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Патент USA US3075936

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United States Patent Oh"1C6
Ll
amaze
2
containing at least two ricinoleyl groups and having an
‘ equivalent weight in terms of its functional hydroxy
3,075,925
FOAMED PQLYURETHANE PLASTZQS AND
PRDCESS FGR MAKENG SAME
_
Patented Jan. 29, W53
,
groups above 200, a polyol containing at least 3 hydroxy
Wiiiiam l). Stewart, Alexandria, Va., and Richard @
Thomas, Washington, B.C., assignor's to Atlantic Re
search Qorporation, Alexandria, Va, a corporation of
groups and having a maximum equivalent weight in
terms of its functional hydroxy groups of about 125,
preferably a maximum of about 100; a polyisocyanate;
No Drawing. Filed May 115, 1959, Set‘. No. 813,334
30 Claims. (6i. zen-25}
a polymerizable, ethylenically-unsaturated monomer con
taining at most one functional hydroxy group; and a foam
ing agent, such as water or a carboxylic acid, which pro
Virginia
This invention relates to rigid, expanded polyurethane
plastics, which are particularly suitable for use as energy
absorbent and heat insulating materials and which can be
10 duces CO2 by reaction with the polyisocyanate.
The
,_ reaction mixture may also include a catalyst to promote
' reaction of‘ the high molecular weight polyricinoleate
foamed in place directly from monomeric components
polyol with the polyisocyanate; an emulsifying agent as
energy-dissipating material for the protection of supplies
and equipment delivered by aerial drop. Increasing the
energy-absorptive properties of the protective foam in
The reaction mixture should not contain a catalyst,
such as an organic peroxide, which promotes polymeriza
tion of the ethylenically-unsaturated monomer. Such
a dispersing and solubilizing agent for the water; and a
without an accessory source of heat.
15 foam stabilizer.
An important area of use for cellular structures is as
catalysts have hitherto been employed in the art, including
creases the altitude from which packages can be dropped 20
the polyurethane art, to induce unsaturated monomer
and their rate of descent. This reduces hazard to person
, polymerization. Their use is objectionable for our pur
nel and aircraft during delivery, decreases the size of para
chute required for drag and stabilization of the packages
during fall, and increases accuracy in placing dropped
material.
Since the low-density cellular structures are exceedingly
bulky, transportation to the area of use is not only ex
pensive but can be a serious, if not insoluble, problem
pose, however, since the foamed polyurethane products
are excessively resilient, apparently because the catalyst
free radicals tend to cause termination of the polymeriza
' tion reaction at relatively low molecular weight levels and
_ to promote linear
polymerization of the unsaturated,
non-polyol monomer rather than cross-linkage at the un
saturated sites in the polyricinoleate polyol, which we be
under urgent ?eld conditions. It is, therefore, not only
is essential for foam rigidity and non-resilience.
desirable, but in many cases essential that the cellular 30 lieve
Upon mixture of the aforedescribed components at
protective material be quickly and easily preparable in
ambient temperature, reaction takes place very rapidly.
the ?eld in a single operation under ambient temperature
Polymerization, foaming, and curing proceed and are
conditions from relatively low cost, stable components,
completed under the exotherm of the reaction mixture
without requiring special equipment or accessory treat
ments other than mixing, such as heating. It is also im 35 without requiring accessory heating. Foaming expansion
occurs within minutes and substantially maximum strength
portant that the cellular product attain quickly the req
and
rigidity of the foamed plastic are generally reached
uisite energy-absorptive properties with a minimum of
within 12 hours or less.
curing time.
The di- and tri-ricinoleic acid (12-hydroxy-9-octadec
To be suitable, the cellular material must crush upon
anoic acid) esters are particularly suitable for our pur
40
impact without bounce, thereby dissipating energy without
pose because the double bonds at the ninth carbons of
any destructive transmittal to the cushioned package.
the acyl groups provide sites for cross-linking and chain
The protective structure must, therefore, be rigid and non
extension which, under the conditions of our process,
res?ient. Cellular material such as foamed glass and
aluminum honeycomb possess good energy-dissipating
yield highly cross-linked, three-dimensional, rigid polyure
properties, but the serious disadvantage of not being pre 45 thane polymers. The ricinoleic acid esters can be the
diesters of a polyhydric alcohol, such as a glycol, e.g.
parable at the point of use. Foamed plastics have hitherto
ethylene glycol, propylene glycol, butylene glycol; a
proven unsatisfactory for such reasons as excessive re
polyglycol, e.g. di-, tri-, and tetra-ethylene or propylene
silience, heating requirements for polymerization, curing
glycol; glycerol; and the like. Such ricinoleic acid
or foaming which are difficult to meet in the ?eld, the
esters are characterized by a high equivalent weight,
short shelf life of reaction components, such as polyure
generally above 200, in terms of hydroxy functionality.
thane prepolymers, and excessive cost.
We prefer to employ castor oil because of its high
The object of this invention is to provide rigid, non
ricinoleic acid ester content combined with its availability
resilient cellular polyurethane plastics which can be
and low cost. Castor oil is a triglyceride of Iii-carbon
foamed in place by the reaction of monomeric components
in a single operation under ambient temperature con 55 fatty acids generally consisting of about 90% hydroxy
acids, practically all ricinoleic, and about 10% non-hy
ditions without requiring an accessory source of heat.
Another object is to provide rigid, foamed polyurethane
plastics which are excellent energy-absorptive materials
because of their non-resilience and crushability under
impact.
Still another object is to provide rigid cellular polyure
thane plastics which can be foamed in place and cure,
without external heating, to the desired rigidity and
crushability within a very short time.
droxy acids, chie?y oleic and linoleic. The oil consists of
about 70% of trihydrcxy ester, glyceryl triricinoleate,
and about 30% of dihydroxy ester, glyceryl diricinoleate
monooleate or glyceryl diricinoleate monolinoleate. In
terms of isocyanate functionality, it is, therefore, about
70% tri-functional and 30% di-functional. Although non
functional relative to the isocyanate, the oleic and linoleic
acid components advantageously provide unsaturated sites
I
Yet another object is to provide rigid, highly energy 65 for cross-linkage and chain extension.
We
are
aware
that
castor
oil
has
been
employed
with
absorptive, foamed polyurethane plastics which also have
diisocyanates to form polyurethanes. Such polymers,
excellent heat-insulative properties.
however, are excessively resilient for energy-absorptive
Other objects and advantages will become obvious from
purposes. Because of the secondary nature of the hy
the following detailed description.
We have discovered that rigid, highly energy-absorp 70 droxyl groups, combinedwith the high equivalent weight
in terms of hydroxy or isocyanate functionalitylabout
tive, foamed polyurethane plastics can be prepared by
340), castor oil'reacts very slowly with diisocyanate at
admixing a polyhydroxy alcohol ester of ricinoleic acid
room temperature,- even in the presence of catalysts, so 7
3,075,926
that accessory heating is required. The polymerization
reaction must be su?iciently rapid to provide an adequately
retentive structure to hold within the body of the mass
the CO2 gas formed by isocyanate reaction with water.
A liquid polyol having at least 3 functional hydroxyl
groups, preferably 4, and a maximum equivalent weight
in terms of hydroxy (and, therefore, isocyanate) func
tionality of about 125, preferably 100, reacts rapidly with
4
enically-unsaturated, non-polyol monomers include:
styrene, vinyl toluene, ethyl acrylate, butyl acrylate, 2
ethyl-hexyl acrylate, methyl methacrylate, ethyl meth
acrylate, diethylene glycol dimethacrylate, tetraethylene
glycol dimethacrylate, diallyl succinate, dimethyl maleate,
' diallyl rnaleate, vinyl acetate, vinyl stearate, diallyl phthal
ate, methyl ‘butenol, divinyl benzene, triallyl cyanurate,
N,N-diallyl melamine, and the like. We have found the
vinyl monomers, such as vinyl toluene, diallyl stearate,
a polyisocyanate at ambient temperature with concom:
itant high exotherm. Examples of such highly reactive 10 diallyl phthalate, N,N’-diallyl melamine, and triallyl
cyanurate, to be particularly suitable.
liquid polyols include N,N,N’,N’-tetrakis-’(Z-hydroxy
Substantially any reactive polyisocyanate can be em
propyl) ethylene diamine (Quadrol), glyceryl 'monoricin-
ployed for our purpose, including aliphatic diisocyanates,
oleate, triethanol amine, glycerol, hexanetriol, and ‘the
such as hexamethylene diisocyanate, and aromatic poly
like. Addition of such polyol derivatives to the poly
such as 2,4-tolylene diisocyanate, mixtures
ricinoleate~polyisocyanate system provides the requisite 15 isocyanates,
of
2,4—tolylene
diisocyanate and 2,6-tolylene diisocyanate,
rapid temperature build-up for complete and fast reac
m-Iphenylene diisocyanate, 3,3’-bitolylene-4,4'-diisocya
tion of the polyricinoleate hydroxyl groups with the dis
nate, diphenylmethane-4,4'-diisocyanate, dianisidine di
isocyanate and the foaming reaction ‘witlr'water. "Such
isocyanate, 1,5-naphthalene diisocyanate, tri-(p-isocyanyl
co-condensation provides an expedient for eliminating the
need for accessory heating. The cured, foamed prod 20 phenyl) methane, the triisocyanate adduct formed by
reaction of 1 mol of hexanetriol and 3 mols of m
uct, however, is resilient and does not, therefore, possess
tolylene
diisocyanate, and the like. The particular poly
the desired’ high energy-absorptive properties without
isocyanate selected is determined to a considerable ex
bounce.
'
We have discovered that the desired foam rigidity and
tent by its reaction rate in a given monomer reaction
mer, having no or at most one reactive hydroxyl group,
polyr'icinoleate, provides an additional element of con
crushability under impact can be achieved'by including 25 system. This, together with suitable selection of the
highly reactive‘ polyol employed in conjunction with the
a liquid, polymerizable, ethylenically-unsaturated mono
trol over the exotherm’of the reaction. Thus, in a highly
into the polyiso‘cyanate reaction system and'initiating
reactive system, the use of a somewhat less reactive
polymerization of the unsaturated monomer by thermal
diis'ocy’anate, such as hexamethylene diisocya
induction of free radicals without accessorvuse of a 30 aliphatic
nate would be advantageous to prevent excessive exo
catalyst, such as an organic peroxide, generally employed
therm or to prevent excessive hardening of the polymeric
to promote such polymerization. We have additionallyv
structure before good cell formation is obtained. In
found that the requisite heat for such thermal induction.
general, we prefer to employ the aromatic diisocyanates.
can be provided by the high exotherm produced by re
action with the polyisocyanate of the aforedescribed-p olyoli 35 because of their more rapid reaction rates, and, in par
ticular, 2,4- or a mixture of 2,4- and 2,6-tolylene diiso
having at least 3 and and preferably 4 functional hyf
cyanate, because of its excellent performance, availability
droxy groups and a maximum equivalent weight in terms.
and low cost. The triisocyanate adduct of hexanetriol
of hydroxy functionality’, of about 125, preferably 100.
and tolylene diisocyanate is particularly suitable for use
Such thermal polymerization of the unsaturated, non
polyol monomer yields foamed copolymers having con 46 under low temperature conditions, e.g. 0° C., because
of its low solidi?cation point.
The foaming component can be water, a carboxylic
‘acid which is soluble in the polyisocyanate reaction com
siderably better physical properties for our purpose at.
the temperatures required for rapid condensation of the
polyricinoleic acid ester, such as castor oil, with poly
isocyanate than those obtained with the aid of peroxide
free radicals. The foamed products obtained under our
thermally induced processing conditions are also consid
erably more rigid and energy-absorptive than foams made
by reaction of prepolymer castor oil-diisocyanate or poly
ponent, or a mixture of both. Although water is, in
45
general, preferred, good foaming can be obtained with
carboxylic acids, preferably of low molecular weight,
such’ as acetic acid, propionic acid, lactic acid, ?-hy
droxy-propionic acid and the like. Use of such acid
foaming agents, either alone or in combination with
ester-diisocyanate adducts with a peroxide-‘catalyzed, un
saturated, non-polyol monomer and water. The thermal 50 Water provides an‘ additional means for controlling re
action temperatures.
conditions of our process apparently promote cross-link
It is conventional practice to speed up the rate of re
ing copolymerization of the unsaturated, non-polyol
action of a relatively slowly reactive polyol, such as
monomer with the polyricinoleate at its double bond sites,
castor oil or a polyester, with, the polyisocyanate by
thereby producing a highly rigid, crushable foam.
of a catalyst, such as an amine, preferably a ter
The unsaturated, non-polyol monomers provide the 55 means
tiary
amine,
e.g. n-methyl morpholine, or triethyl amine,
additional important advantage of dissolving in and,
or metal salts, e.g. iron acetyl acetonate, lead naphthenate,
thereby, depressing the solidi?cation temperature of the
cobalt naphthenate, zinc stearate, tributyl tin methacryl
polyisocyanate. It is essential that the reagent com
ate, dibutyl tin dilaurate, dibutyl tin oxide, sodium ste
ponents be in liquid state for rapid reaction. Many of
arate, sodium ricinoleate, sodium salicylate, sodium sit
the diisocyanates solidify at temperatures, which, while 60 rate, or the like. Although, in general, such catalysis:
in the normal ambient temperature range, would exces
sively slow up the reaction at low temperatures, e.g.
below 40° F. ‘For example, the 65 :35 mixture of the
is, a function of basicity of the reaction mixture, with
inorganic acids acting as inhibitors, Lewis acids, such as.
trimethyl boron, have catalytic activity.
2,4- and 2,6-is0mers of toluene diisocyanate solidi?es at 65
Catalysts, as aforedescribed can advantageously be em
5° C., the 80:20 mixture at 12°C., and the 100% 2,5
ployed with the reaction components of our invention,
isomer at 22° C. Depression of the solidi?cation point
but are not always essentital, since the rapid exotherm
by the unsaturated, non-polyol monomer thus increases
provided by the ‘highly reactive polyol, containing at
least 3 hydroxyl groups and having a maximum equiva
the lower range of ambient temperature at which the
lent weight in terms of hydroxy functionality of 125,
reaction components can effectively react and cure.
may of itself be adequate to promote the desired rate
Vinyl toluene, for example, in adequate amounts can be
of reaction of the less reactive polyricinoleate polyol.‘
used to reduce the solidi?cation point of the 80/20,’
Selection of a highly reactive basic polyol, such as
2,4-/2,6-inixture of toluene diistmjyanateL to as low as.
Quad-rel or triethanolamine alsoelirninates the need for
4-28” C.
an.
additional, catalyst, since the basicity. of the polyol.
75
Illustrative examples of suitable pelymsrizalzle. ethyl;
8,075,926
S
provides the desired catalytic activity. In other instances,
can also react With an isocyanato group to give cross
basic impurities present in a commercially available
linking. The requisite quantity of foaming agent required
polyol, such as glyce-ryl monoricinoleate, resulting from
its method of preparation, provides an adequate catalytic
effect.
to produce the desired density for a particular foamed
product can readily be determined by routine experi
‘
mentation.
It is generally desirable, though not always essential,
The ratio of isocyanto groups to functional hydroxyl
to follow the conventional practice of including an emul
groups in the reaction mixture, e.g. polyricinoleate, high
si?er as a dispersing and solubilizing agent for the water
ly reactive polyol, water, carboxylic acid, can be as low
foaming component since water and most polyisocyanates
as about 0.5 :1. Rigidity and substantial non-resilience
are relatively immiscible and may, therefore, react too 10 are obtained even at such relatively low concentrations
slowly. The emulsi?er can be dispensed with if other
of isocyanate because of the cross-linking provided by the
components, such as the highly reactive polyol or the
unsaturated, non-polyol monomer. Ratios less than 1
foam stabilizer, also possess surface-active characteristics.
of isocyanato groups to hydroxyl groups are advanta
where an organic acid soluble in the other reaction com
geous in the production of high density foams, where the
ponents is used for foaming there is no need for an 15 rate of heat dissipation during reaction is relatively slow,
emulsi?er. Any suitable emulsifying agent can be em
so that excessive temperatures which may cause charring
ployed for our purpose, such as polyoxyethylated vegeta~
and decomposition cannot develop within the foaming
ble oils, polyglycol esters of fatty acids, polyglycol aryl
structure. Reduction in isocyanate concentration can
and higher fatty alcohol ethers, alkyl aryl sulfonates,
dialkyl s-ulfosuccinates, petroleum sulfonates, higher fatty
acid soaps and sulfated fatty acid soaps, etc.
Foam stabilizers can also advantageously be included
in our reaction mixtures to improve uniformity and ?ne
ness of pore size. Any of the well known foam stabiliz
be employed as an expedient for reducing reaction
20
exotherm.
’
For relatively low density foam-s, maximum rigidity,
and non-resilience, it is generally preferable that the
number of isocyanato groups contributed by the poly
isocyanate be at least equivalent to the total number of
ers, such as polyvinyl chloride, ethyl cellulose, cellulose 25 functional hydroxyl groups. Preferably also, some ex
acetate, cellulose acetate-butyrate, silicone oils, e.-g. poly~
cess polyisocyanate is included to provide for cross-link
dimethyl siloxane, polyvinyl alcohol, polyvinyl methyl
ether-maleic anhydride, casein and, gum arabic, can be
employed. Ethyl cellulose, polyvinyl chloride, and the
age through urea groups._ The amount of such excess
will, of course, be largely determined by the number of
such groups formed in the reaction, which in turn is
silicone oils and copolymers are particularly effective for 30 determined by the relative amounts of components such
our purpose.
Finely-divided pigments and ?llers, such as calcium
carbonate, calcium sulfate, calcium oxide, aluminum,
aluminum oxide, carbon black, and the like, can also
be incorporated if desired for special applications.
The amounts of the various components used Will, of
course, vary considerably, depending upon such factors
as the reactivity of the speci?c reagents and the particular
physical characteristics desired in the cured foam, such
as water or amine catalyst present in the reaction mixture.
in general, the practical ‘maximum excess of isocyanato
groups over functional hydroxyl groups in about 20%.
The polymerizable, non-polyol, ethylenically-unsatu
rated, monomer should comprise at least about 5%, pref
erably 10%, by weight of the polyricinoleate.
The amounts of other minor conventional additives,
such as foam stabilizer, emulsifying agent and catalyst
for the polyol-isocyanate reaction, are determined by the
as density.
40 properties of the speci?c additive and the desired foamed
In general, it will be necessary to include at least about
plastic characteristics, such as size of cell. The optimum
10% of the highly reactive polyol by weight of the poly
amounts for particular applications can readily be deter
ricinoleate and, preferably, at least about 20%, to ob
mined by those skilled in the art.
tain an adequate exotherm for reaction at ambient tem—
The reaction components, including the unsaturated
perature. Since the non-polyricinoleate polyol reacts With 4-5 non-polyol
monomer if properly inhibited by conven
the polyisocyanate to form a polyurethane, there is no
tional means, are stable and can be stored prior to use
critical upper limit of amount except that dictated by
for extensive periods of time without deterioration.
the need to avoid an excessive exotherm Which might
The components of the reaction mixture can be hand
cause charring, and the desirability of having sufficient
machine-mixed at ordinary temperature in any desired
of the polyriciuoleate polyol to provide adequate cross 50 or
sequence, except that the polyisocyanate is added last.
linking with the unsaturated non-polyol monomer for
in many cases, it may be desirable to combine the poly
foam rigidity. These factors will, of course, vary With
isocyanate
and the ethylenically-imsaturated, non~polyol
the particular polyols, both highly reactive and poly
monomer prior to storage for eventual use in the foamed
ricinolea-te, the particular unsaturated, non-polyol mono
resin-forming reaction to reduce the solidification tem
mer, the particular polyisocyanate, etc. In general, pre 55 perature of the polyisocyanate and, thereby, to maintain
ferred maximum ratios by weight of highly reactive polyol
its ?uidity under conditions of low ambient temperature.
to polyricinoleate is about 2:1 or 3:1, and the minimum
The blended mixture is poured into place, where it foams
weight concentration of the polyricinoleate in the reac
and cures under its own reaction exotherrn. Curing is
tion composition is about 10%.
generally substantially complete Within a matter of hours.
The foaming component, Water or carboxylic acid, is 60
The rigid, cured foams are substantially non-resilient,
employed in minor amounts, which are determined large
namely, crush under impact Without bounce so that they
ly by the desired foamed product density. The speci?c
can absorb all impact energy without transmittal to cush
quantity is also a factor of the equivalent weight of the
ioned supplies. They can be made in a wide range of
particular compounds in terms of its functional groups
density, eg. from about 1.5 to 30 lbs./ cu. ft., by variation
reactive with isocyanate. In the case of water, the 65 in concentration of the foaming component. In general,
equivalent weight is 9, since it reacts with an iso~
the higher the density, the greater is the energy-absorptive
capacity. Foained polyurethanes having substantially the
cyanato group to form CO2 and a highly reactive primary
energy-dissipating characteristics of foamed glass have
amine, which in turn reacts with another isocy-an-ato
been prepared by our process.
group to form a urea linkage With resultant cross-linking.
The equivalent Weights of carboxylic acids are, of course, 70 In addition to their unique energy-absorptive proper
higher because of the higher molecular weights of such
compounds. Reaction of an isocyanato group with the
carboxyl group of an acid, produces CO2 and an amide,
which, though considerably less reactive than an amine,
ties, our foamed polyurethane products possess superior
insulation and strength characteristics, which make them
very useful Wherever such properties are essential or de
sirable, With the important additional advantage of being
foamable-in-place without heating or other treatment.
3,075,926
was completed within about 1 minute; and cure was sub
Foamed products have been made according to our proc
stantially complete in about 12 hours. The resulting
foamed product was strong, rigid and non-resilient.
ess having thermal conductivities in the range of 0.25 to
4.0 B.t‘.u./hr./ft.2 in. ° F. over the density range of 2.4
to 6.6 lbs./ft.3. Such low thermal conductivities make
EXAMPLE 3
them excellent insulating materials. The high mechani
’ Rigid, non-resilient foams were prepared by a method
cal strength of the foamed plastics also makes them ex
substantially as described in Example 2, employing the
following base formulation and varying the polymerizable,
unsaturated, non-polyol monomer.
density foams are particularly suitable for such purpose.
Gm.
The pour-in-place reaction mixtures can also be employed 10
cellent reinforcing and load supporting components where
light weight is essential, as in airplane parts. The higher
in potting operations to cushion delicate components
Quaclrol
against vibrational or corrosive damage and to serve as a
Castor
dielectric.
15
This illustrates the relative reaction exotherm of a poly
ricinoleate, such as castor oil, and a highly reactive polyol,
,
'
____
_.._
40.0
Emulsi?er comprising sulfonated petroleum oils___ 4.0
Ethyl cellulose _____________________________ __'
6.0
Water ________________________________ __
0.5
EXAMPLE 1
such as Quadrol, with polyisocyanate.
________________ ..'_ ________________ __ 60.0
oil__
Nacconate 80 ____________________________ __ 87.4
.
Recipe 20 grams of following Dens~
No. added to control recipe ity
A.- Castor oil and tolylene diisocyanate (Nacconate 80;
80:20 mixture of 2,4- and 2,6-isomers), in 1:1 equivalent
ratio, were combined with and without catalysts at 23°
C. The castor oil, in the absence of catalyst, reacted very
slowly and did not gel after standing over night at room
temperature. Addition of catalysts, such as zinc stearate,
Methyl methacrylate. 2. 36
thyl methacrylate... 2.44
Foam characteristics
Brittle, large cells.
Do.
Diallyl succinate_‘_---_ 4.42 Very uniform cells, hard,
‘
n-methyl morpholine, triethylamine, sodium tartrate, sodi
um 'stearate, sodium salicylate and sodium citrate, in
strong, brittle.
Ethyl acrylate ______ __ 2.26
N-butyl acrylate ____ __ 3.14
Brittle, large cells.
Non-uniform, brittle.
Dial1ylphthalate___-_ 5.25
Uniform
strong.
small cells,
very
100D," Triallylcyanurate-___ 6.26 Uréif?rm,
tough, small cells,
r to.
creased reaction rate and exotherm to some extent, but
the best of these catalysts, triethylamine, increased tem
9101--- Styrene; ____________ -_ 5.0
Hard,hrittle, large.
perature to a maximum of 56° C.
B. Quadrol admixed with an equivalent weight of tolyl
196.1 gm. Hylene TM (tolylene diisoc anate 80 20 2,4- 2,6-‘somers
substituted for Noeconate 80.
ene diisocyanate, without catalyst, reacted to give a tem
perature of 195° C. in 5.5 minutes.
EXAMPLE 2
The following components were mixed at room tem
Ethyl cellulose N-l00, 86 cps ____________ __
3.0
0.25
40
Quadrol ______________________________ __
Castor oil _____________________________ __
..__
_
45
Gms.
4
Properties of foam
20
4
3. 28
5. 21
Uniform.
20
4
4. 09
Tough, dead cells.
Tetraethyleneglyc ol dlmetham y are
20
4
6.16
Small, uniform cells, tough, dead.
Divinyl benzene 50-60% ......... -_
Vinyl steara-tc ____ -r ____ -_
20 ...... ._
20
4
4.10
6. 30
Irregular cells, brittle.
Very tough, uniform cells.
Diethyleneglycol dimealacryla e-
20
5. ‘10 Uniform, tough.
gilgggyé‘gl‘ggélriiiilfixff:‘ff‘l?‘:
1g } ' 4
assassinate???as}???1
1.2}----- --
4
“a measurem
llellgg?eélgigggi? mmechaorymte'
} _____ __
4
2. 62
4
_
_ . _ _ _ . _ . . .. _
N,N '-diallylmelamine
0 ______________ __
N,N’-diallylmelamine__
Methyl butenol ____ __
122A .... ..
Density
lb./ft.=l
20
Vinyl toluene _______________________ _ _
122E .... -_
B2
2-ethyl herzyl acrylatet _ - .-__
121A _________ __
6.0
10.5
'
Diallyl maleato _____________________ -.
Dimethyl maleate
125C .... -_
____
1 A small amount of water additionally present in emulsi?er B.
A 1
_ .' . .. _ d0 _ _ . _ _ . _ _ . _ _ . _ _
60.0
40.0
Monomer _____________________________ __ Variable
Nacconate 80 ___________________________ __
87.4
Emulsi'?er gm.
Monomer
Diallyl phthalata
)
Ethyl cellulose _________________ _‘_ _______ __
Water
Foaming began within a few seconds; maximum foam rise
.
1
Emulsi?er ____________________ -'_ _______ __ Variable
table oil _______ ..'_ __________________ __
0.20
Nacconate S0 _________________________ __ 43.7
"
I
Gm.
Emulsi?er comprising polyoxyethylated vege
Sample
No.
I ’
er and the unsaturated, non<polyol monomer.
T62A: I
Grams
Quadrol ___.._'.. _______________________ __ 30.0
Water _______________________________ __
’
Rigid, non-resilient foams were prepared substantially
as described in Example 2, employing the following base
formulation and varying the amount of water, the emulsi
perature in the order as given.
Castor oil ____________________________ __ 20.0
Styrene ______________________________ __ 10.0
y
EXAMPLE 4
Tough, uniform cells.
5.10 Very uniform cells, tough, dead.
Large cells, brittle.
Uniform cells, tough, dead.
Cells uniform, small, dead, tough.
Very small cells, fairly tough, dead.
Dead, brittle, uniform.
Uniform cells, brittle.
Tough, brittle uniform cells.
Uniform, small cells (crunchy).
Small, uniform cells, dead, brittle.
N,N’-diallylmelan1ine ________ __
Very dense, uniform.
N,N’-diallylmclarnine _______________ __
Dead, brittle.
Diethylene glycol dimethacrylate
Dimcthylene glycol dimethacrylate. - .
1 Containing sulfonated petroleum oils
? Containing sulfated monoglyceride of coconut fatty acids.
3,075,926
10
EXAMPLE 5
EXAMPLE 8
The following tests illustrate the effect of varying the
amount of water and compensating toluene diisocyanate
A rigid, non-resilient, high-density foam was prepared
by combining the following components:
on foam density.
Gm.
Formulation 108C:
Quadrol
Gms.
Quadrol
60.0
Castor oil ___________________________ __
Vinyl toluene ______________________ __
40.0
20.0
Castor oil ________________________________ __ 180.0
Diallyl phthalate
um oils __________________________ __
4.0
6.0
Water
..
_
3 g. of ethyl cellulose and 3 g. of N-methyl morpholine
15
0. 5
0. 75
0. 90
1.00
1. 20
1. 40
87. 0
89. 4
90. 8
91. 8
93. 3
95. 7
1080H (the triisocyanate adduct of 1 mol of hexane triol
and 3 mols of toluene diisocyanate) with vigorous stirring.
The resulting rigid foamed product had a density of ap
proximately 10.5 'lbs./ft.3 and could support a load in
excess of 200 p.s.i.
Foam density
'I‘Dl', gms.
2.5
were blended with 95 g. of the above mix. This mixture
was poured into a vessel containing 75 g. of Nacconate
Modi?cation
Water, gins.
90.0
Water ___________________________________ __.
Variable
Toluene diisocyanate (Nacconate 80).-.." Variable
'
Emulsifier containing sulfated petroleum oils_____ 18.0
Emulsi?er containing sulfonated petrole
Ethyl cellulose (N-l00) _______________ __
270.0
(lbs/cu. it.)
EXAMPLE 9
20
62.2 gins. of a 3:2:1 mixture by Weight of Quadrol,
castor oil and diallyl phthalate were admixed with 1.5 gms.
of ethyl cellulose, 1.0 gm. of lactic acid (85%) and 0.5
7. 6
6. 2
5. 5
1. 5
gm. of water. To this was added 74 gms. Nacconate
25 1-080H. The resulting, uniformly-celled foam was rigid
4. 8
3. 9
and non-resilient and had a density of 5.6 lbs/cu. ft.
Formulation 100C:
EXAMPLECIVO
Gms.
Castor oil _________________________ __
40.0
The following formulation, employing a reduced con
centration of isocyanate and no emulsi?er, produced a
Diallyl phthalate ___________________ .._
20.0
strong, rigid, substantially non-resilient foam, having a
Quadrol
-
60.0
density of 7.08—8.19 lbs/cu. ft.
lEmulsi?er containing sulfonated petroleum
oils
_
4.0
Ethyl cellulose (N-100) _____________ __
6.0
Water
Nacconate
Gms.
Quadrol
____..
Water
7. 95
0.8
1.0
1.2
1.4
88.5
89.5
90.4
91.4
6.06
5.20
4. 62
4.12
1.77
92.8
3.29
__
60
Diallyl phthalate
20
Ethyl cellulose (86 cps.)__.__.__._________.______ 3
40
TDI,
87.0
gms.
__
Castor oil ________________________________ __ 40
__
Variable
80 ______________________ __ Variable
Water,
0.5 gms.
_..
___
____ __
Nacconate 80-
_._-__
0.85
_ 54.3
EXAMPLE .11
A high density foamed product having a density of
27.80 lbs./ cu. ft. was prepared employing the formula of
45 Example 9 except that no water was added other than
that present in the reacting components. The rigid, non
resilient foamed plastic was tested on a Tinius-Olsen ma
chine, a device for measuring compressive strength. The
EXAMPLE ‘6
plastic withstood, without crushing, the maximum pres
The following illustratesthe formulation of rigid, very
low density foams having densities of 2.5-3.0 lbs/cu. ft.
and energy-absorption values of 30—45 in.-lbs./in.3 of
50 sure which could be exerted by the machine and which,
for the particular dimensions of the test sample, was
809.7 p.s.i.
Many foamed samples were tested for energy-absorptive
crushed volume:
capacity and resiliency by means of a drop-tester in which
Grams 55 an adjustable hammer weight was dropped through a
Quadrol
60.0
maximum distance of 13% ft. on a sample 4" by 4" in
Castor oil
____ __
40.0
cross-section. Some of the illustrative data obtained in
this manner is given in the following table. Sample
Vinyl toluene
20.0
formulation is given by code number cited above or in
Sulfated monoglyceride of coconut fatty acid____ 2.0
60 footnote. Variations in sample densities for a given
Glyceryl monoricinoleate ____________________ __-__ 8.5
formulation were produced either by some‘ variation in
Triethylamine ______________________________ __ 0.5
amount of water foaming agent or differences in ambient
Ethyl cellulose (N-100) _____________________ __ 6.0
initiation temperatures. The samples, except for com
Water
______ __| ___________________________ __
1.0
mercial samples or as noted, were tested when about 2
Nacconate 80
__.._
__ 99.6
65 weeks old.
EXAMPLE 7
It will be noted that the foamed samples, T630, T380,
and 93D, which were not copolymerized with unsaturated,
A rigid, non-resilient foam of excellent uniform cell
non-polyol
ructure and a density of 3.9 lbs/cu. ft. was prepared by
substantial
70
mixing 60.0 gm. Quadrol, 40.0 gm. castor oil, 20.0 gm.
vmade with
VN,N'-diallyl melamine, 6 drops Union Carbide XL—520
Styrofoam
‘(a ‘water-soluble organo-silicone copolymer which func
~
-
hammer bounce. VA foamed polyurethane
polyester prepolymer, 117B, and commercial
were also resilient.
Foamed polyurethanes
made according to our invention‘ have ‘energy-absorptive
tions both as a dispersing agent and foam stabilizer), 1.7
ml. water and 55 ml. Nacconate 80.
monomer, were resilient, as indicated by the
properties equivalent to that of higher-density foamed
76
glass.
.
1
i
"'
'
.1‘
8,075,926
11
Sample
density
Foam formula
Impact
energy”
per vol.
12
this invention can be embodied in other forms but within
the scope of the claims.
We claim:
Table I
Impact Hammer
velocity bounce
(in)
(lbs .lit?) crushed {ft/sec.)
(in-lbs]
m .3)
TGZA ................... _;._-_
TGBCI ............... -.>...-;..
100D ....................... ..
Honeycomb paper ......... ..
‘Styrofoam. - '..'-;--..;--.-'.’--._
T380 2 ..................... ..
.wmesp'ocr
1. A foamed polyurethane comprising the reaction
product of a polyhydroxy alcohol ester of ricinoleic acid
containing at least two ricinoleyl groups and having an
equivalent weight in terms of its vfunctional hydroxy
groups above 200; a second organic polyol containing at
least three functional alcoholic hydroxy groups and hav
10 ing a maximum equivalent weight in terms of its func
tional hydroxy groups of about 125; an organic polyiso
cyanate; a polymerizable ethylenically-unsaturated mon
omer containing at most one reactive hydroxy group;
and a foaming agent, said polyhydroxy alcohol ester of
15 ricinoleic acid comprising at least about 10% by weight of
the composition, the second polyol comprising at least
about 10% by weight of the polyricinoleate, and the ethyl
cnically-unsaturated monomer comprising at least about
5% by weight of the polyhydroxy alcohol ester of ricin
OWrP-GQR
20 oleic acid.
2. The composition of claim 1 in which the second
polyol is an aliphatic compound.
3. The composition of claim 2 in which the polyhydroxy
‘910 ___________ ..
108C 1 day old"-..
alcohol ester of ricinoleic acid is castor oil.
25
1080 13 days old ........... .
4. The composition of claim 3 in which the polyiso
cyanate is an aromatic polyisocyanate.
5. The composition of claim 4 which includes in addi
tion an emulsifying agent and foam stabilizer.
6. The composition of claim 4 in which the ethylenical
30 ly-unsaturated monomer is a vinyl compound.
7. The composition of claim 4 in which the polyiso
cyanate is present ‘in sufficient amount to contribute iso
cy-anate groups in at least a 1:1 ratio to the functional
35
hydroxy groups in the composition.
8. The composition of claim 6 in which the second
polyol is N,N,N',N’~tetrakis-(Z-hydroxypropyl)-ethylene
Al honeycomb 3%" Hexcel___
diamine.
9. The composition of claim 8 in which the polyiso
cyanate is tolylene diisocyanate.
93D 0 .............. ..-. _____ -
4-0
100C --------- --. --------- --.-,-..
10. The composition of claim 8 in which the polyiso
cyanate is the triisocyanate adduct of hexanetriol and
tolylene diisocyanate.
99B ........................ -
11. The composition of claim 8 in which the vinyl mon
omer is vinyl toluene.
45
*Impact energy calculated as product of hammer weight and height.
1 No unsaturated, non-polyol monomer. Quadrol 25 g., castor oil 75 g.,
ethyl cellulose 7.5 $5., water 0.63 g., emulsi?er-poly-oxyethylated vegetable
oil 0.509, TDI (106% 2,4) 70 g.
‘-‘ No unsaturated, non-polyol monomer. Castor oil 30 g., glyceryl
monoricinoleate 3 g., ethyl cellulose 2 g., water 025 g., emulsi?er-poly
cxyethylatcd vegetable oil 0.2 g., N acconate 80-50 g.
3 Made by commercial prepolymer formulation: Selectrofoam Resin
6002 (polyester)—58.0 g., Tween 40-19 g., 2-dim ethylaminoethanol~—0.25
g, water-2.75 g., Selectrofoam Prepolymer 6003 (excess diisocyanate)
100.0 g.
4 100 0 plus 20 g. Al powder ?ller.
5 100 C plus 60 g. Al powder ?ller.
“ No unsaturated, non-polyol monomer. Quadrol~70 g., castor oil—
30 g., sullonatcd petroleum oil-1 g., water-0.5 g., foam stabilizer-6 g.,
triethanolamme-l g., Hylene TIM-43 g.
7
12. The composition of claim 8 in which the vinyl mon
omer is diallyl phthalate.
13. The composition of claim 8 in which the vinyl
monomer is N,N'-diallyl melamine.
14. The composition of claim 8 in which the vinyl
monomer is vinyl stearate.
15. The composition of claim 8 in which the vinyl mon
omer is triallyl cyanurate.
16. A process for making a foamed polyurethane, com
prising admixing a polyhydroxy alcohol ester of ricinoleic
acid containing at least two ricinoleyl groups and having
an equivalent weight in terms of its functional hydroxy
groups above 200 in an amount comprising at least about
10% by weight of the total composition; a second organic
polyol containing at least three functional alcoholic hy
The following test’ data illustrate the low thermal con 60 droxy groups and having a maximum equivalent weight
in terms of its functional hydroxy groups of about 125,
ductivity and excellent insulation properties of our foamed
said second polyol comprising at least about 10% by
products.
weight of the polyhydroxy alcohol ester of ricinoleic acid;
an organic polyisocyanate; a polymcrizable,_ ethylenically
Thermal
EXAMPLE 12
Density
Formulation
lbJft.3
Cell size, conductivity 65 unsaturated‘ monomer containing at most one reactive hy
appr. avg.
‘ mm.
6. 0s
4. 33
2. 58
2. 50
1. 0
0. 8
0. 8
0.8
B .t.u./l1r./
it.2/in./° F
0. 295
0. 282
0. 266
0. 257
droXy group, said unsaturated monomer comprising at
least about 5% by weight of the polyhydroxy alcohol ester
‘of ricinoleic acid; and a foaming agent; and permitting the
mixture to react under the eXotherm produced by reaction
70 of said second polyol with said polyisocyanate, polym
erization of said ethylenically-unsaturated monomer being
thermally induced by said exotherm.
17. The process of claim 16. in which the second polyol
ence to illustrative embodiments thereof, it will‘ be ap
parent to those skilled in the art that the principles of 75 is an aliphatic compound.
Althoughthis invention has beendescribed with refer
13
3,075,926
14
18. The process of claim 17 in which the polyhydroxy
26. The process of claim 25
omer is vinyl toluene.
27. The process of claim 25
omer is diallyl phthalate.
28. The process ofvclaim 25
omer is N,N'-diallyl melamine.
29. The process of claim 25
alcohol ester of ricinoleic acid is castor oil.
19. The process of claim 18 in which the polyisocy
anate is an aromatic polyisocyanate.
20. The process of claim 19 in which the ethylenically
unsaturated monomer is a vinyl compound.
21. The process of claim 19 in which the polyisocya
mate is present in su?cient ‘amount to contribute isocya
in which the vinyl mon
in which the vinyl mon
in which the vinyl mon
in which the vinyl mon
omer is vinyl stearate.
nate groups in at least a 1:1 ratio to the functional hydroxy
30. The process of claim 25 in which the vinyl mon
groups in the composition.
10 omer is triallyl cyanurate.
22. The process of claim 19 in which the second polyol
is N,N,N’,N’-tetrakis~(Z-hydroxypropyl) - ethylene di
References Cited in the ?le of this patent
amine.
UNITED STATES PATENTS
23. The process of claim 22 in which the polyisocya
hate is tolylene diisocyanate.
15
24. The process of claim 22 in which the polyisocya
mate is the triisocyanate adduct of hexanetriol and tolyl
ene diisocyanate.
25. The process of claim 22 in which the ethylenically
unsaturated monomer is a vinyl compound.
20
2,609,349
2,642,403
2,740,743
2,772,245
2,833,730
2,850,464
Cass ________________ __ Sept. 2,
Simon et a1 ___________ __ June 16,
Pace ________________ __ Apr. 3,
Simon et a1 ____________ __ Nov. 27,
Barthel ______________ .._ May 6,
Mitchell ______________ __ Sept. 2,
1952
1953
1956
1956
1958
1958
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