U.S. patent number RE29,014 [Application Number 05/607,134] was granted by the patent office on 1976-10-26 for highly-stable graft copolymer dispersions in polyols containing unsaturation and polyurethanes prepared therefrom.
This patent grant is currently assigned to BASF Wyandotte Corporation. Invention is credited to William W. Levis, Jr., John T. Patton, Jr., Louis C. Pizzini, Gerhard G. Ramlow.
United States Patent |
RE29,014 |
Pizzini , et al. |
October 26, 1976 |
Highly-stable graft copolymer dispersions in polyols containing
unsaturation and polyurethanes prepared therefrom
Abstract
Highly-stable graft copolymer dispersions are prepared by the in
situ polymerization in the presence of a free radical catalyst of a
vinyl monomer in a polyol containing an essential amount of
unsaturation. The dispersions are low-viscous liquids which may be
advantageously employed in the preparation of flexible urethane
foams having enhanced load-bearing properties.
Inventors: |
Pizzini; Louis C. (Trenton,
MI), Ramlow; Gerhard G. (East Windsor, NJ), Patton, Jr.;
John T. (Wyandotte, MI), Levis, Jr.; William W.
(Wyandotte, MI) |
Assignee: |
BASF Wyandotte Corporation
(Wyandotte, MI)
|
Family
ID: |
26978083 |
Appl.
No.: |
05/607,134 |
Filed: |
August 25, 1975 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
311809 |
Dec 4, 1972 |
03823201 |
Jul 9, 1974 |
|
|
Current U.S.
Class: |
524/760; 524/728;
521/137; 524/751; 524/757; 524/762; 525/42; 525/528; 526/250;
526/264; 526/319; 526/335; 528/75; 528/192; 528/306; 524/710;
525/25; 524/759; 524/750; 525/49; 526/263; 526/332; 528/297;
526/347; 526/274; 525/531 |
Current CPC
Class: |
C08F
290/14 (20130101) |
Current International
Class: |
C08F
290/00 (20060101); C08F 290/14 (20060101); C08L
029/02 (); C08F 002/14 (); C08F 016/04 () |
Field of
Search: |
;260/861,33.2R,33.4R,78.5R,85.5R,86.1R,859R,874,898 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Czaja; Donald E.
Assistant Examiner: Nielsen; Earl A.
Attorney, Agent or Firm: Michaels; Joseph D. Swick; Bernhard
R. Dunn; Robert E.
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A highly stable graft copolymer dispersion prepared by the in
situ polymerization in the presence of a free radical catalyst at a
temperature of from 70.degree. C. to about 170.degree. C. of
(a) an ethylenically unsaturated monomer or mixture of said
monomers in
(b) an unsaturated polyol mixture containing from 0.10 mole to 0.70
mole of unsaturation per mole of polyol mixture, .Iadd.said
unsaturation being incorporated into the polyol mixture by the
reaction of a polyol with an organic compound having both ethylenic
unsaturation and a hydroxyl, carboxyl or epoxy group or by
employing said organic compound as a reactant in the preparation of
the polyol, .Iaddend.said polymerization carried out by adding the
monomer and the catalyst to the polyol mixture.
2. The copolymer dispersion of claim 1 wherein the monomer is
styrene.
3. The copolymer dispersion of claim 1 wherein the monomer is a
mixture of acrylonitrile and styrene.
4. The copolymer dispersion of claim 1 wherein the unsaturated
polyol mixture comprises a polyol which is prepared by the reaction
of an alkylene oxide with the reaction product of maleic anhydride
with a polyether polyol having an equivalent weight of from 250 to
5,000.
5. The copolymer dispersion of claim 4 wherein the polyether polyol
is an alkylene oxide adduct of glycerol or propylene glycol.
6. The copolymer dispersion of claim 1 wherein the unsaturated
polyol mixture is prepared by the reaction of a polyhydric alcohol
having from two to six hydroxyl groups with a mixture of propylene
oxide and allyl glycidyl ether.
7. The copolymer dispersion of claim 1 wherein the catalyst is
azobis(isobutyronitrile).
8. The copolymer dispersion of claim 1 wherein the polyol mixture
contains from 0.30 to 0.60 mole of unsaturation per mole of polyol
mixture.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to stable graft copolymer dispersions
of low viscosity and superior particle size distribution. More
particularly, the invention relates to graft copolymer dispersions
prepared by the in situ polymerization of a vinyl monomer in a
polyol having from 0.10 to 0.70 mole of unsaturation per mole of
polyol and to the use of these dispersions in the preparation of
polyurethane polymers.
2. Prior Art
Graft copolymer dispersions prepared from vinyl monomers and
polyether polyols and the use thereof in the preparation of
polyurethane polymers are well known in the art as evidenced by
U.S. Pat. Nos. 3,383,351 to Stamberger and 3,652,639 to Pizzini et
al. In the earlier patent, the polyols employed are essentially
free from ethylenic unsaturation. It is taught that the presence of
ethylenic unsaturation promotes crosslinking and an undesired
increase in viscosity of the resulting dispersions. One of the
major drawbacks of Stamberger is that stable dispersions prepared
from many of the common vinyl monomers such as styrene are not able
to be prepared when amounts of these monomers are employed
sufficient to provide the desired strength properties to
polyurethane polymers. Thereafter, it was determined by Pizzini et
al. that liquid homogeneous graft copolymers based on acrylonitrile
could be prepared by the in situ polymerization of acrylonitrile
with an unsaturated polyol in the presence of a free radical
catalyst. These copolymers are prepared by the simultaneous
addition, at a steady rate, of acrylonitrile and the catalyst to
the unsaturated polyol. The polyols employed by Pizzini et al.
contained at least about one mole of unsaturation per mole of
polyol. One drawback of the graft polyols of Pizzini et al. is
their relatively high viscosity which appears to be the result of
the presence of soluble graft copolymer and/or of graft copolymer
of extremely small particle size rather than crosslinking because
even very viscous graft polyols of this type are completely soluble
in solvents.
SUMMARY OF THE INVENTION
Now in accordance with the present invention graft copolymer
dispersions are prepared by the in situ polymerization of vinyl
monomers in a polyol having from about 0.10 to 0.70 mole of
unsaturation per mole of polyol hereinafter also simply referred to
as "unsaturated polyol." In order to obtain the graft copolymer
dispersions of the present invention, it is necessary that grafting
occurs by the simultaneous addition at a steady rate of a vinyl
monomer and a free radical catalyst to the unsaturated polyol at a
temperature between 70.degree. C. and 170.degree. C., preferably
between 105.degree. C. and 135.degree. C. The dispersions are
surprisingly superior to those prepared from essentially saturated
polyols in regard to their narrow particle size distribution. They
are also surprisingly superior to those prepared from polyols
having high unsaturation in regard to their low viscosities.
Furthermore, polyurethane foams prepared from these graft
copolymers exhibit superior load-bearing properties.
Although not wishing to be bound by theory, it is our belief that
the stability of dispersions obtained by the in situ polymerization
of vinyl monomers in polyols is a result of the formation of
surface stabilizing species. Without a stabilizing species which
provides a repulsive barrier between the polymer particles, the
polymerized material will agglomerate and form irregularly shaped
lumps. We have found that the stabilizer is an amphipathic polymer
consisting of lyophobic vinyl polymer and lyophilic polyether
chains. The vinyl polymer part is absorbed and/or chemically built
in the particle surface while the polyether part reaches out in the
surrounding polyol phase providing a protective shield against
coagulation.
In the case of an in situ polymerization in a saturated polyol,
such as described in Stamberger, U.S. Pat. No. 3,304,273, an
amphiphatic polymer can only be formed via hydrogen abstraction
from the polyether chain. If the chain transfer coefficient between
polyether and monomer, e.g. styrene, is very low, very little, if
any, graft polymer is formed and, therefore, stable dispersions
cannot be prepared.
Contrary to the teachings of Stamberger, we have now found that
polyols containing ethylenic unsaturation are of definite advantage
in the preparation of stable graft copolymer dispersions. If
co-reactive unsaturated groups carrying polyether molecules are
employed, the surface protective amphiphatic species can be formed
by copolymerization of the vinyl monomer with these groups. Since,
in this case, the co-reaction does not depend on grafting through
hydrogen abstraction, more efficient "comb-shaped" structures are
obtained, in which the "teeth" are represented by the polyether
chains and the "backbone" by the vinyl polymer. Furthermore, stable
dispersions can be obtained with monomers which have little
tendency to graft, e.g. styrene. As shown in the Examples
hereinafter, these dispersions not only exhibit improved shelf-life
stability but also they provide improved physical properties to
polyurethane foams prepared therefrom.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The unsaturated polyols employed in the present invention may be
prepared by the reaction of any conventional polyol with an organic
compound having both ethylenic unsaturation and a hydroxyl,
carboxyl, or epoxy group or they may be prepared by employing an
organic compound having both ethylenic unsaturation and a hydroxyl,
carboxyl, or epoxy group as a reactant in the preparation of the
polyol. Representative of such organic compounds include
unsaturated polycarboxylic acids and anhydrides such as maleic acid
and anhydride, fumaric acid and anhydride crotonic acid and
anhydride, propenyl succinic anhydride, and halogenated maleic
acids and anhydrides, unsaturated polyhydric alcohols such as
2-butene-1,4-diol, glycerol allylether, trimethylolpropane
allylether, pentaerythritol allylether, pentaerythritol vinylether,
pentaerythritol diallylether, and 1-butene-3,4-diol, unsaturated
epoxides such as 1-vinylcyclohexane-3,4-epoxide, butadiene
monoxide, vinyl glycidylether(1-vinyloxy-2,3-epoxy propane),
glycidyl methacrylate and 3-allyloxypropylene oxide (allyl
glycidylether). If a polycarboxylic acid or anhydride is employed
to incorporate unsaturation into the polyols, it is then necessary
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 is such to reduce the acid number
of the unsaturated polyol to about one or less. Representative
polyols which may be employed in the preparation of the unsaturated
polyols employed in the present invention are well known 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. 1,922,451,
3,190,927 and 3,346,557.
Representative polyols include polyhydroxyl-containing polyesters,
polyalkylene polyether polyols, polyhydroxy-terminated polyurethane
polymers, polyhydroxyl-containing phosphorus compounds, and
alkylene oxide adducts of polyhydric polythioethers, 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 two or
more different groups within the above-defined classes may also be
used such as 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 a --SH group may be used.
Any suitable hydroxyl-containing polyester may be used such as are
obtained 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-cyclohexane-dicarboxylic acid. Any
suitable polyhydric alcohol including both aliphatic and aromatic
may be used such as ethylene glycol, 1,3-propylene glycol,
1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol,
1,2-butylene glycol, 1,5-pentane diol, 1,4-pentane diol,
1,3-pentane diol, 1,6-hexane diol, 1,7-heptane diol, glycerol,
1,1,1-trimethylolpropane, 1,1,1-trimethylolethane,
hexane-1,2,6-triol, .alpha.-methyl glucoside, pentaerythritol, and
sorbitol. Also included with the term "polyhydric alcohol" are
compounds derived from phenol such as
2,2,(4,4'-hydroxyphenyl)propane, commonly known as Bisphenol A.
Any suitable polyalkylene polyether polyol may be used such as the
polymerization product of an alkylene oxide or of an alkylene oxide
with a polyhydric alcohol having from 2 to 6 hydroxyl groups. Any
suitable polyhydric alcohol may be used such as those disclosed
above for use in the preparation of the hydroxyl-containing
polyesters. Any suitable alkylene oxide may be used such as
ethylene oxide, propylene oxide, butylene oxide, amylene oxide, and
heteric or block copolymers of these oxides. The polyalkylene
polyether polyols may be prepared from other starting materials
such as tetrahydrofuran and alkylene oxide-tetrahydrofuran
copolymers; epihalohydrins such as epichlorohydrin; as well as
aralkylene oxides such as styrene oxide. The polyalkylene polyether
polyols may have either primary or secondary hydroxyl groups and,
preferably, are polyethers prepared from alkylene oxides having
from two to six carbon atoms such as polyethylene ether glycols,
polypropylene ether glycols, and polybutylene ether glycols. The
polyalkylene 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 250 to 5000.
Suitable polyhydric polythioethers which may be condensed with
alkylene oxides include the condensation product of thiodiglycol or
the reaction product of a dihydric alcohol such as disclosed above
for the preparation of the hydroxyl-containing polyesters with any
other suitable thioether glycol.
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.
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 phosphorus having a P.sub.2
O.sub.5 equivalency of from about 72% to about 95%.
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 alkane thiols containing at least two --SH groups
such as 1,2-ethane dithiol, 1,2-propane dithiol, 1,3-propane
dithiol, and 1,6-hexane dithiol; 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-amino aniline,
1,5-diamino naphthalene, methylene dianiline, the condensation
products of aniline and formaldehyde, and 2,4-diamino toluene;
aliphatic amines such as methyl amine, triisopropanol amine,
ethylene diamine, 1,3-propylene diamine, 1,4-butylene diamine, and
1,3-butylene diamine.
As mentioned above, in order to introduce the necessary unsaturated
groups into the polyols useful as starting materials in the present
invention, the organic compound having both ethylenic unsaturation
and a hydroxyl, carboxyl, or epoxy group may be included in the
polyol-forming reaction mixture or the unsaturation is introduced
by reacting a conventional polyol with said organic compound. To
prepare the unsaturated polyols of use in the present invention,
from about 0.10 mole to about 0.70 mole, preferably from 0.30 mole
to 0.60 mole, of said organic compound per mole of polyol is
employed. The preparation of the unsaturated polyols employed in
the present invention follows conventional prior art procedures
such as disclosed in U.S. Pat. No. 3,275,606 and U.S. Pat. No.
3,280,077. Generally, this requires a reaction at a temperature
between 0.degree. C. and 130.degree. C. Both acidic catalysts, such
as Lewis acid catalysts and basic catalysts usch as alkali metal
hydroxides, may be used. In addition, a non-catalyzed reaction may
be used employing temperatures between 50.degree. C. and
200.degree. C.
As mentioned above, the graft copolymers of the invention are
prepared by the in situ polymerization of the above-described
unsaturated polyols with 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,
methylstyrene, 2,4 -dimethylstyrene, ethylstyrene,
isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene,
benzylstyrene, and the like; substituted styrenes such as
chlorostyrene, 2,5 -dichlorostyrene, bromostyrene, fluorostyrene,
trifluoromethylstyrene, iodostyrene, cyanostyrene, nitrostyrene,
N,N-dimethylaminostyrene, acetoxylstyrene, methyl 4-vinylbenzoate,
phenoxystyrene, p-vinyl diphenyl sulfide, p-vinylphenyl phenyl
oxide, and the like; the acrylic and substituted acrylic monomers
such as acrylonitrile, acrylic acid, methacrylic acid,
methylacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl
methacrylate, methyl methacrylate, cyclohexyl methacrylate, benzyl
methacrylate, isopropyl methacrylate, octyl methacrylate,
methacrylonitrile, methyl .alpha.-chloroacrylate, ethyl
.alpha.-ethoxyacrylate, methyl .alpha.-acetaminoacrylate, butyl
acrylate, 2-ethylhexylacrylate, phenyl acrylate, phenyl
methacrylate, .alpha.-chloroacrylonitrile, 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 chloroacetate, vinyl alcohol, vinyl
butyrate, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl
methacrylate, vinyl methoxy acetate, vinyl benzoate, vinyl iodide,
vinyl toluene, vinyl naphthalene, vinyl bromide, vinyl fluoride,
vinylidene bromide, 1-chloro-1-fluoro-ethylene, vinylidene
fluoride, 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 2 -ethylmercaptoethyl
ether, vinyl methyl ketone, vinyl ether ketone, vinyl phosphonates
such as bis(.beta. -chloroethyl)vinyl phosphonate, vinyl phenyl
ketone, vinyl ethyl sulfide, vinyl ethyl sulfone, N-methyl-N-vinyl
acetamide, N-vinyl-pyrrolidone, vinyl imidazole, divinyl sulfide,
divinyl sulfoxide, divinyl sulfone, sodium vinyl sulfonate, methyl
vinyl sulfonate, 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,
dichlorobutadiene, 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.
The amount of ethylenically unsaturated monomer employed in the
polymerization reaction is generally from 1% to 30%, preferably
from 3% to 25%, based on the weight of the unsaturated polyol. The
polymerization occurs by simultaneously adding at a steady or
constant rate the monomer and a free radical catalyst to the
unsaturated polyol at a temperature between about 80.degree. C. and
170.degree. C., preferably from 105.degree. C. to 135.degree. C.
Optionally, the catalyst may be dispersed in a portion of the
polyol and thereafter added along with the monomer to the remaining
portion of the unsaturated polyol.
The concentration of the catalyst is also a critical aspect of the
present invention and can vary from about 1% to about 10%,
preferably from about 2% to about 5% by weight based on the weight
of the monomer. It has been determined that the use of amounts of
catalyst less than one percent does not provide for the stable
dispersions of the subject invention.
Illustrative catalysts are the well-known free radical type of
vinyl polymerization catalysts, for example, the peroxides,
persulfates, perborates, percarbonates, azo compounds, etc.,
including 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, dilauroyl peroxide, difuroyl peroxide, ditriphenylmethyl
peroxide, bis(p-methoxybenzoyl)peroxide, p-monomethoxybenzoyl
peroxide, rubrene 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.
-azo-2-methyl butyronitrile, .alpha.,.alpha.-2-methyl heptonitrile,
1,1'-azo-1-cyclohexane carbonitrile, dimethyl
.alpha.,.alpha.'-azo-isobutyrate, 4,4'-azo-4-cyanopentanoic acid,
azobis(isobutyronitrile), persuccinic acid, diisopropyl peroxy
dicarbonate, and the like; a mixture of catalysts may also be used.
Azobis(isobutyronitrile) is the preferred catalyst.
In a preferred embodiment of the present invention, from 5% to 15%
by weight of acrylonitrile and from 5% to 15% by weight of styrene
based on the weight of the unsaturated polyol is polymerized in an
unsaturated polyol in the presence of from 2% to 4% by weight of
azobis(isobutyronitrile) based on the weight of the polyol at a
temperature between 110.degree. C. to 140.degree. C. The resulting
dispersion contains approximately 20% vinyl polymer, has a
viscosity of about 2,500 cps. at 25.degree. C. and imparts
exceptional load-bearing properties when employed in the
preparation of flexible polyurethane foams. In another preferred
embodiment of the invention, from 10% to 20% by weight of styrene
is polymerized in an unsaturated polyol as described above. It is
only through use of the subject invention that stable dispersions
containing at least 10% styrene have been prepared.
In still another preferred embodiment of the present invention, the
foregoing graft copolymer dispersions are employed in the
preparation of polyurethane compositions, particularly polyurethane
foams. The resulting polyurethane products exhibit marked
improvements in load-bearing properties and tensile strength
without substantial impairment of the other physical properties of
the products. The polyurethane products are generally prepared by
the reaction of the graft copolymer dispersions with an organic
polyisocyanate, optionally in the presence of additional
polyhydroxyl-containing components, chain-extending agents,
catalysts, surface-active agents, stabilizers, blowing agents,
fillers and pigments. Suitable processes for the preparation of
cellular polyurethane plastics are disclosed in U.S. Reissue Pat.
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 also 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 to prepare a foam. Alternately, 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, tolylene-2,4-diisocyanate,
tolylene-2,6-diisocyanate, mixture of 2,4- and
2,6-hexamethylene-1,6-diisocyanate, tetramethylene-
1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotolylene
diisocyanate (and isomers), naphthylene-1,5-diisocyanate,
1-methoxyphenyl-2,4-diisocyanate,
diphenylmethane-4,4'-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, polymethylene
polyphenylisocyanate and tolylene 2,4,6-triisocyanate; and the
tetraisocyanates such as 4,4'-dimethyldiphenylmethane- 2,2',5,5'
-tetraisocyanate. Especially useful due to their availability and
properties are tolylene diisocyanate, diphenylmethane- 4,4'
-diisocyanate and polymethylene polyphenylisocyanate.
Crude polyisocyanate 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
diphenylmethyl diamine. The preferred unreacted or crude
isocyanates are disclosed in U.S. Pat. No. 3,215,652.
As mentioned above, the graft copolymer dispersions are preferably
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 copolymer dispersions of the present invention may be
employed along with the unsaturated polyols in the preparation of
the polyurethane compositions of the present invention.
Chain-extending agents which may be employed in the preparation of
the polyurethane compositions of the present invention include
those compounds having at least two functional groups bearing
active hydrogen atoms such as water, hydrazine, primary and
secondary diamines, amines alcohols, amino acids, hydroxy acids,
glycols, or mixtures thereof. A preferred group of chain-extending
agents includes water and primary and secondary diamines which
react more readily with the prepolymer than does water such as
phenylene diamine 1,4-cyclohexane-bis-(methylamine), ethylene
diamine, diethylene triamine, N-(2-hydroxypropyl)ethylene diamine,
N,N'-di(2-hydroxypropyl)ethylene diamine, piperazine,
2-methylpiperazine, morpholine, and dodecahydro-1,4,7,9
b-tetrazaphenalene.
Any suitable catalyst may be used including tertiary amines, such
as for example, triethylene diamine, N-methyl morpholine, N-ethyl
morpholine, diethyl ethanolamine, N-coco morpholine,
1-methyl-4-dimethylamino ethyl piperazine, 3-methoxy-N-dimethyl
propyl amine, N-dimethyl-N'-methyl isopropyl propylene diamine,
N,N-diethyl-3-diethyl amino propyl amine, dimethyl benzyl amine,
and the like. Other suitable catalysts are, for example. tin
compounds such as stannous chloride, tin salts of carboxylic acids,
such as dibutyltin di-2-ethyl hexoate, tin alcoholates such as
stannous octoate, as well as other organo metallic compounds such
as are disclosed in U.S. Pat. No. 2,846,408.
A wetting agent or 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 wetting agents have been
found satisfactory. Non-ionic surfactants and wetting agents are
preferred. Of these, the nonionic surface-active agents prepared by
the sequential addition of propylene oxide and then ethylene oxide
to propylene glycol and the solid or liquid organosilicones 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
alkylolamine salts of long chain alkyl acid sulfate esters, alkyl
sulfonic esters, and alkyl arylsulfonic acids.
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 were determined by the
following ASTM tests:
______________________________________ Tensile Strength D-412
Modulus D-412 Elongation D-412 Split Tear D-470 Compression Set
D-395 Compression Load D-1564
______________________________________
The absorbance of the graft polymer dispersions is measured by the
following turbidity test. Turbidity is the cloudiness in a liquid
caused by the presence of finely divided suspended material. The
quantity of solid material in a colloidal suspension can be
determined by measuring either the transmitted light or the
scattered light. Absorbance is defined as log.sub.10
(1/Transmittance). As turbidity increases, the transmittance
decreases and the absorbance increases.
The turbidity method employs a Beckman DU spectrophotometer. The
spectrophotometer is operated as per the instructions in the manual
using a wavelength of 800 millimicrons, a tungsten lamp, and the
red phototube light meter is used. The sample is contained in a
curette which is 1 cm. deep and large enough to completely cover
the windows in the cell department. The curette is first placed
against the window of the phototube housing (right side). The
instrument is then adjusted until the sample in this position reads
100% Transmittance. The curette is then moved left against the
window of the monochromator housing. The Transmittance scale is
then turned until the galvanometer reads zero. The Absorbance is
then read off the transmittance scale. The Absorbance=log.sub.10
I.sub.0 /I where I.sub.0 is the intensity of the incident light and
I is the intensity of the light remaining after passage through the
sample.
EXAMPLE I
(A) Preparation of an Unsaturated Polyester-ester Polyol
An autoclave equipped with a thermometer, stirrer, nitrogen source,
inlet means and heat exchange means was charged with 49 parts (0.5
mole) of maleic anhydride and 2400 parts (0.5 mole) of a polyol
prepared by the reaction of ethylene oxide with a propylene oxide
condensate of glycerol, said polyol having an OH number of 35 and
containing thirteen weight percent of ethylene oxide. The charge
was purged with nitrogen and heated to 150.degree. C. With constant
stirring, 132 parts (3.0 moles) of ethylene oxide was added to the
charge over a period of two hours maintaining the temperature at
150.degree. C. Upon completion of the oxide addition, the reaction
mixture was maintained at 150.degree. C for seven hours.
Thereafter, the reaction mixture was cooled to 25.degree. C. and
discharged from the autoclave. The reaction product was stripped at
100.degree. C. for one hour at less than ten millimeters of mercury
to remove volatiles. The product, a clear liquid, had an OH number
of 33.6, an acid number of 0.12, a refractive index at 25.degree.
C. of 1.4552 and a viscosity at 25.degree. C. of 1875 cps.
(B) Preparation of Graft Copolymer Dispersion
A reaction vessel equipped as described above was charged with a
blend of 150 parts of the unsaturated polyol described in (A),
above, and 150 parts of the saturated polyol described in (A),
above. The amount of unsaturation in the polyol blend was 0.5 mole
per mole of polyol. With stirring and under a slight nitrogen flow,
the charge was heated to 125.degree. C. and a stream of 100 parts
of styrene and of 2.0 parts of azobis(isobutyronitrile) dispersed
in 100 parts of the above-described blend was continuously added to
the charge over a forty-minute period. Upon completion of the
addition, the reaction mixture was maintained at 125.degree. C. for
sixty minutes. The reaction mixture was then stripped of volatiles
for thirty minutes at 90.degree. C. under less than five
millimeters of mercury. The stripped reaction product, a white
opaque dispersion, had a viscosity at 25.degree. C. of 4,700 cps.
and a hydroxyl number of 27.9.
EXAMPLE II
(A) Comparative Example: Use of Polyol Essentially Free From
Unsaturation
A reaction vessel equipped as described in Example I was charged
with 300 parts of the saturated polyol described in Example I. With
stirring and under a slight nitrogen flow, the charge was heated to
125.degree. C. and a stream of 100 parts of styrene and of 2.0
parts of azobis (isobutyronitrile) dispersed in 100 parts of the
saturated polyol was continuously added to the charge over a
forty-minute period. Upon completion of the addition, the reaction
mixture was then stripped of volatiles for thirty minutes at
110.degree. C. at less than ten millimeters of mercury. A
completely coagulated mass of polystyrene in polyol was
obtained.
(B) Comparative Example: Use of Polyol Containing Large amounts of
Unsaturation
A reaction vessel equipped as described in Example I was charged
with 300 parts of the unsaturated polyol described in Example I
(unsaturation level of 1.0 mole per mole of polyol). With stirring
and under a slight nitrogen flow, the charge was heated to
125.degree. C. and a stream of 100 parts of styrene and of 2.0
parts of azobis(isobutyronitrile) dispersed in 100 parts of the
unsaturated polyol was continuously added to the charge over a
forty-minute period. Upon completion of the addition, the reaction
mixture was maintained at 125.degree. C. for sixty minutes. The
reaction mixture was then stripped of volatiles at 120.degree. C.
at less than ten millimeters of mercury. The product, a transparent
liquid, had a hydroxyl number of 28 and a very high Brookfield
viscosity at 25.degree. C. of 19,600 cps.
This example illustrates the differences between the graft
copolymers of the subject invention and those of the prior art.
Using a polyol essentially free from ethylenic unsaturation
resulted in a product with a completely coagulated polystyrene
while use of a polyol containing a mole of unsaturation per mole of
polyol resulted in a liquid product having a viscosity of 20,000
cps. The copolymer of the invention as exemplified by Example I,
was a stable white dispersion having a viscosity of 4,700 cps. This
copolymer finds particular utility in the preparation of flexible
polyurethane foams.
EXAMPLE III
Preparation of Graft Copolymer Dispersions
A reaction vessel equipped as described in Example I was charged
with 66 parts of the unsaturated polyol described in Example I and
264 parts of the saturated polyol described in Example I. The
polyol blend had an unsaturation of 0.2 mole per mole of polyol.
With stirring and under a slight nitrogen flow, the charge was
heated to 115.degree. C. and a mixture of 62.5 parts of
acrylonitrile and 62.5 parts of styrene and 3.1 parts of
azobis(isobutyronitrile) in 170 additional parts of the polyol
blend was continuously added to the charge over a period of two
hours at 115.degree. C. Upon completion of the addition, the
reaction mixture was maintained at 115.degree. C. for one hour. The
reaction mixture was then stripped of volatiles for one hour at
100.degree. C. under less than five millimeters of mercury. The
stripped reaction product had a Brookfield viscosity of 2900 cps.
and a hydroxyl number of 27.1.
The above procedure was duplicated varying the ratio of
acrylonitrile to styrene. The polymer dispersions prepared are
presented in Table I, below.
TABLE I ______________________________________ Percent of monomer
blend Viscosity, OH cps at num- Dispersion Styrene Acrylonitrile
25.degree. C. ber ______________________________________ A 50 50
2,900 27.1 B 60 40 2,730 27.6 C 66 33 2,490 27.8 D 33 66 2,410 26.9
______________________________________
Table I illustrates that the monomer ratio can be changed over a
relatively wide range. To the contrary, if a polyol essentially
free from ethylenic unsaturation is used, the monomer ratio
required for the desired low viscosity is far more limited.
EXAMPLE IV
(A) Preparation of an Unsaturated Polyether Polyol
A stainless steel autoclave equipped with a thermometer, stirrer,
nitrogen source, inlet means and heat exchange means was charged
with 17.6 parts of propylene glycol and 530 parts of a 325
molecular weight polyol prepared by the condensation in the
presence of potassium hydroxide of four moles of propylene oxide
with one mole of glycerol. The charge was purged with nitrogen and
heated to 105.degree. C. With constant stirring, a mixture of
4783.6 parts of propylene oxide and 68.4 parts (corresponding to
0.30 mole per mole of product) of allylglycidylether was gradually
added to the reaction mixture over eight hours. Upon completion of
the oxide addition, the reaction mixture was maintained at
105.degree. C. for six hours at which time the reaction mixture was
cooled to 30.degree. C. and discharged from the autoclave. The
reaction product was treated with an adsorbent, filtered to remove
the catalyst and stripped at 100.degree. C. for one hour under less
than five millimeters of mercury to remove volatiles. The product,
a clear colorless liquid, had a hydroxyl number of 59.3, an acid
number of 0.01, a refractive index at 25.degree. C. of 1.4509, and
a Brookfield viscosity at 25.degree. C. of 480 cps.
(B) Preparation of Dispersion
A reaction vessel equipped as described above was charged with 332
parts of the unsaturated polyol prepared in (A), above. Nitrogen
was bubbled through the polyol for about one hour. With stirring
and under a slight nitrogen flow, the charge was heated to
115.degree. C. and a mixture of 62.5 parts of acrylonitrile and
62.5 parts of styrene and a solution of 3.6 parts of
azobis(isobutyronitrile) in 168 parts of the unsaturated polyol was
continuously added to the charge over a period of one hour at
125.degree. C. Upon completion of the addition, the reaction
mixture was maintained at 125.degree. C. for twenty minutes. The
reaction mixture was then stripped for one hour at 105.degree. C.
under less than five millimeters of mercury. The stripped reaction
product was a homogeneous liquid dispersion having a Brookfield
viscosity at 25.degree. C. of 1772 cps and a hydroxyl number of
48.
EXAMPLE V
A reaction vessel equipped as described in Example I was charged
with 332 parts of the unsaturated polyol described in Example
IV(A), above. Nitrogen was bubbled through the polyol for about one
hour. With stirring and under a slight nitrogen flow, the charge
was heated to 115.degree. C. and a stream of 75 parts of
acrylonitrile and 50 parts of styrene and a suspension of 2.5 parts
of azobis-(isobutyronitrile) in 168 parts of the unsaturated polyol
was continuously added to the charge over a period of ninety
minutes. Upon completion of the addition, the reaction mixture was
maintained at 115.degree. C. for one hour. The reaction mixture was
then stripped for twenty minutes at 115.degree. C. under less than
ten millimeters of mercury. The stripped reaction product was an
off-white liquid having a Brookfield viscosity at 25.degree. C. of
1,300 cps. and a hydroxyl number of 47.
Using a one-quart capacity 33/8 inch diameter cylindrical container
equipped with a Lightnin Model V-7 mixer fitted with a 11/4 inch
diameter shrouded mixing blade and operatively connected to a
rheostat control set at 140 volts, a suitable quantity of polyol,
water, conventional catalysts and silicone surfactant was added to
the containers. The mixture was stirred for about thirty seconds,
allowed to set for about fifteen seconds and then stirring was
resumed. After about sixty seconds elapsed time, the polyisocyanate
was added to the container and the resulting mixture was stirred
for about four to five seconds. The content of the container was
then immediately poured into a cardboard cake box and the foam was
allowed to rise therein. After foam rise was completed, the
resulting foam was oven cured for about fifteen minutes.
The following table, Table II, sets forth the ingredients and
amounts thereof used to prepare the foams, as well as the physical
properties of the foams.
TABLE II ______________________________________ Ingredient: Polyol,
parts .sup.a 300 .sup.b 300 Water, parts 9 9
Bis(2,N,N'dimethylamine-ethyl)ether, ml 0.33 0.33 Silicone
surfactant, ml 3.0 3.0 Stannous octoate, ml 0.7 0.7 80/20 mixture
2,4-2,6 toluene diisocyanate, parts 113 119 TDI index 105 105
Physical properties: Density, lbs./ft..sup.3 1.85 1.90 Tensile
strength, p.s.i. 19.6 13.9 Percent elongation 130 200 Tear, p.i.
2.7 2.6 I.L.D.: Sample thickness, in 1.03 1.04 Load at 25%
deflection 2.1 1.2 Load at 65% deflection 4.5 2.4 Load at 25%
return 1.3 0.8 Sag factor 2.1 2.1 Guide factor 1.2 0.6 C.L.D.
(p.s.i.): Load at 25% deflection 0.91 0.48 Load at 65% deflection
1.61 0.89 Compression sets: Percent set at 50% compression 6.3 3.9
Percent set at 90% compression 6.2 4.1 Air flow, c.f.s. 0.35 1.15
______________________________________ .sup.a Polyol prepared in
Example V, above. .sup.b Polyol prepared by reaction of propylene
oxide with glycerine (3,000 molecular weight-OH number of 56).
EXAMPLE VI
A series of graft copolymer dispersions was prepared following the
procedure described in Example I. In all cases, (1) a ratio of 10
parts of acrylonitrile to 7.5 parts of styrene was employed; (2)
5.3 weight percent azobis (isobutyronitrile) was employed; (3) a
temperature of 125.degree. C. was employed; and (4) the addition of
the monomers and the catalyst occurred in about eighty minutes,
followed by a sixty-minute reaction period. The only variable in
the series was the polyol employed. As a control, an essentially
saturated polyol was used. This polyol is the polyol described in
Example IV. Unsaturated polyols were then prepared by replacing
some of the propylene oxide with allylglycidyl ether. The amount of
allylglycidyl ether was varied to prepare polyols of differing
degree of unsaturation. Table III below illustrates graft copolymer
dispersions prepared and the physical properties of the
dispersions.
TABLE III ______________________________________ Polyol Graft
copolymer dispersion Unsatu- Allyl- ration in Viscosity, Percent
glycidyl polyols cps., 25.degree. Absorb- trans- ether, moles
meq./gm.* C. ance mitted ______________________________________ A
0.00 0.045 2,545 1.066 8.59 B 0.30 0.105 2,420 0.426 37.5 C 0.45
0.153 2,425 0.180 66.2 D 0.75 0.175 2,485 0.148 71.1
______________________________________ *Millequivalents per
gram.
EXAMPLE VII
Following the procedure described in Example I, a series of polyols
was prepared with varying levels of unsaturation. The base polyol
employed was a 3,000 molecular weight propylene oxide adduct of
glycerine (OH number of 56). Maleic anhydride was employed to
impart unsaturation to the polyols. A weight ratio of 85:40
acrylonitrile to styrene monomers was employed. All of the polyols
were then employed in the preparation of polyurethane foams as
described in Example V. The polyols prepared and physical
properties thereof, as well as the physical properties of the foams
resulting therefrom, are presented in Table IV, below. All foams
were prepared using the following ingredients and amounts
thereof.
______________________________________ Polyol, grams 300 Water,
grams 9.0 Bis(2 N,N'dimethylamineethyl)ether, ml. 0.33 Silicone
surfactant, ml. 3.0 Stannous octoate, ml. 0.72 TDI (80/20-2,4-,
2,6-isomer mixture), Index 105
______________________________________
TABLE IV
__________________________________________________________________________
Polyol: Moles of unsaturation (g) (b) 0.2 0.4 0.6 0.8 1.0
Viscosity, cps. at 25.degree. C 450 1,075 1,510 1,560 2,750 3,290
4,110 Physical properties of foam: Density, lb./ft..sup.3 1.92 1.88
1.84 1.83 1.87 1.85 1.86 Tensile strength, p.s.i. 14.1 20.4 19.3
18.8 19.2 18.1 18.5 Percent elongation 177 133 122 115 105 103 105
Tear, p.i. 2.6 2.5 2.5 2.3 2.5 2.4 2.3 I.L.D.: Sample thickness, in
1.01 1.06 1.04 1.04 1.06 1.05 1.06 Load at 25% deflection 1.2 2.2
2.3 2.4 2.7 2.6 2.6 Load at 65% deflection 2.6 4.6 4.7 5.1 5.7 5.5
5.2 Sag factor 2.15 2.08 2.03 2.10 2.13 2.09 2.03 Guide factor 0.6
1.2 1.3 1.3 1.4 1.4 1.4 C.L.D.: Load at 25% deflection 0.56 0.94
0.97 0.96 1.07 1.05 1.07 Load at 65% deflection 1.00 1.56 1.59 1.73
1.90 1.83 1.85
__________________________________________________________________________
.sup.a Polyol employed was propylene oxide adduct of glycerine (OH
number of 56), essentially free from unsaturation. .sup.b Polyol
employed was propylene oxide adduct of glycerine (OH number of 56),
essentially free from unsaturation, in which was polymerized the
85:40 acrylonitrile-styrene monomer mixture.
Table IV illustrates that the use of polyols containing minor
amounts of unsaturation positively affects the load-bearing
properties of polyurethane foams prepared therefrom. Furthermore,
the Table shows that an increase in unsaturation from 0.6 mole to
0.8 mole per mole of polyol does not improve the load-bearing
properties of the foams.
EXAMPLE VIII
(A) Preparation of an Unsaturated Polyether-ester Diol
A stainless steel autoclave equipped with a thermometer, stirrer,
nitrogen source, inlet means and heat exchange means was charged
with 123 parts (1.25 moles) of maleic anhydride and 5,000 parts
(2.5 moles) of a 2,000 molecular weight polyol prepared by the
condensation of propylene oxide with propylene glycol in the
presence of potassium hydroxide (OH number of 56.5). The charge was
purged with nitrogen and heated to 175.degree. C. With constant
stirring, 326 parts (5.62 moles) of propylene oxide was gradually
added to the reaction mixture over 0.5 hour. Upon completion of the
oxide addition, the reaction mixture was maintained at 175.degree.
C. for eleven hours, at which time the reaction mixture was cooled
to 30.degree. C. and discharged from the autoclave. The reaction
product was stripped at 100.degree. C. for one hour under less than
five millimeters of mercury to remove unreacted propylene oxide.
The product, a clear golden yellow liquid, had a hydroxyl number of
54.9, an acid number of 0.34, a refractive index at 25.degree. C.
of 1.4510 and a Brookfield viscosity at 27 C. of 475 cps.
(B) Preparation of Graft Copolymer Dispersion
A reaction vessel equipped as described above was charged with 350
parts of the unsaturated polyol prepared in (A), above. The vessel
was purged with nitrogen and with stirring and under a slight
nitrogen flow, the charge was heated to 115.degree. C. and a
mixture of 62.5 parts of acrylonitrile and 62.5 parts of styrene
and a solution of 2.5 parts of azobis-(isobutyronitrile) in 150
parts of the unsaturated polyol was continuously added to the
charge over a period of one hour at 115.degree. C. Upon completion
of the addition, the reaction mixture was maintained at 115.degree.
C. for twenty minutes. The reaction mixture was then stripped for
one hour at 105.degree. C. under less than five millimeters of
mercury. The stripped reaction product was a white homogeneous
liquid dispersion having a Brookfield viscosity at 25.degree. C. of
1725 cps. and a hydroxyl number of 45.3.
(C) Preparation of Polyurethane Foam
Following the procedure described in Example V, above two
polyurethane foams were prepared. The ingredients and amounts
thereof, as well as the physical properties of the foams, are
presented below.
TABLE V ______________________________________ Ingredient: Polyol
A, gm 225 225 Polyol B, gm 75 Polyol C, gm 75 Water, gm 10.5 10.5
Triethylenediamine (30% solution in dipropyl- ene glycol), ml 1.1
1.1 N-ethylmorpholine, ml 0.5 0.5 Silicone surfactant, ml 2.3 2.3
Stannous octoate, ml 0.25 0.25 80/20 2,4- 2,6-toluene dilsocyanate,
gm 135 135 TDI index 105 105.5 Physical properties: Density,
lbs./ft..sup.3 1.8 1.8 Tensile strength, p.s.i. 14.9 16.9 Percent
elongation 175 161 Tear, p.i. 2.5 2.1 I.L.D.: Sample thickness, in
1.05 1.05 Load at 25% deflection 1.25 1.55 Load at 65% deflection
2.65 3.15 Load at 25% return 0.85 1.0 Sag factor 2.10 2.04 Grade
factor 0.7 0.85 C.L.D. (p.s.i.): Load at 25% deflection 0.54 0.66
Load at 85% deflection 0.92 1.06 Compression sets: Percent set at
50% compression 4.7 6.4 Percent set at 90% compression 5.2 6.0 Air
Flow, c.f.s 2.36 1.39 ______________________________________ Notes:
Polyol A = Ethylene oxide capped adduct of 3,000 molecular weight
propylene oxide adduct of glycerol (OH number of 56, 10% by weight
of ethylene oxide). Polyol B = 2,000 molecular weight propylene
oxide adduct of propylene glycol. Polyol C = Unsaturated polyol
prepard in Example VIII(A), above.
EXAMPLE IX
Preparation of Graft Copolymer Dispersions
A reaction vessel equipped as described in Example I was charged
with 66 parts of the unsaturated polyol prepared in Example IV(A).
With stirring and under a slight nitrogen flow, the charge was
heated to 125.degree. C. and a mixture of 10 parts of
bis(.beta.-chloroethyl)vinyl phosphonate and 5 parts of styrene and
0.87 part of azobis(isobutyronitrile) in 19 parts of the polyol
blend was continuously added to the charge over a period of one
hour at 125.degree. C. Upon completion of the addition, the
reaction mixture was maintained at 125.degree. C. for one hour. The
reaction mixture was then stripped of volatiles for one hour at
125.degree. C. under less than five millimeters of mercury. The
stripped reaction product had a Brookfield viscosity of 1120 cps.,
a hydroxyl number of 29.5, a phosphorus content of 1.35%, and a
chlorine content of 3.4%.
EXAMPLE X
(A) Preparation of an Unsaturated Polyether Polyol
A stainless steel autoclave equipped with a thermometer, stirrer,
nitrogen source, inlet means and heat exchange means was charged
with 20.4 parts of propylene glycol and 292 parts of a 335
molecular weight polyol prepared by the condensation in the
presence of potassium hydroxide of four moles of propylene oxide
with glycerine. The charge was purged with nitrogen and heated to
105.degree. C. With constant stirring, a mixture of 4579 parts of
propylene oxide and 39 parts of allylglycidylether (0.3 mole per
mole of polyol) was gradually added to the reaction mixture over
0.5 hour. Upon completion of the oxide addition, the reaction
mixture was maintained at 105.degree. C. for eight hours.
Thereafter, 870 parts of ethylene oxide as added to the reactor
over ninety minutes at a temperature of 105.degree. C. After this
addition, the reactor is heated at 105.degree. C. for one hour at
which time the reaction mixture was cooled to 30.degree. C. and
discharged from the autoclave. The reaction product was treated
with an adsorbent, filtered to remove the catalyst and stripped at
100.degree. C. for one hour under less than five millimeters of
mercury to remove unreacted propylene oxide. The product, a clear
golden yellow liquid, had a hydroxyl number of 33, an acid number
of 0.01, a refractive index at 25.degree. C. of 1.4534 and an
unsaturation level of 0.105 meq./gm.
(B) Preparation of Graft Copolymer Dispersion
A reaction vessel equipped as described above was charged with 350
parts of the unsaturated polyol prepared in (A), above. Nitrogen
was bubbled through the polyol for about one hour. With stirring
and under a slight nitrogen flow, the charge was heated to
85.degree. C. and a mixture of 10 parts of glycidyl methacrylate,
95 parts of vinylidene chloride and 20 parts of ethylacrylate and a
solution of 1.3 parts of azobis(isobutyronitrile) in 150 parts of
the unsaturated polyol was continuously added to the charge over a
period of one hour at 85.degree. C. Upon completion of the
addition, the reaction mixture was maintained at 85.degree. C. for
one hour. The reaction mixture was then stripped for one hour at
85.degree. C. under less than five millimeters of mercury. The
stripped reaction product was an opaque liquid dispersion having a
Brookfield viscosity at 25.degree. C. of 3250 cps. and a hydroxyl
number of 26.1.
EXAMPLE XI
Preparation of Graft Copolymer Dispersion
A reaction vessel equipped as described in Example I was charged
with 750 parts of the unsaturated polyol prepared in Example IV(A).
Nitrogen was bubbled through the polyol for about one hour. With
stirring and under a slight nitrogen flow, the charge was heated to
115.degree. C. and a stream of 250 parts of ethyl hexyl acrylate
and a solution of 5.0 parts of azobis(isobutyronitrile) in 250
parts of the unsaturated polyol was continuously added to the
charge over a period of three hours at 115.degree. C. Upon
completion of the addition, the reaction mixture was maintained at
115.degree. C. for one hour. The reaction mixture was then stripped
for one hour at 115.degree. C. under less than five millimeters of
mercury. The stripped reaction product was a transparent liquid
having a Brookfield viscosity at 25.degree. C. of 950 cps. and a
hydroxyl number of 46.2.
EXAMPLE XII
(A) Preparation of an Unsaturated Polyol
A reaction vessel equipped as described in Example I was charged
with 300 parts (0.1 mole) of a 3,000 molecular weight propylene
oxide adduct of glycerine (OH number of 56) and 0.11 part of sodium
and heated to 120.degree. C. to 130.degree. C. until the sodium was
dissolved. Thereafter the charge was cooled to 85.degree. C. and
over a twenty-minute period 14.2 parts (0.1 mole) of glycidyl
methacrylate was added thereto with constant stirring. After the
addition of the methacrylate, the reaction mixture was heated for
thirty minutes at 70.degree. C. with an adsorbent and filtered to
remove the catalyst. The product was a slightly brown clear liquid
having a hydroxyl number of 55.
(B) Preparation of Graft Copolymer Dispersion
Following the procedure described in Example I, a graft copolymer
dispersion was prepared from the following ingredients and amounts
thereof:
180 parts of the saturated polyol described in (A), above
20 parts of the unsaturated polyol prepared in (A), above
30 parts of styrene
20 parts of acrylonitrile
1 part of azobis(isobutyronitrile)
The resulting white and uniform dispersion had an OH number of 45.5
and a Brookfield viscosity at 25.degree. C. of 2150 cps.
* * * * *