U.S. patent number RE33,291 [Application Number 06/730,085] was granted by the patent office on 1990-08-07 for process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams.
This patent grant is currently assigned to BASF Corporation. Invention is credited to Oscar M. Grace, Robert J. Hartman, Duane A. Heyman, Gerhard G. Ramlow, Curtis J. Reichel.
United States Patent |
RE33,291 |
Ramlow , et al. |
August 7, 1990 |
Process for the preparation of white graft polymer dispersions and
flame-retardant polyurethane foams
Abstract
White graft polymer dispersions in polyoxyalkylene polyether
polyols are employed together with flame retardant compounds to
prepare flame retardant polyurethane foams. The polymer dispersions
employ less than 0.1 mole of induced unsaturation per mole of
polyol mixture. Improved processes for the reparation of these
polymer dispersions employ either isomerized maleate containing
polyetherester polyols or polyetherester polyols prepared by
reacting a polyoxyalkylene polyether polyol, a polycarboxylic acid
anhydride and an alkylene oxide in the presence of salts and oxides
of divalent metals.
Inventors: |
Ramlow; Gerhard G. (Montreal,
CA), Heyman; Duane A. (Monroe, MI), Grace; Oscar
M. (Madison Heights, MI), Reichel; Curtis J. (Wyandotte,
MI), Hartman; Robert J. (Southgate, MI) |
Assignee: |
BASF Corporation (Parsippany,
NJ)
|
Family
ID: |
27002431 |
Appl.
No.: |
06/730,085 |
Filed: |
May 3, 1985 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
364336 |
Apr 1, 1982 |
44454255 |
Jun 12, 1984 |
|
|
Current U.S.
Class: |
521/137; 525/41;
525/43; 525/450; 528/69; 528/75 |
Current CPC
Class: |
C08F
291/08 (20130101); C08G 18/635 (20130101); C08G
63/676 (20130101) |
Current International
Class: |
C08F
291/00 (20060101); C08F 291/08 (20060101); C08G
63/00 (20060101); C08G 63/676 (20060101); C08G
18/00 (20060101); C08G 18/63 (20060101); C08L
075/00 () |
Field of
Search: |
;521/137 ;525/41,43,450
;528/69,75 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Nozaki, JACS, vol. 63, pp. 2681-2683 (1941). .
Szmercsanyi et al., Journal of Applied Polymer Science, vol. 10,
pp. 513-522 (1966). .
Hindersinn et al., J. Org. Chem., vol. 30, pp. 4020-4025 (1965).
.
Barrett, Dispersion Polymerization in Organic Media, John Wiley
& Sons, p. 75 (1975). .
Lewis et al., JACS, vol. 70, pp. 1533-1536 (1948). .
Nozaki et al., JACS, vol. 63, pp. 2583-2586 (1941). .
Seltzer, JACS, vol. 83, pp. 1861-1865 (1961). .
Hammond et al., JACS, vol. 86, pp. 3197-3217 (1964). .
Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 12, pp.
824-825 (1967). .
Meek, Journal of Chemical Education, vol. 52, No. 8, pp. 541-543
(1975). .
Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 14, pp.
778-779 (1981). .
Urushido, Journal of Polymer Science: Polymer Letters Edition, vol.
19, pp. 59-63 (1981). .
Brandrup et al.: Polymer Handbook, Wiley-Interscience, pp. II-314,
-317 (1975). .
Encyclopedia of Polymer Science and Technology Interscience, vol.
3, New York, pp. 575-576 (1965). .
Ham, "Vinyl Polymerization--Part I": Marcel Dekker: New York, pp.
47-56 (1967). .
Chemical Abstracts, vol. 85, p. 41 (CA 85: 124955g) (1976). .
Encyclopedia of Chemical Technology, Kirk-Othmer, vol. 16, pp.
159-161, 1968, John Wiley & Sons. .
Encyclopedia of Chemical Technology, Kirk-Othmer, vol. 20, pp.
791-805, 1969, John Wiley & Sons. .
Mononer-Isomerization Polymerization of Dialkyl Maleates by Radical
Mechanism, Ostn et al., Makromol. Chem. Rapid Comm., 2, 79-81
(1981). .
Maleic Anhydride, Trived; and Culbertson, 1982, Planum Press, N.Y.
.
Rate Constants for Polymerization Reactions, Journal of Polymer
Science, vol. XIII, pp. 417-426 (1954). .
Copolymerization, Ham, 1964, John Wiley & Sons..
|
Primary Examiner: Kight, III; John
Assistant Examiner: Hampton-Hightower; P.
Attorney, Agent or Firm: Conger; William G.
Claims
The embodiments of the invention in which an exclusive privilege or
property is claimed are defined as follows: .[.1. In a process for
the preparation of a white stable, low viscosity graft polymer
dispersion which comprises the polymerization in a polyol mixture
of from 5 to 60 weight percent based on the total weight of the
polymer dispersion of an ethylenically unsaturated monomer, or
mixture of said monomers, the improvement which comprises
conducting the polymerization in a polyol mixture containing from
0.001 to 0.09 mole of induced unsaturation per mole of said polyol
mixture..]. .[.2. In a process for the preparation of a graft
polymer dispersion which comprises the polymerization of an
ethylenically unsaturated monomer or mixture of said monomers in
the presence of an effective amount of a free radical initiator in
an unsaturation containing polyol mixture containing from 0.001 to
0.09 mole of unsaturation per mole of polyol mixture, the
improvement which comprises conducting the polymerization in an
isomerized polyether-ester polyol prepared by the reaction of a
polyoxyalkylene polyether polyol with
maleic anhydride and an alkylene oxide..]. 3. In a process for the
preparation of polyether-ester polyols by the reaction of a
polyoxyalkylene polyether polyol and a polycarboxylic acid
anhydride to form a half acid ester followed by the reaction of the
half acid ester with an alkylene oxide to obtain a product having
an acid number of less than 5 mg KOH/gm the improvement which
comprises conducting the reaction between the polyether 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 zinc, neodeconoate, calcium
naphthenate, copper naphthenate and cobalt naphthenate. 4. A white
stable, .Iadd.low viscosity .Iaddend.graft polymer dispersion
comprising .[.a polymerized.]. .Iadd.from about 25 to 60 weight
percent based on the total weight of the polymer dispersion of an
.Iaddend.ethylenically unsaturated monomer or mixture of monomers
.Iadd.polymerized in situ .Iaddend.in a .Iadd.polyol
.Iaddend.mixture .Iadd.initially .Iaddend.containing from
0.001 to 0.09 mole of induced unsaturation per mole of said
mixture. 5. A white stable.Iadd., low viscosity .Iaddend.graft
polymer dispersion comprising .[.a polymerized.]. .Iadd.from 25 to
60 weight percent based on the total weight of the polymer
dispersion of an .Iaddend.ethylenically unsaturated monomer or
mixture of monomers .Iadd.polymerized in situ .Iaddend.in .Iadd.a
polyol mixture containing .Iaddend.a macromer said macromer
prepared by the reaction of a conventional polyol with an organic
compound having both ethylenic unsaturation and a hydroxyl,
carboxyl, anhydride, isocyanate or epoxy group said .[.macromer.].
.Iadd.polyol mixture initially .Iaddend.containing from 0.001 to
0.09 mole of induced unsaturation per mole of said .[.macromer.].
.Iadd.polyol
mixture.Iaddend.. 6. A white stable.Iadd., low viscosity
.Iaddend.graft polymer dispersion comprising .Iadd.from about 25 to
60 weight percent based on the total weight of the polymer
dispersion of .Iaddend.a polymerized ethylenically unsaturated
monomer or mixture of monomers in a polyol mixture .Iadd.initially
.Iaddend.containing 0.001 to 0.09 mole of unsaturation per mole of
the polyol mixture wherein the polyol mixture comprises an
isomerized polyether-ester polyol prepared by the reaction of a
polyoxyalkylene-polyether polyol with maleic anhydride and an
alkylene
oxide. .[.7. In a process for the preparation of a flame retardant
polyurethane foam prepared by the reaction of an organic
polyisocyanate, a polyol, a blowing agent and flame retardants the
improvement which comprises employing the graft polymer dispersion
of claim 4..]. .[.8. In a process for the preparation of a flame
retardant polyurethane foam prepared by the reaction of an organic
polyisocyanate, a polyol, a blowing agent, and flame retardants the
improvement which comprises employing the graft polymer dispersion
of claim 5..]. .[.9. In a process for the preparation of a flame
retardant polyurethane foam prepared by the reaction of an organic
polyisocyanate, a polyol, a blowing agent, and flame retardants the
improvement which comprises employing the graft
polymer dispersion of claim 6..]. .Iadd.10. The dispersion of claim
4 wherein the viscosity of the dispersion is from 2000 to 8000 cps
at 25.degree. C. .Iaddend. .Iadd.11. The dispersion of claim 4
wherein the monomer content is from about 30 to about 45 weight
percent based on the total weight of the polymer dispersion.
.Iaddend. .Iadd.12. The dispersion of claim 5 wherein the viscosity
of the dispersion is from 2000 to 8000 cps at 25.degree. C.
.Iaddend. .Iadd.13. The dispersion of claim 5 wherein the monomer
content is from about 30 to about 45 weight percent based on the
total weight of the polymer dispersion. .Iaddend. .Iadd.14. The
dispersion of claim 6 wherein the viscosity of the dispersion is
from 2000 to 8000 cps at 25.degree. C. .Iaddend. .Iadd.15. The
dispersion of claim 6 wherein the monomer content is from about 30
to about 45 weight percent
based on the total weight of the polymer dispersion. .Iaddend.
.Iadd.16. A process for the preparation of a white, stable, low
viscosity, high solids content graft polymer dispersion which
comprises polymerizing in situ an ethylenically unsaturated monomer
or a mixture of ethylenically unsaturated monomers in a polyol
mixture containing from 0.001 to 0.09 moles of induced unsaturation
per mole of said polyol mixture in the presence of an effective
amount of a reaction moderator and a free radical
initiator. .Iaddend. .Iadd.17. The process of claim 16 wherein the
solids content is from 25 to 60 percent, based on the total weight
of the dispersion. .Iaddend. .Iadd.18. The process of claim 16
wherein the solids content is from 30 to 50 percent, based on the
total weight of the dispersion. .Iaddend. .Iadd.19. The process of
claim 16 wherein 55 to 100 weight percent of the monomer is
styrene. .Iaddend. .Iadd.20. The process of claim 16 wherein the
viscosity is from 2000 to 8000 cps at 25.degree.
C. .Iaddend. .Iadd.21. The process of claim 16 wherein the
viscosity is from 3000 to 5000 cps at 25.degree. C. .Iaddend.
.Iadd.22. The process of claim 16 wherein the polyol mixture
contains an isomerized maleate-containing macromer. .Iaddend.
.Iadd.23. The process of claim 16 wherein the polyol mixture
contains an isomerized maleate-containing macromer, wherein 55 to
100 weight percent of the monomer is styrene, and wherein the
viscosity is 3000 to 5000 at 25.degree. C. .Iaddend. .Iadd.24. The
process of claim 22 wherein the maleate-containing macromer is
prepared in the presence of a divalent metal salt or oxide
catalyst. .Iaddend. .Iadd.25. The process of claim 23 wherein the
macromer is prepared in the presence of a divalent metal salt or
oxide catalyst. .Iaddend. .Iadd.26. The process of claim 24 wherein
the divalent metal salt is calcium naphthenate. .Iaddend. .Iadd.27.
The process of claim 25 wherein the divalent metal salt is calcium
naphthenate. .Iaddend.
.Iadd. The process of claim 16 wherein the polyol mixture contains
a macromer prepared from a compound containing fumarate
unsaturation. .Iaddend. .Iadd.29. A white, stable, low viscosity,
high solids content graft polymer dispersion prepared by a process
comprising polymerizing in situ an ethylenically unsaturated
monomer or mixture of ethylenically unsaturated monomers in a
polyol mixture containing from 0.001 to 0.09 moles of induced
unsaturation per mole of said polyol mixture in the presence of an
effective amount of free-radical initiator and a reaction
moderator. .Iaddend. .Iadd.30. The product of claim 29 wherein the
solids content is from 25 to 60 percent, based on the total weight
of the dispersion. .Iaddend. .Iadd.31. The product of claim 29
wherein the solids content is from 30 to 50 percent, based on the
total weight of the dispersion. .Iaddend. .Iadd.32. The product of
claim 29 wherein 55 to 100 weight percent of the monomer is
styrene. .Iaddend. .Iadd.33. The product of claim 29 wherein the
viscosity is less than 10,000 cps at 25.degree. C.
.Iaddend. .Iadd.34. The product of claim 29 wherein the viscosity
is from 3000 to 5000 cps at 25.degree. C. .Iaddend. .Iadd.35. The
product of claim 29 wherein the polyol mixture contains an
isomerized maleate-containing macromer. .Iaddend. .Iadd.36. The
product of claim 31 wherein the polyol mixture contains an
isomerized maleate-containing macromer, wherein 55 to 100 weight
percent of the monomer is styrene, and wherein the viscosity is
3000 to 5000 at 25.degree. C. .Iaddend. .Iadd.37. The product of
claim 35 wherein the maleate-containing macromer is prepared in the
presence of a divalent metal salt or oxide catalyst. .Iaddend.
.Iadd.38. The product of claim 36 wherein the macromer is prepared
in the presence of a divalent metal salt or oxide catalyst.
.Iaddend. .Iadd.39. The product of claim 37 wherein the divalent
metal salt is calcium naphthenate. .Iaddend.
.Iadd. The product of claim 38 wherein the divalent metal salt is
calcium naphthenate. .Iaddend. .Iadd.41. The product of claim 29
wherein the polyol mixture contains a macromer prepared from a
compound containing fumarate unsaturation. .Iaddend. .Iadd.42. The
process of claim 3 wherein the catalyst is calcium naphthenate.
.Iaddend. .Iadd.43. A polyurethane foam characterized by flame
retardancy prepared by a process comprising reacting the graft
polymer dispersion of claim 29 with an organic polyisocyanate.
.Iaddend. .Iadd.44. A polyurethane foam characterized by flame
retardancy prepared by a process comprising reacting the graft
polymer dispersion of claim 30 with an organic polyisocyanate.
.Iaddend.
.Iadd.45. A polyurethane foam characterized by flame retardancy
prepared by a process comprising reacting the graft polymer
dispersion of claim 34 with an organic polyisocyanate. .Iaddend.
.Iadd.46. A polyurethane foam characterized by flame retardancy
prepared by a process comprising reacting the graft polymer
dispersion of claim 35 with an organic
polyisocyanate. .Iaddend. .Iadd.47. A polyurethane foam
characterized by flame retardancy prepared by a process comprising
reacting the graft polymer dispersion of claim 36 with an organic
polyisocyanate. .Iaddend. .Iadd.48. A polyurethane foam
characterized by flame retardance prepared by a process comprising
reacting the graft polymer dispersion of claim 41 with an organic
polyisocyanate. .Iaddend.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to low viscosity white graft polymer
dispersions in polyoxyalkylene polyether polyols and flame
retardant polyurethane foams prepared therefrom. More particularly,
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 0.1 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. Further, the invention relates to an improved process
employing free radical polymerization in a polyetherester
polyol-polyoxyalkylene polyether polyol mixture containing less tha
0.1 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 prepared by reacting a
polyoxyalkylene polyether polyol, a polycarboxylic acid anhydride
and an alkylene oxide in the presence of an effective amount of a
catalyst selected from the group consisting of salts and oxides of
divalent metals.
2. Description of the Prior Art
The prior art, as evidenced by U.S. Pat. Nos. .[.3,652,658.].
.Iadd.3,652,639.Iaddend.; 3,875,258; 3,950,317, and U.S. Pat. Nos.
Re. 28,715 and 29,014 teaches the preparation of graft polymer
dispersions which are useful in the preparation of polyurethanes by
the polymerization of ethylenically unsaturated monomers in the
presence of polyols. The above patents disclose various methods of
preparing graft polymer dispersions. U.S. Pat. No. 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.S. Pat. No. 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 weight based on the weight of vinyl monomer.
Stable dispersions of polymers in polyols have found broad
commercial use in the preparation of polyurethanes. The use of
these dispersions, known in the trade as 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 employed.
The use of high levels (.gtoreq.50 percent by weight) of
acrylonitrile and, correspondingly, relatively low levels of the
most common comonomer, styrene (.ltoreq.50 percent) had two very
undesirable effects. The resulting dispersions are tan to brown in
color with a strong tendency to turn ever 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 industry.
As mentioned before, there have been attempts to prepare high
polymer (.gtoreq.30 percent) containing dispersions 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 of 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 flame-retardant polyurethane foams may
be prepared by employing graft 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 unsaturation per mole of polyol mixture. Furthermore, it
has been found that improved dispersions may be prepared by
employing radical polymerization in a polyetherester
polyol-polyoxyalkylene polyether polyol mixture containing less
than 0.1 mole of induced unsaturation 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 group 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 polymerization 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 containing 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
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
conducting the polymerization in a polyol mixture employing as part
of the mixture a polyetherester 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 comprises conducting the reaction between
the polyoxyalkylene polyether 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 "macromers." Chain
transfer agents may be employed as reaction moderators particularly
at temperatures below 105.degree. C. The polymerization reaction
may be carried out at temperatures between 25.degree. C. and
180.degree. C., preferably between 80.degree. C. and 135.degree. C.
The polyol mixture contains less than 0.1 mole of unsaturation per
mole of polyol mixture and ranges from 0.001 to 0.09 mole of
unsaturation.
The alkylene oxides which may be employed for the 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 25.degree. C. Preferably they have
viscosities ranging from 2000 to 8000 cps at 25.degree. C.
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-bromophenylacetonitrile, p-nitrophenylacetylene, allyl
alcohol, 2,4,6-trinitroaniline, p-ethynylanisole,
2,4,6-trinitroanisole, azobenzene, benzaldehyde,
p-cyanobenzaldehyde, 2-butylbenzene, 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,
1-phenylbutyne, p-cresol, p-bromocumene, dibenzonaphthacene,
p-dioxane, pentaphenyl ethane, ethanol, 1,1-diphenylethylene,
ethylene glycol, ethyl ether, fluorene, N,N-dimethylformamide,
2-heptene, 2-hexene, isobutyraldehyde, diethyl bromomalonate,
bromotrichloromethane, dibromoethane, diiodomethane, naphthalene,
1-naphthol, 2-napthol, methyl oleate, 2,4,4-triphenyl-1-pentene,
4-methyl-2-pentene, 2,6-diisopropylphenol, phenyl ether,
phenylphosphine, diethylphosphine, dibutylphosphine, phosphorus
trichloride, 1,1,1-tribromopropane, dialkyl phthalate,
1,2-propanediol, 3-phosphinopropionitrile, 1-propanol,
pyrocatechol, pyrogallol, methyl stearate, tetraethylsilane,
triethylsilane, dibromostilbene, .alpha.-bromostyrene,
.alpha.-methylstyrene, tetraphenyl succinonitrile,
2,4,6-trinitrotoluene, p-toluidine, N,N-dimethyl-p-toluidine,
.alpha.-cyano-p-tolunitrile, .alpha.,.alpha.'-dibromo-p-xylene,
2,6-xylenol, diethyl zinc, dithiodiacetic acid, ethyl
dithiodiacetic acid, 4,4'-dithio-bisanthranilic acid, benzenethiol,
o-ethoxybenzenethiol, 2,2'-dithiobisbenzothiazole, benzyl sulfide,
1-dodecanethiol, ethanethiol, 1-hexanethiol, 1-napthalenethiol,
2-naphthalenethiol, 1-octanethiol, 1-heptanethiol, 2-octanethiol,
1-tetradecanethiol, .alpha.-toluenethiol, isopropanol, 2-butanol,
carbon tetrabromide and tertiary dodecyl mercaptan.
The chain transfer agents employed will depend on the particular
monomers or mixtures of monomers employed and the molar ratios of
such mixtures. The concentration of the chain transfer agent which
is 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 catalytic 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. Pat. Nos. 1,922,459; 3,190,927; and
3,346,557. Representative polyols include polyhydroxyl-containing
polyesters, polyoxyalkylene polyether 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.
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, .alpha.-hydromuconic acid, .beta.-hydromuconic acid,
.alpha.-butyl-.alpha.-ethyl-glutaric acid,
.alpha.,.beta.-diethylsuccinic acid, isophthalic acid, terephthalic
acid, hemimellitic acid, and 1,4-cyclohexanedicarboxylic acid. Any
suitable polyhydric alcohol, including both aliphatic and aromatic,
may be used such as ethylene glycol, propylene glycol, trimethylene
glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,
1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol,
1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane,
1,1,1-trimethylolethane, 1,2,6-hexanetriol, .alpha.-methyl
glycoside, pentaerythritol, 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 condensing an amino alcohol such as
ethanolamine with the polycarboxylic acids 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 the
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 tetrahydrofuran and alkylene
oxide-tetrahydrofuran mixtures; epihalohydrins 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 polyoxyethylene glycol, polyoxypropylene glycol,
polyoxybutylene glycol, polytetramethylene glycol, block
copolymers, for example, combinations of polyoxypropylene and
polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene
glycols, poly-1,4-oxybutylene and polyoxyethylene glycols, 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 Technology,
Vol. 7, pp. 257-262, published by Interscience Publishers, Inc.
(1951) or in U.S. Pat. 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. Pat. No. 3,639,542.
Preferred polyhydroxyl-containing phosphorus compounds are prepared
from alkylene oxides and acids of phosphorous having a P.sub.2
O.sub.5 equivalency of from about 72 percent to about 95
percent.
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-propanedithiol, 1,3-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 include
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,
triisopropanolamine, 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 containing reactive hydrogen atoms. A more comprehensive
discussion of these polyols and their method of preparation can be
found in U.S. Pat. Nos. 3,585,185; 3,639,541 and 3,639,542.
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.
Representative 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 halogenated maleic acids and
anhydrides, unsaturated polyhydric alcohols such as
2-butene-1,4-diol, glycerol allyl ether, trimethylolpropane allyl
ether, pentaerythritol allyl ether, pentaerythritol vinyl ether,
pentaerythritol diallyl ether, and 1-butene-3,4-diol, unsaturated
epoxides such as 1-vinylcyclohexene-3,4-epoxide, butadiene
monoxide, vinyl glycidyl ether(1-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
ethylene or propylene oxide, to replace the carboxyl groups with
hydroxyl groups prior to employment in the present invention. The
amount of alkylene oxide employed in such as to reduce the acid
number of the unsaturated polyol to about 5 or less.
The maleated macromers are isomerized at temperatures ranging from
80.degree. C. to 120.degree. C. for one-half hour to three hours in
the presence of an effective amount of an isomerization catalyst.
The catalyst is employed at concentrations greater than 0.01 weight
percent based on the weight of the macromer.
When preparing the polyetherester polyol employing the catalyst
selected from the group consisting of salts and oxides of divalent
metals, the concentration of catalyst which may be employed ranges
from 0.005 to 0.5 weight percent based on the weight of polyol
mixture. The temperatures employed range from 75.degree. C. to
175.degree. C. The equivalent weight of the macromer may vary from
1000 to 10,000, preferably from 2000 to 6000.
Among the divalent metals which may be employed are: zinc acetate,
zinc chloride, zinc oxide, zinc neodecanoate, tin chloride, calcium
naphthenate, calcium chloride, calcium oxide, calcium acetate,
copper naphthenate, cadmium acetate, cadmium chloride, nickel
chloride, manganese chloride, and manganese acetate.
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
others 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 unsaturated monomer or a mixture of
ethylenically unsaturated monomers. 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, .alpha.-methylstyrene, 2-methylstyrene,
3-methylstyrene and 4-methylstyrene, 2,4-dimethylstyrene,
ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene,
cycloexylstyrene, benzylstyrene, and the like; substituted styrenes
such as cyanostyrene, nitrostyrene, N,N-dimethylaminostyrene,
acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene,
p-vinylphenyl oxide, and the like; the acrylic and substituted
acrylic monomers such as acrylonitrile, acrylic acid, methacrylic
acid, methyl acrylate, 2-hydroxyethyl acrylate, methyl
methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
isopropyl mthacrylate, octyl methacrylate, methacrylonitrile, ethyl
.alpha.-ethoxyacrylate, methyl .alpha.-acetaminoacrtylate, butyl
acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl
methacrylate, N,N-dimethylacrylamide, N,N-dibenzylacrylamide,
N-butylacrylamide, 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-vinylpyrrolidone,
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, dimethylaminoethyl 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 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 consisting of acrylonitrile, styrene and mixtures
thereof.
The amount of ethylenically unsaturated monomer employed in the
polymerization reaction is 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 25.degree. C. and 180.degree. C., preferably from 80.degree.
C. to 135.degree. C. It is preferred that at least 55 to 100 weight
percent of the monomer employed is 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, persulfates, 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-.alpha.-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, ascaridol, t-butyl peroxybenzoate, diethyl
peroxyterephthalate, propyl hydroperoxide, isopropyl hydroperoxide,
n-butyl hydroperoxide, t-butyl hydroperoxide, cyclohexyl
hydroperoxide, trans-decalin hydroperoxide, .alpha.-methylbenzyl
hydroperoxide, .alpha.-methyl-.alpha.-ethyl benzyl hydroperoxide,
tetralin hydroperoxide, triphenylmethyl hydroperoxide,
diphenylmethyl hydroperoxide, .alpha.,.alpha.'-azobis-(2-methyl
heptonitrile), 1,1'-azo-bis(cyclohexane carbonitrile),
4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(isobutyronitrile),
1-t-butylazo-1-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,
1-t-amylazo-1-cyanocyclohexane,
2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile,
2,2'-azobis-2-methylbutyronitrile,
2-t-butylazo-2-cyano-4-methylpentane,
2-t-butylazo-2-isobutyronitrile, to butylperoxyisopropyl carbonate
and the like; a mixture of initiators may also be used. The
preferred initiators are 2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(isobutyronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2-t-butylazo-2-cyano-4-methoxy-4-methylpentane,
2-t-butylazo-2-cyano-4-methylpentane, 2-t-butylazo-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 initiator based on 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, stabilizers, dyes, fillers and
pigments. Suitable processes for the preparation of cellular
polyurethane plastics are disclosed in U.S. Pat. No. Re. 24,514
together with suitable machinery to be used in conjunction
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 polyisocyanate is reacted in a first
step with the polyol of the present invention to prepare a
prepolymer having free isocyanate groups which is then reacted in a
second step with water 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" technique of preparing
polyurethanes. Furthermore, instead of water, low boiling
hydrocarbons such as pentane, hexane, heptane, pentene, and
heptene; azo compounds such as azohexahydrobenzodinitrile;
halogenated hydrocarbons such as dichlorodifluoromethane,
trichlorofluoromethane, dichlorodifluoroethane, vinylidene
chloride, and methylene chloride may be used as blowing agents.
Organic polyisocyanates which may be employed include aromatic,
aliphatic, and cycloaliphatic polyisocyanates and combinations
thereof. Representative of these types are the diisocyanates such
as m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene
diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate,
hexamethylene diisocyanate, tetramethylene diisocyanate,
cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and
isomers), naphthalene-1,5-diisocyanate,
1-methoxyphenyl-2,4-diisocyanate, 4,4'-diphenylmethane
diisocyanate, 4,4'-biphenylene diisocyanate,
3,3'-dimethoxy-4,4'-biphenyl
diisocyanate,3,3'-dimethyl-4,4'-biphenyl diisocyanate and
3,3'-dimethyldiphenylmethane-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 polyphenylene
polyisocyanate. Especially useful due to their availability and
properties are toluene diisocyanate, 4,4'-diphenylmethane
diisocyanate and polymethylene polyphenylene polyisocyanate.
Crude polyisocyanates may also be used in the compositions 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.S. Pat. No. 3,215,652.
As mentioned above, the graft polyols may be employed along with
another polyhydroxyl-containing component 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
the 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 water such as phenylene
diamine, 1,4-cyclohexane-bis-(methylamine), ethylenediamine,
diethylenetriamine, N-(2-hydroxypropyl)ethylenediamine,
N,N'-di(2-hydroxypropyl)ethylenediamine, piperazine, and
2-methylpiperazine.
Any suitable catalyst may be used including tertiary amines such
as, for example, triethylenediamine, N-methylmorpholine,
N-ethylmorpholine, diethylethanolamine, N-cocomorpholine,
1-methyl-4-dimethylaminoethylpiperazine,
3-methoxypropyldimethylamine, N,N,N'-trimethylisopropyl
propylenediamine, 3-diethylaminopropyldiethylamine,
dimethylbenzylamine, and the like. Other suitable catalysts are,
for example, stannous chloride, dibutyltin di-2-ethyl hexanoate,
stannous oxide, as well as other organometallic compounds such as
are disclosed in U.S. Pat. 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 surface 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 acids.
It has been found in the preparation of the flame retardant
polyurethane foam products which have incorporated therein the
graft polymer dispersions of the invention that less flame
retardant compound is necessary to impart flame retardency. Among
the flame retardants which may be employed are: pentabromodiphenyl
oxide, dibromopropanol, tris(.beta.-chloropropyl)phosphate,
2,2-bis(bromoethyl) 1,3-propanediol,
tetrakis(2-chloroethyl)ethylene diphosphate,
tris(2,3-dibromopropyl)phosphate,
tris(.beta.-chloroethyl)phosphate,
tris(1,2-dichloropropyl)phosphate, bis-(2-chloroethyl)
2-chloroethylphosphonate, molybdenum trioxide, ammonium molybdate,
ammonium phosphate, pentabromodiphenyloxide, tricresyl phosphate,
hexabromocyclododecane 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. All
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
Compression Set--D395
Compression Load--D1564
Humid Aging--D1564
The following abbreviations are employed in the examples 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 oxide adduct
containing 12.5 percent ethylene oxide, and a hydroxyl number of
50.
Polyol C is a glycerine, propylene oxide, ethylene oxide adduct
containing 18.5 percent ethylene oxide, having a hydroxyl number of
35.
Polyol D 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 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 the polymer and
having a hydroxyl number of 32.5.
Polyol G see procedure D.
Polyol H is a glycerine, ethylene oxide propylene oxide adduct
containing 16.5 percent ethylene oxide and having a hydroxyl number
of 35.
Polyol I see procedure E.
Polyol J see procedure B.
Catalyst A--zinc neodeconate as ppm zinc.
Catalyst B--calcium naphthenate as ppm calcium.
Catalyst C--copper naphthenate as ppm copper.
Catalyst D--cobalt naphthenate as ppm cobalt
Initiator A--2,2'-azobis(2-methylbutyronitrile)
DE-71 is pentabromodiphenyl oxide manufactured by Great Lakes
Chemicals.
Thermolin 101 is tetrakis(2-chloroethyl)ethylene diphosphate.
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 catalyst 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.
L-5043 is a silicone surfactant manufactured by Dow Corning
Corporation.
T-12 is dibutyltin dilaurate
DABCO 33LV is a 33 percent solution of triethylene diamine in 67
percent dipropylene glycol.
NIAX A-1 is an amine catalyst manufactured by Union Carbon and
Carbide Corporation.
AN is acrylonitrile
Sty is styrene
Antiblaze 19 reputedly has the structure ##STR1## wherein x is
equal to 0 or 1.
Procedure A
Charges:
The following charges were employed in examples 1 through 17 except
as noted otherwise in Table I.
2000 gm Polyol A
30.6 gm maleic anhydride (0.8 equivalents per mole of Polyol A)
10 gm catalyst B 200 ppm calcium
96 gm ethylene oxide (0.01 percent maximum water)
A 3-liter round-bottom flask with a stirrer, thermometer and gas
inlet was charged with polyol A, maleic anhydride and calcium
naphthenate. The contents were heated to 125.degree. C. and allowed
to react for 1 hour. This intermediate was transferred to a
1-gallon steam heated stainless steel autoclave. After heating to
125.degree. C. 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 volatiles at 105.degree. C. for 1 hour at <10
mm Hg. 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 1-dodecanethiol
Stream #2:
975 g polyol B
10.5 g initiator A
Reaction Conditions: reaction temperature, 90.degree. C.; monomer
addition time, 210 minutes; polyol initiator addition time, 220
minutes; reaction time, 30 minutes; 300 rpm stirring.
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 90.degree.
C. and holding for 30 minutes under nitrogen, the streams #1 and #2
were added through a Kenics static mixer over the specified time
period. Upon completion of stream #1 addition, the reaction mixture
was heated to 110.degree. C. and reacted for the specified time.
After the reaction period was completed, the reaction mixture was
vacuum stripped for 30 minutes at 115.degree. C. 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 110.degree.
C. The polyol was then flash stripped at less than 10 mm Hg into a
clean, dry 60-gallon reactor. Stripping was continued until the
residual water level had been reduced 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
heated to 150.degree. C. After reacting for 4 hours, excess
ethylene oxide was added over 5 hours at 150.degree. C. 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 reactor:
10.67 lbs. polyol E
93.33 lbs. polyol B
0.053 lbs. morpholine
0.21 lb. initiator A
Stream #1:
28.0 lbs. acrylonitrile
84.0 lbs. styrene
1.12 lbs. 1-dodecanethiol
Stream #2:
104.0 lbs. polyol B
1.12 lbs. initiator A
Reaction Conditions: reaction temperature 90.degree. C.; monomer
addition time, 210 minutes; polyol-initiator addition time, 220
minutes; reaction time, 30 minutes.
The reactor charges were added under a nitrogen atmosphere to a
50-gallon reactor. After heating the polyol reaction mixture to
90.degree. C. 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 #1 addition, the reaction mixture was
heated to 110.degree. C. and reacted for the specified time. After
the reaction period was completed, the reaction mixture was vacuum
stripped for 3 hours at 125.degree. C. 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 lbs. initiator A
Stream #1:
24 lbs. acrylonitrile
72 lbs. styrene
0.96 lb. 1-dodecanethiol
Stream #2:
112.0 lbs. polyol C
0.96 lb. initiator A
Reaction Conditions: reaction temperature, 90.degree. C.; monomer
addition time, 180 minutes; polyol-initiator addition time, 190
minutes; reaction time, 30 minutes.
The same reaction procedure was used here as in procedure D.
This product is designated polyol I.
EXAMPLES 1-17
The products of these examples were prepared employing various
catalysts, at various concentrations and at variable maleic
anhydride contents using procedure A.
TABLE I
__________________________________________________________________________
Maleic Catalyst Anhydride, Level, Saponification Unsaturation
Viscosity Examples Equivalents* Catalyst ppm OH No. Acid No. No.
mole/mole** cps, 25.degree. C.
__________________________________________________________________________
1 0.8 A 800 25.5 0.57 22.2 0.6 11,900 2 0.8 B 800 25.2 0 13.8 0.4
12,200 3 0.8 C 800 22.2 1.3 18.6 0.6 2,760 4 0.8 D 800 22.5 0.05
15.6 0.35 15,250 5 0.8 B 800 26.3 0.22 15.1 0.45 9,425 6 1.0 B 800
21.6 0 19.2 0.40 17,290 7 1.5 B 800 23.9 0 27.1 -- 100,000 8 0.8 B
400 24.0 0 11.3 0.37 8,485 9 0.8 B 200 21.6 0 11.6 0.48 7,370 10
0.8 B 100 20.7 0 16.3 0.55 11,390 11 0.8 B 200 22.3 0 16.7 0.48
8,030 12 0.8 B 200 17.9 0.8 16.6 0.35 16,830 13 0.8 B 200 21.7 0
19.3 0.55 10,230 14 0.75 B 200 24.8 0 16.9 0.50 8,360 15 0.85 B 200
25.6 0 -- 0.50 9,430 16 0.9 B 200 21.2 0 24.0 0.50 12,070 17 0.8 B
200 23.4 0 17.2 0.55 10,000
__________________________________________________________________________
*equivalents of maleic anhydride per mole of polyol. **moles of
induced unsaturation per mole of polyol.
EXAMPLES 18-41
The products listed in Table II and III were prepared by procedure
B employing the indicated polyols, monomers and concentrations.
TABLE II
__________________________________________________________________________
Polyol D, g Polyol B, g Dodecanethiol, g AN, Sty, Temperature
Viscosity Examples Charge Charge Feed Feed g g .degree.C. cps,
25.degree. C.
__________________________________________________________________________
18 50 925 975* 10.5 260 790 90 2840 19 50 925 975 13.5 260 790 90
2830 20 50 925 975 13.5 260 790 95 2970 21 60 915 975 13.5 260 790
90 2910 22 50 925 975 10.5 260 790 90 coagulated 23 50 925 975 13.5
260 790 90 3020 24 50 925 975 13.5 260 790 90 2750 25 60 885 945
14.0 278 832 90 3750 26 50 925 975 13.5 260 790 90 2700 27 10 185
195 2.1 52 158 90 2640 28 50 925 975 10.5 260 790 90 7380 29 75 900
975 10.5 260 790 90 6010 30 10 185 195 2.1 52 158 90 2860 31 50 925
975 10.5 260 790 90 -- 32 50 925 975 13.5 260 790 90 3100 33 50 925
975 13.5 260 790 90 2900 34 50 925 975 12.5 260 790 90 3190 35 50
925 975 13.5 260 790 90 3100 36** 50 925 975 10.5 260 790 90 2860
37 50 925 975 14.5 260 790 90 2910
__________________________________________________________________________
g = grams *3 gms methylbenzyldiphenylamine added. **Initiator
2t-butylazo-2-cyano-4-methylpentane.
TABLE III
__________________________________________________________________________
Polyol D, g Polyol C, g Dodecanethiol, g AN, Sty, Temperature
Viscosity Examples Charge Charge Feed Feed g g .degree.C. cps,
25.degree. C.
__________________________________________________________________________
38 10 185 195 2.1 52 158 90 3980 39 50 1000 105 9.0 225 675 90 3260
40 50 1000 105 9.0 225 675 90 2990 41 60 990 1050 9.0 225 675 90
3240
__________________________________________________________________________
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
90.degree. C. 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.
TABLE IV
__________________________________________________________________________
Exam- Polyol E, g Polyol B, g Dodecanethiol, g AN, Sty, Temperature
Viscosity ples Charge Charge Feed Feed g g .degree.C. csp,
25.degree. C.
__________________________________________________________________________
42 100 875 975 10.1 260 790 85 3350 43 75 900 975 10.5 260 790 90
6760 44 75 900 975 10.5 260 790 90 5840 45 100 875 975 10.1 260 790
80 3050 46 75 900 975 10.5 260 790 90 3340 47 20 175 195 2.1* 52
158 90 3020 48 20 175 195 2.1 52 158 90 3800 49 100 845 945 11.1
278 832 90 4440 50 75 900 975 10.5 260 790 90 4580 51 75 900 975
10.5 260 790 90 5750 52 75 900 975 10.5 260 790 90 12780 53 75 705
117 10.5 260 790 90 3200 54 100 845 945 11.1 278 832 90 3860 55 75
900 975 10.5 260 790 90 7890 56 20 175 195 2.1 42 168 90 3270 57 20
175 195 2.1 52 158 90 3290 58 100 875 975 10.5 260 790 90 3480 59
100 875 975 10.5 260 790 90 3050 60 20 175 195 2.1 21 189 90 36000
61 20 175 195 2.1 63 147 90 7960 62 40 350 390 4.2 104 316 90 11520
63 20.6 160.4 180.1 2.4 60.1 180 75-119 5810 64 20 175 195 2.1 52
158 90 4080 65 20 175 195 2.1 52 158 90 4600 66 20 175 195 2.1 52
158 90 4630 67 10 185 195 2.1 52 158 90 6180 68 20 175 195 2.1 52
158 90 3660 69 20 175 195 2.6 52 158 90 4870 70 15 180 195 2.1 52
158 90 3060 71 15 180 195 2.1 52 158 90 3210 72 75 900 975 10.5 260
790 90 3440 73 100 875 975 10.5 260 790 90 3760 74 100 875 975 10.5
260 790 90 3020 75 100 550 1300 10.5 260 790 90 3600 76 100 875 975
10.5 260 790 90 2910 77 100 875 975 10.5 260 790 90 3250 78 100 825
975 10.5 260 790 90 3300 79 50.6 144.4 195.2 2.1 52 158 90 8900 80
20.1 175 195.2 2.1 52 158 90 4010 81 20.0 160 180 2.4 60 180.1 90
8170 82 20 175 195 2.1 52 158 85 4410 83 100 875 975 10.5 260 790
90 3540 84 100 875 975 10.5 260 790 90 4130 85 15 180 195 2.1 52
158 90 3620 86 20 175 195 2.1 52 158 90 3500 87 18 177 195 2.1 52
158 90 3340 88 16 179 195 2.1 52 158 90 3300 89 22 173 195 2.1 52
158 90 4000 90 20 175 195 2.1 52 158 90 3440 91 20 240 130 2.1 52
158 90 3320 92 20 175 195 2.1 52 158 90 3300 93 20 370 -- 2.1 52
158 90 4500
__________________________________________________________________________
*bromotrichloromethane used instead of dodecanethiol.
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.
TABLE V
__________________________________________________________________________
Polyol E, g Polyol B, g Dodecanethiol, g AN, Sty, Temperature
Viscosity Examples Charge Charge Feed Feed g g .degree.C. csp,
25.degree. C.
__________________________________________________________________________
94 60 135 195 2.1 52 158 95 5340 95 70 160 190.4 1.8 45 135 90 3070
96 50 160 210 1.4 45 135 90 21200 97 49.9 160 210 1.8 45 135 90
2680 98 50 145 195.3 2.1 52 158 90 4260 99 60.1 134.9 195.1 2.1 52
158 90 4550 100 60 135 195 2.1 52 158 90 3940 101 60 135 195 1.6 52
158 90 5010 102 60 135 195 2.1 52 158 85 3960 103 300 675 975 10.5
260 790 90 4290 104 60 135 195 2.1 52 158 80 3560 105 60 135 195
1.9 52 158 90 3960 106 60 135 195 1.7 52 158 90 4020 107 60 135 195
2.3 52 158 90 3830 108 60 135 195 2.5 52 158 90 3830 109 60 135 195
2.1 52 158 90 5600 110 20 175 195 2.1 52 158 90 7270
__________________________________________________________________________
EXAMPLES 111-127
The polyurethane foams of Tables VI, VII and VIII were prepared by
charging a one 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 employing
the polymer dispersions of the instant invention.
TABLE VI
__________________________________________________________________________
Example 111 112 113 114 115 116 Polyol G G G F F F
__________________________________________________________________________
Formulation, pbw Polyol 100.0 100.0 100.0 100.0 100.0 100.0 DE-71
6.0 6.0 6.0 6.0 6.0 6.0 THERMOLIN 101 3.0 6.0 12.0 3.0 6.0 12.0
REACTINT Blue X-44 0.25 0.5 1.0 0.25 0.5 1.0 Water 2.8 2.8 2.8 2.8
2.8 2.8 DABCO TL 0.11 0.11 0.11 0.11 0.11 0.11 T-10 0.4 0.4 0.4 0.4
0.4 0.4 DOP 0.8 0.8 0.8 0.8 0.8 0.8 TDI 37.1 37.1 37.1 37.1 37.1
37.1 Foam Properties Density, pcf 2.18 2.25 2.24 2.17 2.19 2.33
Tensile strength, 23.3 25.8 25.6 28.1 25.4 27.8 psi Elongation, %
77 87 110 73 90 93 Tear, pi 2.4 2.3 3.1 2.0 2.1 2.5 Resilience, %
30 26 28 32 24 26 ILD, lb/50 sq. in. (4 inch) 25% 118.0 112.0 102.0
124.0 116.4 110.0 65% 247.2 231.6 211.6 264.0 242.0 232.4 25%
return 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 Recovery, %
59.0 60.0 56.0 55.0 55.0 57.0 50% 57.1 71.3 89.7 14.5 58.2 72.0 90%
81.1 95.7 98.0 83.4 95.8 96.8 Humid aged 5 hrs. at 250.degree. F.
CLD, % of original 50% 61.1 71.0 74.0 80.0 84.0 79.0 Compression
sets, % 50% 57.4 66.9 87.0 25.4 57.7 66.1 90% 76.3 92.9 97.6 26.2
83.8 90.2 Heat aged 22 hrs. 29.6 31.8 31.6 31.5 33.0 34.9 at
284.degree. F. tensile strength, psi Air flow, cfm 0.80 0.86 0.45
1.92 1.10 1.10 Foam color white tan
__________________________________________________________________________
Example 117 118 119 120 121 122 Polyol G G G F F F
__________________________________________________________________________
Water 2.8 2.8 2.8 2.8 2.8 2.8 DE-71 6.0 6.0 6.0 6.0 6.0 6.0
THERMOLIN 101 3.0 6.0 12.0 3.0 6.0 12.0
__________________________________________________________________________
CALIFORNIA NO. 117 SECTION A PART I - OPEN FLAME TEST
__________________________________________________________________________
Spec. Original Max. Afterflame, sec. average 5.0 18.6 2.6 2.6 30.0
34.0 37.0 maximum 10.0 22.0 4.0 3.0 32.0 35.0 38.0 Char length, in.
average 6.0 5.4 2.6 2.6 12.0 12.0 12.0 maximum 8.0 6.0 3.3 2.9 12.0
12.0 12.0 Heat aged 24 hrs./220.degree. F. Afterflame, sec. average
5.0 16.8 3.4 3.2 32.0 35.0 38.0 maximum 10.0 20.0 4.0 4.0 32.0 35.0
38.0 Char length, in. average 6.0 5.3 2.7 2.6 12.0 12.0 12.0
maximum 8.0 5.9 3.0 3.0 12.0 12.0 12.0
__________________________________________________________________________
CALIFORNIA NO. 117 SECTION D PART II - SMOLDERING SCREENING TEST
__________________________________________________________________________
Spec. Min. Non-smoldered 80.0 93.8 97.7 burned completely residue,
% BUTLER CHIMNEY Weight retention, % 69.1 92.7 95.5 0 63.0 94.5
Flame height, cm 25+ 22 19 25+ 25+ 20+
__________________________________________________________________________
DOC FF-1-70 MENTHENAMINE PILL FLAME TEST
__________________________________________________________________________
Spec. Min. Inches burned >1 2.9 3.4 3.3 2.9 3.2 3.1 from outer
ring OXYGEN INDEX % O.sub.2 19.7 21.3 24.3 19.7 20.9 21.5
__________________________________________________________________________
TABLE VII ______________________________________ FLAME TEST DATA ON
30/70 BLENDS OF POLYOL I/POLYOL H Example 123 124
______________________________________ Formulation Polvol I 30 30
Polyol H 70 70 Water 2.0 2.0 DEOA 0.8 0.8 L-5043 0.8 0.8 THERMOLIN
101 3.0 3.0 T-12 0.06 0.06 DABCO 33LV 0.18 0.18 NIAX A-1 0.06 0.06
TDI index 108 108 California No. 117 Section A Part I - Open Flame
Test Spec. 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 Screening Test
Spec. Min. Non-smoldered residue, % 86.4 89.0 80
______________________________________
TABLE VIII ______________________________________ Example 125 126
127 ______________________________________ Formulation Polyol J
100.0 100.0 100.0 THERMOLIN 101 3.0 12.0 -- DE-71 -- -- 12.0
ANTIBLAZE 19 -- -- 5.0 Silicone L-5720 1.0 1.0 1.0 Water 2.4 2.4
2.4 DABCO TL 0.1 0.1 0.1 T-10 0.4 0.4 0.3 DOP 0.8 0.8 0.6 TDI (115
index) 32.5 32.5 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 65 266.4 244.4 238.1 25% return 71.2 72.0 49.2
Sag factor 2.23 2.04 2.45 Guide factor 54.4 51.6 42.7 Recovery, %
60.0 60.0 51.0 Compression sets, % 50% 25.4 82.4 73.9 90% 53.4 96.1
96.2 Humid aged 5 hrs. at 250.degree. F. CLD, % of original 50%
80.0 67.0 82.0 Compression sets, % 50% 23.9 65.4 59.5 90% 27.7 95.6
92.5 Heat aged 22 hrs. at 284.degree. F. 33.5 30.6 30.1 tnesile
strength, psi Air flow, cfm 0.53 0.50 0.50 Color white CALIFORNIA
NO. 117 SECTION A PART I - OPEN FLAME TEST Spec. Original Max.
Afterflame, 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
Heat aged 24 hrs./220.degree. F. 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 CALIFORNIA NO. 177 SECTION D PART
II - SMOLDERING SCREENING TEST Spec. Max. Non-smoldered 80.0 96.6
99.2 99.9 residue, % 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 >1 3.5 3.1 from outer ring
______________________________________
* * * * *