Urethane-coupled block polymers of quinone-coupled polyphenylene oxides

Linear, branched and/or cross-linked urethane-coupled block polymers of quinone-coupled polyphenylene oxides are described. The polymers are prepared by contacting polyfunctional isocyanates with quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greater than zero including 2.0 or less. The polymers either alone or in combination with other polymers can be formed into useful articles of manufacture by conventional molding, extruding, etc., processing techniques.

CROSS REFERENCE TO RELATED APPLICATIONS 
This invention is related to subject matter disclosed in copending U.S. 
application Ser. Nos. 800,635, 800,641, now U.S. Pat. No. 4,156,699, 
800,644, now U.S. Pat. No. 4,165,422, 800,645, now U.S. Pat. No. 
4,156,773, 800,646 now U.S. Pat. No. 4,140,675, 800,647, now U.S. Pat. No. 
4,154,771, 800,648, now U.S. Pat. No. 4,156,772, 800,656, now U.S. Pat. 
No. 4,156,770 filed May 26, 1977, respectively; Ser. Nos. 807,990, now 
U.S. Pat. No. 4,156,771, 808,021, now U.S. Pat. No. 4,158,728, both filed 
June 20, 1977; and Ser. No. 907,589 filed May 19, 1978. All of the 
aforesaid applications are assigned to the assignee of this application, 
and all of the subject matter disclosed and referenced therein is 
incorporated herein in its entirety by reference. 
BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to linear, branched, and/or cross-linked 
urethane-coupled block polymers of quinone-coupled polyphenylene oxides. 
The polymers are prepared by contacting polyfunctional isocyanates with 
quinone-coupled polyphenylene oxides having an average hydroxyl group per 
molecule value greater than zero including 2.0 or less. 
2. Description of the Prior Art 
Self-condensation reactions of certain phenols employing oxygen in 
combination with an effective oxidative coupling catalyst system to form 
prior art polyphenylene oxides, i.e., polyphenylene oxides having an 
average hydroxyl group per molecule of 1.0 or less, are described in 
various U.S. patent applications including Hay's U.S. Pat. Nos. 3,306,879; 
3,914,266; 4,028,341, a continuation-in-part of Ser. No. 441,295, filed 
Feb. 11, 1974, now abandoned; and Olander's U.S. Pat. Nos. 3,956,442; 
3,965,069; 3,972,851 and 4,054,553. 
Block polymers of prior art polyphenylene oxides employing simple 
bifunctional coupling compounds such as diacyl halides, diisocyanates, 
bis(haloaryl)sulfones, etc., are described in White's U.S. Pat. Nos. 
3,793,564; 3,770,850; 3,809,729 and 3,875,256. 
DESCRIPTION OF THE INVENTION 
This invention embodies new linear, branched, and/or cross-linked 
urethane-coupled polymers of quinone-coupled polyphenylene oxides. The 
polymers are prepared by contacting polyfunctional isocyanates with 
quinone-coupled polyphenylene oxides having an average hydroxyl group per 
molecule value greater than zero including 2.0 or less. 
In general, illustrative of the broad group of urethane-coupled block 
polymers of quinone-coupled polyphenylene oxides that are included within 
the scope of this invention are those described, among others, by the 
following model segmented polymer structures: 
##STR1## 
The above illustrative model structures include polyfunctional 
quinone-coupled polyphenylene oxide units represented by --B--, 
polyfunctional coupling agents units represented by --Z-- and 
##STR2## 
etc., and monofunctional polyphenylene oxide units represented by --A, 
which units are described in greater detail hereafter. 
In general, the expression "polyfunctional polyphenylene oxides" as 
employed herein and in the claims includes quinone-coupled polyphenylene 
oxides having an average hydroxyl group per molecule greater than zero 
including 2.0 or less. These polyphenylene oxides--which can be prepared 
by the methods described in U.S. applications Ser. Nos. 800,635 and 
800,646--are described by the formula (II) set out hereafter: 
##STR3## 
wherein independently each --OEO-- is a divalent quinone residue, E is a 
divalent arene radical, either a or b is at least equal to 1, the sum of a 
plus b is preferably at least equal to 10, more preferably 40 to 170, the 
sum of r and s being a number average of from about 0.001 to about 2.0, 
and R is hydrogen, a hydrocarbon radical, a halohydrocarbon radical, a 
hydrocarbonoxy radical or a halohydrocarbonoxy radical. The polyfunctional 
polyphenylene oxide units of the block polymers can be conceptualized by 
the structure of formula (II) above wherein the hydrogen atoms are 
disassociated from the polyhydroxy groups of the quinone-coupled 
polyphenylene oxide, e.g. where r and s are equal to zero. When r and s 
are zero the difunctional radical of formula (II) can be described as a 
quinone-coupled polyphenoxy radical or a divalent phenoxy radical, and for 
brevity can be abbreviated as a polymer segment of the formula --B--. 
In general, the expression "monofunctional polyphenylene oxides" as 
employed herein and in the claims includes polyphenylene oxides having an 
average hydroxyl group per molecule value greater than zero including 1.0 
less. These polyphenylene oxides--which can be prepared by any of the 
methods of the prior art--are described by formula (III) set out 
hereafter: 
##STR4## 
wherein independently each R is the same as in formula (II) above, n is a 
number of at least 1, preferably 10, and more preferably 40 to 170, and m 
being a number average of from 0.001 to about 1.0. The monofunctional 
polyphenylene oxide units of the block polymers can be conceptualized by 
the structure of formula (III) above wherein the hydrogen atom is 
disassociated from the monohydroxy group of the polyphenylene oxide, e.g. 
where m is zero. When m is zero, the difunctional radical of formula (III) 
can be described as a phenoxy radical or a monovalent phenoxy residue, and 
for brevity can be abbreviated as a polymer segment of the formula --A. 
In general, the expression "polyfunctional coupling agent" as employed 
herein and in the claims includes any polyfunctional isocyanate having at 
least two isocyanate coupling reaction sites. The term "polyfunctional 
isocyanate" includes, among others, any di- or tri-functional isocyanates 
illustrated by the formula: 
EQU R"--(NCO).sub.c, (IV) 
where c is a number at least equal to 2, and R" is C.sub.2-8 alkylene, 
e.g., ethylene, propylene, isopropylene, the various isomeric butylenes, 
the various isomeric pentylenes, the various isomeric hexylenes (including 
cyclohexylenes) the isomeric heptylenes, the isomeric octylenes, 
phenylene, biphenylene, i.e., 
##STR5## 
e.g., 2,2'-, 2,3'-, 2,4'-, 3,3'-, 3,4'- and 4,4'- biphenylene; 
bis(phenylene)-C.sub.1-8 alkane, i.e., 
##STR6## 
where R.sub.a is C.sub.1-8 alkylene or alkylidene, e.g., methylene, 
ethylidene, isopropylidene, butylidene, etc. and the various other 
examples given above for R"; biphenylene oxide, i.e., 
##STR7## 
poly (C.sub.2-8 oxyalkylene), having an average of 2 to 10 repeating 
units, i.e., --(R.sub.b --O).sub.p where p is 2-10 and R.sub.b is 
alkylene, examples of which are given above for R", and the 
above-mentioned groups containing a phenylene or biphenylene group, e.g., 
the various phenylenes, biphenylenes, bis(phenylene)-C.sub.1-8 alkanes, 
and (biphenylene) oxides, wherein, one up to the total number of aromatic 
hydrogens have been replaced with halogen, preferably chlorine, and/or 
C.sub.1-8 groups. 
Illustrative of specific examples of a portion of presently preferred 
polyfunctional isocyanates that can be employed are: 
polymethylene diisocyanates, e.g., 
ethylene diisocyanate, 
trimethylene diisocyanate, 
tetramethylene diisocyanate, 
hexamethylene diisocyanate, 
octamethylene diisocyanate, etc.; 
alkylene diisocyanates e.g., 
propylene-1,2-diisocyanate, 
butylene-1,2-diisocyanate, 
butylene-1,3-diisocyanate, 
butylene-2,3-diisocyanate, etc.; 
alkylidene diisocyanates, e.g., 
ethylidene diisocyanate, 
propylidene diisocyanate, 
isopropylidene diisocyanate, etc.; 
cycloalkylene diisocyanates, e.g., 
cyclopentylene-1,3-diisocyanate, 
cyclohexylene-1,2-diisocyanate, 
cyclohexylene-1,3-diisocyanate, 
cyclohexylene-1,4-diisocyanate, etc.; 
aromatic diisocyanates, e.g., 
o-phenylene diisocyanate, 
m-phenylene diisocyanate, 
p-phenylene diisocyanate, 
1-chloro-2,4-phenylene diisocyanate, 
4-chloro-1,3-phenylene diisocyanate, 
4,6-dichloro-1,3-phenylene diisocyanate, 
2,4,6-tribromo-1,3-phenylene diisocyanate, 
2,4,6-trichloro-1,3-phenylene diisocyanate, 
tetrachloro-1,3-phenylene diisocyanate, 
methylene-4,4'-bis(phenyl isocyanate), 
2,4-tolylene diisocyanate, 
2,6-tolylene diisocyanate, 
3,3'-dimethyl-4,4'-biphenylene diisocyanate, 
methylene-4,4'-bis(2-methylphenyl isocyanate), 
2,2', 5,5'-tetramethyl-4,4'-biphenylene diisocyanate, 
1-chloro-2,4-phenylene diisocyanate, 
4chloro-1,3-phenylene diisocyanate, 
4,6-dichloro-1,3-phenylene diisocyanate, 
2,4,6-tribromo-1,3-phenylene diisocyanate, 
2,4,6-trichloro-1,3-phenylene diisocyanate, 
tetrachloro-1,3-phenylene diisocyanate, etc. 
The polyfunctional isocyanate coupling agent residue of the polymers can be 
conceptualized by the structure 
##STR8## 
wherein c is a number equal to 2 or 3, etc., R" being as defined above, 
and for brevity can be abbreviated in the polymer models in FIG. I as a 
polymer segment of the formulas --Z--, or 
##STR9## 
etc. 
In general, the process of preparing urethane-coupled block polymers of 
quinone-coupled polyphenylene oxides comprises contacting polyfunctional 
polyphenylene oxides and polyfunctional coupling agents in the presence of 
an aqueous solution of a water soluble base and a catalytic phase transfer 
agent. Any amount of functional (reactive) polyphenylene oxide and 
coupling agent can be employed, e.g. from 1/1000 to 1000 times the 
stoichiometric requirements required to couple all of the reactive 
polyphenylene oxide. 
Any water soluble base can be employed, however preferably is an aqueous 
solution of a water soluble base, e.g. an aqueous alkaline metal or 
alkaline earth metal hydroxide or carbonate solution. Specific examples 
include aqueous solutions of potassium hydroxide, sodium hydroxide, sodium 
monocarbonate, barium carbonate, etc. Any amount of water soluble base 
(WSB) can be employed. Generally effective mole proportions of WSB 
relative to the amount of coupling agent that are employed are coupling 
agent:water soluble base proportions of from about 1:100 to about 50:1 and 
more frequently from about 1:10 to about 10:1. 
Any catalytic phase transfer agent can be employed, however, preferably is 
a phase transfer agent selected from the group consisting of quaternary 
ammonium, quaternary phosphonium, and tertiary sulfonium compounds or 
mixtures thereof. These catalytic phase transfer agents can be described 
by the formulas: 
##STR10## 
wherein each R' is independently selected from aliphatic hydrocarbon 
radicals having from about 1 to about 30 carbon atoms, preferably from 
about 2 to about 15 carbon atoms, each X.sup.- is selected from the group 
consisting of Cl.sup.-, Br.sup.-, F.sup.-, CH.sub.3 SO.sub.3.sup.-, 
CH.sub.3 CO.sub.2.sup.-, CF.sub.3 CO.sub.2.sup.- or OH.sup.-, and each 
Y.sup.-- is selected from the group consisting of SO.sub.4.sup.--, 
CO.sub.3.sup.--, or C.sub.2 O.sub.4.sup.--. Any amount of catalytic phase 
transfer agent (PTA) can be employed, however generally effective molar 
proportions of PTA relative to the amount of water soluble base are within 
the range of from about 1:10 to about 1:1000 and more frequently within 
the range of from 1:100 to 1:1000. 
The coupling reactions can be carried out at any temperature. Preferably 
temperatures within the range of from 0.degree. to 150.degree. C. or even 
higher, and more preferably from 50.degree. C. to 100.degree. are employed 
.

In order that those skilled in the art may better understand my invention, 
the following example is given which is illustrative of the best mode of 
practicing my invention. 
EXAMPLE I 
(A) Polymer Preparation, and (B) Catalyst Deactivation 
A 2.5 gallon stainless steel reactor equipped with an air-driven paddle 
stirrer, oxygen inlet tube, and water-cooled coil and jacket was charged 
with 150 g. 2,6-xylenol, 2.3 liters of toluene. 1.5 g. of Adogen.RTM. 464, 
i.e. trialkyl(C.sub.8-10)methyl ammonium chloride, 3.4 g. 
N,N'-di-t-butylethylenediamine (DBEDA), 47.5 g. dimethyl-n-butylamine 
(DMBA), 15 g. di-n-butylamine (DBA), and 4.2 ml. of a catalyst stock 
solution formed by dissolving 19.30 g. of cuprous oxide in 500 ml. of a 
chilled 47.2% aqueous hydrobromic acid solution. Oxygen was bubbled 
through the reaction medium at a rate of 8.3 moles per hour and the 
mixture was stirred vigorously. 1350 g. of 2.6-xylenol in 1.5 liters of 
toluene was pumped into the reactor while the reaction temperature was 
maintained at 25.degree..+-.1.degree. C. over a 30-minute period. The 
temperature was then allowed to rise to 35.degree..+-.1.degree. C. After 
the desired reaction product viscosity was obtained the reactor was purged 
of oxygen by passing nitrogen instead of oxygen through the reaction 
medium and a 38% aqueous solution of a trisodium salt of EDTA, i.e. 
ethylenediamine tetraacetic acid was added to deactivate the catalyst 
system. Summarily, the reaction parameters relative to molar ratios of 
2,6-xylenol: Cu:DBEDA:DMBA:Br:DBA were as follows: 1124:1:1:8:43:3.2:10.5. 
______________________________________ 
Summary of Reaction Parameters and 
Properties of Poly(2,6-dimethyl-1,4-phenylene oxide) 
React. React. OH 
Run TMDQ Temp. Time [.eta.] 
Absorbance 
GPC 
No. (%) (.degree.C.) 
(min.) 
(dl./g.) 
@3610cm.sup.-1 
--M.sub.w /--M.sub.n 
______________________________________ 
1 0.91 25-35 103 0.37 0.182 -- 
______________________________________ 
(C) Quinone Coupling 
The reaction mixture as described in sections (A) and (B) above with a 
steady nitrogen sweep was heated to 50.degree. C. and maintained at 
50.degree.-55.degree. C. until the deep orange TMDQ color disappeared 
leaving a very light green solution. Methanol was added to the reaction 
mixture to precipitate the polymer. The polymer was collected on a filter, 
washed with methanol, and dried in a circulating air oven at 90.degree. C. 
______________________________________ 
Summary of Reaction Parameters and 
Properties of 
Quinone-Coupled Poly(2,6-dimethyl-1,4-phenylene oxide) 
React. React. OH 
Run TMDQ Temp. Time [.eta.] 
Absorbance 
GPC 
No. (%) (.degree.C.) 
(min.) 
(dl./g.) 
@3610cm.sup.-1 
--M.sub.w /--M.sub.n 
______________________________________ 
1 &lt;0.001 50-55 .about.90 
0.31 0.301 3.43 
______________________________________ 
(D) Coupling With Toluene 2,4-Diisocyanate 
A solution containing 10 g. of quinone-coupled polyphenylene oxide prepared 
as in part (C) above and 30 ml. monochlorobenzene was added to a 300 ml. 
Waring blender, kept under a nitrogen atmosphere and contacted with 0.5% 
Adogen.RTM. 464 and 1.3 ml. of a 50% aqueous sodium hydroxide solution. 
The mixture was stirred in the blender at maximum speed (high fluid shear 
stress reaction conditions) and 0.19 g. of toluene 2,4-diisocyanate was 
added over a four minute period. Stirring was continued an additional 2-3 
minutes. Toluene was added and the polymer was precipitated by 
acidification with concentrated HCl and the addition of methanol. The 
polymer was filtered and dried in vacuo at 60.degree. C. overnight. 
The intrinsic viscosity of the polymer before coupling was 0.31 dl./g. and 
after coupling was 0.47 dl./g. 
The diisocyanate coupled quinone-coupled polyphenylene oxide phenolic 
hydroxyl absorbance at 3610 cm..sup.-1 (in carbon disulfide) was 0.026 
absorbance units for a 2.5% solution in a 1.0 cm. cell. 
As illustrated by the foregoing example, polyfunctional isocyanates can be 
reacted with quinone-coupled polyphenylene oxides under widely varying 
reaction conditions to form urethane-coupled quinone-coupled polyphenylene 
oxides. Preferred urethane coupled polymers prepared in accordance with 
our process are linear polymers wherein the polymers are essentially 
linear polymers and more preferably are essentially linear polymers 
wherein all available hydroxyl components have been end-capped so that the 
hydroxyl content of the resulting polymer is essentially nil. 
The urethane-coupled quinone-coupled polyphenylene oxides of our process 
can have any intrinsic viscosity and any weight average molecular weight 
M.sub.w. Presently preferred polymers of our process generally have an 
M.sub.w value of 10,000 to 120,000, more preferably 30,000 to 60,000, 
having generally corresponding intrinsic viscosities of 0.17 to 1.7, and 
0.4 to 0.7, respectively. 
The polymers of this invention can be combined with other fillers, 
modifying agents, etc., such as dyes, pigments, stabilizers, flame 
retardant additives with beneficial results.