strength. As many widely different embodiments of this inven
(D) A mixture of 25 parts of the polyurethane poly- tion may be made without departing from the spirit and
epoxide of Example 7(A), 75 parts of a commercial epoxy 55 scope thereof, it is to be understood that this invention is
resin having the formula not limited to the specific embodiments thereof except as
CE. defined in the appended claims.
-- Ž ~ What is claimed is:
citchch,0-(
O
)--(
Ces
>-octrict O ch 60 of 1.from
A polyurethane polymer having a molecular weight
about 1000 to 11,000 and being characterized by
and 14 parts of a liquid diamine, which consists of equal the formula --
O O O O .. O O

of Si-OH,-0--NH-B-ENE-6-0-0-0--NH-BNH-i-o-CH-4 Sch,
parts of m-phenylenediamine and 2,4-diaminocumene, is wherein. O-G-O is a bivalent radical resulting from re
stirred at 100° C., poured into molds and cured for 2 moval of the terminal hydrogen atoms from a polyalkyl
hours at 100° C. The product is a hard plastic which is eneether glycol having a molecular weight of from about
less brittle and has higher impact strength than a plas- 750 to 3500; B is a bivalent organic radical, said radical
tic prepared from 100 parts of the commercial epoxy resin being inert to isocyanate groups; n is an integer ranging
alone. from about 1 to 11; and R is selected from the group con
Example 10 - sisting of hydrogen and a methyl radical.
. - .. . . . . 2. The polymer of claim 1 wherein R is hydrogen.
(A) A polyformal glycol is prepared by heating 416 3. The polymer of claim 2 wherein the bivalent organic
parts of 1,5-penetanediol, 127 parts of paraformaldehyde, 75 radical, B, is an arylene radical.
 2,830,038
9 O
4. The polymer of claim 3 wherein B is a tolylene urethane polymer having a molecular weight of from about
radical. 1000 to 11,000 and being characterized by the formula
O O O O O O

of St-CH-O-(-NH-B-ENE-3-O-G-O-(-NH-p NH-C-O-CH-64 SoH,

Z N
R
/. N

5. The polymer of claim 3 wherein the bivalent radical wherein O-G-O is a bivalent radical resulting from re
O-G-O is obtained by removal of the terminal hydrogen moval of the terminal hydrogen atoms from a polyalkyl
atoms from a polytetramethyleneether glycol. eneether glycol having a molecular weight of from about
6. The polymer of claim 4 wherein the bivalent radical 750 to 3500; B is a bivalent organic radical, said radical
O-G-O is obtained by removal of the terminal hydro being inert to isocyanate groups; n is an integer ranging
gen atoms from a polytetramethyleneether glycol. 5 from about 1 to 11; and R is selected from the group con
7. A curable composition comprising (a) a poly sisting of hydrogen and a methyl radical; and (b) an
organic polycarboxylic acid anhydride. -
urethane polymer having a molecular weight of from about 9. The curable composition of claim 7 wherein the or
1000 to 1,000 and being characterized by the formula ganic polyamine is m-phenylenediamine.
O O O O O O
N. N. M. N.
on. S-CH-O-(-NH-B-ENE--o-o-o--NH-BNH-i-o-CH-4
R
- Sch, R

wherein O-G-O is a bivalent radical resulting from re 10. The curable composition of claim 8 wherein the or
moval of the terminal hydrogen atoms from a polyalkyl ganic polycarboxylic acid anhydride is phthalic anhydride.
eneether glycol having a molecular weight of from about References Cited in the file of this patent
750 to 3500; B is a bivalent organic radical, said radical
being inert to isocyanate groups; n is an integer ranging 30 UNITED STATES PATENTS
from about 1 to 11; and R is selected from the group con 2,730,531 Payne et al. ------------ Jan. 10, 1956
sisting of hydrogen and a methyl radical; and (b) an FOREIGN PATENTS
organic polyamine. 733,624 Great Britain ----------- July 13, 1955
8. A curable composition comprising (a) a poly 758,433 Great Britain ------------ Oct. 3, 1956
 UNITED STATES PATENT OFFICE
Certificate of Correction
Patent No. 2,830,038 April 8, 1958
Dexter B. Pattison
It is hereby certified that error appears in the printed specification of
the above numbered patent requiring correction and that the said Letters
Patent should read as corrected below.
Column 2, line 35, for “othr' read -other-; column 5, line 43, for
“-maphthylamine' read -naphthylamine-; column 6, line 63, for “pthalic'
read - phthalic-; column 9, claim 7, the extreme left-hand portion of the
formula should appear as shown below instead of as in the patent
O
of So-OH,-
Signed and sealed this 20th day of May 1958.

sRAL

Attest:
KARL H. AXLINE, ROBERT C. WATSON,
Attesting Officer. Commissioner of Patents.