Note: Descriptions are shown in the official language in which they were submitted.
- 111409~
This in~ention relates to polyurethane cellular
forms prepared by the reaction of polyisocyanates and amine
epichlorohydrin condensation products and oxyalkylated
derivatives thereof.
U. S. Patent 2,938,004 teaches the preparation of
condensation products of diamines with alkylene oxides. It
teaches the preparation of glycidyl ethers and the reaction
of these glycidyl ethers with diamines as crosslinking agents.
Further disclosures include the reaction of alkyl glycidyl
ether, glycidyl propionate, and styrene oxide, with diamines.
The epoxides disclosed in this patent are incapable of pre-
paring the oxyalkylated products which are employed in the
polyurethane foams of the subject invention.
U. S. 3,336,245 discloses the use of certain
oxyalkylated amines in the p`reparation of urethane foam. The
structures disclosed in this patent are dissimilar from the
product produced in the instant invention. Further, the
I product structure in the claims and the disclosure of the
j patent make it obvious that the products of the subject
invention employed in the preparation of polyurethane foams
are not anticipated. If epichlorohydrin were used in the
,: .
synthesis of the compounds of this patent one would not
obtain products which correspond to the products disclosed
in this patent.
The present invention proposes new polyurethane
cellular foams prepared by reacting an organic polyisocyanate
with a oxyalkyIated epihalohydrin condensation product which
is~prepared in the following manner. At least two moles
of amine are reacted with one mole of epihalohydrin followed
3~0 ~by~neutralization of the resultant hydrogen chloride with
aqueous inorganic base equivalent to the amount of
epibalohydrin employed. The oxyalkylated der~v~tives are
~ B~ ~ - 2 -
~ ~.. ., ~ ! , . . . .
` ` 1114~9.
then prepared by treating the above reaction products with
enough alkylene oxide to react with all of the active hy-
drogens in the organic substance. These products can be
purified and used at this stage of oxyalkylation or, pre-
ferably, catalytic amounts of a catalyst such as potassium
hydroxide may be added, the reaction products stripped of
water under reduced pressure and then further alkylene oxide
added to achieve a higher desired molecular weight.
As aforesaid, the polyurethane cellular foams
according to the invention are prepared by reacting an organic
polyisocyanate with an oxyalkylated condensation product
prepared by the addition of an alkylene oxide to a condensation
product. The condensation product in accordance with this
invention is prepared by reacting an amine with an epihalohy-
drln in the presence of an alkaline catalyst. More specifical-
ly, the condensation products are obtained by reacting at least
two moles of amine with one mole of epihalohydrin. The
resulting product is then treated with an amount of aqueous
caustic equivalent to the amount of epichlorohydrin employed.
The reaction proceeds to give a condensation product of amines
bridged by the residue of the epihalohydrin chain. The
product is then oxyalkylated in the presence of an alkaline
catalyst to a desired molecular weight. In the condensation
reaction the epihalohydrin acts as a difunctional compound.
Various condensation products are possible depending upon
the ratio of the amine to the epihalohydrin used in the
condensation reaction. Furthermore, various conditions of
temperature, pH and the presence of additional active hydrogen
compounds will cause a variation in the condensation product
produced. The reaction can be used to prepare, for example,
an aromatic amine chlorohydrin intermediate followed by the
addition of either aliphatic amines, diamines, or even ammonia
` B 3
to give mixture of aromatic amines linked to aliphatic amines.
In accordance with the invention, the amines which
may be employed for the preparation of the condensation
products, can be selected from the group consisting of
the aliphatic, olefinic, aromatic, alicyclic~ alkyl aryl,
alkyl alicyclic, alkyl heterocyclic and heterocyclic primary
amines, and secondary polyamines. Examples of these include
methylamine, /,
l , ' , / "
/
. ' /
! ` /
` ~ /
. /
, .. ~ ~ /
'::
~; 4
~ B
;. .
i-.. ~, ~ . ...... ~ ... .. . . . . .. .... . . .
.. .... ....... ~ . . . .. .. .
.. . . . . . . . ..
-" 1~1~9 '
ethylamine, propylamine, allylamine, butylamine, amylamine,
cyclohexylamine, 1,3-dimethylbutylamine, bis(l,~-dimethyl-
butyl)amine~ 2-aminoheptane, 2-amino-4-methylhexane, 1,4-di-
methylpentylamine, 2-ethylhexylamine, bis(2-ethylhexyl)amine,
l-cyclopentyl-2-aminopropane, bis(l-ethyl-3-methylpentyl)-
amine, l,1,3,3-tetramethylbutylamine, hexylamine, heptyl-
amine, octylamine, dodecylamine, tetradecylamine, hexadecyl-
amine, octadecylamine, docosylamine, ethylenediamine,
N-(2-hydroxypropyl)ethylene diamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine, pentaethylene-
hexamine, propylene diamine, l,3-diaminopropane, iminobis-
propylamine, tetramethylenediamine, hexamethylenediamine
and methanediamine.
Suitable aromatic amines include:
2,4-tolylene diamine,
2,6-tolylene diamine, or mixtures thereo;
, 1,5-naphthalene diamine,
1,4-naphthalene diamine,
4,4'-diphenyl methane diamine,
4,4'-diamino-3,~'-dichlorodiphenyl methane1
4,4'-diamino-3,3'dimethyl diphenyl methane,
4,4'-diamino-3,3'-dimethoxy diphenyl methane,
4,4'-diamino diphenyl dimethyl methane,
, ." ' - .
.
~ . -5~
': ' ': '
'' ~' -
.-,, . . , , . . : .
4,4',2-triamino-~,3'-dimethyl diphenyl methane,
diamino biphenyl,
phenylene diamine,
tolylene triamine,
naphthalene triamine,
xylylene diamine,
xylylene triamine,
3,3'-dichloro-4,4'-diaminodiphenylene,
3,3'-dibromo-4,4'-diaminodiphenylene,
3,3'-dimethyl-4,4'-diaminodiphenylene,
3,3'-diisopropoxy-4,4'-diaminodiphenylene,
3,3'-diethyl-4,4'-diaminodiphenylene,
3,3'-dipropyl-4,4'-diaminodiphenylene,
3,3'-dibutyl-4,4'-diaminodiphenylene,
3,3'-diisopropyl-4,4'-diaminodiphenylene,
3,3'-diisobutyl-4,4'-diaminodiphenylene,
3,3'-dimethoxy-4,4'-diaminodiphenylene,
~j3'-diisopropoxy-4,4'-diaminodiphenylmethane,
'
3,3'-dimethyl-4,4.'-diaminodiphenylmethane,
3,3'-diethyl-4,4!-diaminodiphenylmethane,
3,3'-dipropyl-4,4'-diaminodiphenylmethane,
3,3'-dibutyl-4,4'-diaminodiphenylmethane,
3,3'-diisopropyl-4,4'-diaminodiphenylmethane,
,
;
--6--
~
.
.
3J3'-diisobutyl-4,4'-diaminodiphenylmethane,
~,3'-dimethoxy~4,4'-diaminodiphenylmethane,
3,3'-diisopropoxy-4,4'-diaminodiphenylethane,
3,~'-dimethyl-4,4'-diaminodiphenylethane,
3,3'-diethyl-4,4'-diaminodiphenylethane,
3,3'-dipropyl-4,4'-diaminodiphenylethane,
3,3'-dibutyl-4,4'-diaminodiphenylethane,
3,3'-diisopropyl-4,4'-diaminodiphenylethane,
3,3'-disobutyl-4,4'-diaminodiphenylethane, ;:
3,3'-dimethoxy-4,4'-diaminodiphenylethane, . ::
3,3'-diisopropoxy-4,4'-diaminodiphenylpropane,
3,3'-dimethyl-4,4'-diaminodiphenylpropane,
3,3'-diethyl-4,4'-diaminodiphenylpropane,
3,3'-dipropyl-4,4'-diaminodiphenylpropane,
. . .
3,3'-dibutyl-4,4'-diaminodiphenylpropane,
. 7,3'~diisopropyl-4,4'-diaminodiphenylpropane,
3,~'-diisobutyl-4,4'-diaminodiphenylpropane,
3,3'-dimethoxy-4,4'-diaminodiphenylpropane, ,:
3-methyl-3'-ethyl-4,4'-diaminodiphenylene,
_ ,.... ... _. i
3 methyl-3'-ethyl-4,2'-diaminodiphenylene,
1~ 3-methyl-3'-ethyl-4,3'-diaminodiphenylene,
1 3-methyl-3'-ethyl-2,4'-diaminodiphenylene, ¦
¦~ 3-methyl-3'-ethyl-3,3'-diaminodiphenylene,
1 ~ s
. :
, ~ '
1~ 4~9
3-methyl-2'-ethyl-4,4'-diaminodiphenylene,
2-chloro-3'-methoxy-4~4'-diaminodiphenylene,
3-propoxy-~'-bromine-4,4'-diaminodiphenylene,
3-methyl-3'-ethyl-4,4'-diaminodiphenylmethane,
3-methyl-2'-ethyl-4,4'-diaminodiphenylmethane
. 2-chloro-3'-methoxy-4,4'-diaminodiphenylmethane,
3-propoxy-~'-bromine-4,4'-diaminodiphenylmethane,
3-methyl-3'-ethyl-4,4'-diaminodiphenylethane,
. 3-methyl-2'-ethyl-4,4'-diaminodiphenylethane,
2-chloro-3'-methoxy-4,4'-diaminodiphenylethane,
3-pLopoxy-3'-bromine-4,4'-diaminodiphenylethane,
3-methyl-3'-ethyl-4,4'-diaminodiphenylpropane,
3-methyl-2'-ethyl-4,4'-diaminodiphenylpro.pane,
2-chloro-3'-methoxy-4,4'-diaminodiphenylpropane,
3-propoxy-3'-bromine-4,4'-diaminodiphenylpropane,
3-methyl-5-ethyl-4,4'-diaminodiphenylene,
3-methyl-5-ethyl-4,4'-diaminodiphenylmethane,
3-methyl-5-ethyl-4,4'-diaminodiphenylethane,
3-methyl-5-ethyl-4,4'-diaminodiphenylpropane,
3,5,3'-tripropyl-4,4'-diamInodiphenylene~ ;
3,5,3'-triethoxy-4,4'-dia!minodiphenylene,
3,5,3'-trimethoxy-4,4'-diaminodiphenylene,
~,5-3'-trichloro-4,4'-diaminodiphenylene,
3,5,3'-tribromo-4;4'-diaminodiphenylene,
:- ' ~ . ~ .' '
` 1~1 4C~99
3,5,~'-tripropoxy-4,4'-diaminodiphenyleneJ
3,5,3'-tripropyl-4,4'-diaminodiphenylmethane,
3,5,3'-trimethoxy-4,4'-diaminodiphenylmethane,
3,533'-trichloro-4,4'-diaminodiphenylmethane,
3,5,~-tripropyl-4,4!-diaminodiphenylethane, ''
~,5,~'-trimethoxy-4,4'-diaminodiphenylethane,
3,5,3'-trichloro-4,4'-diaminodiphenyletha7e,
~,5,3'-tripropyl-4,4'-diaminodiphenylpropane,
3,5,3'-trimethoxy-4,4'-diaminodiphenylpropane,
. 3,5,3'-trichloro-4,4'-diaminodiphenylpropane,
2-bromo-3-propoxy-3'-methyl-4,5'-diaminodiphenyl-
ene,
2-chloro-3-ethoxy-3'-propyl-4,5'-dia~ino~iphenyl-
ene,
2-chloro-3-methoxy~ ethyl-4,5'-diaminodiphenyl-
ene,
2-bromo-3-butoxy-~'-butyl-4,5'-diaminodiphenylene,
2-chloro-3-methoxy-3'-ethyl-4,5'-diaminodiphenyl-
methane,
2-chloro-3-methoxy-3'-ethyl-4,5'-diaminodiphenyl-
ethane,
2-chloro-3-methoxy-3'-ethyl-4,5'-diaminodiphenyl-
propane,
"'
' '
~ . .
_g_
~ .
,
.,` ` ~1
2,~-diaminotoluene,
2,5-diaminotoluene,
3,4-diaminotoluene,
l-chloro-2,4-diaminobenzene,
l-ethoxy-2,4-diaminobe~zene,
l-propyl-2,4-diaminobenzene,
l-ethyl-2,4-diaminobenzene,
l-bromo-2,4-diaminobenzene,
l-butoxy-2,4-diaminobenzene,
~-chloro-2,4-diaminobenzene,
dimethoxynaphthalene diamine,
dichloronaphthalene diamine,
benzidine. :
Other amines which are contemplated include: ...
p-p'-diamino diphenyl sulfone, 1,3-diamino-4-iso-
propylbenzene, 1,~-diamino-4,5-diethyl benzene, .
diamino-stilbene, n,n'-bis-(cyclohexyl)-p-phenyl-
enediamine, N-cyclohexyl~NI-methylcyclohexyl-p-
phenylenediamine, N-methyl-N'-cyclohexyl-p-phenyl-
. enediamine, N-sec-butyl-N'-methylcyclohexyl-p-
phenylenediamine, N-alkyl-N'-aryl-p-phenylene-
diamine wherein ~he aryl radicals are phenyl,
tolyl, xylyl, and naphthyl, N-ethyl-N'-cyclopentyl-
. I .
.
- 10-
1.
11140~9
.
p-phenylenediamine,
N,N'-dinonyl-p-phenylenediamine,
N,N'-dedodecyl-p-phenylenediamine, ..
N-methyl-N'-sec-butyl-p-phenylenediamine,
N-sec-butyl-N'-isopropyl-p-phenylenediamine,
N,N'-di-(l-methyloctyl)-p-phenylenediamine,
N-totyl-N'-cyclopentyl-p-phenylenediamine,
N-phenyl-N'-undecyl-p-phenylenediamine~
1,3-diamino-4-methylbenzene, 1,4-diamino-2-methyl-
benzene, 1,4-diamino-2,5-dimethylbenz~ne,
1,4-diamino-2-methoxybenzene, 1,4-diamino-
2,5-dimethoxybenzene, 1,4-diamino-2,5-diethoxy-
benzene, 1,3-diamino-4,6-dimethylbenzene,
3,3'-dimethyl 4,4'-diaminodiphenyl, 3,3'-diethoxy- ~ .
4,4'-diaminodiphenyl, 2,7-diaminodiphenylene oxide,
1,5-dlaminoanthraquinone, 2,8-diaminochrysene, . .::
2-(4'-aminophenyl)-6-aminobenthiazole, 2,7-diamino- .
carbazole, piperazine, 2-methylpiperazine, and
~I,N'-dimethyl ethylene diamine.
It is further contemplated that mixtures of the
foregoing amines may be employed.
/ .:
. -
~, / ~ ' . .
.
/ ' ,.
.
:
- 11 -
~rs
: `: ,Ei
~ ;' ~' '
~` 1 11 4C~9~9
The epihalohydrin which is employed in thisiinven-
tion may be selected from the group consisting of epichloro-
hydrin, epibromohydrin or epiiodohydrin. Epichlorohydrin
is preferred due to its lower cost and ready availability.
The quantity of epihalohydrin which is contemplated for the
products and process of the instant invention i9 directly
related to the concentration of the amine employed. The
molar ratio of amine to epihalohydrin employed should be
at least 2 moles of amine to 1 mole of epihalohydrin and
may be as much as 4 moles of amine to 1 mole of epihalo-
hydrin, preferably a ~:1 mole ratio of amine to epihalo-
hydrin.
The process for preparing an oxyalkyl~ted conden-
sation product of amine and epihalohydrin comprises:
(a) rea~ing at least two moles of amine with
1 mole of epihalohydrin,
(b) adding to the product of step (a) an amount
of alkali about equivalent to the quantity of
, epihalohydrin employed therein,
(c) further reacting the product of step (b)
forming the condensation product~ and
(d) reacting the condensation product of step (c)
with sufficient alkylene oxide to react with
~; .
.~ ,
~, . .. . . . . .. . .. . . . .
- 1 1 1 4~9~9
all of the active hydrogens in the product.
More specifically the products are produced by
reacting a desired ratio of amine and epihalohydrin at a
temperature range from about 25C. to about 1~0~., prefer-
ably from about 50C. to about 100C. The time of reaction
may vary from o.5 hour to about 3 hours, however J the re-
action is generally complete within about 1 hour. Upon
completion of this reaction, an alkaline solution is added
to the reaction mixture. The alkaline solution may be pre-
pared from sodium hydroxide, potassium hydroxide, or lithium
hydroxide. Strongly basic amines as for example, isopropyl-
amine or ethylene diamine may also be employed. It is
preferred, however, that either sodium hydroxide or potas-
sium hydroxide are used in this epoxide formation step. The
amount of alkali employed is equivalent to a slight excess
o the amount of epihalohydrin employed. This amount.is
necessary to neutralize the acid formed from the halohydrin
group. This reaction occurs at a temperature of from about
60 - 150C., preferably from about 90 - 100C. These amine
condensation products can be oxyalkylated by the addition
o alkylene oxide in the presence of an alkaline catalyst.
Additional alkaline catalyst is added to the condensation
products to catalyze the oxide addition. Sufficient alkylene
~ ~ .
-13
, ~11~0~
oxide is then added to react with all of the active hydro-
gens in the product resulting in products having a molecular
weight ranging from about 250 to abou~ 600. The tempera-
tures employed for the oxide addition rnay vary from about
45C. to about 165C. at atmospheric or superatmospheric
pressures. Additional alkylene oxide may further be added
to increase the molecular weight from about 600 to about
10,000. The procedures employed for the oxyalkylation
reactions are well known to those skilled in the art and
further clarification is not deemed necessary. The alkylene
oxides which may be employed are selected from the group
consisting of ethylene oxide, propylene oxide, butylene
oxide, 8tyrene oxide, allyl glycidyl ether, or mixtures
thereof.
The amine conden~ation products of this invention
may be used as cross-linking agents in urethane-urea compo-
sitions such as those employed in cast-elastomers~ integral
- . . .
skin foa~s, microcellular foams, etc-. The oxyalkylated
amine condensation products prepared in accordance with this
invention may be employed in the preparation of urethanes
for use in surface coatings, flexible and rigid foams and
the like. Due to the high functionality which results from
~ the use of components which contain multiple active hydrogen
,`~ groups, together with the aromatic amine groups, these prod-
,~ .
.
-14-
'
.
1 11 4 0~99
ucts may be usefully employed in the preparation of rigid
polyurethane foams which are useful in the preparation of
sandwich panels for insulating applications in home refrig-
erators and freezers, refrigerated trucks and other car-
riers. Semiflexible foams useful in automotive crash pads,
weather stripping and the li~e can be prepared from higher
molecular weight polyols prepared from these condensation
products. The oxyalkylated derivatives are also useful in
the preparation of non-cellular urethane compositions such
as those used in coatings, sealants, seamless flooring,
; elastomers and similar applications. Rigid foams prepared
from the oxyalkylated amine condensation products exhib,it
improved humid aging properties compared to oxyalkylated
I amine products.
¦ The polyurethane foams employed in the present
lnvention are generally prepared by the reaction of the oxy-
~ alkylated product with an organic polyisocyanate in the
¦ presence of a blowing agent and optionally in the presence
; of additional polyhydroxyl-containing components, chain,
ex ending agents, catalysts, surface-active agents, stabi-
lizer~, dyes, fillers and pigments. When water is added as
the blowing agent, corresponding quantities of excess iso-
cyanate to react with the water and produce carbon dioxide
may be used. It is also possible to proceed with the prep-
aration of the polgurethane plastics by a prepolymer tech-
-15-
` 1114099
nique wherein an excess of organic polyisocyanate is reacted
in a first step with the polyol of the present invention to
prepare a prepolymer having free isocyanate groups which is
then reacted in a second step with water to prepare a foam.
Alternately, the components may be reacted in a single
working step commonly known as the "one-shot" technique of
preparin~ polyurethanes. Furthermore, instead of watér, low
boiling hydrocarbons such as pentane, hexane, heptane, '
pentene, and heptene; azo compounds;such as azohexahydro-
; 10 benzodinitrile; halogenated hydrocarbons such as dichloro-difluoromethane, trichlorofluoromethane, dichlorodifluoro-
ethane, vinylidene chloride, and methylene chloride may be
used as blowing agents.
Organic polyisocyanates which may be employed
include aromatic, aliphatic, and cycloaliphatic polyiso-
cyanates and combinations thereof. Representative of these
types are the diisocyanates such as m-phenylene diiso-
, ~ cyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyan- -
ate, mixtures of 2,4 and 2,6-tolylene diisocyanate, hexa-
methylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate,
cyclohexane-1,4-diisocyanate, hexahydrotolylene diisocyanate
~and isomers), naphthylene-1,5-diisocyanate, l-methoxyphenyl-
2,4-diisocyanate, diphenylmethane-4,4-diisocyanate, 4,4'-bi-
~ ~ phenylene diisocyanate, 3,~'-dimethoxy-4,4'-biphenyl di-
,j ' ' :~ ~',
-16- -
:~ .
. , .
'
~ . . . . .. - . . . . . . . . -
` :
111409~
isocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate and
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; the tri-
isocyanates such as 4,4',4'-triphenylmethane triisocyanatè,
polymethylene polyphenylisocyanate and tolylene 2,4,6-tri-
isocyanate; and the tetraisocyanates such as 4,4'-dimethyl-
---- diphenylmethane-2,2'-5,5'-tetraisocyanate. Especially use-
ful due to their availability and properties are tolylene
diisocyanate, diphenylmethane-4,4'-diisocyanate and poly-
methylene polyphenylisocyanate.
Crude polyisocyanate may also be used in the
compositions of the present invention, such as crude tolu-
ene diisocyanate obtained by the phosgenation of a mixture
of toluene diamines or crude diphenylmethane isocyanate
obtained by the phosgenation of crude diphenylmethyl
diamine. The pre~erred unreacted or crude isocyanates
are dislosed in U. S. Pat. No. 3,215,652.
~¦ The polyisocyanate may be used in an amount which
provides an NCO/OH ratio from about 0.9:1 to 1.5:1, prefer-
ably an NCO/OH ratio from about 1.00:1 to 1.2:1. The
NCO/OH ratio is defined as the ratio of total NCO equivalents
to total active hydrogen equivalents (i.e., hydroxyl plus
~ water).
!~ Chain-extending agents which may be employed in
the preparation of the polyurethane foams include those -
: .
,,
... . . . .. ~ . . .
1$1409!~
compounds having at least two functional groups bearing
active hydrogen atoms such as water, hydrazine, primary
and secondary diamines, amino alcohols, amino acids,
hydroxy acids, glycols, or mixtures thereof. A preferred
group of chain-extending agents includes water and primary
and secondary diamines which react more readily with the
prepolymer than does water such as phenylene diamine,
1,4-cyclohexane-bis-(methylamine~, ethylene diamine, di-
ethylene triamine, N-(2-hydroxypropyl~ethylene diamine,
N,N'-di(2-hydroxypropyl)ethylene diamine, piperazine,
2-methylpiperazine, morpholine, and dodecahydro-1,4,7,9b-
tetrazaphenalene.
Any suitable catalyst may be used including
. . .
tertiary amines, such as for example, triethylene diamine,
N-methylmorpholine, N-ethyl morpholine, diethyl ethanol-
amine, N-coco morpholine, l-methyl-4-dimethylamino ethyl
piperazine, 3-methoxy-N-dimethyl propyl amine, N-dimethyl-
N'-methyl isopropyl propylene diamine, N,N-diethyl-~-diethyl
amino propyl amine, dimethyl benzyl amine, and the like.
Other suitable catalysts are, for example, tin compounds ~ -
such as stannous chloride, tin salts of carboxylic acids,
such as dibutyltin di-2-ethyl hexoate, tin alcoholates such
as stannous octoate, as well as other organo metaLlic com-
~; pounds such as are dislosed in U. S. Pat. No. 2,846,408.
'i~ '
-18-
..
~: - . . . .. .
4{~
A wetting agent or surface-active agent is gener-
ally necessary for production of high grade polyurethane
foam according to the present invention, since in the
absence of same the foams collapse or contain very large
uneven cells. Numerouswetting agents have been found
satisfactory. Nonionic surfactants and wetting agents are
preferred. Of these, ~he nonionic surface-active agents
prepared by the sequential addition of propylene oxide and
then ethylene oxide to propylene glycol and the solid or
liquid organosilicones have been found particularly desir-
able. Other surface-active agents which are operative,
although not preferred, include polyethylene glycol ethers
of long chain alcohols, tertiary amine or alkylolamine
salts of long chain alkyl acid sulfate esters, alkyl
sulfonic esters, and alkyl arylsulfonic acids.
The following Examples are illustrative of the
present invention and therefore are not intended in any way
as a limitation on the scope thereof. Parts and percents
are by weight unless otherwise indicated. These Examples
illustrate the process for preparing the amine condensation
products, the products thereof, their oxyalkylated deriva-
tives and the polyurethane compositions produced therefrom.
.
. .
.
' '
., 19 ' ~
.
, . -
A 3-liter flask equipped with stirrer, thermom- -
eterJ condenser and addition funnel was charged with!717
grams of crude methylenedianiline. The polyamine was
heated to a temperatùre between 64 and 78C. and 92.5 grams
of epichlorohydrin was added over a two hour period. Upon
completion of the addition, the reaction mixture was stirred
for one hour at temperatures of about 39C. and 40 grams
of sodium hydroxide dissolved in 72 milliliters of water
was added to the reaction mixture over a period of about one
hour at temperatures ranging between 66 to 70C. The
mixture was allowed to react for one hour at a temperature ~;
of 78 to 82C. and then the addition of 790 grams of
propylene oxide was begun at a temperature of 112C. The
oxide addition took approximately 16 hours, while the tem-
perature ranged between 48 and 107C. Upon completion of
the oxide addition the reaction mixture was stirred at 70
to 109C. for five hours. 1.3 grams of potassium hydroxide
was added to the reaction mixture and water was stripped off
at temperatures of 148 to 160C. at 2 to 4 millimeters of
mercury pressure. Additional propylene oxide, 730 grams,
was added over a period of 24 hours at temperatures ranging
I from 117 to 161C. Upon completion of the second addition,
the reaction mixture was stirred at a temperature of about
150C. for two hours. Subsequently 1.335 grams of 85 per-
~
.
'' ' ` 1*~'409~ ' ~
cent phosphoric acid was added to neutralize the catalyst.
The reaction mixture was filtered through a Buchner funnel
at 110C. to remove the salts. The resulting filtrate was
stripped at 120C. for one hour at 1 millimeter mercury
pressure. The resulting product had a hydroxyl number of
about 358 corresponding to a molecular weight of 10~5,
assuming a functionality of 6.6.
ExamPle ?
A 3-liter flask equipped with-stirrer, thermom-
eter, condenser, and addition funnel was charged with 557.7
grams of toluene diamine. A quantity of epichlorohydrin,
141 grams, was added over a period of approximately two hours
at temperatures ranging from 44 to 130C. The reaction
mixture was stirred for half an hour at a temperature of
140C. Upon cooling the reaction mixture, 61 grams, of
sodium hydroxide dissolved in 16 milliliters o water was
added and the mixture allowed to react at a temperature of
11~C. for one hour. After allowing the reaction mixture
to stand overnight, 995 grams of propylene oxide was added
.
over a 24 hour period at temperatures ranging from 99 to
~ 108C. Upon completion of this addition, the reaction
`~ ~ ~ mixture was stirred for one hour at reflux temperatures then
1.15 grams of potassium hydroxide was added. Subsequently,
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water was stripped from the reaction mixture at tempera-
tures of 128 C. at 1 millimeter of mercury pressure over
a period of approximately two hours. A quantity of
propylene oxide, 905 grams, was added at temperatures
ranging from 71 to 176C. over a period of approximately
96 hours. The reaction mixture was allowed to react at
156C. for 16 hours. The catalyst was then neutralized
with 1.04 grams of 85 percent phosphoric acid, and the ,~
reaction mixture stripped at temperature ranging from 126
to 144C., and 1 millimeter mercury pressure, for two hours.
The resulting product had a hydroxyl number of 413 which
corresponds to a molecular weight of about 750 assuming a
functionality of 5.5.
Example ~
A 500 milliliter flask equipped with stirrer,
thermometer, condenser, and addition funnel was charged with
99 grams of methylene dianiline. The amine was heated to a
temperature of approximately 90C. and 46.25 grams of epi-
chlorohydrin was added at temperatures ranging from 70 to
110C. over a period of approximately 45 minutes. Sub-
sequently, the reaction mixture was stirred at temperatures
ranging from 74 to 78C. for one hour. 125 milliliters of
benzene were then added. The mixture was cooled to approx-
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imately 40C. and over a time period of 25 minutes, 105
grams of diethanolamine was added. After the addition,
the reaction mixture was heated at reflux temperatures of
80C., for one and a half hours. Potassium hydroxide, 28.05
grams, dissolved in ~0 mils of distilled water was added
to the mixture. Water was then removed by azeotropic dis-
tillation at a temperature of 72 to 83C. Benzene was then
removed by stripping by heating the reaction mixture to a
temperature range of 76 to 102C. at 17 millimeters mercury
pressure. Propylene oxide, 261 grams, was added during a
period of 16 hours at temperatures ranging from 90 to 132C.
The reaction mixture was then stirred at 132 for 8 hours.
The resulting product had a hydroxyl number of 518, which
corresponds to a molecular weight of 715, assuming a func-
tionality of 6.6.
I Example 4
j A l-liter flask equipped with stirrer, thermometer,
condenser, and addition funnel was charged with 157.5 grams
of diethanolamine. Epichlorohydrin, ~6.25 grams, was added
to the reaction flask at temperatures ranging from 26 to
80C. over a period of about one hour and 20 minutes. The
reaction mixture was thèn stirred at temperatures ranging ¦
from 75 to 80C. for one hour and 45 minutes. Sodium
1.
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hydroxide, 20 grams, dissolved in 25 milliliters of water,
was added at a temperature of 80C. The reaction mixture -
was then stirred for one hour at temperatures ranging from
65 to 80C. 232 grams of propylene oxide was added at
temperatures ranging from 65 to 95C. during nine and, a
half hours. The reaction mixture was then stirred for one
half hour at 90C. and volatiles were stripped off at a .. ,
temperature range of 90 to 106C. at less than 1 millimeter
of mercury pressure. The resulting product had a hydroxyl
number of 584 which corresponds to a molecular weight of
388, assuming a functionality of 4.
Example 5
Foam A was prepared using the propylene oxide
adduct of the amine condensation product prepared in '
Example 1.
Foam B was prepared using the propylene oxide
adduct of the amine condensation product prepared in
Example 2.
Foam C was prepared using the propylene oxide
adduct of toluene diamine having a molecular weight of
about 575.
Foam D was prepared using the propylene oxide
adduct of crude methylene dianiline having a molecular
weight of about 785.
,,
-24-
` 1114~99
Foam E was prepared using the propylene oxide
adduct of the amine condensation product prepared in
Example ~.
Foam F was prepared using the propylene oxide,
adduct of the amine condensation product prepared in
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Example 4.
The propylene oxide adducts of toluene dlamine
and crude methylene dianiline were prepared by procedures
well known to those skilled in the art.
Hand-mixed rigid polyurethane foams were prepared
using the formulations as listed. Physic 1 properties Qf
, the foams obtained are listed below in the Table.
3 The physical properties of the polyurethane foams were determined by the following ASTM test6:
Tensile Strength D-412
Humid Aging D-1564
Yield Strength D-1621
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The data in the Table indicates that the ~ volume
increase upon Humid Aging is substantially less for the
condensation products of the instant invention as compared
to the prior art products. Thus, Foam D showed a volume
increase of 12.5% whereas Foams A and E~ prepared from the
same amine and linked with epichlorohydrin, showed a volume
increase of 8.6 and 7.7% respectively. Similarly, Foam C
increased in volume by 18.1% whereas Foam B, prepared from
the same amine and linked with epichlorohydrin showed a
voLume increase of 8.2%.
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