e

United States Patent Office Patented a. 265,669

9, 1966
2
methylene polyaniline; tolidine; dianisidine; 3,3'-dichloro
3,265,669 benzidine; and the like, are related to the nuclear Sub
LIQUID AMINE HARDENER COMPOSITIGNS stituents.
FOR POLYURETHANE RESNS In spite of the superiority of the aryl diamines (for
Frank N. Hirosawa, Los Angeles, Calif., assigilor to example, 4,4'-methylene bis(2-chloroaniline) and 3,3'-di
Furane Piastics Incorporated, Los Angeles, Calif., chlorobenzidine) as curing agents for urethane resins,
a corporation of California wherein good physical properties and longer working life
No Drawing. Filed Aug. 19, 1963, Ser. No. 303,170
7 Claims. (C. 260-77.5) of the final polymers are attained, the use of these ma
terials is attended with certain disadvantages that have
This invention relates to hardener compositions in O limited more widespread acceptance. Specifically, these
liquid form for use as co-reactants in the production of substances have relatively high melting points, making it
cured urethane resins. More particularly, it relates to the difficult to get a uniform mix. The initial mixing is some
preparation of high molecular weight urethane polymers times effected by powdering the curing agent, but even
by reaction of isocyanates with organic nitrogen com then, due to the elevated melting point, it must be melted
pounds. 15 and further uniformly dispersed in the polyisocyanate pre
Polyurethane polymers, particularly elastomers, are use polymer, which it is intended to cure. This heating
ful because of their unique properties, such as high shortens the working life considerably and at times Sets
strength and elasticity, good load-bearing capacity and the mixture to an insoluble, infusible polymer before it
resilience, high tear strength, resistance to oils, OXygen can be mixed properly.
and ozone, good low temperature properties, and excep 20 The principal object of the present invention is to pro
tional abrasion resistance. Polyurethane polymers are vide a curing agent in liquid form for easy uniform mixing
formed by reacting a di- or poly-functional isocyanate with the polyisocyanate prepolymer, which results in opti
with polyether polyols or with hydroxy-terminated poly mum properties when cured at the ambient room tempera
esters, ture. Another objective is to provide a liquid curing com
In reacting monoisocyanate with a compound contain position that can be used as a hardener, cross-linking
ing a simple reactive hydrogen, a single urethane is agent or chain extender for polyisocyanate prepolymers,
formed; if the two reactants are bifunctional, the resulting at ambient room temperature or by the application of
product is polymeric; and if one of the reactants is poly slight heat.
meric, the ultimate product will be a polymer of high Another objective is to provide a liquid curing agent
molecular weight. Such a compound with reactive iso 30 that can be compounded with conventional compounding
cyanate-terminated polymers that may be further chain ingredients such as carbon black, silica, or coloring in
extended, cross-linked, cured or hardened to high molec gredients, and be subsequently mixed with polyisocyanate
ular weight compounds is represented, typically, in the prepolymers to form highly useful polyurethane elasto
following equation: IeS.
35 I have discovered that by dissolving the aryl amines
in certain solvents, a new room temperature liquid curing
O=C=N-RNC-ORO-C-N-RN-C=O hardener is provided, which not only produces the desired
The isocyanate-terminated reactive intermediate reac final physical properties, but also may give a reduction in
tion product is known in industry as (1) an isocyanate viscosity and a lengthening of the working life of the
terminated prepolymer, or (2) a polyurethane prepoly 40 hardener-polyisocyanate mixture. The working life is
mer, or (3) a polyisocyanate prepolymer. The prepoly considerably longer than is possible with the use of the
Inner which contains an excess of unreacted isocyanate conventional dry powder curing agents such as Moca, etc.
groups may be subsequently chain extended, cross-linked In particular, I have discovered that new and useful
or cured by reaction with an arylene diamine, producing urethane hardening agents in liquid form may be prepared
linkage of the substituted urea type as for example in the by dissolving appropriate amine compounds in N-substi
following equation: tuted 2-pyrrollidone of the structure
HC-CH

50
where R is a substituent of the class consisting of a simple
The reaction of the type shown above has been en or Substituted alkyl, alicyclic, aralkyl, alkaryl or aryl
ployed in the preparation of the polyisocyanate prepoly groups. While R may be in the range of C to C, the
mer, which has a viscosity range from several hundred 55 most convenient and preferred substituent is methyl; other
centipoises to viscous syrupy materials. substituents such as ethyl, propyl, butyl and vinyl may be
The reaction of isocyanate with compounds that con used for preparation of non-crystallizing liquid amine
tain nitrogen hydrogen bonds has been found to be gov hardeners.
erned primarily by the basicity or nucleophilicity of the The ratio of amines to N-substituted 2-pyrrolidone is
nitrogen-hydrogen bond, and the basicity of aromatic 60 selected so that the desired viscosity of the hardener mix
amines is decreased when electronegative groups, Such as may be obtained, limited by the amount of the pyrroli
halogen atoms or nitro groups are introduced into the done which can be tolerated in the final product. The
nucleus, especially ortho-standing groups exert the great preferred ratio is in the range of 10 to 90 percent by
est effect. It is generally recognized that arylamine cured weight of selected amine to N-substituted 2-pyrrolidone,
elastomers will have higher modulus, increased tensile 65 based upon the final mixture.
strength, better tear strength, greater solvent resistance, For the preparation of such liquid hardener composi
and usually require much shorter cure time than glycol tions, the appropriate amine is mixed with N-substituted
cured elastomers. 2-pyrrollidone, and the mixture heated enough to complete
The reactivities of the aryl diamines and of the amines the solution in a dry atmosphere, at a temperature rang
which are currently used as urethane curatives, Stich as 70 ing from about 20° C. to about 150° C.
44' - methylene bis(2-chloroaniline); methylene bis(2- This invention is illustrated by reference to the follow
methylaniline); methylene bis(2-methoxyaniline); poly ing typical examples, although the invention is not limited
 3,265,669
3 4.
to these examples. Parts are by weight unless otherwise Example V
indicated. Proceeding as in Example I, and substituting N-vinyl
Example I 2-pyrrollidone for the N-methyl-2-pyrrollidone a low vis
A preferred hardening agent in accordance with my cosity liquid hardener was obtained. Thirty-three parts
invention consists of 50 parts of dry N-methyl-2-pyrroli of this curing agent was mixed with 100 parts of prepoly
done and 50 parts of dry 4,4'-methylene bis(2-chloroani mer (amine equivalent of 630), obtaining a mixture that
line). These were introduced into a closed vessel, and had a pourable working life of 1 hour and 30 minutes at
the mixture was stirred and gradually heated to about 80' F. A polyurethane elastomer was thus obtained hav
ing physical properties comparable with samples cured as
100° C., and the heating continued until a clear solution o
was obtained. The contents of the vessel was then cooled described in Example I.
down to room temperature and stored in a sealed con Example VI
tainer in a dry atmosphere, to avoid excessive moisture Two thousand parts of 4,4'-methylene bis(2-chloroani
pickup. line), 600 parts of 3,3'-dichlorobenzidine, 1300 parts of
The liquid curing agent obtained in the manner de 5 N-methyl-2-pyrrolidone, and 300 parts of N-vinyl-2-pyrrol
scribed had a viscosity of 100 cps. and did not crystal idone was placed in a 5 liter three neck Pyrex flask
lize upon cooling to room temperature. When tested equipped with thermometer, stainless steel paddle stirrer,
after two weeks, in a 150 F. air circulating oven, the “Glas-col' heating mantle and an inert gas inlet. While
material remained stable, retaining its fluidity and curing the vessel was being flushed with inert gas (oil pumped
properties. 20 dry nitrogen) and the mixture stirred, heat was applied
Example II until a temperature of 100 C. was reached. The reac
The liquid curing agent prepared as illustrated above tion mass was heated at 100° C. until a clear solution was
may be admixed with a polyisocyanate prepolymer and obtained. The product was then cooled to room tempera
the mass allowed to cure at room temperature to obtain ture and stored in a sealed container to avoid excessive
25 moisture pickup.
a resilient, tough rubber-like elastomer.
The liquid polyisocyanate prepolymer used above with The liquid hardener thus produced had the following
my new liquid curing agent consisted preferably of the properties:
reaction product of polypropylene ether triol and a 80/20 Viscosity (Brookfield viscometer) at 25 C., cps.---- 176
mixture of 2,4- and 2,6-tolylene diisocyanate in the pro 30 Color (Gardner-Holdt) ------------------------ 16
portion of one to three. Amine equivalent ----------------------------- 213
Other, suitable polyols may similarly be employed, and
among these are: polyethylene ether glycol of the approxi 34 parts of the above hardener and 100 parts of polyiso
mate molecular weight range of 200 to 4000; polypropyl cyanate prepolymer, prepared from polypropylene triol
ene ether glycol with a molecular weight range of 200 to 35
adduct of 80/20 isomer mixture of tolylene diisocyanate
4000; varying molecular weight hydroxy terminated poly (in the ratio of one to three) was mixed thoroughly and
esters, such as ethylene adipate, propylene adipate, ethyl cured at room temperature for 7 days. Following typical
ene sebacate, and the like; suitable polyisocyanates may physical properties were obtained:
similarly be employed and examples of these are: m
phenylene diisocyanate; hexamethylene disocyanate, 2,4- 40 R. T. Cure Post Cure,
tolylene diisocyanate; 3,3'-dimethyl-4,4'-biphenylene di 3 hrs. at 50F.
isocyanate; and the like.
In some mixtures the chain growth does not proceed Tensile Strength, p.s.i
Elongation, percent-
1,500
600
2,400
450
smoothly at ambient room temperature and some heat is Hardness, Shore A 75 80
required to obtain optimum physical properties. In some
cases, it is desirable to add small but sufficient amounts
of an accelerator or catalyst to facilitate a room or low Sometimes a higher viscosity liquid hardener is required.
temperature cure, such catalysts including organic metal This may be effected by the addition of 1 to 20 percent by
salts, such as lead naphthenate, lead octoate, copper Weight of any polyisocyanate prepolymer to the prepared
naphthenate, manganese naphthenate, cobalt naphthenate, liquid hardener.
and equivalent materials. 50 The viscosity of the liquid hardener prepared Example
Example III VI may be controlled by further reacting the liquid hard
ener with a selected molecular weight prepolymer with
The curing agent of this invention is particularly suited an amine equivalent of 50-1000. The ratio of prepolymer
for chain-extending, cross-linking or curing polyisocyan to liquid amine hardener is selected to give the desired
ate prepolymers that are low in viscosity at room tem 55 viscosity while avoiding the tie up of all of the potentially
perature, such as those having amine equivalents of 600 available reactive hydrogen groups, which are required to
2000. For each 100 parts of polyisocyanate prepolymer be available to initiate the curing reaction when the hard
having an amine equivalent of 630, 42 parts of the curing ener is Subsequently mixed with the polyisocyanate pre
agent prepared in Example I are used, and the mixture polymer, as in Example VII.
was cured at room temperature for 4 days to obtain a ure 60
Example VII
thane elastomer having tensile strength of 2,500 p.s. i. and
elongation of 420 percent. Proceeding as in Example VI, the liquid amine hardener
Example IV was further reacted by the slow addition of 200 parts
(based on Example IV reaction ratio) of polyisocyanate
When 3,3'-dichlorobenzidine is substituted for 4,4'- prepolymer (amine equivalent of 630). In addition, the
methylene bis(2-chloroaniline) as in Example I, a low temperature was raised to 130° C. during a period of one
viscosity hardening agent having an equivalent weight of hour. The product was then cooled to room temperature
253 was obtained. Forty parts of this hardener was and stored in a sealed container. The liquid hardener
mixed thoroughly with 100 parts of prepolymer (amine thus obtained had the following physical properties:
equivalent 630) and a mixture was obtained that had a Viscosity (P 25 C., cps. ----------------------- 380
pourable working life of 2 hours at 80 F. compared to Gardner color ------------------------------- 16
an equivalent cure prepared from dry powdered 3,3'-di Amine equivalent ----------------------------- 215
chlorobenzidine, had a working life of 7 minutes at 190°
F., and both samples showed comparable physical prop Comparative physical properties of the urethane elasto
erties after 5 days cure at room temperature. mers cured with the above prepared liquid amine hardener
 3,265,669
5 6
and the conventional powder curing system are tabulated line); polymethylene polyaniline; tolidine; dianisidine and
in the following table: 3,3'-dichlorbenzidine.
Curing Amount, Hardness Tensile i Elonga
Polyisocyanate Prepolymer Eq. Wt. Agent P.B.W. Pot Life Shore A Strength, ation,
p.s.i. percent

Polypropylenetriol------------------- 650 Ali 34 1.5 hr. at 80° F. 80 1,900 440

MOCA2 20 10 min. at 150 F. 85 2,500 400
Polyester Ethylene-adipate type----- 1,400 A ------------ 3 hrs., at 80° F. 90 2,650 500
MOCA ------------ 30 min. at 150 F. 90 2,500 400
Poly (oxytetronethylene)-glycol------ 650 A1 32 3 hrs. at 80 F. 90 6,350 580
MOCA2 20 15 min. at 150°F, 95 3,980 425
1 Liquid amine hardener prepared as in Example VII.
4,4'-methylene bis-(2-chloroaniline) prepolymer was heated to 150 F. and molten curing agent was added at 150 F.
Conventional compounding ingredients such as carbon l? 5. The liquid curing agent defined in claim 1 in which
black, silica, pigments and other modifying fillers, are the aromatic polyamine curative is 4,4'-methylene bis(2-
readily dispersed with the resin-forming materials prior to chloroaniline) and the pyrrolidone is N-methyl-2-pyrroli
the curing, because of the relatively low viscosity of the done,
mixture prior to curing. 6. The liquid curing agent defined in claim 1 in which
The advantages of the new liquid amine hardener will be 20 the aromatic polyamine curative is 3,3'-dichlorobenzidine
understood from the above description. The curing is and the pyrrollidone is N-methyl-2-pyrrollidone.
exceedingly simple, and the physical properties of the final 7. The method of curing a polyurethane prepolymer to
product obtained are equivalent or superior to the present form a thermosetting rubber-like composition which con
ly used powder curing system. sists of the steps of pre-dissolving the urethane curing
I claim: agent defined in claim 1 in N-substituted 2-pyrrolidone by
1. A liquid room temperature curing agent for produc gentle heating until a clear solution is obtained, uniform
tion of a thermosetting rubber-like composition from poly ly mixing said curing solution with said polyurethane pre
urethane prepolymers comprising an aromatic diamine polymer in proportions in the range from 1 to 9 and 9 to 1,
having two active nitrogen-hydrogen bonds, dissolved in a and holding said mixture at substantially room tempera
N-substituted 2-pyrrollidone having the structure 30 tures until cured, wherein said urethane curing agent is
an aryl diamine,
H2C-CH
References Cited by the Examiner
UNITED STATES PATENTS
2,917,489 12/1959 Gladding ----------- 250.77.5
2,929,800 3/1960 Hill ------------- 260-77.5
where R is a member of the group consisting of a lower 2,957,852 9/1960 Frankenburg -------- 260-77.5
alkyl and a vinyl group. 2,957,872 10/1960 Frankenbugg ------- 260-77.5
2. The liquid curing agent defined in claim 1 in which 40 3,004,945. 10/1961 Farago ------------ 260-30.2
the substituent R is a vinyl group. 3,038,876 1/1962 Farago ------------- 260-30.2
3. The liquid curing agent defined in claim 1 in which 3,162,429 1/1965 Wich -------------- 260-30.2
the aromatic polyamine curative is an aryl diamine. 3,166,429 1/1965 Wich -------------- 260-20.2
4. The liquid curing agent defined in claim 1 in which 3,216,983 11/1965 Shelanski et al. ----- 260-77.5
the aromatic polyamine curative is selected from the group
consisting of 4,4'-methylene bis(2-chloroaniline); methyl LEON J. BERCOVITZ, Primary Examiner.
ene bis(2-methylaniline); methylene bis(2-methoxyani M. C. JACOBS, Assistant Examiner.