Note: Descriptions are shown in the official language in which they were submitted.
D.75,927-FB
-- 1 --
BIS(AMINOETHYL)ETHER DERIVATIVES AND
PRODUCTION OF POLYURETHAN~S
The invention relates to certain novel tertiary
amino catalyst which contain ether and hydroxyl moieties,
and their use in the production of polyurethanes.
The use of a catalyst in preparing polyurethanes
by the reaction of a polyisocyanate, a polyol and perhaps
other -ingredients -is -~nown.--- The catalyst is employed
to promote at least two, and sometimes three major
reactions~ that must proceed simultaneously and compet-
itively at balanced rates during the process, in order
to provide polyurethanes with the desired physical
characteristics. One reaction is a chain extending
isocyanate-hydroxyl reaction by which a hydroxy~~containing
molecule i~ reacted with an isocyanate-containing molecule
to form a urethane. This increases the viscosity of
the mixture and provides a polyurethane containing a
secondary nitrogen atom in the urethane groups. A seco~d
reaction is a crosslinking isocyanate/urethan~ reaction,
by which an lsocyanate-containing molecule reacts with
a urethane group containing a secondary nitrogen atom.
The thir~ reaction which may be involved i5 an isocyanate-
water reaction by whi~h an isocyanate~terminated molecule
is extended and by which carbon dioxide is ganerated
to blow or a~sist in khe blowing of the foam. The third
reaction is not essential i~ an extraneous blowing agent,
such as a halogenated, normally liquid hydrocarbon or
carbon dioxide, is employed, but is e~sential if all
or even a part of the gas for foam generation is to
be generated by this in situ reaction (e.g. in th2
preparation of "one-shot" flexible polyurethane foams~.
The reactions must proceed simult~neously at optimum
balanced rates relative to each other in ord0r to obtain
a good foam structure. If carbon dioxide evolution
is too rapid in comparison with chain extension, the
. ~,~,,
6~
-- 2 --
~oam will collapse. If the chain extension is too rapid
in comparison with carbon dioxide evolution, ~oam rise
will be restricted, resulting in a high density foam
with a high percentage of poorly defined cells. The
5 ~oam will not be stable in the absence of adequate cross-
1 inking .
It has long been known that tertiary amines, such
as trimethylamine and triethylamine, are effective for
catalyzing the second crosslinking reaction. Other
typical tertiary amines are set forth in U.S. Paten~s
No. 3,925,368; 3,1279436 and 3,243,387, and in German
Offenlegungsschrifts No. 2,354,952 and 2,259,980. Some
of the tertiary amines are effective for catalyzing
the third water-isocyanate reaction for carbon dioxide
evolution, but tertiary amines are only partially effective
as catalysts for the first chain extension reaction.
To overcome this problem, the so-called "prepolymer"
technique has been developed, wherein a hydroxy-containing
polyol component is partially reacted with the isocyanate
component in order to obtain a liquid prepolymer containing
free isocyanate groups. This prepolymer is then reacted
with additio~al polyol in the presence of a tertiary
ami~e to provide a foam. This method is still commonly
employed in preparing rigid urethane foams, but has
proven less satis~actory for the production of flexible
urethane foams.
For flexible foams, a one-step or "one-shot" process
has been developed, wherein a tertiary amine, such as
triethylenediamine, is employed in conjunction with
an organic tin compound. Triethylenediamine is particularly
active for promoting the water-isocyanate reaction and
the tin compound is particularly active in synergistic
combination with the triethylenediamine for promoting
the chain extension reaction. Even here, ho~ever, the
results obtained leave much to be desired. Triethylene-
diamine is a solid and must be dissolved be~ore use
to avoid processing difEiculties. Also, triethylenediamine
and other of the prior art amines can impart a strong
- -- 3 ~
amine odour to the polyurethane foam.
In addition to problems of odour and handling due
to solid character, other tertiary amines have still
further deficiencies. For example, in some instances
the compounds are relatively volatile, leading to obvious
safety problems. In addition, some catalysts of this
type do not provide sufficient delay in foaming. Such
a delay is particularly desirable in moulding applications
to allow sufficient time to inject a preformed mixture
into the mould. Yet other catalysts, while meeting
specifications in this area do not yield foams ~ith
a desirable tack-free time.
Lastly, while certain tertiary ~mines are somewhat
suitable a~ pol~urethane catalysts they nevertheless
do not have a suf~iciently high tertiary amine content,
in terms of the number of tertiary amine groups compared
to overall molecular weight. It is believed that the
hi8her the tertiary amine content, the more rapid the
catalytic activity.
It would be an advance in the art if a new class
of amine catalysts were discovered which would overcome
so~e of the aforementioned disadvantages of the prior
art. It would also be advantageous if an unused by-
product stream from an existing process could be adapted
to provide the new amine catalysts.
In the production of morpholine and 2-~2-amino~thoxy)
ethanol ~rom ammonia and diethylene glycol, a by-product
stre~n that contains methoxyethylmorpholine and bis(amino-
ethyl)ether is produced. This by-product stream may
be purified by adding ethylene oxide to react with the
bis(aminoethyl)ether and then distilling off t~e useful
methoxyethylmorpholine according to the teaching of
U.S. Patent No. 3,420,828. No use has, however, been
made of the ethylene oxide adduct of bis(aminoethyl)ether
until the invention of the novel tertiary amine ether
urethane catalysts herein.
Other tertiary amine ethers useful as catalysts
for isocyanate reactions are the beta-(N,N-dimethyl-
6~
_ 4 _ ~
amino)alkyl ethers described in U.S. Patent No. 3,330,782.Other tertiary amines which also have hydroxyl substituents
are the hydroxyalkyl tertiary amines of U.S~ Paten~s
No. 4,026~840 and 4,101,470.
The present invention provides a composition of
rnat ter having the formula
~/ ~/\ N CH3 ( I )
- R" l~ OH
R
where R is hydrogen or alkyl and R" is methyl or
-CH2CHOH
R
This invention also provides a method for preparing
these components, which proceeds as follows. Bi~(amino-
ethyl)ether of the formula
H2NCH2CH20CH2CH2NH2
is reacted with an alkylene oxide of the formula
~ .
OCH2C~R
This reaction can be carried out in accordance with
the method of U.S. Patent No. 3,420,828, to produce
a cornpound of the formula
R \ ~ ~ N / H
H ~ OH
Where R' is hydrogen or -CH2~HOH
~ y the method of this invention9 compound 11 is
reacted with formaldehyde in the presence of hydrogen
and a hydrogenation-dehydrogenation catalyst to make
compound 1.
This invention also provides a method ~or producing
6~
- 5 -
a polyurethane which comprises reacting an organic
polyisocyanate with an organic polyester polyol or polyether
polyol in the presence of a catalytic amount of a
composition of matter having the formula (I).
The reactions to make the polyurethane catalyst
should be conducted at an elevated temperature, generally
in -the range from 75 to 250C. The alkoxylation step
is preferably conducted at a tempera-ture from 50 to
150C, while the hydrogenation is preferably carried
out at a teMperature from 75 to 250C. The hydrogen
pressure in the second step is preferably from atmospheric
to 210 bars and is especially preferred to be on the
order of about 70 bars. The catalyst may be any
hydrogenation-dehydrogenation catalyst, though it is
preferred that the catalyst contain nickel, copper and
chromium oxide, or cobalt, copper and chromium oxide,
and it is especially preferred that the catalyst be
prepared according to the method described in U.S. Patent
No. 3,152,998.
The starting materials are bis(aminoethyl)ether
and alkylene oxides. The alkylene oxides are pre~erably
ethylene oxide, propylene oxide or butylene oxide, although
higher oxides may be used. The formaldehyde reactant
of the second step may be employed in another form,
such as paraformaldehyde. The preparation of the novel
compounds o* this înventlon is further illustrated by
the following two Examples.
. .
1~3~j~2~
-- 6 --
EXAr~pT.~ _l
PREPARATION OF 2-[N-(DIMETHYL-
AMINOETHOXYETHYL) N-METHYLAMINO]ETHANOL
A 1500 ml kettle was charged with gOO 8~ of a mixture
of methoxyethylmorpholine, bis(aminoethyl)ether, aminoethyl-
morpholine and water in the weight proportions 19:61:5:6.
The mixture was heated to 80C and 229.7 g. of ethylene
oxide were added. The reaction mixture was then digested
at 90C for 1.5 hours. The material was then put through
a wiped film evaporator at 90~C and 0.4 rnm Hg vacuum.
There was obtained 876.7 g~ of bottoms material.
500 g. of this material was added to a flask which contained
334.5 g. of paraformaldehyde and 1500 ml of isopropanol.
This mixture was then transferred to an autoclave and
reduced using a nickel 9 copper, chromium oxide catalyst
at 110C and 70 bars of hydrogen. Following the hydrogen-
ation, the reaction mixture was filtered then fractionally
distilled. The resulting 2-CN-~dimethylaminoethoxyethyl)-
N-methyl~nino~ ethanol had a boiling point of 110-115C
at 0.5 mm Hg.
EXAMPLE 2
2~
PREPARATION OF 2-CN-DIMETHYLAM~NO-
ETHOXYETHYL)-N-METHYLAMINO~ l-METHYLETHANOL
A 1500 ml kettle was charged with 900 g. of the
mi~-ture of bls(aminoethyl)ether and N-methoxyethylmorpholine
in the same proportions as in Ex~mple 1. The mixture
was heated to 80C and then 15104 g. of propylene oxide
was added. After digesting at 90C for 1.5 hours, the
reaction mixture was discharged into a 2 litre flask.
3~ ~he unreacted portion was then removed under vacuum,
leaving 386.6 g. of material. 300 g. of this material
were reductively alkylated using 16Zo3 g. of paraformalde
hyde and- a nickel, copper~ chrornium oxide catalyst at
-- 7 --
70 bars of hydrogen and 110C. The product was purified
using a wiped film evaporator at 120C and 0.25 mm Hg
vacuum. The overhead fraction contained mainly the
l-propylene oxide adduct, with a little 2-propylene
oxide adduct also being present.
The suit~bility of the new bis(aminoethyl)ether
derivatives as catalysts for foam formulations is shown
in the remaining Examples. The quantities listed in
all Examples are parts by weight. The foams are all
prepared by conventional means using conventional polyols,
isocyanates and additives. For examples of conventional
foam preparation, see U.S. Patent No. 4,101,470.
To prepare~polyurethanes using the catalysts according
to the present invention9 any aromatic polyisocyanate
may be used. Typical aromatic polyisocy~nates include
m-phenylene diisocyanate, ~-phenylene diisocyanate,
polymethylene polyphenylisocyanate, 2,4-toluene diiso-
cyanate, 2,6-toluene diisocyanate, dianisidine diisocyanate,
bitolylene diisocyanate, naphthalene-l 7 4~diisocyanate,
xylylene-1,4-diisocyanate 9 xylylene-1,3-diisocyanate,
bis(4-isocyanatophenyl)methaneg bis(3-methyl-4-isocyanato-
phenyl~methane, bis(3-methyl-4-isocyanatophenyl)methane~
and 4,4'~diphenylpropane diisocyanate.
Greatly preferred aromatic polyisocyanates used
ln the practic2 of the invention are 2,4- and 2,6-toluene
diisocyanates, and methylene-bridged polyphenyl polyiso-
cyanate mixtures which have a functionality of Erom
2 to 4. These latter isocyanate compounds are generally
produced by the phosgenation of corresponding me-thylene
bridged polyphenyl polyamines, which are conventionally
produced by the reaction of formaldehyde and primary
aromatic amines, such as aniline, in the presence of
hydrochloric acid a~d/or other acidic catalysts. Known
processes ~or preparing polyamines and corresponding
methylene-bridged polyphenyl polyisocyanates therefrom
are described in the literature and in many patents,
for e~ample 9 U.S. Patents No. 2 7 683 7 730; 2,950,263;
3,012,008; 3,344,162 and 3,362,979.
- 8
The most preferred methylene-bridged polyphenyl
polyisocyanate mixtures used in accordance with this
invention contain 20 to 100 weight per cent of methylene
diphenyldiisocyanate isomers? with the remainder being
polymethylene polyphenyl polyisocyanates having higher
functionalities and higher molecular weights. Typical
of these are polyphenyl polyisocyanate mixtures containing
20 to 100 weight per cent of methylene diphenyldiisocyanate
isomers, of which 20 to 95 weight per cent thereof is
the 4,4' isomer, with the remainder being polymethylene
polyphenyl polyisocyanates of higher molecular weight
and functionality that have an average functionality
of from 2.1 to 3.5. These îsocyanate mixtures are known,
commercially available materials and can be prepared
by the process described in U.S. Patent No. 3,362,979.
The hydroxyl-containing polyol component which
reacts with the isocyanate may suitably be a polyester
polyol or a polyether polyol having a hydroxyl number
from 700 to 25, or lower. When it is desired to provide
a flexible foam, the hydroxyl number is preferably in
the range from 25 to 60. For rigid fo~ms, the hydroxyl
number ls preferably in the range from 350 to 700.
Semi-rigid foams of a desired flexibility are pro~ided
when the hydroxyl number is intermediate to the ranges
just given. Also for a fl~xible urethane foam, the
polyol should preferably have an average functionality
of from 2 to 4 and a molecular weight of from 2,000
.i to about 6,000. For rigid foams, the functionality
of the polyol component is preferably from 4 to 8~
When the polyol is a polyester polyol, it is preferably
a resin having a relatively high hydroxyl value and
a relatively low acid value made from the reaction of
a polycarboxylic acid with a polyhydric alcohol. The
acid component of the polyester is pre~erably dibasic
or polybasic and is usually free of reactive unsaturationS
such as ethylenic groups or acetylenic groups. The
unsaturation, such as occurs in the rings of such aromatie
acids as phthalic acid9 terephthalic acid, isophthalic
- 9 -
acid, is non-ethylenic and non-reactive. Thus, aromatic
acods may be employed for the acid component. Aliphatic
acids, such as succine acid, adipic,acid, sebacic acid
and azelaic acid, may also be employed , and aer preferred.
The alcohol component for the polyester should preferably
contain a plurality of hydroxyl groups and is preferably
an aliphatic alcohol, such as ethylene glycol, glycerol,
pentaerthritol, trimethyloletane, trimethylolpropane,
mannitol, sorbitol, or methyl glucside. Mixtures of
two or more or the above identified alcohols may be
employed also if desired.
When the hydroxyl-containing component is a polyether
polool, for use in flexible polyurethane foam, the polyol
may be an alkylene oxide of adduct of a polyhydric alcohol
with a vuctionally of from 2 to 4. The alkylene oxide
may suitably be ethllene oxide, propylene oxide, or
1,2-butylene oxide, or a mixture of some or all of these.
The polyol will suitably have a molecular weight of
from 2,000 to 7,000. For flexible polyether polyurethabe
foams, the alkylene oxide is preferably propylene oxide,
odr a mixture of propylene oxide and etyylene oxide.
For rigid polyether polyurethane foams, the polyol
should have a functionally of from 4 to 8 and a molecular
weith of from 300 to 1,200. Polyols for rigid polyether
polyurthane foams may gbe made in various ways, including
the addition of an alkylene oxide as above to a polyhydric
alcohol with a functionally of from 4 to 8. These
polyols may alos be, for example, Mannich condensation
products of a phenol, an alkanolamine, and formaldehyde,
which Mannich condensation product is then reacted with
an alkylene, oxide (see U.A. Patent No. 3,297,597).
The amount of hydroxyl-cintaining pllyol compound
ro vew used relative to the ixocyanate compound in both
polyestef and polyethrer foams normally ahould be sucyh
thqaat the isocyanate groups are present in a t least an
equivalent amount, and Preferably, in slight execss,
xompared with the free hydrocyl groups. Preferably,
the amounts of the ingredients will be such as to provide
-- 10 --
from 0.9 to 1.5 mole equivalents of isocyanate groups
per mole equivalent of hydroxyl groups. For certain
shock absorbing foams, however, we have found that by
using the catalyst of our invention the mole equivalents
of isocyanate to hydroxyl groups can be as low as 0.4.
When water is used, the amount of water, based
on the hydroxyl compound, is suitably from 0.05 to 10.0
moles per mole equivalent of hydroxy compound.
It is within the scope of the pre~ent invention
10 to utilize an extraneously added inert blowing agent,
such as a gas or gas-producing material. For example,
halogenated low-boiling hydrocarbons, such as -trichloromono-
fluoromethane and methylene chloride, carbon dioxide
and nitrogen, ~ay be used. The inert blowing agent
15 reduces the amount of excess isocyanate and water that
is required in preparing flexible urethane foam. For
a rigid foam9 the use of water is often avoided and
only the extraneous blowing agent is used. Selection
of the proper blowing agent is well within the knowledge
20 of ~hose skilled in the art. See, for example, U.S.
Patent No. 3,072,082.
Th~ catalysts according to this invention, which
are use~ul in the preparation of rigid or flexible polyester
or polyether polyurethane foams, are employed in an
25 amount from 0.03 to 4.0 weight per cent, based on the
combined weight of the hydroxyl-containing compound
and polyisocyanate. ~ore often, the amount of catalyst
used is 0.06 to 2.0 weight per cent.
The catalysts according to this invention may be
~0 u~ed either alone or in a mix~ure with one or more other
catalysts, such as tertiary amines, or with an organic
tin compo~nd, or other polyurethane catalysts. The
organic tin compound, particularly useful in making
flexible foams may suitably be a stannous or stannic
35 compound,- such as a stannous salt of a carboxylic acid,
a trialkyltin oxide9 a dialkyltin dihalide, or a dialkyltin
oxide, wherein the organic grouFs of the organic portion
OI the tin compound are hydrocarbor. groups containing
from 1 to 8 carbon atoms. For example, dibutyltin
dilaurate, dibutyltin diacetate, diethyltin diacetate,
dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin
dioxide, stannous octoate, stannous oleate, or a mixture
thereof, may be used.
Such tertiary amines include trialkylamines (e.g.,
trimethylamine or triethylamine), heterocyclic amines,
such as N-alkylmorpholines (e.g., N-methylmorpholine
or ~-ethylmorpholine), 1,4-dimethylpiperazine or tri-
ethylenediamine, and aliphatic polyamines, such as N,N,N'N'-
tetramethyl-1,3-butanediamine.
- Conventional formulation ingredients are also employed,
for example, foam stabilizers, also known as silicor.e
oils or emulsifiers. The ~oam stabilizer may be an
organic silane or siloxane. For example, compounds
may be used having the formula:
RSiCO-(R2SiO)n-(oxyalkylene)mR]3
wherein R is an alkyl group containing from 1 to 4 carbon
atoms; n is 4 to 8; m is 20 to 40 and the oxyalkylene
groups are derived from propylene oxide ~nd ethylene
oxide. See, for example, U.S. Patent No. ~,194,773.
In preparing a flexible foam, the ingredients may
be simultaneously, intimately mixed with each other
by the so-called "one-shot" method to provide a foam
by a one-step proces. In this instance, water ~hould
comprise at least a part (e.g. 10 to 100%) of the blowing
agent. The foregoing methods are known to those skilled
in the art, as evidenced by the following publication:
duPont Foam Bulletin, "Evaluation of Some Polyols in
One-Shot Resilient Foams", March 22, 1960.
When it is desired to prepare rigid foams 9 the
"one-shot" method or the so-called "quasi-prepolymer
method" can be employed, wherein the hydroxyl-containing
component preferably contains from 4 to 8 reactive hydro~yl
groups, on the average, per molecule.
Xn accordance with the "quasi-prepolymer method",
a portion of the hydroxyl-containing component is reacted
in the absence of a catalyst with the polyisocyanate
component in proportions so as to provide from 20 per
cent to 4Q per cent of free isocyanateo groups in the
reaction product~ based on the polyol. To prepare a
foam, the remaining portion of the polyol is added and
the two components are allowed to react in the presence
of cataly-tic systems 9 such as those discussed abo-ve,
and other appropr-ate additives, such as blowing agents,
foam stabilizing agents, and fire retardants. The blowing
agent (e.g., a halogenated lower aliphatic hydrocarbon),
the foam-stabilizing agent, and the fire retardant,
may be added to either the prepolymer or remaining polyol,
or both, before the mixing of the component, whereby
at the end of the reaction a rigid polyurethane foam
is provided.
Urethane elastomers and coatings may be prepared
also by known techniques in accordance with the present
invention wherein a tertiary amine of this invention
is used as a catalyst. See 7 for example, duPont Bulletin
PB-2, by Remington and Lorenz 7 entitled "The Chemistry
of Urethane Coatings".
The polyurethane-forming reaction according to
this invention will be further illustrated with respect
to the following specific Examples.
- 13 -
EXAMPLE 3
This Example illustrates the use of these compounds
as catalysts for flexible urethane foams.
, ~ A B C D E
~, ~ HANUL F-30161 ~ 100 100100 100 100
Silicone L-62022 1.1 1.11.1 1.1 1.1
Water 2.1 2.12.1 2.1 2.1
50~ Stannous octoate in
dioctylphthalate 0.6 0.60.6 0.6 0.6
Catalyst Example 1 0.5
Catalyst Example 11 --- 0.5 --- --~ ---
Prior Art Catalyst 13 --- --- 0.5 -~
Prior Art Catalyst 113 ~ -- 0.5 ---
Prior Art Catalyst 1113 --- --- --- --- 0.5
Methylene chloride 8.0 8.08.0 8.0 8.0
Toluene diisocyanate 28.928.9 28.9 28.9 28.9
Index 1.05 1.05 1.05 1.05 1.05
Cream time (sec) 6 7 10 11 11
Rise time (sec) 110 134145 136 154
Density, (Kg/m3) 33.32 -_- ___ 32.68 33.00
An ethoxylated-propoxylated glycerine of hydroxyl number 56'
sold by Texaco Chemical Co.
2A silicone surfactant sold by Union Carbide Corp.
3Prior art catalyst I is taken from U.S. Patent No.4,026,840
and has the following structure
CH
N ~ N''''~`------OH
CH3 CH3
Prior art catalysts 11 and 111 are taken from U.S.
Patent No. 4,101,470 and have the following structures,
respectively
- 14 -
CH3\N~ ~ N~ ''~ CH3 3\N--'^~--~'~N~'~ ~CH3
CH3 ~ 3 CH ~ < ~CH3
HO ~ OH
Comparing foams A, C and D from Example lll, one can
see that the catalyst of this invention is more efficient
than the catalysts in C or D (rise time of 110 seconds
vs. 145 a~d 136). The catalysts in C and D also have
a lower amine equivalent weight than the catalys~ from
Example I (foam C equivalent weight is 73, foam D is
77, while cataLyst of Example I has an equivalent weight
of 9530 Thus the catalysts from Example I give a ~aster
reaction profile with less equivalents o~ amine being
reacted. The same effect can also be obserYed in the
propanol amine compounds (foams B and E).
, EXA~PLE 4
This Example illustrates .the use of these amines
as catalysts for rigid urethane foams.
THANOL R-4801 ~ 35 35
Silicone L-5420 0.5 0.5
Water 0.3 0.3
Trichlorofluorom2thane 13 13
Catalyst Example 1 0.8
Catalyst Example ll 0~8
MONDUR NR3 ~ 51.2 51.2
Index 1.04 1.04
- Cream time (seconds) 10 12
Gel time (seconds) 55 76
Tack free time (seconds) 70 104
Rise time tse~onds) 90 154
~n ~ crosc p~lyol, hydroxyl number 5307 sold by
Texaco ChemicaL Co.
A silicone sur~actant sold by Union Carbide Corp.
3A polymeric isocyanate sold by Mobay Chemica:L Co.
-~k ~fl D,~ 7J~ J'Z /~
~g6~
- 15 -
EXAMPLE 5
This Example illustrates the use of these compounds
as catalysts ~or highly resilient ~oams. Again, the
unexpec-ted high catalytic activity of these compounds
can be observed (for the hydroxyl series ~oams A, C,
and D and for the hydroxypropyl series foams B and E~.
In each instance, when used at an equal weight basis,
the cataly~ts of this in~ention gave faster rise times
than the other amines. Note also that the same weight
of catalyst of this invention contains fewer equivalents
of amine than the other catalysts.
THANOL F-65031 60 60 60 60 60
15 NIAX 34-282 ~ 40 40 40 40 40
Water . ~ 3.5 3.5 3.5 3.5 3.5
silicone L_53Q93~r 2.0 2.0 2.0 2.0 2.0
FOMRE~ UL-14 ~ OoOl O~Ol O~Ol O~Ol O~Ol
Catalyst Example I 0. 5
20 Cataly~ Exaanple 11 --- 00 5 --- --- ---
Prior Art Catalyst ll -~ 0.5 -~
Prior Art Gat;alyst I --~ 0 .5 ---
Prior Art Catalyst lll ~ 0.5
Toluene diisocyanate/PAPI 42 42 42 42 42
25 Cream time (seconds) 7 8 8 8
Rise time tseconds) 125 120 140 140 145
., _
A propoxylated-ethoxylated glycerine, hydroxyl number
27, sold by Texaco Chemical Co.
2 A polymer-polyol, hydroxyl number 28, sold by Union
Carbide Corp.
3 A silicone surfactant sold by Union Carbide Corp.
4 Toluene diisocyanate 80% by weight, PAPI 20% by weight,
PAPI is a polymeric isocyanate sold by Upjohn.
Highly resilient polyurethane foams require that
an organic polyisocyanate be employed in the formulation.
~R~D~ ,~nf~
- - 16 -
Frequently, a blend is used that consists of toluene
diisocyanate a~d another polyisocyanate.
A blend of polyols must be used to make foams of
high resiliency. One of the blend components is a polyether
polyol ~ormed by the addition of a polyhydric alcohol
ha~ing a functionality of from 2 to 4 with an alkylene
oxide of 2 to 4 carbon atoms. The polyether polyol
should have a ~unctionality o~ from 2 to 4 and a hydroxyl
number of from 20 to 60. The second blended polyol
is preferably a grafted polymer polyol containing from
4 to 25 wei~ht per cent of acrylonitrile and ~rom O
to 10 weight per cent of styrene. The rnolecular weight
of the base polyol is preferably from 2,800 to 5,000.
The hydroxyl number of the resulting graft polyol is
preferably from 25 to 45. These latter graft po~yols
are described in detail in U.S. Patents No. 3,304,273
and 3,383,351.
The mole equivalent ratio of isocyanate groups
to hydroxyl groups should be 009 to 1.2, to obtain the
highly resilient foams of this invention.
EX~MPLE 6
The compound of Example 1 may be used to prepare
a packaging foam as shown below:
THANOL SF-2750 100
Water 20
Trichlorofluoromethane35
Sllicone L-520 1.5
Catalyst Example I 4.0
MO~DUR MR 140.5
Cream time ~seconds) 8
Rise time (seconds) 43
Gel time (seconds) 45
. _
1 Polyol sold by Texaco Chemical Co., hydroxyl number 220.
2 A silicone surfactant sold by Union Carbide Corp.
