Note: Descriptions are shown in the official language in which they were submitted.
-- Mo~1792-JG
PU-031
TOLUENE DIAMINE INITIATED PO YETHE~ _OLYOLS
BACKGROUND OF THE INVENTION
_
Polyether polyols which are formed by alkoxylating
various amines are known. Thus, in U. S. Patents 3,423,344
and 3,499,009, polyols are described which are produced by
reacting methylene-his(phenylamine) with various alkylene
oxides. Although these polyols, when used to produce rigid
polyurethane foams, have met with some success, the resultant
foams still suffer from problems relative to dimensional
stability and surface friability.
Alkoxylated toluene diamines are also broadly known.
Thus, in British Patent 972,772, a product is broadly des-
cribed which is the alkoxylated product of tetra-~-hydroxyl
ethyl-2,4-diamino toluene. However, this reference gives no
guidelines as to ratios of the various alkylene oxides to be
used in pxoducing foams of good dimensional stability and good
surface friability.
DESCRIPTION OF THE INVENTION
It has now been found that the novel polyols dis-
closed herein, when used to produce polyurethane foams, yield
foams having excellent dimensional stability and good surface
friability.
The polyols of the instant invention comprise:
Mo-1792
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~37~
(a) from 10 to 100 percent by weight of an adduct
; obtained by reacting toluene diamine sequentially first with
from three to five moles, and preferably four moles of ethylene
oxide ~nd second with from one to about five moles, particularly
one to 5.1 moles, pre~erably one to 4.1 moles o~ a vicinal
alkylene oxide of from 3 to 9 carbon atoms with the proviso
that the total number of moles of ethylene oxide plus vicinal
alkylene oxide does not exceed 8.1 and is no less than 5; and
(b) from 0 to 90 percent by weight of a material
10 containing from 2 to 8 hydroxyl groups and preferably containing
alkylene oxide residues, the amount of ethylene oxide
residues in the polyol blend being less than 80 percent based
on the total number o~ alkylene oxide segments present in
said blend.
The adduct of the instant invention may also be
~; characterized by the following general formula:
CH3 N ~ (C2H4)a (RO)W
(I) ~ ~ (C2H4)b (RO)X
~/ ~ N , ~ (C2H4O)C ( )y
~: . ~ (C2H4o)d -- (RO)z -H
- where R represents an alkylene: group of from 3 to 9 carbon ~.
atoms,
-~ 20 a, b, c, d, w, x, y and z represent numbers from
:: 0 to 2,
: a + b + c + d is from 3 to 5,
w -~ x + y + z is from 1 to 5.1, and wherein the
relationship of a, b, c, d, w, x, y and z to each other
25 satisfies the following:
Mo-1792 -2-
PU-031
j~ .
3~
5 ~ a + b ~ c + d + w + x ~ y + ~ - 8.1.
Whenever used herein, and as used in the claims,
the term "toluene diamine" is intended to mean 2,4-toluene
diamine, 2,6-toluene diamine and mixtures thereof~
In preparing the adduct of the instant invention,
toluene diamine is reacted firstly with ethylene oxide and the
reaction product so obtained is reacted with a vicinal alkylene
oxide having at least 3 carbon atoms. The term vicinal alkylene
oxide having at least 3 carbon atoms means an alkylene oxide
having the formula
o
(II) Rl~ H-R2
wherein Rl represents an alkyl group of from 1 to 9 carbon
atoms and R2 is selected from the class consisting of hydrogen
and an alkyl group of from 1 to 6 carbon atoms. Examples of
vicinal alkylen~ oxides having at least 3 carbon atoms include
1,2-propylene oxide, 1,2-butylene oxide, 1,2-heptylene oxide,
3,4-octylene oxide, 2,3-nonylene oxide, and the like.
In carrying out the first alkoxylation step, one
mole of toluene diamine is reacted with from three to five
moles of ethylene oxide (preferably four moles). The reac-
tion between ethylene oxide and the toluene diamine is
carried out at a temperature in the range of from about
100C to about 220C, preferably from 105 to 110C at
atmospheric pressure, i.e., in an autoclave or similar closed
vessel. Of course, lower temperatures could be used, but the
reaction time will be necessarily extendedO At atmospheric
pressure, it is usually preferred to maintain the reaction
Mo~1792
PU~031 -3-
~37~
mixture at the desired temperature and to pass the ethylene
oxide below the surfa~_e of the reaction mixture at about the
rate at which the oxide is consumed. At superatmospheric
pressure the alkylene oxide is advantageously addedl ei.ther
continuously or intermittently, at such a rate that the reac-
tion temperature and pressure can be maintained at the desired
levels.
It has been found the reaction of the ethylene
oxide and the toluene diamine proceeds readily without a
catalyst until the amount of ethylene oxide consumed corres-
ponds to 4 moles per mole of amine. At this point, each of
the free hydrogens on the amino moieties of the amine has
been replaced by a 2-hydroxyethyl group. Theoretically when
the stage has been reached at which one of the two hydrogen
atoms on a primary amino group of the amine has been replaced
by 2-hydroxyethyl, the second equivalent of ethylene oxide
can attack either the remaining N-H bond on the amino group
or the O-H linkage of the 2-hydroxyethyl group. The reactivity
of the N-H linkage is however significantly higher than that
of the O-H linkage so that the second equivalent of ethylene
oxide attacks the N-H linkage preferentially.
.
If desired, an alkoxylation catalyst can be used.
~ Any alkoxylation catalyst known in the art can be employed
; for this purpose. Examples of such catalysts are tertiary
amines such as pyridine, triethylamine and the like, alkali
metals such as sodium, potassium, and lithium and alkali metal
hydroxides such as sodium hydroxide, potassium hydroxide,
lithium hydroxide, and the like.
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3~
The amount of alkoxylation catalyst employed in
the above process is generally within the range of about
O.OOOlto about 1 part by weight of catalyst per lO0 parts
by weight of amlne.
Although a reaction diluent is usually not necessary
in carrying out the above ethoxylation, an inert liquid
diluent can be present in the reaction mixture, if desired,
to aid in the dispersion of the alkylene oxide in the amine
mixture. Examples of suitable diluents include monochloro-
benzene, N,N-dimethylformamide, toluene, xylene, and the
like.
The reaction product of ethylene oxide and the amine
obtained, as described above, can be purified, if desir~d, but
is preferably employed, without ~urther treatment, in the
second alkoxylation step. If purification of the ethylene
oxide reaction product is desired before use of the product
in the second alkoxylation, said purification can be effected
using procedures known in the art. For example, the excess r
of ethylene oxide, if any is present, can be removed by
entrainment in a stream of inert gas such as nitrogen, argon,
xenon, and the like; if an inert organic solvent has been
employed as reaction solvent, this can be removed by distilla-
tion under reduced pressure and the residue from such treat-
ment or treatments can be purified by chromatography, counter-
current distillation and the like.
'~
The second alkoxylation step in which the ethoxy-
lated product from the first stage above is reacted with a
Mo-1792
PU-031 -5-
~37~
vicinal alkylene oxide containin~ at least 3 carbon atoms, is
carried out advantageously at a temperature in the range of
from about 100C to about 250C, preferably from 105C to 110C,
at atmospheric or superatmospheric pressure in the presence of
an alkoxylation catalyst. Lowar reaction temperature could be
employed with an increase in reaction times. Preferably the
catalyst employed is the same as that emp:Loyed in the first
stage of the process of the invention, if that stage has been
conducted in the presence of a catalyst. Where an alkoxyla-
tion catalyst has been employed in the ethoxylation stage of
the process of the invention, the reaction product from the
first stage can be employed, without further treatment, in the
second stage and no ~urther addition of catalyst is generally
necessary.
~hen an alkoxy ation catalyst is employed in the
second alkoxylation stage of the process of the invention,
said catalyst is employed in an amount within the range set
; forth above for the ethoxylation stage (first stage) of the
process.
The amount of vicinal alkylene oxide employed in
this second alkoxylation step is generally from 1 to 5.1 moles
of alkylene oxide for each mole of diamine employed as starting
~ material in the first step of the process of the invention.
; When the vicinal alkylene oxide is unsymmetrical,
- 25 i.e., the groups Rl and R2 are not identical, it ~ill be seen
from the following reaction schemes that the addition of the
vicinal alkylené oxide across the O-~ bond of a hydroxyethyl
.
Mo-1792
PU-031 -6-
group in -the reaction product from the first step of the
: reaction, can occur in the two possible ways giving rise to
a mixture of products.
(III) 2 2 1 HC CH R2 -~
T
X-cH2c~2-o-fH2 CH R2
Rl
+
: OH
X-CH2CH20--fH2-CH
R2 Rl
In the above equation, X represents the residue of the reaction
product obtained in the first step of the process hereinbefore
defined. The above equation typifies the reaction that will
occur in respect of each of the plurality of hydroxyethyl .
substituents present in the reaction from the first step of
. 10 the process of the invention. When the vicinal alkylene oxide
is em~loyed in an excess over that required to alkoxylate each
. of the hydroxyethyl groups in the starting material, further
reaction of the alkylene oxide with the products shown in the
~; above equation will occur with analogous results.
Where R2 in the alkylene oxide (II) represents
hydrogen, it will be seen that one of the possible reaction
products shown in the above equation will contain a secondary
hydroxyl group~ while the other product will have a texminal
primary hydroxy group. In general, it has been found that
Mo~1792
PU-031 -7-
93~
the reaction product having the secondary hydroxyl group is
the predominate isomer although the product usually contains
at least a minor amount, e.g., about 10 percent, of -the pri-
mary hydroxy configuration.
The products obtained in the second alkoxylation
stage of the invention can be isolated and purified, if desired,
by known procedures. For example, any excess of vicinal
alkylene oxide can be removed by purging the reaction mixture
with an inert gas such as nitrogen, argon, xenon, and the like.
If an inert organic solvent has been used as reaction solvent,
this can be removed by distillation under reduced pressure.
The sequentially alkoxylated product so obtained can be puri-
fied, or in the case oE a mixture, can be separated into its
individual components, if desired, by conventionai purification
and separation techniques such as chromatography, counter-
current distribution, fractional distillation and the like, or
any combination of these techniques.
The sequentially alkoxylated products of the inven-
tion can be represented by the following general formula:
CH3 N ~ (C2H4O)a (RO) --H
, ~ ```(C2H4lb ~RO)X
;~ ~ / ~C2H4O)C (RO)y H
-r -~ N~
J \ (C2H4O)d - (RO)z - H
where R represents an alkylene group of from 3 to 9 carbon
atoms,
a, b, c, d, w, x, y and z represent numbers from
0 to 2,
Mo-1792
PU-031 -~-
~3~
a + b ~ c + d is from 3 to 5,
w + x + y ~ z is from 1 to 5.1, and wherein the
relationship of a, b, c, d, w, x, y and z to each other
satisfies the following:
5 - a + b + c + d + w ~ x + y ~ z - 8.1.
Put another way, the adduct of the invention is produced by
sequentially reacting toluene diamine fi:rst with from 3 to 5
moles of ethylene oxide per mole of tolue~e diamine and
second with from 1 to 5.1 moles per mole of starting diamine
of a vicinal alkylene oxide havin~ from 3 to 9 carbon atoms.
The vicinal alkylene oxide is preferably propylene oxide.
As hereinbefore noted, the total number o moles of ethylene
oxide and vicinal alkylene oxide should be at least 5 and
should not exceed 8.1. It has been found that these limits
are essential to obtaining foams having an excellent balance
of properties including low friability and good dimensional
stability. For most purposes, it is preferred that the tolu-
ene diamine be reacted first with four moles of ethylene
oxide and then with from 1 to 4.1 moles of vicinal alkylene
oxide. The number of moles of vicinal alkylene oxide per
mole of amine is more preferably from 2 to 4.1 and is most
preferably from 2.5 to 3.5.
While the moles of vicinal alkylene oxide can be
varied within the range of 1 to 5.1, the preferred ranges
noted above yield certain advantageous properties when used
to make a polyurethane foam. Thus, foams produced using
polyols having vicinal alkylene oxide contents of from 1 to
4.1 moles exhibi~ excellent surface friability characteristics.
Mo-1792
PU-031 -9-
~3~@~
However, if more than 3 moles are used, the resultant foam
is not as dimensionally stable as a foam produced from an
adduct containing from 1 to 3 moles of vicinal alkylene oxide.
Similarly, if less than 3 moles are used, compatability of
the adduct with any blowing agent present may become a problem.
In any event, it has been found that an excellent
balance of pxoperties can be obtained when using a polyol
comprising from 10 to 100 percent by weight of the adduct,
and from 0 to 90 percent by weight of a hydroxyl group con-
taining material containing from 2 to 8 hydroxyl ~roups and
preferably containing alkylene oxide li.e., ~ O-R~--] residues,
; the amount of ethylene oxide residues in the polyol blend being
~ less than 80 percent, preferably less than 7Q percent and most
; preferably less than 60 percent, based on the total number of
alkylene oxide residues in the blend. The amount of the
hydroxyl group containing material will necessarily vary
depending upon the moles of vicinal alkylene oxide used to
produce the adduct, and the particular property desired. For
example, relative to blowing agent compatibility lesser
amounts of the hydroxyl group containing material will be
needed as the vicinal alkylene oxide content in the adduct
increases. Similarly, for ~urposes of dimensional stability,
the amount of material needed will increase with increasing
vicinal alkylene oxide content in the 3dduct.
The materials which can be used in combination with
the adducts of the instant invention can be any of those
commonly known and used in the polyurethane art. Essentially
any polyol having from 2 to 8 hydroxyl gxoups can be used,
Mo-1792
PU-031 -1
~ ~ 3t~
including polyether polyols, polyester polyols, polythioether
polyols and the like, which materials are generally known and
used in the polyurethane art. It is generally preferred, how~
ever, to utilize polyethers which contain alkylene oxide
residues. The only proviso relative to the polyether is that
the total amount of ethylene oxide units present in the polyol
blend is less than 80 percent of the total amount of alkylene
oxide residues present in the blend. Specific useful materials
include polyoxypropylene glycols, prepared by the addition of
1,2-propylene oxide to water, propylene glycol or dipropylene
glycol; mixed oxyethylene-oxypropylene polyglycols prepared in
a similar manner utilizing a mixture of ethylene oxide and
propylene cxide or a se~uential addition of e-thylene oxide and
1,2-propylene oxide; polyether glycols prepared by reacting
ethylene oxide, propylene oxide or mixtures thereo~ with mono~
and polynuclear dihydroxy benzenes, e.g., catechol, resorcinol,
hydroquinone, orcinol, 2,2-bis(p-hydroxyphenyl~ propane, bis
(p-hydroxyphenyl) m~thane, and the like; polyethers prepared
by xeacting ethylene oxide, propylene oxide, or mixtures
thereof with aliphatic polyols such as glycerol, sorbitol,
trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol,
sucrose or glycosides, e.g., methyl, ethyl, propyl, butyl~
and 2-ethylhexyl, arabinoside, xyloside, ructoside, gluco-
sid~, rhamnoside, etc.; polyethers prepared by reacting
ethylene oxide, propylene oxide or ~ixtures thereof with
alicyclic polyols such as tetramethylolcyclohexanol; polyols
containing a heterocyclic nucleus such as 3,3,5-tris(hydroxy-
methyl)-5-methyl-4-hydroxytetrahydropyran and 3,3,5,5-
Mo 1792
PU-031 -11-
3~
tetrakis(hydroxymethyl)-4-hydroxytetrahydropyran; or polyols
- containing an aromatic nucleus such as 2,2-bis-~hydroxyphenyl)ethanol, pyrogallol, phloroglucinol, tris(hydroxyphenyl)
alkanes, e.g., 1,1,3-tris(hydroxyphenyl) ethanes, and l,1,3-
tris(hydroxyphenyl)propanes, etc. tetrakis(hydroxyphenyl)
alkanes, e.g., 1,1,3-tris(hydroxyphenyl)-ethanes, and
~ 1,1,3-tris~hydroxyphenyl)propanes, etc., tetrakis(hydroxy-
`~ phenyl)alkanes, e.g., 1,1,3,3-tetrakis~hydroxy-3-methyl-
,:
phenyl)propanes, l,1,4,4-tetrakislhydroxyphenyl)-butanes,
and the like.
~ :
Illustrative of polyester polyols which can be
employed in the invention are those prepared from dibasic
; carboxylic acids and polyhydric alcohols, preferably trihydric
; alcohols. The dibasic carboxylic acids useful in preparing
the polyesters have no functional groups containing active
hydrogen atoms other than their carboxylic acid groups. They
are preferably saturated. Acids such as phthalic acid, tere-
phthalic acid, isophthalic acid, succinic acid, glutaric acid,
adipic acid, and pimelic acid are suitable. Anhydrides of
these acids may be used also. The polyol component or com-
ponents of the polyester are preferably trihydric. Examples
of suitable polyols include trimethylolethane, trimethylol-
propane, mannitol, hexanetriol, glycerine and pentaerythritol.
Small amounts of dihydric alcohols such as ethylene glycol,
diethylene glycol 1,2-propylene glycol, 1,4 butanediol, and
cyclohexandeiol may also be used. In preparing rigid poly-
urethane foams, it is recommended that no more than about
20~ of ~he hydroxyl groups of the polyester used by supplied
Mo-1792
PU-031 -12-
3~
by a diol. The above polyesters are typical of those which
can be employed in the one-shot, but preferably in the pre-
polymer, methods of foaming.
The novel polyols of the invention are useful as
intermediates in the preparation of polyurethanes in
accordance with procedures known in the art and are distingu-
ished from polyols hitherto prepared by their superior pro-
perties in relation to viscosity and compatibility in such
use, and by the improved properties imparted to the resulting
polyurethanes.
In preparing polyurethanes from the polyols of the
invention, the procedures well-known in the art for the
preparation of such materials are employed, the polyols of
the invention being used to replace a part or the whole of
the polyol components employed in the art procedures. While
the polyols of the invention can be applied to the formation
of any type of polyurethane, including cellular and non-
cellular polyurethanes, they are of particular application in
the preparation of cellular polyurethane products. Accordingly,
the use of the polyols of the invention in the preparation of
polyurethanes will be illustrated by reference to the prepara-
; tion of cellular products, but it is to be understood that the
invention is not limited thereto but is of general application
to the preparation of polyurethanes of all types.
The various methods for the preparation of poly-
urethane foams are well known in the art and do not require
detailed discussion; see, for example, Dombrow, "Polyurethanes,"
Mo-1792
PU-031 -13-
3~
Reinhold Publishing Corporation, New York, pages 1 - 105
(1957); S,aunders et al "Polyurethanes'l, Part I, Interscience
Publishers, New York (1962). One of the commonest procedures
consists in reacting a polyol, for example, a polyester or
polyether, with an organic polyisocyanate and with a blowing
~ agent, if necessary in the presence of catalysts, surface
- active agents o~ other auxiliary agents, whereby simul~aneousinteraction between the isocyanate, blowing agent and the
polyol occurs to give the required foam product. This is the
so-called 'lone-shot" procedure. Alternatively, the polyol may
be reacted with sufficient polyisocyanate to give an inter-
mediate reaction product containing free isocyanate groups
and this product, known as prepolymer, may then be reacted
with water, if desired in the presence of catalyst, surface
active agents or other auxiliary agents, in order to produce
the final foamed product. This latter is the so~called
"prepolymer'l process. Many variations in the method of
carrying out these basic processes are known.
~ny of the prior art polyisocyanates conventionally
used in the preparation of rigid polyurethane foams can be
employed in the process of the present invention. Illustra-
tive of such isocyanates are 2,4-tolylene diisocyanate,
2,6 tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
dianisidine diisocyanate, tolidine diisocyanate, hexamethylene
diisocyanate, m-xylylene diisocyanate, 1,5-napthalene diiso-
cyanate, and other di- and higher polyisocyanates such as
those listed in the tables of Siefken, Ann. 562, 122 - 135
(1949). ~ixtures of two or more of the above isocyanates
Mo-1792
PU-031 -14-
37~3~
can be used if desired. Preferred polyisocyanates are pro-
ducts obtained by phosgenation of mixtures of methylene-
bridged polyphenyl polyamines obtained by the interaction
of formaldehyde, hydrochloric acid, and primary aromatic
amines, for example, aniline, o-chloroanilinet o-toluidine,
or mixtures thereof. Such polyisocyanates are known in the
art, e.g., U. S. Patents 2,683,730; 2,950,263; and 3,012,008;
Canadian Patent 665,495; and German Patent 1, 131,877. A
particularly preferred polyisocyanate of this type is the
polymethylene polyphe~yl isocyanate available commercially
under the trademark Mondur MR~
In making rigid foams in accordance with the process
of the invention it may be advantageous to add a hydroxyl
terminated cross-linking polyol to the reaction mixture to
form the best network for foam formation. Advantageously the
cross-linking polyol should have at least 3 hydroxy groups in
the molecule and can be added to the foam reaction mix at any
point at which the other polyols are added. Examples o~ such
cross--linking polyols include trimethylolpropane, glycerol,
1,2,~-hexanetriol, pentaerythritol, hydroxyalkylated aliphatic
diamines such as N,N,N',N'-tetrakis(2-hydroxypropyl)ethylene-
diamine, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine,
and the like, and alkylene oxide reaction products of sugars
such as sucrose, and the like.
In preparing polyurethane foams according to the
invention, it is desirable, in accordance with conventional
procedures, to employ a catalyst in the reaction o~ the
Mo-1792
PU-031 -15-
37;~
polyisocyanate and polyol. Any of the catalysts conventionally
employed in the art to catalyze the reaction of an isocyanate
with reactive hydrogen containing compound can be employed for
this purpose; see, for example, Saunders et al., Ibid, Volume
I, pages 228 - 232; see, also Britain et al. "J. Applied
Polymer Science," 4,207 - 4,211; 1960. Such catalysts include
organic and inorganic acid salts of and organometallic
derivatives of, bismuth, lead, tin, iron, antimony, uranium,
cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel,
cerium, molybdenum, vanadium, copper, manganese, and zirconium,
as well as phosphines and tertiary organic amines. The pre-
ferred catalysts for use in the process and compositions of
the invention are the tertiary organic amines of which the
following are representative: triethylamine, triethylene-
diamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-
tetraethylethylene diamine, N-methylmorpholine, N-ethylmor-
pholine, N,N,N'N'-tetramethylguanidine, N~N,N',N'-tetra-
methyl-1,3-butanediamine, N,N-dimethylethanolamine, N,N-
diethylethanolamine, and the like, or mixtures of two or
more such amines. The amount of catalyst employed is
generally within the range of about 0.1 to about 2.0% by
weight based on total weight of reactants in the polyure-
thane forming reaction mixture.
The ratio of isocyanate groups to active hydrcgen
containing groups in the foam mixtures of the invention is
within the normal limits employed in the production of poly-
urethane foams. This said ratio is advantageously within
the range of from 1.50 to 0.65:1 and preferably within the
Mo-1792
PU-031 -16-
3~
range of 1.20:1 to 1~1, whether the isocyanate and polyol are
employed separately in the one-shot process or whether the two
components have been reacted to form a prepolymer.
The final foam density of the products produced by
the process of the invention can be controlled in accordance
with methods well known in the art. For example, this control
can be accomplished by regulating the amount of water present
in the foam mixture or by using a combination of water and a
conventional blowing agent having a boiling point below about
110C and preferably below abou-t 50C, such as a volatile
aliphatic hydrocarbon or a volatile highly halogenated hydro-
carbon, for example, trichloromonofluoromethane, chlorotri-
fluoromethane, l,l-dichloro-l-fluoroethane, l-chloro-l-,
l-difluoro-2, 2-dichloroethane and 1,1,1-trifluoro-2-chloro-
2-fluorobutane or mixtures thereof.
Optional additives such as dispersing agents, cell
stabilizers, surfactants, flame retardants, and the like which
are commonly employed in the fabrication of rigid polyurethane
foams, can be employed in the process of the invention. Thus,
a finer cell structure may be obtained if water-soluble organo-
silicone polymers are used as surfactants. Organosilicone
polymers obtained bycondensing a polyalkyoxy polysilane with
the monoether of a polyalkyleneether glycol in the presence
of an acid catalyst are representative of those surfactants
which can be used for this purpose. The organosilicone
copolymer available under the trade name L5420 is typical of
such polymers. Other surfactants such as ethylene oxide
Mo-1792
PU-~31 -1~-
7~
.
modified sorbitan monopalmitate or ethylene oxide modified
~` polypropyleneether glycol may be used, if desired, to obtain
better dispersion of the components of the foam mixture.
Other additives such as dyes, pigments, soaps and
metallic powders and other inert fillers may be added to the
foam mixture to obtain special foam properties in accordance
with practices well-known in the art.
$he polyurethane foams produced using the novel
- polyols of the instant invention are useful in a variety of
commercial and industrial applications including for example,
the production of foam-insulation, structural foam sporting
goods, and the like.
The following examples are provided to lllustrate
the present invention. Unless otherwise specified, all parts
are by weight.
Mo-1792
PU-031 -18-
. "
~3~
E~MPLES 1 THROUGH 3
In producing the adducts of these examples, the
following procedure was followed:
The toluene diamine was charged to a pressure
reactor and was heated to 105C under 6 to 8 psi nitrogen.
The addition of the ethylene oxide was then begun. The
addition was at a rate such as to keep the temperatures between
105C and 110C. Coolingor heating was applied to maintain
this temperature range. When all the ethylene oxide had been
added, the reaction mixture was kept for two hours at 105C
to 110C.
Aqueous (50%) po-tassium hydroxide was added to the
reactor in an amount equal to 0.5 percen~ by weight of the
total batch feed. The water was distilled off at 110C.
The addition of the propylene oxide was then started
at a rate such as to maintain the temperature between 105C to
110C at a pressure of 6 to 8 psi nitrogen. After the addi-
tion was complete, the mixture was maintained at 105C to
110C for three hours.
The finished product was neutralized with sulfuric
acid and the resultant potassium sulfatP was filtered off,
leaving the product.
The amounts of materials used, ~ogether with the
moles of combined alkylene oxide and hydroxyl number o:F the
product are indicated in Table 1.
Mo-1792
PU-031 -lg-
7~
TABLE 1
Exampl~ 2 3
Toluene Diamine gms 25.5 22.8 34.3
E~hylene Oxide gms 33.2 32.8 49.4
Propylene Oxide gms 41.2 44.4 16.3
Product:
_ .
Moles TDA/EO/PO 1/3.6/3.39 1/4/4.1 1/4/1
Hydroxyl Number 470 418 630
EXAMPLE 4
Toluene diamine (47.7 parts) and 68.9 parts of
ethylene oxide were charged to a pressure reactor and reacted
for two days at 50C. The reaction mixture was then cooled
to room temperature and charged with 45.4 parts of propylene
oxide and reacted for two days at 80C. The resultant adduct
had an OH number of 540 and a molar ratio of components of
TDA/ethylene oxide/propylene oxide of 1/4/2.
EXAMPLES 5 THROUGH 20
The adducts of ~xamples 1 through 4 were used to
produce foams. The foams in each of these examples were pre-
pared by hand mixing. They were prepared under ambient con-
ditions according to the formulations shown in Table 2 (all parts
being parts by weight).
Mo-1792
PU-03I ` -20-
Mixing was accomplished by a high speed air driven
mixer equipped with a single three-winged blade. The adduc-t,
polyol (when used), surfactant, catalyst, combustibility
modifier (when used), blowing agent, and water (when used)
were pre-blended in a cylindrical cardboard container. The
indicated quantity of isocyanate was added and mixed inti-
mately with the above blend. The mixed liquid was then poured
into a 13" x 13" x 6" box and the foam allowed to rise freely.
The reaction times were recorded on the foaming material and
surface friability was determined thirty minutes after the
initial foaming reaction. The results were as indicated in
Table 3. Additionally, in some instances, the various
physical properties noted in Table 3 were recorded.
In Table 3, the following terms appear and are
defined as follows:
(1) Mix time: the duration of mixing after the isocyanate is
added to the resin blend.
(2) Cream time: the elapsed time from the start of mix time
until the time at which a change in color
of the mixed liquid from brown to creamy
tan is noted.
~3) Gel time: the elapsed time from the start of mix time
until the time at which a l/8" diameter
applicator stick inserted 2" into the rising
foams, pulls with it a 6" long "string" when
it is quickly removed from the foam.
Mo-1792
PU-031 -21-
~;3!'7~
(4) Tack free time: the elapsed time Erom the start oE mix
time until the time a~ which a clean
dry tongue depressor lightly touched
to the foam surface can be removed with-
out pulling off the foam surface.
(5) Rise time: the elapsed time from the start of mix time
until the time at which no additional visible
foam rise can be observed.
~6) Surface friability: the characteristic of a foam sur~
face to powder when slightly com-
pressed or lightly scraped with a
tongue depressor or fingernail.
This characteristic is usually
fleeting.
(7) Non-friable (NF): a foam surface which up to 30 minutes
after foam mixing shows no friability.
(8) V ry-slightly friable (VSF): a foam surface which up to
30 minutes after foam mixing
shows no more than 1/32"
of powdering when scraped.
(9) Sli~ ia~ SFI: a foam surface which up to 30
minutes after foam mixing shows
no more than 1/16" of powdering
when scraped.
(10) Friable (F): a foam surface which up to 30 minutes after
foam mixing shows no more than 1/~" of
powdering when scraped.
Mo-1792
PU-031 -22-
3~
(ll) Very frlable (VF): a foam surface which up to 30
minutes after foam mi~ing shows
more than l/8" of powdering when
scraped.
Mo-1792
PU-031 23-
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Mo-1792
PU-031 -24-
3~
1 R-8020 ' is a blend of 80 percent by weight oE dimethyl ethanol-
amine and 20 percent by weight of triethylenediamine.
DC193 is a commercial silicone surfactant available from
Dow-Corning Corporation.
3 RllB is Freon blowing agent.
4 Fyrol 6 is O,O-diethyl-N,N-bis(2-hydroxyethyl)amino-
methyl phosphonate.
5 Polyol A is an ethylene diamine initiated polyether polyol
having an OH number of 630.
' 10 6 Polyol B is an ethylene diamine initiated polyet,her polyol
having an OH number of 470.
7 ~olyol C is a sucrose polyether polyol of 460 OH number.
8 Polyol D is a sucrose polyether polyol of 380 OH number.
9 Polyol E is a methylene-dianiline initiated polyether polyol
having an OH number of 410.
.
~, 10 The isocyanate used was a polyphenylpolymethylene poly-
; isocyanate containing about 50 percent by weight
of diphenylmethane diisocyanate and having an
isocyanate content of about 32 percent.
,
Mo-1792
PU-031 -25-
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Mo-1792
PU-031 -26-
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Mo-1792
PU-03~ -27-
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~o-1792
PU-031 -28-
