Note: Descriptions are shown in the official language in which they were submitted.
s
BacX~ound of the Invention
l. Field of the Invention
The present invention relates to low viscosity
white graft polymer dispersions in po1yoxyalkylene polyether
polyols and flame retardant polyurethane foams prepared
therefrom. Dispersions of this type are also dealt with
in co~pending Canadian application no. 424,626. More particu-
larly, the invention relates to graft polymer dispersions
prepared by the improved process employing free radical
polymerization of an ethylenically unsaturated monomer or
mixture of monomers in a polyol mixture containing less than
O.l mole of induced unsaturation per mole of polyol mixture.
This improved process yields stable, non-settling dispersions
with graft polymer contents of 30 percent by weight and higher
employing monomer mixtures which contain more than about 55
percent by weight styrene as the comonomer. Furtherl the
invention relates to an improved process employing free
radical polymerization in a polyetherester polyol-polyoxy-
alkylene polyether polyol mixture containing less than O.l
mole of induced unsaturation per mole of polyol mixture
wherein the unsaturated moiety is an isomerized maleate
containing polyetherester polyol. Even more particularly
the invention relates to an improved process employing free
radical polymerization in a polyol mixture containing
polyetherester polyol-polyoxyalkylene polyether polyol
mixture which was
S';L~5
prepared by reactiny a polyoxyalkylene polyether polyol, a
polycarboxylic acid anhydrlde and an alkylene oxide in the
presence of an effective amount of a catalyst selected fxom
the group consisting of salts and oxides of divalent metals.
20 Description of the Prior Art
The prior art, as evidenced by U.S. Patent Nos.
3,652,658; 3,875,258; 3,950,317, and Reissue Patent Nos.
28,715 and 29,014 teaches the preparation of graft polymer
dispersions which are useful in the preparation of poly-
urethanes by the polymerization of ethylenically unsaturatedmonomers in the presence of polyols. The above patents
disclose various methods of preparing graft polymer disper-
sions. U.S. 3,931,092 teaches the preparation of polymeric
solids by polymerizing in the presence of a free-radical
initiator and an organic solvent. The solvent concentration
employed is from about 1 part to 19 parts by weight per part
of the hydroxy-terminated organic compound which has a
polymerizable carbon double bond. U.SO 3,953,393 teaches
the preparation of graft copolymer dispersions by employing
alkylmercaptan chain transferring agents at concentrations
from 0.1 to 2 percent by weigh~ based on the weight of vinyl
monomer.
Stable dispersions of polymers in polyols have
found broad commercial use in the preparation of poly-
urethanes. The use of these dispersions, known in the tradeas graft or polymer polyols, improves processing and, among
other properties, the firmness of the polyurethane products,
often expressed as load bearing or modulus. There have been
many attempts to improve the products representing the
present state of the art~ Efforts have been directed
towards increasing the amount of polymer which is dispersed
in the polyol, the obvious benefit being that firmer
polyurethanes can be produced. Two major obstacles have
been found: the viscosities of the resulting dispersions
were too high and/or relatively high levels of acrylonitrile
had to be used in the monomer mixtures employedO
The use of high levels (> 50 percent by weight) of
acrylonitrile and, correspondingly, relatively low levels of
the most common comonomer, styrene (< 50 percent) had two
very undesirable effects. The resulting dispersions are tan
to ~rown in color with a strong tendency to turn even darker
in color during the highly exothermic polyurethane foam
formation giving, for example, slab foams with a strong
tendency to scorch. But even more undesirable, polyurethane
foams made from these products cannot be satisfactorily
flame retarded to pass flammability tests which are standard
in the industryO
As mentioned before, there have been attempts to
prepare high polymer (> 30 percent) containing dispersions
4~i
with acceptable viscosities. These products contain ratios
of acrylonitrile to styrene of >50/50 and are tan colored.
None of the prior art teaches that polymer dispersions in
unsaturated polyols containing less than 0.1 mole oE induced
unsaturation per mole of polyol mixture may be employed for
flame-retardant polyurethane foams. Neither has the prior
art taught that in situ free radical polymerizations may be
conducted in a polyetherester polyol-polyoxyalkylene
polyether polyol mixture containing less than 0.1 mole of
induced unsaturation per mole of polyol mixture wherein the
unsaturated moiety is an isomerized maleate containing
polyetherester polyol. Also, the prior art is silent on the
preparation of polyetherester polyols, by the reaction of a
polyoxyalkylene polyether polyol, a polycarboxylic acid
anhydride, and an alkylene oxide, in the presence of a
catalyst selected from the group consisting of salts and
oxides of divalent metals.
Summary of the Invention
It has been discovered that flamè-retardant
polyurethane foams may be prepared by employing gra~t
polymer dispersions. These dispersions are prepared by an
improved process employing free radical polymerization of
ethylenically unsaturated monomer or monomers in a polyol
mixture containing less than 0.1 mole of induced unsatura-
tion per mole of polyol mixture. Furthermore, it has been
--4--
iiiLI~S
found that improved dispersions may be prepared by employing
radical polymerization in a polyetherester polyol-polyoxy-
alkylene polyether polyol mixture containing less than 0.1
mole of induced unsa~uration per mole of polyol mixture
wherein the unsaturation moiety is an isomerized maleate
containing polyetherester polyol. Still furthermore, it has
been found that improved dispersions may be prepared by
conducting the free radical polymerization in the presence
of a polyetherester polyol which was prepared by reacting a
polyether polyol, a polycarboxylic acid anhydride, and an
alkylene oxide in the presence of an effective amount of a
catalyst selected from the qroup consisting of salts and
oxides of divalent metals.
Description of the Preferred Embodiments
In accordance with the improved process for the
preparation of white graft polymer dispersions which are
employed for the preparation of flame-retardant polyurethane
foams, the improvement comprises conducting the polymeriza-
tion of an ethylenically unsaturated monomer or mixtures of
monomers in the presence of an effective amount of a free-
radical initiator in an unsaturated polyol mixture con-
taining less than 0.1 mole of induced unsaturation per mole
of polyol mixture. In another embodiment of the invention
the polymerization of an ethylenically unsaturated monomer
or mixture of monomers in the presence of an effective
--5--
5~
amount of a free radical initiator in an unsaturation
containing polyol mixture containing less than 0.1 mole of
unsaturation per mole of polyol mixture employs an improved
process which comprises conduc~ing the polymerization in a
polyol mixture employing as part of the mixture a polyether-
ester polyol prepared by the reaction of a polyoxyalkylene
polyether polyol with maleic anhydride and an alkylene
oxide. This polyetherester polyol is isomerized by methods
well known by those skilled in the art. These include heat,
or isomerization catalysts such as morpholine, dibutylamine,
diethylamine, diethanolamine, thiols and the like. In
another improved process for the preparation of these graft
polymer dispersions, the improvement consists of preparing a
polyetherester polyol by the reaction of a polyoxyalkylene
ether polyol, a polycarboxylic acid anhydride to form a half
acid ester and an alkylene oxide to obtain a product having
an acid number of less than 5 mg KOH/gram which cornprises
conducting the reaction between the polyoxyalkylene poly-
ether polyol and the anhydride and the following reaction
with the alkylene oxide in the presence of an effective
amount of a catalyst selected from the group consisting of
salts and oxides of divalent metals. The polyols having
induced unsaturation are hereinafter referred to as ~Imacro-
mers." Chain transfer agents may be employed as reaction
moderators particularly at temperatu-res below 105C. The
--6--
s~s
polymerization reaction may be carried out at temperatures
between 25C and 180C, preferably between 80C and 135C~
The polyol mixture contains less than 0.1 mole o~ unsatura-
tion per mole of polyol mixture and ranges from 0.001 to
0.09 mole of unsaturation~
The alkylene oxides which may be employed for ~he
preparation of the polyetherester polyols include ethylene
oxide, propylene oxide, butylene oxide, amylene oxide and
mixtures of these oxides~
The graft polymer dispersions of this invention
have viscosities less than 10,000 cps at 25C. Preferably
they have viscosities ranging from 2000 to 8000 cps at 25C.
Among those chain transfer agents which may be
employed are as follows: acetic acid, bromoacetic acid,
chloroacetic acid, ethyl dibromoacetate, iodoacetic acid,
tribromoacetic acid, ethyl tribromoacetate, trichloroacetic
acid, ethyl trichloroacetate, acetone, p-bromophenylaceto-
nitrile, p-nitrophenylacetylene, allyl alcohol, 2,4,6-
trinitroaniline, p-ethynylanisole, 2,4,6-trinitroanisole,
azobenzene, benzaldehyde, p-cyanobenzaldehyde, 2-butyl-
benzene, bromobenzene, 1,3,5-trinitrobenzene, benzochrysene,
ethyl trinitrobenzoate, benzoin, benzonitrile, benzopyrene,
tributylborane, 1,4-butanediol, 3,4-epoxy-2-methyl-1-butene,
t-butyl ether, t-butyl isocyanide, l-phenylbutyne, p-cresol,
p-bromocumene, dibenzonaphthacene, p-dioxane, pentaphenyl
~,~2S4~5
ethane, ethanol, l,l-diphenylethylene, ethylene glycol,
ethyl ether, ~luorene, N,N dimethylformamide, 2-heptene, 2-
hexe~e, isobutyraldehyde, diethyl bromomalonate, bromotri-
chloromethane, dibromoethane, diiodomethane, naphthalene, 1-
naphthol, 2-napthol, methyl oleate, 2,4,4-triphenyl-1-
pentene, 4-methyl-2-pentene, 2,6-diisopropylphenol, phenyl
etherl phenylphosphine, diethylphosphine, dibutylphosphine,
phosphorus trichloride, l,l,l-tribromopropane, dialkyl
phthalate, 1,2-propanediol, 3-phosphinopropionitrile, 1-
propanol, pyrocatechol, pyrogallol, methyl stearate,tetraethylsilane, triethylsilane, dibromostilbene, a~
bromostyrene, ~-methylstyrenel tetraphenyl succinonitrile,
2,4,6-trinitrotoluene, p-toluidine, N,N-dimethyl-p-tolu-
idine, a-cyano-p-tolunitrile, ~,~'-dibromo-p-xylene, 2,6-
xylenol, diethyl zinc, dithiodiac~tic acid, ethyl dithiodi-
acetic acid, 4,4'-dithio-bisanthranilic acid, benzenethiol,
o-ethoxybenzenethiol, 2,2'-dithiobisbenzothiazole, benzyl
sulfide, l-dodecanethiol, ethanethiol, l-hexanethiol, 1-
napthalenethiol, 2-napthalenethiol, l-octanethiol, 1-
heptanethiol, 2-octanethiol, l-tetradecanethiol, ~-toluene-
thiol, isopropanol, 2-butanol, carbon tetrabromide and
tertiary dodecyl mercaptan.
The chain transfer a~ents employed will depend on
the particular monomers or mixtures of monomers employed and
the molar ratios of such mixtures. The concentration of the
~ ~r~;~a~t~
chain transfer agent whish i5 employed may range from 0.1 to
10 percent by weight based on the weight of monomer.
Representative polyols essentially free from
ethylenic unsaturation which may be employed in combination
with the macromers of the invention are well known to those
skilled in the art. They are often prepared by the cata-
lytic condensation of an alkylene oxide or mixture of
alkylene oxides either simultaneously or sequentially with
an organic compound having at least two active hydrogen
atoms, such as evidenced by U.S. Patent Nos. 1,922,459;
3,190,927; and 3,346,557. Representative polyols include
polyhydroxyl-containing polyesters, polyoxyalkylene poly-
ether polyols, polyhydroxy-terminated polyurethane polymers,
polyhydroxyl-containing phosphorus compounds, and alkylene
oxide adducts of polyhydric polythioesters, polyacetals,
aliphatic polyols and thiols, ammonia, and amines including
aromatic, aliphatic, and heterocyclic amines, as well as
mixtures thereof. Alkylene oxide adducts of compounds which
contain 2 or more different groups within the above-defined
classes may also be used, for example, amino alcohols which
contain an amino group and a hydroxyl group. Also, alkylene
oxide adducts of compounds which contain one SH group and
one OH group as well as those which contain an amino group
and an SH group may be used. Generally, equivalent weight
of the polyols will vary from 100 to 10,000, preferably from
1000 to 3000.
_g_
Any suitable hydroxy-terminated polyester may be
used such are prepared, for example, from polycarboxylic
acids and polyhydric alcohols. Any suitable polycarboxylic
acid may be used such as oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid, brassylic acid, thapsic
acid, maleic acid, fumaric acid, glutaconic acid, -hydro-
muconic acid, ~-hydromuconic acid, ~-butyl-~-ethyl-glutaric
acid, a, ~-diethylsuccinic acid, isophthalic acid, tere-
phthalic acid, hemimellitic acid, and 1,4-cyclohexanedi-
carboxylic acid. Any suitable polyhydric alcohol, including
both aliphatic and aromatic, may be used such as ethylene
glycol, propylene glycol, trimethylene glycol, l,2-butane~
diol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-
pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane
diol, glycerol, l,l,l-trimethylolpropane, l,l,l-trimethylol-
ethane, 1,2,6-hexanetriol, -methyl glucoside, penta-
erythritol, and sorbitol. Also included within the term
"polyhydric alcohol" are compounds derived from phenol such
as 2,2-bis(4-hydroxyphenyl)propane, commonly known as
Bisphenol A.
The hydroxyl-containing polyester may also be a
polyester amide such as is obtained by including some amine
or amino alcohol in the reactants for the preparation of the
polyesters. Thus, polyester amides may be obtained by
--10--
S
condensing an amino alcohol such as ethanolamine with the
polycarboxylic acid~ set forth above or they may be made
using the same components that make up the hydroxyl
containing polyester with only a portion of the components
being a diamine such as ethylene diamine.
Any suitable polyoxyalkylene polyether polyol may
be used such as the polymerization product of an alkylene
oxide or a mixture of alkylene oxides with a polyhydric
alcohol. Any suitable polyhydric alcohol may be used such
as those disclosed above for use in ~he preparation of the
hydroxy-terminated polyesters. Any suitable alkylene oxide
may be used such as ethylene oxide, propylene oxide,
butylene oxide, amylene oxide, and mixtures of these
oxides. The polyoxyalkylene polyether polyols may be
prepared from other starting materials such as tetrahydro-
furan and alkylene oxide-tetrahydrofuran mixtures; epihalo-
hydrins such as epichlorohydrin; as well as aralkylene
oxides such as styrene oxide. The polyoxyalkylene polyether
polyols may have either primary or secondary hydroxyl
groups~ Included among the polyether polyols are polyoxy-
ethylene glycol, polyoxypropylene glycol, polyoxybutylene
glycol, polytetramethylene glycol, block copolymers, for
example, combinations of polyoxypropylene and polyoxy-
ethylene glycols, poly-1,2-oxybutylene and polyoxyethylene
glycols, poly-1,4-oxybutylene and polyoxyethylene glycols,
--11--
and random copolymer glycols prepared from blends of two or
more alkylene oxides or by the sequential addition of two or
more alkylene oxides. The polyoxyalkylene polyether polyols
may be prepared by any known process such as, for example,
the process disclosed by Wurtz in 1859 and Encyclopedia of
Chemical Technolo~y, Vol. 79 pp. 257-262, published by
Interscience Publishers, Inc. (1951) or in UOS. Patent
No. 1,922,459. Polyethers which are preferred include the
alkylene oxide addition products of trimethylolpropane,
glycerine, pentaerythritol, sucrose, sorbitol, propylene
glycol, and 2,2'-~4,4'-hydroxyphenyl)propane and blends
thereof having equivalent weights of from 100 to 5000.
Suitable polyhydric polythioethers which may be
condensed with alkylene oxides include the condensation
product of thiodiglycol or the reaction product of a
dicarboxylic acid such as is disclosed above for the
preparation of the hydroxyl-containing polyesters with any
other suitable thioether glycol.
Polyhydroxyl-containing phosphorus compounds which
may be used include those compounds disclosed in U.S. Patent
No. 3,639,542. Preferred polyhydroxyl-containing phosphorus
compounds are prepared from alkylene oxides and acids of
phosphorus having a P2O5 equivalency of from about 72
percent to about 95 percent.
-12-
Suitable polyacetals which may be condensed with
alkylene oxides include the reaction product of formaldehyde
or other suitable aldehyde with a dihydric alcohol or an
alkylene oxide such as those disclosed above.
Suitable aliphatic thiols which may be condensed
with alkylene oxides include alkanethiols containing at
least two -SH groups such as 1,2-ethanedithiol, 1,2-propane-
dithlol, l,3-propanedithiol, and 1,6-hexanedithiol; alkene
thiols such as 2-butene-1,4-dithiol; and alkyne thiols such
as 3-hexyne-1,6-dithiol.
Suitable amines which may be condensed with
alkylene oxides inclu~e aromatic amines such as aniline,
o-chloroaniline, p-aminoaniline, 1,5-diaminonaphthalene,
methylene dianiline, the condensation products of aniline
and formaldehyde, and 2,3- 2,6-, 3,4 , 2,5-, and 2,4-
diaminotoluene; aliphatic amines such as methylamine,
tri~sopropanolamine, ethylenediamine, 1,3-diaminopropane,
1,3-diaminobutane, and 1,4-diaminobutane.
Also, polyols containing ester groups can be
employed in the subject invention. These polyols are
prepared by the reaction of an alkylene oxide with an
organic dicarboxylic acid anhydride and a compound contain-
ing reactive hydrogen atoms. A more comprehensive dis-
cussion of these polyols and their method of preparation can
be found in U.S. Patents NosO 3,585,185; 3,639,541 and
3,639,542.
-13-
~25i;~3S
The unsaturated polyols or macromers which are
employed in the present invention may be prepared by the
reaction of any conventional polyol such as those described
above with an organic compound having both ethylenic
unsaturation and a hydroxyl, carboxyl, anhydride, isocyanate
or epoxy group or they may be prepared by employing an
organic compound having both ethylenic unsaturation and a
hydroxyl, carboxyl, anhydride, or epoxy group as a reactant
in the preparation of the conventional polyol~ Representa-
tive of such organic compounds include unsaturated mono- and
polycarboxylic acids and anhydrides such as maleic acid and
anhydride, fumaric acid, crotonic acid and anhydride,
propenyl succinic anhydride, acrylic acid, acryoyl chloride,
hydroxy ethyl acrylate or methacrylate and halogena~ed
maleic acids and anhydrides, unsaturated polyhydric alcohols
such as 2-butene-1,4-diol, glycerol allyl ether, trimethyl-
olpropane allyl ether~ pentaerythritol allyl ether, penta-
erythritol vinyl ether, pentaerythritol diallyl ether, and
l-butene-3,4-diol, unsaturated epoxides such as l-vinyl-
cyclohexene-3,4-epoxide, butadiene monoxide, vinyl glycidyl
ether(l-vinyloxy-2,3-epoxy propane), glycidyl methacrylate
and 3-allyloxypropylene oxide (allyl glycidyl ether). If a
polycarboxylic acid or anhydride is employed to incorporate
unsaturation into the polyols, it is preferable to react the
unsaturated polyol with an alkylene oxide, preferably
-14-
'~2,ZS48S
ethylene or propylene oxide, to replaee the earboxyl groups
with hydroxyl groupæ prior to employment in the present
invention. The amount of alkylene oxide employed is such as
to reduee the aeid number of the unsaturated polyol to about
5 or less.
The maleated maeromers are isomerized at tempera-
tures ranging from 80C to 120C for one-half hour to three
hours in the presence of an effeetive amount of an isomeri-
zation eatalyst. The catalyst is employed at eoncentrations
greater than 0~01 weight percent based on the weight of the
maeromer.
When preparing the polyetherester polyol employing
the eatalyst seleeted from the group eonsisting of salts and
oxides of divalent metals, the coneentration of catalyst
which may be employed ranges from 0.005 to 0.5 weight
percent based on the weight of polyol mixture. The tempera-
tures employed range from 75C to 175C. The equivalent
weight of the macromer may vary from 1000 to 10,000,
preferably from 2000 to 60000
Among the divalent metals which may be employed
are: zine acetate, zinc chloride, zinc oxide, zinc neodec-
anoate, tin chloride, calcium naphthenate, ealcium ehloride,
ealeium oxide, calcium acetate, copper naphthenate, cadmium
acetate, cadmium chloride, nickel chloride, manganese
chloride, and manganese acetate.
-15-
~5~S
Certain of the above-mentioned catalysts such as
- calcium naphthenate promote the isomerization of the maleate
to the fumarate structure during the preparation of the
macromer, while othars such as zinc chloride, which is an
effective catalyst for the polymerization, inhibit this
isomerization.
As mentioned above, the graft polymer dispersions
of the invention are prepared by the in situ polymerization,
in the above-described polyols of an ethylenically un-
10 saturated monomer or a mixture of ethylenically unsaturatedmonomers. Representative ethylenically unsaturated monomers
which may be employed in the present invention include
butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-
octadiene, styrene, -methylstyrene, 2-methylstyrene, 3-
methylstyrene and 4-methylstyrene, 2,4-dimethylstyrene,
ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene,
cyclohexylstyrene, benzylstyrene, and the like; substituted
styrenes such as cyanostyrene, nitrostyrene, N,N-dimethyl-
aminostyrene, acetoxystyrene, methyl 4-vinylbenzoate,
phenoxystyrene, p~vinylphenyl oxide, and the like; the
acrylic and substituted acrylic monomers such as acrylo-
nitrile, acrylic acid, methacrylic acid, methyl acrylate, 2-
hydroxyethyl acrylate, methyl methacrylate, cyclohexyl
-16-
4~S
me~hacrylate, benzyl methacrylate, isopropyl methacrylate,
octyl methacrylate, methacrylonitrile, ethyl ~-ethoxy-
acrylate, methyl ~-acetaminoacrtylate, butyl acrylate,
2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate,
N,N-dimethylacrylamide, N,N-dibenzylacrylamide, N-butyl-
acrylamide, methacrylyl formamide, and the like; the vinyl
esters, vinyl ethers, vinyl ketones, etc., such as vinyl
acetate, vinyl butyrate, isopropenyl acetate, vinyl formate,
vinyl acrylate, vinyl methacrylate, vinyl methoxyacetate,
vinyl benzoate, vinyltoluene, vinylnaphthalene, vinyl methyl
ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butyl
. ethers, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl
2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl
ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxy diethyl
ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl
- phosphonates such as vinyl phenyl ketone, vinyl ethyl
sulfone, N-methyl-N-vinyl acetamide, N-vinyl-pyrrolidone,
vinyl imidazole, divinyl sulfoxide, divinyl sulfone, sodium
vinylsulfonate, methyl vinylsulfonate, N-vinyl pyrrole,and
the like; dimethyl fumarate, dimethyl maleate, maleic acid,
crotonic acid, fumaric acid, itaconic acid, monomethyl
itaconate, t-butylaminoethyl methacrylate, dimethylamino
ethyl methacrylate, glycidyl acrylate, allyl alcohol, glycol
monoesters of itaconic acid, vinyl pyridine, and the like.
Any of the known polymerizable monomers can be used and the
-17-
~L2ZS~LlY5i
compounds listed above are illustrative and not restrictive
of the monomers suitable for use in this invention.
Preferably, the monomer is selected from the group con-
sisting of acrylonitrile, styrene and mixtures thereofO
The amount of ethylenically unsaturated monomer
employed in the polymerization reaction i5 generally from 25
percent to 60 percent, preferably from 30 percent to 45
percent, based on the total weight of the product. The
polymerization occurs at a temperature between about 25C
and 180C, preferably from 80C to 135C. It is preferred
that at least 55 to 100 weight percent of the mGnomer
employed i5 styrene or 4-methylstyrene.
Illustrative polymerization initiators which may
be employed are the well-known free radical types of vinyl
polymerization initiators such as the peroxides, per-
sulfates, perborates, percarbonates, azo compounds, etc
These include hydrogen peroxide, dibenzoyl peroxide, acetyl
peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide,
di-t-butyl peroxide, lauroyl peroxide, butyryl peroxide,
diisopropylbenzene hydroperoxide, cumene hydroperoxide,
paramenthane hydroperoxide, diacetyl peroxide, di-l-cumyl
peroxide, dipropyl peroxide,diisopropyl peroxide, isopropyl-
t-butyl peroxide, butyl-t-butyl peroxide, difuroyl peroxide,
bis(triphenylmethyl) peroxide, bis(p-methoxybenzoyl)
peroxide, p-monomethoxybenzoyl peroxide, rubene peroxide,
-18-
5~L8 5;
ascaridol, t-butyl peroxybenzoate, diethyl peroxyterephtha-
late, propyl hydroperoxide~ isopropyl hydroperoxide, n-butyl
hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroper-
oxide, trans-decalin hydroperoxide, ~-methylbenzyl hydroper-
oxide, ~-methyl-~-ethyl benzyl hydroperoxide, tetralin
hydroperoxide, ~riphenylmethyl hydroperoxide, diphenylmethyl
hydroperoxide, ,~'-azobis-(2-methyl heptonitrile~, 1,1'-
-azo-bis(cyclohexane carbonitrile), 4,4'-azobis(4-cyanopen-
tanoic acicl), 2,2'-azobis(isobutyronitrile), l-t-butylazo-l-
cyanocyclohexane, persuccinic acid, diisopropyl peroxy
dicarbonate, 2,2'-azobis(2,4-dimethylvaleronitrile),
2-t-butylazo-2-cyano-4-methoxy-4-methylpentane,2,2'-azobis-
2-methylbutanenitrile, 2-t-butylazo-2-cyanobutane, l-t-
amylazo-l-cyanocyclohexane, 2,2'-azobis~2,4-dimethyl-4-
methoxyvaleronitrile, 2,2'-azobis-2-methyl-butyronitrile, 2-
t-butylazo-2-cyano-4-methylpentane, 2-t-butylazo-2-iso-
butyronitrile, to butylperoxyisopropyl carbonate and the
like; a mixture of initiators may also be used. The
preferred initiators are 2,21-azobis(2-methylbutyronitrile),
2,2'-azobis(isobutyronikrile), 2,2'-azobis(2~4-dimethyl-
valeronitrile), 2-t-butylazo-2-cyano-4-methoxy-4-methyl
pentane, 2-t-butylazo-2-cyano-4-methylpentane, 2-t-butylaæo-
2-cyano-butane and lauroyl peroxide. Generally, from about
0.1 percent to about 10 percent, preferably from about 1
percent to about 4 percent, by weight of initator based on
--19--
S~5
the weight of the monomer will be employed in the process of
the invention.
The polyurethane foams employed in the present
invention are generally prepared by the reaction of a graft
polymer dispersion with an organic polyisocyanate in the
presence of a blowing agent and optionally in the presence
of additional polyhydroxyl-containing components, chain-
extending agents, catalysts~ surface-active agents, stabil-
izers, dyes, fillers and pigments. Suitable processes for
the preparation of cellular polyurethane plastics are
disclosed in U.S, Reissue Patent 24,514 together with
sui~able machinery to be used in con~unction therewith.
When water is added as the blowing agent, corresponding
quantities of excess isocyanate to react with the water and
produce carbon dioxide may be used It is possible to
proceed with the preparation of the polyurethane plastics by
a prepolymer technique wherein an excess of organic polyiso-
cyanate is reacted in a first step with the polyol of the
present invention to prepare a prepolymer having free
~ isocyanate groups which is then reacted in a second step
with water and/or additional polyol to prepare a foam.
Alternatively, the components may be reacted in a single
working step commonly known as the "one-shot'l technique of
preparing polyurethanes Furthermore, instead of water, low
boiling hydrocarbons such as pentane, hexane, heptane,
20-
~ 2 ~L~ 5
pentene, and heptene; azo compounds such as azohexahydro-
benzodinitrile; halogenated hydrocarbons such as dichlorodi-
fluoromethane, trichlorofluoromethane, dichlorodi~luoro~
ethane, vinylidene chloride, and methylene chloride may be
used as blowing agents.
Organic polyisocyanates which may be employed
include aromatic, aliphatic~ and cycloaliphatic polyiso-
cyanates and combinations thereof~ Representative of these
types are the diisocyanates such as m-phenylene diiso-
cyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate,
mixtures of 2,40 and 2,6-toluene diisocyanate, hexamethylene
diisocyanate, ~etramethylene diisocyanate, cyclohexane-1,4-
diisocyanate, hexahydrotoluene diisocyanate (and isomers),
naphthalene-l,S-diisocyanate, l-methoxyphenyl-2,4-diiso-
cyanate, 4,4' diphenylmethane diisocyanate, 4,4'-biphenylene
diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate,
~3'-~imethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyl-
diphenylmethane-4,4'-diisocyanate; the triisocyanates such
as 4,4',4"-triphenylmethane triisocyanate, and toluene
2,4,6-triisocyanate; and the tetraisocyanates such as
4,4'-dimethyldiphenylmethane-2,2'-5,5'-tetraisocyanate and
polymeric polyisocyanates such as polymethylene poly-
phenylene polyisocyanate. Especially useful due to their
availabillty and properties are toluene diisocyanate, 4,4'-
diphenylmethane diisvcyanate and polymethylene polyphenylene
polyisocyanate.
-21-
~2S~S
Crude polyisocyanates may also be used in the
composition~ of the present invention, such as crude toluene
diisocyanate obtained by the phosgenation of a mixture of
toluene diamines or crude diphenylmethane isocyanate
obtained by the phosgenation of crude diphenylmethane
diamine. The preferred or crude isocyanates are disclosed
in U.SO Patent No. 3,215,652.
As men~ioned above, the graft polyols may be
employed along with another polyhydroxyl-containing compo-
nent commonly employed in the art. Any of the polyhydroxyl-
containing components which are described above for use in
the preparation of the graft polyols may be employed in the
preparation of the polyurethane foams useful in ~he present
invention.
Chain-extending agents which may be employed in
the preparation of the polyurethane foams include those
compounds having at least two functional groups bearing
active hydrogen atoms such as water, hydrazine, primary and
secondary diamines, amino alcohols, amino acids, hydroxy
acids, glycols, or mixtures thereof~ A preferred group of
chain-extending agents includes water, ethylene glycol,
1~4-butanediol and primary and secondary diamines which
react more readily with the prepolymer than does wa~er such
as phenylene diamine, 1,4-cyclohexane-bis-(methylamine),
ethylenediamine, diethylenetriamine, N-(2-hydroxypropyl)-
-22-
~2~4~3~S
ethylenediamine~ N,N'-di(2~hydroxypropyl)ethylenediamine,
pipera~ine, and 2-methylpiperazine.
Any suitable catalyst may be used including
tertiary amines such as, for example, triethylenediamine,
N-methylmorpholine, N-ethylmorpholine, diethylethanolamine,
~l-cocomorpholine, l-me~hyl-4-dime~hylaminoethylpiperazine,
3-methoxypropyldimethylamine, N,N,N'-trimethylisopropyl
propylenediamine, 3-diethylaminopropyldiethylamine, dio
methylbenzylamine, and the like. Other suitable catalysts
are, for example, stannous chlorideldibutyltin di-2-ethyl
hexanoate, stannous oxide, as well as other organometallic
compounds such as are disclosed in U.S. Patent No.
2,846,408.
A surface-active agent is generally necessary for
production of high grade polyurethane foam according to the
present invention, since in the absence of same, the foams
collapse or contain very large uneven cells. Numerous
surface-active agents have been found satisfactory.
Nonionic ~urface active agents are preferred. Of these, the
nonionic surface-active agents such as the well-known
silicones have been found particularly desirable Other
surface-active agents which are operative, although not
preferred, include polyethylene glycol ethers of long chain
alcohols, tertiary amine or alkanolamine salts of long chain
alkyl acid sulfate esters, alkyl sulfonic esters, and alkyl
arylsulfonic acid~.
~2S'~
It has been ound in the preparation ~f the flame
retardant polyurethane foam products which have incorporated
therein the graf~ polymer disper~ions of the invention that
less flame retardant compound is necessary to impart flame
retardency. Among the flame retardants which may be
employed are: pentabromodiphenyl oxidP, dibromopropanol,
tris(~-chloropropyl)phosphate, 2,2-bis(bromoethyl) 19 3-
propanediol, tetrakis(2-chloroethyl)ethylene diphosphate~
tris(2,3-dibromopropyl~phosphate, tris(~-chloroethyl~-
phoshate, tris(l,2-dichloropropyl)phosphate, bis-~2-chloro-
ethyl) 2-chloroethylphosphonate, molybdenum trioxide,
ammonium molybdate, ammonium phosphate, pentabromodiphenyl-
oxide, tricresyl phosphate 9 hexabromocyclodoa~cane and
dibromoethyl- dibromocyclohexane. The concentrations of
flame retardant compounds which may be employed range from 5
to 25 parts per 100 parts of polyol mixture.
The following examples illustrate the nature of
the invention. A11 parts are by weight unless otherwise
stated. In the examples, the physical properties of the
polyurethane foam were determined by the following ASTM
tests:
Density - D1622-63
Tensile Strength - D1623-72
Elongation - D412
Split Tear D470
-2
s
Compression Set - D395
Compression Load - D1564
Humid Aging - D1564
The following abbreviations are employed in the
exampl~s below:
Polyol A is a trimethylolpropane, propylene oxide,
ethylene oxide adduct containing 15 percent
ethylene oxide, and a hydroxyl number of 25.
Polyol B is a glycerine, propylene oxide, ethylene 02ide
adduct containing 12.5 percent ethylene oxide, and
a hydroxyl number of 500
Polyol C is a glycerine, propylene oxide, ethylene oxide
adduct containing 18.5 percent ethylene oxide,
having a hydroxyl number of 35.
Polyol ~ is Polyol A containing 0.5 mole of unsaturation
per mole of polyol.
Polyol E is Polyol A containing 0.7 mole of unsaturation
per mole of polyol.
Polyol F is a glycerine, ethylene oxide, propylene oxide
adduct containing 6 percent ethylene oxide having
a reduced unsaturation of 0.3 mole per mole of
polyol, containing 36 weight percent of 3:1
acrylonitrile:styrene based on the total weight of
~he polymer and having a hydroxyl number of 32.5.
Polyol G see procedure D.
-25-
~254~5
Polyol H is a glycerine~ ethylene oxide propylene oxide
adduct containing 16.~ percent ethylene oxide and
having a hydroxyl number oE 35.
Polyol I see procedure E~
Polyol J see procedure B.
~atalyst A - zinc neodeconate as ppm zinc.
Catalyst B - calcium naphthenate as ppm calcium.
Catalyst C - copper naphthena~e as ppm copper.
Ca~alyst D - cobalt naphthenate aæ ppm cobalt
Initiator A - 2,2'-azobisl2-methylbutyronitrile)
DE-71 is pentabromodiphenyl oxide manufactured by
Great Lakes Chemicals~
Thermolin*101 is tetrakis(2-chloroethyl)ethylene diphos-
phate .
Reactant Blue X-44 is a dye manufacture by Milliken, Inc~
L-5720 is a silicone surfactant manufactured by
Union Carbon and Carbide Corporation.
DABCO*TL is an amine cataly~t manufactured by Air
Products, Inc.
T 10 is an organo tin catalyst manufactured by M~T
Chemicals, Inc.
DOP is dioctylphthalate.
TDI is toluene diisocyanate.
-26-
* Trademark
~2~Z59L~35
.
L-5043 is a silicone surfactant manufactured by Dow
Corning Corporation.
T-12 i dibutyltin ~ilaurate
DABCO*33LV is a 33 percent ~olution of triethylene
diamine in 67 percent dipropylene glycol.
NIAX*A-l is an amine eatalyst manufactured by Union
Carbon and Carbide Corporation.
AN is acrylonitrile
Sty is styrene
Antiblaze 19 repu~edly has the structure
O CH2CH3 0
( CE~ 3-- ) xP~ ~ OCH 2--C ~ ,, P--CH 3 ) 2--X
CH3 2
wherein x i~ equal to 0 or 1.
Procedure A
Charses:
The following ~harges were employed in examples 1
through 17 ex~ept as noted otherwise in Table I.
2000 gm Polyol A
30.6 gm maleic anhydride (0.8 equivalents per mole
of Polyol A)
gm catalyst B 200 ppm calcium
96 gm ethylene oxide (0~01 percent maximum
water )
* Trademark -27-
~;$
~z~s
A 3-liter round-bot~om flask with a stirrer,
thermometer and gas inlet was charged with polyol A, maleic
anhydride and calcium naphthenata. The contents were heated
to 125C and allowed to react for 1 hour. This intermediate
was transferred to a l-ga~llon steam heated stainless steel
autoclave. After heating to 125C and pressurizing the
reactor to 34 psig with nitrogen, ethylene oxide was added
during 1 hour and the mixture was reacted for 8 hours. The
product was isolated after discharging by stripping the
10volatiles at 105C for 1 hour at <10 mm ~g. This product is
designated as polyol D.
Procedure B
Charges: To reactor: 50 g polyol D
925 g polyol B
2.0 g initiator A
Stream #1: 260 g acrylonitrile
790 g styrene
13.5 g l-dodecanethiol
Stream #2: 975 g polyol B
20 10.5 g initator A
Reaction Conditions: reaction temperature, 90C; monomer
addition time, 210 minutes; polyol initiator addition time,
220 minutes; reaction time, 30 minutes; 300 rpm stirring.
-28-
The reactor charges were added to a 5-liter 4-neck
flask fitted with a stirrer, nitrogen inlet, addition tube,
water condenser and thermowell. After heating the polyol
reaction mixture to 90C and holding for 30 minutes under
nitrogen, the streams #l and $2 were added through a Kenics
static mixer over the specified time period. Upon comple-
tion of stream #l addition, the reaction mixture was heated
to 110C and reacted for the specified time. After the
reaction period was completed, the reaction mixture was
vacuum stripped for 30 minutes at 115C and 1 mm Hg. The
polyol from this procedure is designated as polyol J.
Procedure C
Charges: 400 lbs. polyol A
7.72 lbs. maleic anhydride
17.24 lbs. ethylene oxide
The indicated amount of polyol A was charged to a
clean, dry, nitrogen purged 90-gallon reactor, sealed and
heated to 110C. The polyol was then flash stripped at less
than 10 mm Hg into a cleanr dry 60-gallon reactor. Strip-
ping was continued until the residual water level had beenreduced to 0.01 weight percent. After stripping was
completed, maleic anhydride was added to the polyol, the
reaction mixture was padded with 34 psi nitrogen and then
-29-
:~fZZ~S
heated to 150C. AEter reacting for 4 hours, excess
ethylene oxide was added over 5 hours at 150C. This
reaction mixture was allowed to react 8 to 12 hours or until
the acid number had dropped below 0.2 mg KOH/g. The mixture
was then stripped to remove excess ethylene oxide. This
product was designated as polyol E.
Procedure D
Charges: To reac~or: 10.67 lbs~ polyol E
93.33 lbs. polyol B
0.053 lb. morpholine
0.21 lb. initiator A
Stream #1: 28.0 lbs. acrylonitrile
84.0 lbs. styrene
1.12 lbs~ l-dodecanethiol
Stream #2: 104.0 lbs. polyol B
1,12 lbs. initiator A
Reaction Conditions: reaction temperature, 90C; monomer
addition time, 210 minutes; polyol-initiator addition time,
220 minutes; reaction time, 30 minutes.
The reactor ch~rges were added under a nitrogen
atomsphere to a 50-gallon reactor. After heating the polyol
reaction mixture to 90C and holding for 30 minutes, streams
#1 and #2 were added through a Kenics static mixer over the
specified time period. Upon completion of stream #l
addition, the reaction mixture was heated to 110C and
-30-
12~ S
reacted for the specified time. After the reaction period
was completed, -the reaction mixture was vacuum stripped for
3 hours at 125C and 5 mm Hg. This product is designated as
polyol G.
Procedure E
Charges: To reactor~ 85.3 lbs. polyol C
26.7 lbs. polyol A
0.19 lb. initiator A
Stream #1: 24 lbs. acrylonitrile
72 lbs. styrene
0.96 lb. l-dodecanethiol
Stream ~2: 112.0 lbs. polyol C
0.96 lb. initator A
Reaction Conditions: reaction temperature, 90C; monomer
addition time, 180 minutes; polyol-initiator addition time,
190 minutes; reaction tim~, 30 minutes.
. The same reaction procedure was used here as in
procedure D.
This product is designated polyol I.
~s~
Examples 1-17
The products of these exam~les were prepared
employing various catalystsl at various concentrations and
at variable maleic anhydride contents using procedure A.
-32-
~2~59~5
.~U o o o o In o o u~ O c~ o o o o o o o
O O ~ O CO l~ CJ~ ~ ~ ~ ~ ~ ~`
u~ ~ o~ ~ ~ ~ o ~r ~ ~ o o~ ~ ~ el~ O O
8 ~ ~ ~ ~ u~ ~ 1~ o oo ~ o oo ~ ~ o
,, a.J
u~ ~ o ~ In o o o u~
. ooooooIOOOOOOOOOO
.~
~ l~
u~ o ~ ~
~ o o --~ o o o o o o o o o o o o o o
H
~ ~u~ o ~ I` ~ ~ r~ oo ~ ~ ~ ~
i~ ~3~ ~ ~ ~ ~) ~r --i O ~ I~ ~ r ~ ~ ~
. O
OOOOOOOOOOOOOOOOO ~
ooooooooooooooooo c~a~
a
~i~: m u ~ a: m m m m m m m m m m m m ''
~ ~'
u~
~g ooooo_i_ioooooooooo
O,~
a) g o
--33--
Examples 18-41
The products listed in Table II and III were
prepared by procedure B emplo~ing the indicated polyols,
monomers and concentrations.
~2Z5~35
o o o o ~ o o o o o o o o o o o o o
U~ ~ el' r~ t` ~ ,1 ~ U~ U~ O er 0~ ~ ~9 1 O ~
O a~ ~ ~ ~ ~ o ~ I` 1` ~D ~ O ~ I ~ a~ ~ ~ co ~
~c~ oonoooooc:~ooooo~ooooo
~, I o o o o o o C: ~ o oo o o CO o o o o o o o
oooooooCOo~oo~ooooooo
~ a) ~ o ~ ~ ~ o ~ r~ 7 ~ o o ~ o ~ ~ ~ ~ o
li~ C)
~a ~
b
a ~ OoOoOOOoOoOu~OoOoOoOO ~
~1~ In In In ~ In In u~ ~D In _I m r~ ~ m In In In Ln u~ In ~ i~
~$
co c~ o _l ~ ~ ~ n ~ co ~ o ~ * t~
~ 1~
~ ~ ~:
--35--
~2~
~ ~` C~ D ~
~, ~ ~ æ æ
~ .
~ ~ U~ ~ ~ ~
.~
H ~ ~ ~1 0 0 0
H ~ 1~ C~ CS~
Ul O
o , ~ u
~ ~ a~
~ ~ O O O O
r~l L
~1
. ~ CO ~ O _~
--36--
Examples 42-93
Examples 48 and 52 were prepared by adding to a
500 ml flask fitted with a stirrer and a nitrogen inlet
tube, 700 grams of polyol E and 0.7 grams of morpholine.
The reaction mixture was heated to 90C for 1 hour, then
vacuum stripped for 30 minutes at 1 mm Hg pressure.
Analysis by nuclear magnetic resonance showed 0.85 moles of
fumarate unsaturation. This product was used in preparing
the products of Examples 48 and 52. The remainder of the
examples were prepared employing procedure D.
-37-
S4~S
m ~ ~ ~ 2 " ~ o
8 ~ ~ 1~ ~ o~ ~ o ~ ~ ~ ~`
~ ~
InC~OOOOOOOOOC~OOOO
~IOOOOO0~CO~OOOO~OCl~CO
~Iooooo~o~oooo~o~
:> ~ ~ ol ~ o o ~ t`i ~`i j ~ o ~
~ ~ .o
a~ ~ o o In o In U~ U~ O O O U~ U~ O U~ ~
~oor~ol`I`~oooo~ro1`r~ ~
:d~
O ~ o ~ u~ o Lr) o o o Ln u~ O ut O o
~` I` o r~ ~ ~ o 1~ 1` 1` ~ ~ 1`
~o
u
--38--
~,2~
,~u
n c~ooooooooooooooo
N O~) ~ O U~ N ~ ) O ~ ~ ~9 1` ~D _I e~' ~
~3 ` ~ ~ r ` ~ ~1 ~ co ~o ~ d~ 1_
U~ ~ ~ ~
OOOOO~OOOOOO~OOO
I o o a~ D O ~0 ~0 ~ CO ~0 OD ~0 C~ O O
O O _I ~ d' O ~ `I 1~ ~ ~ ~ ~ O O
~ ~0
:~ a) a)
H i~ O O ~l ~ ~ O O
i~ ~ ,_1
c~l ~ ~ O o u~ u~ u~ U~ ~ u7 ~ ~ In ul
m
~ Ln O U ~ o g n
pl ~ OD ~0 --I ~1 ~ r t r~l r~
O ~ ~9
OOOOOOOOOOOOLnInU~O
r~ o o ~ ~ ~r ~ ~ ~ ~ ~ ~ ~ ~ _1 r~ o
U~
a~ o ~ ~ r~ ~ ~ o
--39--
~2~ 5
oooooooC:
~n ~ ~ ;~ ~ In o o
8 o ~ o
~ ~
a~
o o o o o o o o
~ _l
I O o o o o ~o CO o
L'')
I O O O O O ~ ~ O
111 L'~ L't L'l L'~
l ~i a~ . . . . . ~ ~
> ~ OOOOO ~
Ln O L'~ L') Il- L'~ L") O
t-- O ~ t~ I` ~ ~ CO
a) ~ ~ a~
m ~ ~
~ ~J LO O L'~ L') L'') ~ L') O
~ r ~ ~
~ CO L') 00 OQ 0 _I r-l r~l
aJ ~ ~ o
-l ~ o o o o o o o o
o ~ o o o o o ~n
~o
-40
~5~
o o C~ o o o o ~ o o o o
~ ~ a o ~ o g ~r ~ ~ o
O ~ ~ r~ ~ ~ ~ ~ ~ er
U~ ~
~ U
~ooooooooooo
o o ~ ~ ~
.~
~ o
l ~ ~
:~ ~ $
H ~ C~ ~1 0 ~ ~I ~ ~ t~ t~l ~ t~ t~l ~
~ $ ~ a~
m
~c)
u~ u~ ~ o ~ ~ o~ o u~ o
o ~ ~ o o u~ o ~ ~ ~ o o ~ o
~o o, ~
--41--
~5~
Examples_94-110
The products of Table V were prepared employing
procedure E except products of Examples 111 and 112 where
polyol E was replaced by polyol A.
-~2-
~t.
o ~ o o o o o o C~ o ~ o o o o o o o
~ ~Oæ ~
U1 o ~ o O o O o In O O O O C~ O O O
~5 ~ o o o u~
m ~ ~ ~ ~ ~ ~ _~ ~ ~ ~ ~ ,~ ~ ~ ~ ~ ~ ~
o
u~ o o o Is~
o~ oOo~ooooooooooooo
rn ~ Ln ~ o - I ~ ~) ~ In ~ I~ oo a~ o
~ c~ ~o o ~ o o ~o ~ ~ ~ ~ ~
--43--
~.22~ 5
Examples 111-127
The polyurethane foams of Tables VI, VII and VIII
were prepared by charging a cne quart cylindrical container
with a suitable quantity of the polyol, water, catalysts,
silicone surfactant and flame retardant compounds. The
mixture was stirred for about 30 seconds, allowed to set for
about 15 seconds and then stirring was resumed. After about
60 seconds elapsed time, the polyisocyanate was added to the
container, and the resulting mixture was stirred for about 4
to 5 seconds. The content of the container was then
immediately poured into a cardboard cake box, and the foam
was allowed to rise therein. After the foam rise was
completed, the resulting foam was oven cured for about 15
minutes.
Tables VI, VII and VIII set forth the ingredients
and amounts thereof used to prepare the foams as well as the
physical properties of the foams.
The flame retardancy tests, as exemplified by the
California No. 117 open flame test, indicate that flame
retardancy may be obtained with reasonably low levels of
flame retardant compounds employin~ the polymer dispersions
of the instant invention.
-44-
12'254BS
TABIE VI
EKample 111 112 113 114 115 116
Polyol G G G F F F
E~rnulation, p~w
Polyol 100.0
DE-71
q~lE~LIN~01 3, 0 6.0 12.0 3.0 6.0 12.0
RE~r ~lue X-44 0~25 GoS 1~0 0~25 0~5 1~0
~ater 2. 8 -- --
1 0 ~*TL O . 11
T-10 û. 4~
D~P 0.~ ____
TDI 37.1~------
Foam Pro~erties
Den~ity, pcf ~.18 2.25 2.24 2.17 2.19 2.33
Tensile strength,
psi 23.3 25.8 25.6 28.1 2~.4 27.8
Elon~ation, % 77 87 110 73 90 93
Tear, pi 20~ 2.3 3.1 2.0 201 2.5
2 0 P~silienoe, % 30 26 28 32 24 26
ILD, lb/~0 sq.in. (4 inch)
2s% 118.0112.0 10~.0 124.0 116.4 110.0
65% 247.2231.6 211.6 264.0 242.0 232.4
25~6 retllrn 69.2 67.2 57.2 68.8 64.4 62.8
Sag factor 2.09 2.07 2.07 2.13 2.08 2.11
Guide factor 54.1 49.8 45.5 57.1 53.2 47.2
~very, % 5~.0 60.0 ~6.0 55.0 55.0 57.~
50~ 57.1 71.3 89.7 14.5 58~2 72.0
9096 81.1 95.7 9~1.0 83.4 95.8 96.8
30 ~nid aged 5 hrs. at ~50F
CLD, % of ori~3inal
5096 61.1 71.0 7~.0 80.0 84.0 79.0
~npression sets, %
50P6 57.4 66.9 87.0 25.4 57.7 66.1
90~ 76.3 92.9 97.6 26.2 83.8 ~0.2
Heat aged 22 hrs.
at 284~F tensile
strength ,psi 29. 631. 8 31. 6 31. 5 33. 034 . 9
Air flowi c~n 3.80 0086 0.~5 1.92 1.10 1.10
Foam ~olor white tan
*Trade mark
--45--
~`. ' '~
.:J
~Z'~5
~r~sLE VI - continued
Exa~le 117118 119 120 121 122
Polyol G G G F F F
Water 2. 8~
DE-71 6~0------------- ~~~ - ~ ~~~~~~ -
~ERMOLIN 101 3.0 600 12.0 3.0 600 12.0
CALIFOKNIA NO. 117 SECTION A PART I -- OPEN FI~ME TEST
.
Spec.
Original Max.
Afterflame, sec.
10average 5.0 18~6 2.6 2.630.034.037nO
maximum 10.0 22~0 4~0 3~032~035~038.0
Char length, in.
average 6.0 5~4 2~6 2~612.012.012.0
maxim~n 8.0 6.0 3~3 20912.0120012.0
Heat aged 24 hrs./220F
Afterflame, sec.
average 5.0 16.8 3.4 3.232.035~038~0
maximum 10.0 20~0 4~0 4~032~035~03~0
Char length, in.
20average 600 5~3 2~7 2~612~012~012~0
maximum 8.0 5.9 3.0 3.012~012~012~0
CALIFORNIA NO~ 117 SECTION D PART~ II -- S~LDERING SCREENING TEST
.
Spec.
Min.
Non smoldered
residue, % 80.0 93.8 97.3 97.7 bumed co~pletely
BurL~ CHI~EY
~eight retention,96 69.1 92.7 95~5 0 63~0 941~5
Flame height,cm 25+ 22 19 25+ 25+ 20+
DOC FF-1--70MENqHE~sMINE PILL ~ME TEST
Spec.
3 o Min.
Inches bun.ed
fromouter ring >1 2.93~4 3~3 2.9 3.2 3.1
OXYGEN INDEX
% 2 19.721.3 24.3 1~.7 20.9 21~5
--46~
TABLE VII
FLAME TEST DATA ON 30/70
BLENDS OF POLYOL I/ POLYOL H
Example 123 124
Formulation
.
Eblyol I 30 30
Pblyol H 70 70
Water 2.0 2.0
DEOA 0.8 0.8
L 5043 0.8 0.8
TffERMOLIN 101 3.0 3.0
T-12 0.06 0.06
~BCO 33L~l 0.18 0.18
NIAX A-l 0.06 0.06
TDI index 108 108
California No. 117 Section A Part I - Open Flame Tbst
Sp~c.
Max.
Afterflame, sec.
average 0.7 0.7 5.0
maximum 0.8 0.8 10.0
Char length, in.
average 2.1 2.3 6.0
maximum 2.2 2.5 8.0
California No. 117 Section D Part II - Smoldering & reening Test
Spec.
Min.
Non-smoldered residue, % 86.4 89.0 80
-47-
~,2259L~5;
TABI~ VIII
Ex~mple 125 126 127
Formulation
Polyol J 100.0~
'lff~RMOLIN 101 3.0 12.0 --
DE~71 -- -- 12.0
ANTIBL~ZE 19 ~ -- 5.0
Silicone Lr5720 1.0--- ~---~---- ----------
Water 2.4-- -- -- -~ - ~-~ --
DABCO TL 0.1-- - ---- - - -------~
T'10 0.4 0.4 3
DOP 0.8 0.8 Q.6
TDI (115 index) 32.5--- -
Foam Properties
Density, pcf 2.19 2,32 2.27
Tensile strength, psi 24.6 26.2 25.3
Elongation, % 70 127 100
Tear, pi 2.5 2.9 2.5
Resilience, % 26 30 32
ILD, lb/50 sq.in. (4 inch)
25% 119.2 119.6 97.0
266.4 244.4 23~.1
25% retNrn 71.2 72.0 49.2
Sag factor 2.23 2.04 2.45
Guide factor 54.4 51.6 42.7
~eoovery, % 60.0 60.0 51.0
Compression sets, %
50% 25.4 82.4 73.9
9o% 53.4 96.1 96.2
Humid aged 5 hrs. at 250F
CLD, % of ori~inal 50% 80.0 67.0 82.0
Compression sets, ~
50~ 23.9 65.4 59.5
90~ 27.7 95.6 9205
Heat aged 22 hrs. at 284F
tensile strength, psi 33.5 30.6 30.1
Air flow, cfm 0.53 0.50 0.50
Color white
-48-
~,,2S~8S
TABLE VIII - c~on~inued
EXample 125 126 127
CALIFORNIA NO. 117 SECTION A PART I - OPEN FLAME TEST
Spec.
Original Max.
AEterflame, sec.
average 5.0 19.4 1.6 1 6
maximum 10.0 26.0 3.0 2.0
Char length, in.
average 6.0 7.8 2.0 2.4
maximum 8.0 9.0 3.1 3.0
~leat aged 24 hrs./220F
Afterflame, sec.
average 5.0 15.2 1.4 1.2
maximum 10.0 21.0 3.0 2.0
Char length, in.
average 6.0 6.5 2.3 2.8
maximum 8.0 8.7 3.1 3.1
CA~IFORNIA NO. 117 SECTION D PART II - SMDLDERING SCREENING TEST
.
Spec.
Max.
Non-sm~ldered
residue, % 80.0 96.6 99.2 99.9
BUTLER CHIMNEY
Weight retention, % 34.6 94.3 92.9
Flame height, cm 25+ 17 14
DOC FF-1-70 MENTHENAMINE PILL FLAME TEST
Spec.
Min.
Inches burned
from outer ring >1 3.5 3.3 3.1
-49-
