CA1131656A - Acyl capped quinone-coupled polyphenylene oxides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

New polymers comprising acyl capped quinone-coupled Polyphenylene oxides are described. The resulting new polymers have improved color and in combination with styrene resins provide thermoplastic compositions having improved chemical and physical properties.

Description

` RD 8133 ~3~

This invention relates to acyl capped quinone-coupled polyphenylene oxides, the uncapped polymers being generally described in my United States patents 4,L56,699 issued May 29, 1979, 4,156,770 issued May 29, 1979 and 4,234,706 issued ~lovember 18, 1980, all assigned to the present asslgnee .
Hay et al United States patent 4,048,143 issued September 13, 1977 discloses the capping of polyphenylene oxides having an average hydroxyl group per molecule value of 1.0 or less, as described in various United States patents including Hayls United States patents 3,306,875 issued February 28, 1967, 3,914,266 issued October 21, 1975 and 4,028,341 issued June 7, 1977, and Olander's United States patents 3,956,242 issued May 11, 1976, 3,965,069 issued June 22, 1976, 3,972,851 issued August 3, 1976 and 4,054,553 issued October 18, 1977.
In my aforesaid United States patents, new quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greatçr than 0, including 2.0 or less, are described. These new polymers can be acyl capped to form new polymers having increased oxidative and thermal stability.
This invention embodies new acyl capped quinone-coupled polyphenylene oxldes having increased oxidative and thermal stability.
Broadly, the new acyl capped quinone-coupled poly-phenylene oxides are illustrated by the formula:

(I) P` ~ C ( ~ ~ ~OEO ~ 3 C - R, . RD 8133 ~3~S~

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 at least equal to 10 and is preferably 40 to 500, 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, R is alkyl, cycloalkyl, aryl or mixtures thereof. A presently preferred acyl capped quinone-coupled polyphenylene oxide is of formula (I) above wherein independently each R' is hydrogen, a hydrocarbon radical, a halohydrocarbon radical, and even more preferably is a methyl radical, R" being hydrogen.
Broadly, the acyl capped quinone-coupled polyphenylene o~ides can be prepared by reacting a quinone-coupled polyphenylene oxide with an acylating capping agent as described in George R. Loucks et al United States patent 4,140,675 issued February 20, 1979 and assigned to the present assignee. Illustra-tive of quinone-coupled polyphenylene oxides are compounds of the following formula: :

(I~) H J O - ~ EO ~ O ~ -wherein independently each -~OEOt- 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 lease equal to 10 and more preferably 40 to 500, and R is hydrogen, a hydrocarbon radical, a halohydrocarbon radical, a hydrocarbonoxy radical or a halohydrocarbonoxy radical.

~3ll J

~ 5~ R~ 8133 Illustrative of acylating capping agents are compounds of the following formulae:
o (III) R-C-X

O O
,. .-(IV) R-C-O-C-R
including mixtures thereof, wherein R as defined hereinbefore is alkyl, cycloalkyl, aryl or mixtures thereof, such as alkaryl, alkcycloalkyl, aralkyl, arcycloalkyl, cycloalkaryl, etc., and X is chlorine, bromine, fluorine or iodine.
Preferred R groups contain from about 1 to about 30 carbon atoms, and more preferably contain from about l to about 20 carbon atoms.
Representative examples of specific acylating capping agents include the following:
(A) monoacyl halides of formula (III) above, e.g.
acetyl fluoride, acetyl chloride, acetyl bromide, the propionyl halides, butyryl halides, stearoyl halides, benzoyl chloride, toluoyl halides, naphthoyl halides, cinnamoyl halides, etc.;
(B) anhydrides of monocarboxylic acids of formula (IV) above, e.gO acetic anhydride, propionic anhydride, octanoic anhydride, benzoic anhydride, toluic anhydride butyric anhydride, pivalic anhydride, m-dichlorobenzoic anhydride, ~,3,4,5,6-tentachlorobenzoic anhydride, pentaoic anhydride, palmatoic anhydride, stearic anhydride, etc;
Broadly, the acyl capped quinone-coupled polyphenylene oxides can be prepared by contacting a quinone-coupled polyphenylene oxide with an acylating capping agent in the presence of an aqueous solution of a water soluble base and a catalytic phase transfer agent. Any amount of acylat~ng agent can be employed, however, for obvious reasons, ~3~6~6 RD 8133 economic primarily, the amount of acylating agent employed is preferably the stoichiometric amount required to react with all of the hydroxyl groups associated with the reaction products of quinone-coupled polyphenylene oxides. Accordingly, the quantities of acylating agent employed can vary from 1/10 to 1/100 or 1/1000 times the stoichiometric requirements required to completely cap all of the hydroxyl groups associated with the polymer. Excess capping agent is advantageously employed when a quinone-coupled polymer reaction medium contains primary, secondary or tertiary amines, on a weight basis, in excess of 1-1/2 to 2~ based on the weighk of polymer, since undesirable competitive side reactions can occur involving amines and the capping agent.
Illustratively, any water soluble base can be employed to prepare my compositions, e.g. any aqueous solution of an alkaline metal or alkaline earth metal hydroxide or carbonate. Specific examples include aqueous solutions of potassium hydroxide, sodlum hydroxide, sodium monocarbonate, barium carbonate, etc. Any amount of water soluble base can be employed, however, generally effectiye mole porportions relatlve to the amount of acylating agent that can be employed effectively are acylating agent: water soluble base proportions of from about 1:100 to about 50:1 -and more frequently within the range of ~rom about 1:10 to about 10:1.
Illustratively, any catalytlc phase transfer agent can be employed to prepare my compositions, e.g. any quaternary ammonium, quaternary phosphonium, tertiary sulfonium compound, or mixture thereof. Specific examples can be described by the formulas:

~3~ 133 E ` + LR-~N_~ Y ;

~-P-R'~ Y , ~ ~Rl~ y~ ;

L'_S~R Y , ~R'-S-R~ Y

Any amount of phase catalytic phase transfer agent can be employed relative to the amount of water soluble base and effective molar proportions of catalytic phase transfer agent to water soluble base are within the range of from about l:l0 to about l:l000 and more frequently within the range of from l:l00 to l:l000.
The acylating reaction can be carried out at any reaction temperature but preferably is carried out at temperatures within the range of from 0 to 150 C. or even higher, more preferably from 50 C. to 100 C.
~XAMPLE I
(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 l.
toluene, 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 l.0 l.), 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 l0 SCFH
while vigorously agitating the admixture, 1600 g. of - ~3~5~ RD 8133

2,6-xylenol dissolved in 1.8 l. toluene was pumped into the reactor over a 30 minute period. Summarily, the reaction parameters relative to molar ratios of 2,6-xylenol:Cu:
DBEDA:DMBA: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 tPrminated.
(B) Catalyst Deactivation The reaction was terminated after 58 minutes (measured from start of monomer addition) by replacing oxy~en with nitrogen and the addition of 16.0 ml. 38%
Na3EDTA in water. Polymer analysis showed an ~n~ 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 the polymer sample collected on a filter, washed with methanol and dried in a circulating air oven at 80 C.
showed an ~n] equal to 0.53 dl./g., and an OH absorbance of 0.139 units.
(D) Acyl Capping (1) one-half of the resulting quinone-coupled polyphenylene oxlde reaction mix-ture was cooled to 60 C., transferred to a 2.5 gallon stainless steel reactor equipped with a high-shear stirrer (polytron homogenizer), nitrogen inlet tube and heating coils. 35.5 ml. of a 10% solution of Al~quatR 336 in toluene and 16.7 g.50% aqueous NaOH was added. The mixture was stirred vigorously under nitrogen for 2 minutes and then 19.7 ml. acetic anhydride in 30 ml.

~3~ D 8133 toluene was added over a 3 minute period. The reaction mixture was diluted with an equal volume of toluene, washed with an equal volume of water and passed through a liquid-liquid centrifuge to remove the aqueous phase. Methanol was added to precipitate the aceta-te capped polymer. Polymer analysis a~ter methanol washing and drying showed an intrinsic viscosity n equal to 0.53/dl./g. as measured in chloroform at 25 C., a hydroxyl end group infrared absorbtion at 3610 cmO 1 of 0.004, and a nitrogen content of 1038 ppm.
(2) The remaining half of the resulting quinone-coupled polyphenylene oxide reaction mixture was acetylated and washed as described in (D)(l) above, then isolated by steam precipitation by spraying the capped quinone-coupled polyphenylene oxide reaction mixture with steam through a nozzle into water at 95 C. at a rate sufficient to provide rapid azeotropic removal o~ toluene and other materials such as amines. The steam precipitated solid polymer is collected on a filter, washed with additional water and dried at 90 C. in a circulating air oven. Polymer analysis showed an intrinsic viscosity ~n~ equal to 0.53 dl./g., and OH absorbance at 3610 cm. 1 of 0.001 units, in a nitrogen content of 1267 ppm.
A summary o~ polymer processing and results are set out in Table I hereafter:
T~BLE I

OH
ReactOon n Absorbance_ Process Step(s) Temp. C. dl./g. @ 2~610 cm.
(A) Polymer Preparation, and (B) Catalyst Deactivation 25-40 0.59 0.042 (C) Quinone Coupling 50-95 0.53 0.139 (D) Acyl Capping 60 (1) Methanol Precipitation 0.53 0.004 (2) Steam Precipitation 0.53 0.001 ~3~56 RD ~133 As illustrated by the foregoing examples, acyl halides can be reacted with quinone-coupled polyphenylene oxides to form acyl capped quinone-coupled polyphenylene oxides. Preferred acyl capped polymers are polymers wherein substantially all available hydroxyl components have been end capped so that the hydro~yl content of the resulting polymer is essentially nil.
The acyl capped quinone-coupled polyphenylene oxides can have any intrinsic viscosity and any number average molecular weight Mn. Presently preferred polymers generally have an Mn value of 5,000 to 60,000, more preferably 15,000 to 30,000, 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 dies, pigments, stabilizers, flame retardant additives with beneficial results.

Claims (12)

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

1. An acyl capped quinone-coupled polyphenylene oxide of the formula:
(I) , 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, 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, and R is an alkyl, cycloalkyl or aryl radical.

2. A claim 1 compound, wherein ?OEO? is of the formula:

wherein R' and R" are as defined hereinbefore.

3. A claim 1 compound, wherein the sum of a plus b is at least equal to 10.

4. A claim 1 compound, wherein the sum of a plus b is equal to 40 to 500.

5. A claim 1 compound, wherein each R' is hydrogen, a hydrocarbon radical, or a halohydrocarbon radical.

6. A claim 5 compound, wherein each R and R' is a methyl radical and R" is hydrogen.

7. A process for capping quinone-coupled polyphenylene oxides which comprises contacting quinone-coupled polyphenylene oxides with a capping agent selected from the class consisting of monoacyl halides, monosulfonyl halides, anhydrides of monocarboxylic acids, alkyl halides, or dialkylsulfates, wherein said contacting is carried out at a temperature within the range of from about 0°-150° C. in the presence of a water soluble base and a catalytic phase transfer agent.

8. A claim 7 process, wherein the quinone-coupled polyphenylene oxide is of the formula , 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, 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 halohydrocar-bonoxy radical having at least two carbon atoms between the halogen atoms and phenol nucleus, R" being the same as R' and, in addition, halogen, and wherein the monoacyl halides, mono-sulfonyl halides, anhydrides of monocarboxylic acids, alkyl halides, and dialkylsulfates are of the formulae, respectively:

, R - SO2 - X, , R - X, R - 0 - SO2 - 0 - R, including mixtures thereof, wherein R is alkyl, cycloalkyl, aryl or mixtures thereof, and X is chlorine, bromine, fluorine, or iodine.

9. A claim 8 process, wherein the water soluble base is selected from alkali metal or alkaline earth metal hydroxide or carbonate bases and the catalytic phase transfer agent is selected from quaternary ammonium, quaternary phosphonium, tertiary sulfonium compounds or mixtures thereof.

10. A claim 9 process, wherein R' is hydrogen, a hydrocarbon or a halohydrocarbon radical and the sum of a plus b is at least 10.

11. A claim 10 process, wherein each R' is a hydro-carbon radical and the sum of a plus b is 40 to 170.

12. A claim 11 process, wherein each R and R' is a methyl radical.