CA1116637A - Quinone-coupled polyphenylene oxides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Ouinones and polyphenylene oxides are reacted to provide quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greater than the average hydroxyl group value associated with polyphenylene oxide reactants. The resulting new polymers have improved color and in combination with styrene resins provide thermoplastic compositions having improved chemical and physical properties.

Description

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This invention relates to quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greater than the average hydroxyl group value associated with poly-phenylene oxide reactants employed in the reaction with quinones.
Self-condensation reactions of certain phenols employing oxygen in combination with an effective oxidative coupling catalysts 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. Patents No. 3~306~879 dated February 28 ~ 1967 ~ 3 ~ 914 ~ 266 dated October 21 ~ 1975 ~
U.S. patent No. 4~028~341 dated June 7~ 1977 and Olander's U.S. Patents 3~956~442 dated May 11, 1976~ 3~965~069 dated June 22, 1976~ 3~972~851 dated August 3~ 1976~ and U.S.
Patent No. 4 ~ 054 ~ 553 dated October 18 ~ 1977.
Cooper's U.S. patent No. 3 ~ 496 ~ 236 dated February 17 ~
1970 discloses the equilibration of polyphenylene oxide and certain phenols in the presence of a phenoxy radical carried out under oxidizing reacting conditions. My U.S. patent No. 3, 367~ 978 dated February 6~ 1968 discloses the preparation of novel compositions of matter resulting from the reaction of a phenol and a polyphenylene oxide under equilibration reaction conditions, i.e., carried out under oxidizing reaction conditions.
Heretofore, quinone reaction product species known to be most deleterious to the color of polyphenylene oxides have been separated therefrom by precipitating the polymer from a solvent system in which the quinone species are soluble.
Heretofore, multiple solvent precipitation and/or extraction techniques have been employed to remove significant amounts of quinone, e.g., up to one percent of quinone based on the weight of polymers, prior to isolation of prior art polypheny-~ - ."

lene oxides as a solid reaction product suited to further processing to form a suitable commercial end product.
Unexpectedly and advantageously I have found that quinones can be reacted with polyphenylene oxides to form novel quinone-coupled polyphenylene oxides having an average hydroxyl group value greater than the hydroxyl group value associated with the polyphenylene oxide reactants. The resulting quinone-coupled polyph nylene oxides are new com-positions of matter substantially free of quinone color entities, which are suited to the manufacture of thermoplastic compositions having improved chemical and physical properties.
This invention embodies new quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greater than the average hydroxyl group value associated with the polyphenylene oxide reactant.
Broadly, a presently preferred quinone-coupled poly-phenylene oxides are illustrated by the formula:

t R' R'' ~ ~ 0 ~ H

wherein independently each (OZO) is a divalent quinone residue, Z 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, and more preferably 40 to 500, even more preferably 125 to 250, R' is hydrogen, a hydrocarbon radical, a halohydrocarbon radical having at least 2 carbon atoms between the halogen atoms and phenol nucleus, a hydro-3Q carbonoxy radical, or a halohydrocarbonoxy radical having atleast two carbon atoms between the halogen atoms and phenol nucleus, a hydrocarbonoxy radical, or a halohydrocarbonoxy radical having at least two carbon atoms between the halogen atoms and phenol nucleus, R" being the same as R' and, in addition, halogen. A presently preferred quinone-coupled polyphenylene oxide is of formula (I) above wherein in-dependently each R' is hydrogen, a hydrocarbon radical, a halohydrocarbon radical, and even more preferably is a methyl radical, R" being hydrogen.
Representative of the classes of substituents, such as R' and R" which can be associated with a quinone-coupled polyphenylene oxide of formula (I) above are any of the substituents associated and positioned in analogous locations relative to the hydroxyl group of any of the phenol reactants described by Hay and Olander in their U.S. patents and applications referred to hereinbefore.
Accordingly, the descriptions of representative substituents as described by Hay and Olander U.S. Patent.
Broadly, the quinone-coupled polyphenylene oxides can be prepared by reacting polyphenylene oxides containing quinones under any reaction conditions, e.g., time, tem-perature and pressure, which facilitates reaction of at least a portion, and preferably all of any quinone species of polyphenylene oxides, subject to the proviso that the reaction is carried out in a reaction medium substantially free of (1~ any monophenol reactant and (2) any active oxidative coupling catalyst system known to those skilled in the art which promotes self-condensation of mono-phenols to form polyphenylene oxides.
Accordingly, any prior art quinone containing poly-phenylene oxide reaction product can be employed including, illustratively, those of Hay and Olander referred to herein, subject to the proviso that the reaction products be se-parated from substantially all of the active catalyst system as well as substantially all of any unreacted phenol prior to reacting the quinone with the polyphenylene oxide.
Separation of the active catalyst system from the Hay and Olander prepared prior art polyphenylene oxides can be carried out by any means, e.g., by purging oxygen from the reaction medium via inert gas displacement by argon, nitrogen, etc., whereby substantially all of the oxygen or air employed in the oxidative coupling process is -separated from the polymer; by centrifuging the reaction products whereby substantially all of any copper or manganese component of the active catalyst system and/or any unreacted monophenol contained within the aqueous phase reaction products is separated from the organic phase which comprises substantially all of the polyphenylene oxide and quinone plus minor amounts of any primary, secondary or tertiary amines employed in the prior art catalytic processes.
The organic phase as separated from the oxidative

2 a coupling catalyst system and phenol reactant can be employed without further refinement. In the reaction of quinone with polyphenylene oxide, substantially all of the quinone entrained by the polyphenylene oxide reaction products is integrated into the polymer backbone in a nonextractable form. Not limiting my invention to any theory, I believe that the quinone entities are coupled with individual polymer entities in accordance with the following postulated theoretical reaction mechanism:

~ RD-6695 0~ 0 + H ~ 0 ~ H

_ ~ ~ n o il IJ _ ' ~ redistribution H0 ~ >--O / ~ ~ t ~

o ~ o ~o)--~- k~- t~

j(n-m) ~ - v)m where n = number average degree of polymerization and m = 0, 1, 2, 3, ... etc.
In general, any reaction temperature can be employed.
Presently, temperatures of from 0C. to 150C. or even higher, preferably 50C. to 100C. are used. In a preferred embodiment of this invention, the quinone-containing polyphenylene oxide is prepared in accordance with a process employing the hydroly-tically stable catalyst system described in Hay's U.S. Patent No. 3,914,266 dated October 21, 1975, since the quinone-containing polyphenylene oxide reaction products associated with the process after separation from the oxidative coupling catalyst system can be reacted with the quinone at elevated temperatures, e.g., in excess of 50C without deleteriously affecting the intrinsic viscosity of the quinone-coupled polyphenylene oxides, i.e., without decreasing by 10-50%
the value of the intrinsic viscosity associated with poly-phenylene oxide charged to the reaction medium.
Any polyphenylene oxide can be employed regardless of intrinsic viscosity or the amount of quinone contained within ~ 3 ~`~ RD-6695 the polyphenylene oxide charged to the reaction medium prepared according to any of the prior art methods of Hay or Olander.
Broadly, the polyphenylene oxides of Hay and Olander that can be employed are illustrated by the formula ~ R' R-~`
(II) H r ~ ~ H

~ R '' a wherein independently each a is at least equal to 10, pre-ferably 40 to 170, R', R" are as defined hereinbefore with respect to formula (I).
Preferably, the polyphenylene oxides employed in the quinone-coupling reaction is a polyphenylene oxide which contains quinone limited to 1% or less by weight based on the weight of polymer and more preferably contains less than 1% by weight of quinone as well as less than 2% and more preferably less than 1-1/2% by weight of any primary or secondary or tertiary amine.
Polymers prepared herein having enhanced hydroxyl content and being free of known species which are deleterious to polymer color characteristics can be advantageously coupled and/or capped as described in my related U.S.
patents No. 4,156,770 dated May 29, 1979 and No. 4,165,422 dated August 21, 1979 to further enhance their molecular weight and/or color stability, respectively. The resulting quinone-coupled polyphenylene oxide polymer reaction products canbe em-ployed in conjunction with other polymers such as high impact polystyrene, etc., prepared polymer blends as taught by Cizek U.S. patent No. 3,383,435 dated May 14, 1968 in the pre-' - 6 -paration of polyphenylene oxide resin combinations well known to those skilled in the art as Noryl~ resins "Encyclopedia of Polymer Science and Technology", entitled Phenols, Oxidative Polymerization,Vol. _, published by Interscience Publishers (1969).
(A) Polymer Preparation A 2.5 gallon stainless steel polymerization reactor equipped with stirrer, heating and cooling coils, thermo-couples, monomer inlet tube, oxygen/nitrogen inlet tube, reflux condenser and an external circulation loop with pressure gauge to monitor viscosity was charged with 5.81 1.
toluene, 255.9 g. N,N-dibutylamine, 67.2 g. methanol, 6.64 g.
cupric chloride, 10~17 g. sodium bromide and 1.5 g. Aliquate 336, i.e. tricaprylylmethyl-ammonium chloride. Oxygen was bubbled through the stirred mixture and 1600 g. 2,6-xylenol, also known as 2,6-dimethylphenol, dissolved in 1800 ml.
toluene was added over a 40 minute period. The initial heat of reaction brought the temperature up to 40C. which tem-perature was maintained during the course of the reaction.
(B) Catalyst De~activation .
After a total reaction time of 85 minutes, the oxygen flow was replaced with nitrogen and 69.5 g. of an aqueous 38~ trisodium EDTA solution was added. Analysis of the reaction mixture showed a poly(2,6-dimethyl-1,4-phenylene oxide) having an intrinsic viscosity [ r ] equal to 0.62 dl./g. as measured in chloroform as 25C., and a hydroxyl end group infrared absorption at 3610 cm.l of 0.043 units based on a 2.5% solution in CS2 over a 1 cm. path cali-brated against CS2 in a matched cell. Spectrophotometric analysis of the reaction mixture (diluted with benzene and measured over a 1 cm. path at 422 nm.) showed 1~ by weight of 2,6-xylenol had been converted to 3,3',5,5'-tetramethyl-1, ~ RD-6695 4-diphenoquinone (TMDQ).
(C) Quinone Coupling (l) The TMDQ containing reaction mixture during a two hour period was diluted with toluene to a 10% solids level, heated at 50C., washed with an equal volume of water and passed through a Westphalia liquid-liquid centrifuge to remove the aqueous phase which contained copper salts and a portion of the amine. Methanol (2.5 volumes) was added to half of the centrifuged reaction mixture to precipitate the polymer. The polymer was collected on a filter, washed with methanol and dried in a circulating air oven at 80 C.
Polymer analysis showed: [~ ] equal to 0.55 dl./g., an OH
absorbance of 0.090 units, a nitrogen content of 1051 ppm, and a TMDQ content of less than 0.01% by weight based on the weight of 2,6-xylenol TMDQ.
(2) The remaining half of the TMDQ containing mixture was precipitated by spraying with steam through a nozzle into water at 95 C. at a rate sufficient to provide azeotropic removal of toluene and other volatiles, such as amines and methanol. The steam precipitated solid polymer was collected on a filter, washed with additional water and dried at 90C. in a circulating air oven. Polymer analysis showed a yellow pelletized material, an [~ ] equal to Q.55 dl./g., a OH absorbance of 0.25 units, a nitrogen content of 1136 ppm, and a TMDQ content of 0.1% based on the weight of 2,6-xylenol.
A summary of polymer processing and results is set out in Table I.

TABLE I
OH
Reaction [~] Absorbance 1 Process Step(s) Temp. C. dl./g. @ 2610 cm.
(A) Polymer Preparation, plus (B) Catalyst Deactivation40 0.62 0.043 (C) Quinone Coupling (1) Methanol precipitation 40-50 0.55 0.090 (2) Steam precipitation 95 0.55 0.250 (A) Polymer Preparation 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 5.48 1. toluence, 121.2 ml. of a stock catalyst solution, i.e. (29.5 ml. bromine added slowly to a chilled solution of 7.76 g. cuprous oxide and 132.0 g. 2,6- xylenol in methanol, then diluted to 1.0 1.), 4.51 g. N,N'-di(t- butyl)ethylenediamine (DBEDA), 26.5 g.
N,N-dimethylbutylamine (DMBA), and 16.0 g. di(n-butyl)amine (DBA).
Oxygen was bubbled into the resulting admixture at a rate of 10 SCFH while vigorously agitating the admixture, 1600 g. of 2,6-xylenol dissolved in 1.8 1. toluene was pumped into the reactor over a 30 minute period.
Summarily, the reaction parameters relative to molar ratios of 2,6-xylenol: Cu:DBA:Br:DBA were as follows: 1000:1:2:20:8:9.4. The reaction temperature was maintained at 25 C. throughout the monomer addition, and was increased to and maintained at 40 C. until the reaction was terminated.
(B) Catalyst Deactivation The reaction was terminated after 58 minutes (measured from start of monomer addition~ by replacing oxygen with nitrogen and the addition of 16.0 ml. 38% Na3EDTA in water. Polymer anaylsis showed an [~] equal to 0.59 dl./g. and an OH absorbence of 0.042 units.
(C) Quinone Coupling The resulting TMDQ containing reaction mixture was heated under nitrogen at 50 to 60 C. for 30 minutes and then at 95 C. for 15 minutes.
At this point the mixture no longer exhibited the characteristic TMDQ

color. Polymer analysis after methanol precipitation, washing and drying as described in Example I(C)(C) showed an [ ] equal to 0.53 dl./g., and an OH absorbance of 0.139 units.
A summary of polymer processing and results are set out in Table II.
TABLE II

OH
ReactOon [~ ] Absorbance 1 ~Process Step(s) Temp. C. dl./g. @ 2610 cm.

(A) Polymer Preparation, and (B) Catalyst Deactivation 25-40 0.59 0.042 (C) Quinone Coupling 50-95 0.53 0.139 EXAMPLE III
The (A) Polymer Preparation and (B) Catalyst Reactivation processes of Example II, described above, were repeated.
(C) Quinone Coupling The reaction temperature was 60C. Polymer analysis showed an [ ] equal to 0.55 dl./g., and an OH absorbance of Q.055 units.
A summary of polymer processing and results are set out in Table III.
TABLE III
OH

ReactOOn [~] Absorbance 1 Pro-ces-s StepTemp. C. dl./g. @ 2610 cm.

(A~ Polymer Preparation, plus (B) Catalyst Deactivation 40 0.60 0.017 (C~ Quinone Coupling 60 0.55 0.055 EXAMPLE IV
(A) Polymer Preparation A reactor equipped as in Example II was charged with 4.0 1. toluene, 240 g. 2,6-xylenol, 24.0 g. di(n-butyl)amine, 64 g. 50% NaOH in 200 ml. methanol, and 900 ml. methanol.

Oxygen was bubbled through the stirred mixture at 10 SCFH.
After 5 minutes, a solution of 3.97 g. benzoin oxime and 1.10 g. manganese chloride in 100 ml. methanol was added.
A solution containing 2.89 kg. 2,6-xylenol in 1.8 1. toluene was added to the rate of 96 ml./min. An additional 445 ml.
toluene was added to wash in any residual reagents. The reaction temperature was maintained at 28 C.
(B) Catalyst Deac*ivation and Partial Quinone Coupling After 90 minutes the oxygene flow was replaced with nitrogen, the temperature was raised to 40C., and equal volume of water was added, and the aqueous phase was se-parated during a two hour liquid-liquid centrifugation step.
(C~ Additional Quinone Coupling Partial quinone coupling occurred during the centri-fugation step. The resulting polymer solution was further quinone reacted by heating at 60C. for 15 minutes and then 90 C. for 10 minutes. The final reaction mixture was divided into two portions, one for isolation by the addition of two volumes of methanol, the other for isolation by steam pre-cipitation. A summary of product analysis at the various stages of thIs Example is set out hereafter:

TABLE IV

OH
Reaction [~] Absorbance Process Step Temp. C. Isolation dl./g. @ 2610 cm.

(A) Polymer Preparation 28 Methanol Ppt. 0.65 0.036 (B) Catalyst Deactivation, plus Partial Quinone Coupling 40 " " 0.57 0.058 (C) Additional Quinone Coupling 60 " " 0.55 0.085 " " 0.53 0.106 " " 90 Steam Ppt. 0.52 0.163 (A) Polymer Preparation, and (B) Catalyst Deactivation A 2.5 gallon stainless steel reactor equipped with an air-driven paddel stirrer, oxygen inlet tube, and water-cooled coil and jacket was charged with 4.6 1. toluene, a catalyst premix composed of 6.28 g. of cupric chloride, 9.62 g. of sodium bromide, 6.8~ g. of Aliquate~ 336,33.1 g.
N,N-dimethylbutylamine (DMBA), and 42.3 g. di-n-butylamine (DBA). Oxygen was bubbled through the reaction medium at a rate of 10 SCFH with vigorous mixing of the reaction mixture.
2000 g. 2,6-xylenol in 2.4.1. of toluene was pumped into the reactor over a 30-minute period. The temperature of the reaction mixture rose to 45C. and was maintained at 45 C.
until after a total reaction time of 70 minutes, the polymer portion was precipitated with methanol containing 0.5~ acetic acid, filtered was washed, dried in a circulating air oven at 80C. Polymer analysis showed an intrinsic viscosity [~ ] equal to 0.24 dl./g/ and a TMDQ content less than 0.01% based on the weight of 2,6-xylenol. Summarily, the reaction parameters relative to molar ratios of 2,6-xylenol:
Cu:DMBA:Br:DBA were as follows:350:7:7:2:1. The resulting polymer was employed in a series of reactions described hereafter where TMDQ was added to the polymer on a controlled weight percent basis to evaluate the increases in hydroxyl ~OH] content as well as any changes in the intrinsic viscosity of the resulting quinone reacted polymer.
(C) Quinone Coupling A series of reactions were carried out according to the procedure employed in Run No.5 set out in Table V hereafter.
The procedure employed in Run No. 5 was as follows:

A solution of 10 g. of poly(2,6-dimethyl-1,4-phenylene oxide) having an intrinsic viscosity of 0.31 dl./g. dissolved in 80 ml. of toluene at 80 was charged with 3 g. 3,3',5,5'-~ 3~

tetramethyl-4,4-diphenoquinone (TMDQ) and stirred under positive nitrogen pressure. After 34 minutes the TMDQ had dissolved completely to form a clear orange colored solution.
After a total reaction time of one hour the solution was cooled, 400 ml. methanol was added slowly with stirring to precipitate the polymer, the polymer was washed with methanol, and dried at 80C. in a vacuum oven.
A summary of polymer processing and results is set out in Table V.

r ~ 7 -TABLE V
Summary of a Series of Reactions of Low Molecular Weight [ n] 0.3i~
dlo/~. Poly(2.6-dimethYl-1 4-phenylene oxide)s With TMDQ
Time for OH
5ReactO ReactO TMDQ to Absorb- GPC
Run TMDQ TempO Time Dissolve Yield [ n] ence M /M
NoO ~V/o?l (C!2 (minO-) (min.) t%)l (dlo/~o2 at 3610 w n 1 0 80 60 n~aO 98~9 ~31 o22 2~0 2 0~5 80 30 <5 98~8 ~32 ~27 309

3 1 ~ 0 80 30 10 99 ~ 3 ~ ~8 ~ 33 2 O 8

4 l o S 80 60 30 lOl o O ~ 31 ~ 36 2.1 3 80 60 34 99~4 ~32 o48 2~3 6 6 80 60 a 9805 o35 o60 2~6 7 12 ~0 60 2 102~5 ~34 ~57 2~6 83 12 80 60 2 103 ~ 7 o 33 ~ 51 2 ~ 6 9 12 80 15 2104~9 ~35 o67 2~2 12 80 30 2104~9 ~30 ~48 2~4 11 12 80 120 299~3 ~31 ~40 2~7 12 1~5 80 2 298~8 ~34 ~37 2~6 13 105 80 5 298~8 ~31 ~31 2~3 14 1 O 5 80 15 2 99 ~ 5 ~ 29 ~ 35 3 ~ 7 1.5 80 30 30 99 O 0 ~ 31 ~ 36 3 O9 16 105 80 120 30 99~4 ~31 ~37 4~1 17 1~5 50 30 298~2 o35 ~22 2~1 18 1.5 110 30 d 99 ~ 0 ~ 30 ~ 40 2 ~ 8 19 3 50 60 ~98 ~ 2 ~ 35 ~ 23 2 O 1 3 110 60 ~10 99~4 ~27 ~43 2~2 21 12 50 60 a106 O 5 ~ 31 ~ 27 1 O 8 22 12 110 60 50 94O 0 o 25 l o O 3 O 0 1 = Based on weight of initial PPOO
2 = Not completely dissolved at end of reaction periodO
3 = Benzene was the solvent.
n.aO = NonapplicableO

EXAMPLE VI
~ .
35 (A) Polymer Preparation and (B) Catalyst Deactivation A series of poly(2,6-dimethyl-1,4-phenylene oxide)s were polymerized by procedures similar to those described in Examples I, II and V and were separated by methanol precipitation, washed with me~hanol and dried in a circu-40 lating oven at 80 C, The resulting polymers were employed ~ 14 ~

~ RD-6~95 in a series of reactions described hereafter where TMDQ was added to the various polymers on a controlled weight percent basis to evaluate the increases in the hydroxyl content as well as any changes in the intrinsio viscosities of the resulting quinone reacted polymer.
(C) Quinone Coupli~~
A series of reactions were carried out according to the general procedure described by Run NoO 5 in Example V above.
A summary of the polymer processing and results is set out in Example VIo TABLE VI

Summary of a Series of Reactions of High Molecular Weight [n]-0.44 to 1.0 dl./go Poly(2,6-dimethyl-1,4-phenylene oxide)s With TMDQ

ReactO React. OH 3610 cm~
Run TMDQ Time Temp, Yield [n] (dlo/~) Absorbance No~ (minO) (C.) (%)3 Initial Final Initial Final 13 105 60 80 101 O44 o41 ol2 o30 2 3 3 60 80 101 o 44 O 38 o 12 ~ 40 33 6 60 80 97 .44 O44 ol2 O47 4s 3 120 80 98 ~ 50 O 38 ~ 03 ~ 28

5~ 3 1201 309 7 O 50 ~ 38 o O3 ~ 28 66 3 120 ~0 99~ o6~ .49 oO8 ~5 76 3 120 80 99 1 ~ 00 ~ 89 ~ 03 ~ 22 l = Solvent was toluene in Run NosO 1-5, 7 and 80 Solvent was chlorobenzene in Run No. 60 a = Yield was based on initial weight of polymer - 100%.
3 ~ Polymer prepared by a procedure similar to one as set out in Example V.
4~ Polymer prepared by a procedure similar to one as set out in Example I except with diethylamine instead of dibutylamine.
5 = Polymer prepared by a procedure similar to one as set out in Example II except for the omission of the dibutylamine.

~ RD-6695 EXAMPLE VII
(A) Polymer Preparation and (B) Catalyst Deactivation A series of poly(2,6-dimethyl-1,4-phenylene oxide)s were polymerized as described in Example V and were separated by methanol precipitation, washed with methanol and dried in a circulating oven at 80 CO The resulting polymers were employed in a series of quinone coupling reac~ions described hereafter where TMDQ and basic as well as acetic additives were added to the various polymers on a controlled weight percent basis to evaluate the incr~ses in the hydroxyl content as well as any changes in the intrinsic viscosities of the resulting quinone reacted polymerc (C) Quinone Couplin~
A series of reactions were carried out according to the general procedure described by Run NoO 5 in Example V above.
A summary of the polymer processing and results is set out in Example VII hereafter.

RD-66a 5 ~ ~l o ~ ~ ~ o o ~ o ~ o ~o u~ ~ ~
o a Z -1~1 I~n_ co 0~ ~ O c~O O _I ~ ~ o .C

:~ ~ ~ ~ I~ ~ c~ ~o o o ~ ~ ~ ~ a~
~ X V ~ ~ ~ o O O ~ O O O~ o ao a~

o ~ o ~o u~ o o~ o o 1~ o o o o u~ o o ~ ~ Pl, H ~ ~? ~1 ~t ~ E~
P~ C~o.~ E3 ~ ~- V V \~ V o ~ ~ 1 ~ 1oooooooooooooooooo ~8 .C ¦ u o ~ ,~ , ~ C
O

~o ~ o o U~ O V~ _ o U~ o o o~

~o C ~ ~0 c ~ ~a u ~
~ C~ Z U
u~ z, ~ 2 X C~ O _ C~ D ~ X ~ ~
Z ~ U

,,~ o ~ o U~ -.

~ 3 ~ RD-6695 As ;llustrated by the foregoing examples, quinones can be reacted effectively with polyphenylene oxides to form novel quinone-coupled polyphenylene oxide having an average hydroxyl group values greater than the average hydroxyl group value associated with the polyphenylene oxide reactant.

Analogous results are obtained wherein any prior art polyphenylene oxide is employed in the preparation of quinone-coupled poly-phenylene oxides which can contain quinone species of the general formula:

R' R" R" R' o~ O, R' R" R ~ R' wherein R' and R" are as defined hereinbefore, which are other than those employed in the Examples such as TMDQo Other modifications and variations of the present invention are possible in light of the above teachingsO

Claims (8)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. A quinone-coupled polyphenylene oxide of the formula , wherein independently each is a divalent quinone residue, Z is a divalent arene radical, either a or b is at least equal to 1 and the sum of 1 plus b is at least equal to 10, R' is hydrogen, a hydrocarbon radical, a halohydrocarbon radical having at least 2 carbon atoms between the halogen atoms and phenol nucleus, a hydrocarbonoxy radical, or a halohydrocarbonoxy radical having at least two carbon atoms between the halogen atoms and phenol nucleus, R" being the same as R' and, in addition, halogen.

2. A claim 1 compound, wherein is of the formula , where R' and R" are as defined in claim 1.

3. A claim 2 compound, wherein each R' is a methyl radical and R" is hydrogen.

4. A claim 3 compound, wherein the sum of a plus b is at least equal to 40 to 500.

5. A claim 4 compound, wherein the sum of a plus b is equal to 40 to 170.

6. A claim 2 compound, wherein each R' is hydrogen, a hydrocarbon radical, or a halohydrocarbon radical and R"
is hydrogen.

7. A claim 6 compound, wherein the sum of a plus b is at least equal to 40 to 500.

8. A claim 7 compound, wherein the sum of a plus b is equal to 40 to 170.