CA1117692A - Process for the preparation of polyphenylene oxide compositions - Google Patents
Process for the preparation of polyphenylene oxide compositionsInfo
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- CA1117692A CA1117692A CA000314472A CA314472A CA1117692A CA 1117692 A CA1117692 A CA 1117692A CA 000314472 A CA000314472 A CA 000314472A CA 314472 A CA314472 A CA 314472A CA 1117692 A CA1117692 A CA 1117692A
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- impact modifier
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Abstract
ABSTRACT OF THE DISCLOSURE
A process is described for the preparation of a com-position that includes a polyphenylene oxide resin, an alkenyl aromatic resin and a rubbery impact modifier.
The composition is prepared by dissolving polyphenylene oxide and a rubbery impact modifier in an alkenyl aromatic monomer and thereafter heating the mixture to thermally polymerize the alkenyl aromatic monomer.
A process is described for the preparation of a com-position that includes a polyphenylene oxide resin, an alkenyl aromatic resin and a rubbery impact modifier.
The composition is prepared by dissolving polyphenylene oxide and a rubbery impact modifier in an alkenyl aromatic monomer and thereafter heating the mixture to thermally polymerize the alkenyl aromatic monomer.
Description
1~ 7~ 8CI1-2054 This invention provides a novel process for the preparation of polyphenylene oxide compositions that include a rubbery impact modifier and an alkenyl aromatic resin. The process comprises dissolving the polyphenylene oxide and the rubbery impact modifier in the alkenyl aromatic monomer and thereafter heating the mixture to thermally polymerize the alkenyl aromatic monomer.
The term "polyphenylene oxide resin" includes a family of polymers that are well known to those skilled in the art. These polymers may be made by a variety of catalytic and non-catalytic process from the corresponding phenols or reactive derivati~es thereof. By way o~
illustration, certain of the polyphenylene oxides are dis-closed in Hay, U.S. patent Nos 3,306,874 and 3,306,875 both dated February 28, 1967, and in Stamatoff, U.S. patent 3,257,357 dated June 21, 1966 and U.S. patent No. 3,257,388 dated June 21, 1966 to Bower et al.
--~ 3C~1-2054 In the Hay patents, the polyphenylene oxides are prepared by an oxidative coupling reaction comprising passing an oxygen-containing gas through a reaction solution of a phenol and a metal-amine complex catalyst. Other disclosures relating to processes for preparing polyphenylene oxide polymers including graft copolymers of polyphenylene oxides with styrene type compounds, are found in Fox, U.S. 3,356,761; Sumitomo, U.K. 1,291,609; Bussink et al;
U.S. 3,337,499; Blanchard et al, U.S. 3,219,626; Laakso et al, U.S.
3,342,892; Hori et al, U.S. 3,384,619; Faurote et al, U.S.
3,440,217; and disclosures relating to metal based catalysts which do not include amines, are known from patents such as Wieden et al, U.S. 3,442,885 (copper-amidines); Nakashio et al, U.S. 3,573,257 (metal-alcoholate or phenolate); Kobayashi et al, U.S. 3,455,880 (cobalt chelates); Olander, U.S. 3,956,242 and the like. In the Stamatoff patents, the polyphenylene ethers are produced by reacting the corresponding phenolate ion with an initiator, such as a peroxy acid salt, an acid peroxide, a hypohalite and the like, in the presence of a complexing agent. Disclosures relating to non-catalytic processes, such as oxidation with lead dioxide, sllver oxide etc., are described in Price et al, U.S. 3,382,212. Cizek, U.S. 3,383,435 discloses polyphenylene ether-styrene resin compositions. Canadian Patent No. 1,035,881 dated August 1, 1978 to Bennett et al, a process is described for preparing compositions of a polyphenylene oxide, a rubber and an alkenyl aromatic monomer. This process is based on the use of the alkenyl aromatic monomer as the reaction solvent for the phenolic monomer.
After the polyphenylene oxide is formed, the alkenyl aroma-tic monomer is polymerized to an alkenyl aromatic resin by a free radical catalyst. Thermal polymerization of the alkenyl aromatic resin by a free radical catalyst. Thermal polymeriza-tion of the alkenyl aromatic monomer is also mentioned in this application.
~17~ 8CH-2054 The present invention is based on the discovery that a preformed polyphenylene oxide resin may be dissolved in an alkenyl aromatic monomer with a rubhery impact modifier and subjected to a thermal polymerization cycle which results in a composition having improved physical properties over compositions that are prepared using a free radical catalyst.
Accordingly, it is a primary object of this invention to provide an improved process for the preparation of a composition of a polyphenylene oxide, an alkenyl aromatic resin and a rubbery impact modifier.
The invention comprises a process for the preparation of a composition which comprises:
(a) a polyphenylene ether resin;
(b) an alkenyl aromatic resin; and (c) a rubbery impact modifier.
The process comprises forming a mixture which consists essentially of a polyphenylene oxide resin and the rubbery impact modifier in an alkenyl aromatic modifier and thereafter heating the mixture to cause the alkenyl aromatic monomer to polymerize and form a composition of a poly-phenylene oxide, a rubbery impact modifier and an alkenyl aromatic resin.
The polyphenylene oxides may be prepared from phenolic monomers of the formula:
~17~2 8CH-2054 qH
;.. ~ Q, wherein X is substituent selected from the group consisting of hydrogen, chlorine, bromine and iodine, Q is a monovalent substituent selected from the group consisting of hydrocarbon ;-radicals, hydrocarbonoxy radicals, halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the ~- phenol nucleus; halohydrocarbon radicals, having at least two carbons ;, .
between the halogen atom and the phenol nucleus; and Q' and Q"
` are the same as Q and in addition may be halogen, with the proviso that Q,Q' and Q" are all free of a tertiary alpha-carbon atom. Polymer formed fr~r ~ e pheD ~ d to bhe formula:
Q Q" ~;
wherein the oxygen ether atom of one repeating unit is connected ;~ to the phenylene nucleus of the next repeating unit and Q, Q' and Q" are as above defined; an n is an integer equal to at least 50.
The preferred polyphenylene oxides are those wherein Q and Q' are lower alkyl and Q" is hydrogen. Poly (2,6-dimethyl-l,4-phenylene oxide) is the most preferred polyphenylene oxide.
The alkenyl aromatic monomers may be of the formula:
.~ .
; - 4 -.
,: .
Q54~ ~ 7~ ~
C,R = CHR
The term "polyphenylene oxide resin" includes a family of polymers that are well known to those skilled in the art. These polymers may be made by a variety of catalytic and non-catalytic process from the corresponding phenols or reactive derivati~es thereof. By way o~
illustration, certain of the polyphenylene oxides are dis-closed in Hay, U.S. patent Nos 3,306,874 and 3,306,875 both dated February 28, 1967, and in Stamatoff, U.S. patent 3,257,357 dated June 21, 1966 and U.S. patent No. 3,257,388 dated June 21, 1966 to Bower et al.
--~ 3C~1-2054 In the Hay patents, the polyphenylene oxides are prepared by an oxidative coupling reaction comprising passing an oxygen-containing gas through a reaction solution of a phenol and a metal-amine complex catalyst. Other disclosures relating to processes for preparing polyphenylene oxide polymers including graft copolymers of polyphenylene oxides with styrene type compounds, are found in Fox, U.S. 3,356,761; Sumitomo, U.K. 1,291,609; Bussink et al;
U.S. 3,337,499; Blanchard et al, U.S. 3,219,626; Laakso et al, U.S.
3,342,892; Hori et al, U.S. 3,384,619; Faurote et al, U.S.
3,440,217; and disclosures relating to metal based catalysts which do not include amines, are known from patents such as Wieden et al, U.S. 3,442,885 (copper-amidines); Nakashio et al, U.S. 3,573,257 (metal-alcoholate or phenolate); Kobayashi et al, U.S. 3,455,880 (cobalt chelates); Olander, U.S. 3,956,242 and the like. In the Stamatoff patents, the polyphenylene ethers are produced by reacting the corresponding phenolate ion with an initiator, such as a peroxy acid salt, an acid peroxide, a hypohalite and the like, in the presence of a complexing agent. Disclosures relating to non-catalytic processes, such as oxidation with lead dioxide, sllver oxide etc., are described in Price et al, U.S. 3,382,212. Cizek, U.S. 3,383,435 discloses polyphenylene ether-styrene resin compositions. Canadian Patent No. 1,035,881 dated August 1, 1978 to Bennett et al, a process is described for preparing compositions of a polyphenylene oxide, a rubber and an alkenyl aromatic monomer. This process is based on the use of the alkenyl aromatic monomer as the reaction solvent for the phenolic monomer.
After the polyphenylene oxide is formed, the alkenyl aroma-tic monomer is polymerized to an alkenyl aromatic resin by a free radical catalyst. Thermal polymerization of the alkenyl aromatic resin by a free radical catalyst. Thermal polymeriza-tion of the alkenyl aromatic monomer is also mentioned in this application.
~17~ 8CH-2054 The present invention is based on the discovery that a preformed polyphenylene oxide resin may be dissolved in an alkenyl aromatic monomer with a rubhery impact modifier and subjected to a thermal polymerization cycle which results in a composition having improved physical properties over compositions that are prepared using a free radical catalyst.
Accordingly, it is a primary object of this invention to provide an improved process for the preparation of a composition of a polyphenylene oxide, an alkenyl aromatic resin and a rubbery impact modifier.
The invention comprises a process for the preparation of a composition which comprises:
(a) a polyphenylene ether resin;
(b) an alkenyl aromatic resin; and (c) a rubbery impact modifier.
The process comprises forming a mixture which consists essentially of a polyphenylene oxide resin and the rubbery impact modifier in an alkenyl aromatic modifier and thereafter heating the mixture to cause the alkenyl aromatic monomer to polymerize and form a composition of a poly-phenylene oxide, a rubbery impact modifier and an alkenyl aromatic resin.
The polyphenylene oxides may be prepared from phenolic monomers of the formula:
~17~2 8CH-2054 qH
;.. ~ Q, wherein X is substituent selected from the group consisting of hydrogen, chlorine, bromine and iodine, Q is a monovalent substituent selected from the group consisting of hydrocarbon ;-radicals, hydrocarbonoxy radicals, halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the ~- phenol nucleus; halohydrocarbon radicals, having at least two carbons ;, .
between the halogen atom and the phenol nucleus; and Q' and Q"
` are the same as Q and in addition may be halogen, with the proviso that Q,Q' and Q" are all free of a tertiary alpha-carbon atom. Polymer formed fr~r ~ e pheD ~ d to bhe formula:
Q Q" ~;
wherein the oxygen ether atom of one repeating unit is connected ;~ to the phenylene nucleus of the next repeating unit and Q, Q' and Q" are as above defined; an n is an integer equal to at least 50.
The preferred polyphenylene oxides are those wherein Q and Q' are lower alkyl and Q" is hydrogen. Poly (2,6-dimethyl-l,4-phenylene oxide) is the most preferred polyphenylene oxide.
The alkenyl aromatic monomers may be of the formula:
.~ .
; - 4 -.
,: .
Q54~ ~ 7~ ~
C,R = CHR
2 ~= R4 wherein Rl and R2 are selected from the group consisting of 6 lower alkyl or lower alkenyl groups of from 1 tD 6 carbon atoms 7 and hydrogen; R3 and R4 are selected from the group consisting 8 of chloro, bromo, hydrogen and lower alkyl of from 1 to 6 carbon 9 atoms; R5 and R6 are selected from the group consisting of hydrogen and lower alkenyl groups of 1 to 6 carbon atoms or 11 R5 and ~6 may be concatenated together wi~h hydrocarbyl groups 12 to form a naphthyl group. These compounds are free of any 13 substituent having a tertiary carbon atom.
The preferred alkenyl aromatic monomers include 16 styrene, chlorostyrene, vinyl naphthalene, vinyl xylene and 17 alpha-methylstyrene.
19 The rubbery impact modifier may be a polybutadiene rubber, styrene butadiene rubber, nat~ral rubber, neoprene, 21 butyl rubber, ethylene propylene copolymer. EPDMrubbers, 22 acrylonitrile rubber, A-B block copolymer wherein the A represent 23 a polymerized block of styrene and B represents a polymerized 24 block of butadiene or an A-B-A block copolymer wherein A and B
have the same meanings set ~orth hereinabove. The A-~-A block 26 copolymers are described in Zelinski, U.S. 3,251,905 and Holden 27 et al, U.S. 3,231,635 dated January 25, 1966.
29 The compositions of the invention may also be prepared in the presence of reinforcing amounts of a suitable -~/5 CH-205., 1 reinforolng filler. For example, from 5 to 40% by weight based 2 on the weight of the total composition may co~prise fibrous
The preferred alkenyl aromatic monomers include 16 styrene, chlorostyrene, vinyl naphthalene, vinyl xylene and 17 alpha-methylstyrene.
19 The rubbery impact modifier may be a polybutadiene rubber, styrene butadiene rubber, nat~ral rubber, neoprene, 21 butyl rubber, ethylene propylene copolymer. EPDMrubbers, 22 acrylonitrile rubber, A-B block copolymer wherein the A represent 23 a polymerized block of styrene and B represents a polymerized 24 block of butadiene or an A-B-A block copolymer wherein A and B
have the same meanings set ~orth hereinabove. The A-~-A block 26 copolymers are described in Zelinski, U.S. 3,251,905 and Holden 27 et al, U.S. 3,231,635 dated January 25, 1966.
29 The compositions of the invention may also be prepared in the presence of reinforcing amounts of a suitable -~/5 CH-205., 1 reinforolng filler. For example, from 5 to 40% by weight based 2 on the weight of the total composition may co~prise fibrous
3 glas 8 .
The compo~itions preparet in the process of the 6 invention may comprise from lD-90 parts by weight and more 7 preferably from 20-50 parts by weight of a polyphenylene oxide, 8 from go-20 parts by weight and more preferably from 80-50 parts 9 by weight of an alkenyl aromati~ resin; and from 1-20 parts by weight and more preferably from 5-15 parts by weight of a ll rubbery impact modifier.
13 ThP process of the invention may be carried out by 14 di8solving the polyphenylene oxide resin and the rubber in an alkenyl aromatic monomer in a sui~able reactor. If necessary, 16 the reactor may be heated to about 40-60C to aid in dissolving 17 the resin and the rubber. Thereafter the reactor i9 heated for 18 a period of time and at a temperature that is sufficient to cause 19 the alkenyl aromatic monomer to polymerize to form an alkenyl aromatic resin. Generallly temperatures from 105-175C may be 21 employed for reaction cycles of 0.5 to 12 hours depending on 22 the de~ired molecular weight. If temperatures ab~ve the boiling 23 point of the alkenyl aromatic monomer are used, preæsure 24 vessels should be employed to prevent vaporization. Generally the intrinsic viscosity of the alkenyl aromat~e resin may be -26 between 0.20 dl/g and 0;75 dl/g as measured in toluene at 30C.
28 The composition of the phenylene oxide resin and the 29 al~enyl aromatic resin may be passed through a vacuum vented, devolatilizing extruder to polymerize any residual alkenyl aromatie ~ ~. :
~7~ CH-2054 monomer. This is preferably done by passing the composition through the extruder at a temperature that ranges from about 50-300C. The temperature at the feed port of the extruder should be below the boiling point of the alkenyl aromatic monomer to prevent frothing of the composition due to any unpolymerized monomer. The extruder should be operated at a speed of from 10-50 rpm. and if desired from 0.1 to 2.5% by weight of total composition of a peroxide compound may be added. Suitable peroxide compounds include benzoyl peroxide; lauroyl peroxide; octanoyl peroxide;
2,4-dichlorobenzoyl peroxidei l,l-di-t-butyl peroxy-3,5,-5-trimethyl cyclohexane and dicumyl peroxide.
Description of the Preferred Embodiments - The process of the present invention is further illustrated in the following examples which are set forth as further descriptions of the invention, but are not to be construed as limiting the invention hereto.
A 1.5 liter stainless steel resin pot fitted with a stirrer, nitrogen gas inlet and a reflux condenser was used to dissolve 195g of poly(2,6-dimethyl-1,4-phenylene oxide)* and 45g of styrene-butadiene** rubber in 360g of styrene monomer.
* having an intrinsic viscosity of about 0.5 has measured an chloroform at 30C.
** Solprene 1205, a solution polymerized styrene-butadiene block copolymer containing about 75% by weight butadiene.
, /
The resin pot was externally heated by a silicone oil bath at 40-50C to dissolve the poly(2,6-dimethyl-1,4-phenylene oxide) and the rubber. The temperature was raised to the stated temperature for a period of 3 hours. The polystyrene was separated from tl~e composition by extraction with methylene chloride according to the method of Factor U.S. patent No.
3,644,227 dated February 22, 1972. The I.V. of the polystyrene was measured in toluene at 30C.
RunReaction Temperature I.V. dl/g 1 145C 0.62 2 138C 0.58
The compo~itions preparet in the process of the 6 invention may comprise from lD-90 parts by weight and more 7 preferably from 20-50 parts by weight of a polyphenylene oxide, 8 from go-20 parts by weight and more preferably from 80-50 parts 9 by weight of an alkenyl aromati~ resin; and from 1-20 parts by weight and more preferably from 5-15 parts by weight of a ll rubbery impact modifier.
13 ThP process of the invention may be carried out by 14 di8solving the polyphenylene oxide resin and the rubber in an alkenyl aromatic monomer in a sui~able reactor. If necessary, 16 the reactor may be heated to about 40-60C to aid in dissolving 17 the resin and the rubber. Thereafter the reactor i9 heated for 18 a period of time and at a temperature that is sufficient to cause 19 the alkenyl aromatic monomer to polymerize to form an alkenyl aromatic resin. Generallly temperatures from 105-175C may be 21 employed for reaction cycles of 0.5 to 12 hours depending on 22 the de~ired molecular weight. If temperatures ab~ve the boiling 23 point of the alkenyl aromatic monomer are used, preæsure 24 vessels should be employed to prevent vaporization. Generally the intrinsic viscosity of the alkenyl aromat~e resin may be -26 between 0.20 dl/g and 0;75 dl/g as measured in toluene at 30C.
28 The composition of the phenylene oxide resin and the 29 al~enyl aromatic resin may be passed through a vacuum vented, devolatilizing extruder to polymerize any residual alkenyl aromatie ~ ~. :
~7~ CH-2054 monomer. This is preferably done by passing the composition through the extruder at a temperature that ranges from about 50-300C. The temperature at the feed port of the extruder should be below the boiling point of the alkenyl aromatic monomer to prevent frothing of the composition due to any unpolymerized monomer. The extruder should be operated at a speed of from 10-50 rpm. and if desired from 0.1 to 2.5% by weight of total composition of a peroxide compound may be added. Suitable peroxide compounds include benzoyl peroxide; lauroyl peroxide; octanoyl peroxide;
2,4-dichlorobenzoyl peroxidei l,l-di-t-butyl peroxy-3,5,-5-trimethyl cyclohexane and dicumyl peroxide.
Description of the Preferred Embodiments - The process of the present invention is further illustrated in the following examples which are set forth as further descriptions of the invention, but are not to be construed as limiting the invention hereto.
A 1.5 liter stainless steel resin pot fitted with a stirrer, nitrogen gas inlet and a reflux condenser was used to dissolve 195g of poly(2,6-dimethyl-1,4-phenylene oxide)* and 45g of styrene-butadiene** rubber in 360g of styrene monomer.
* having an intrinsic viscosity of about 0.5 has measured an chloroform at 30C.
** Solprene 1205, a solution polymerized styrene-butadiene block copolymer containing about 75% by weight butadiene.
, /
The resin pot was externally heated by a silicone oil bath at 40-50C to dissolve the poly(2,6-dimethyl-1,4-phenylene oxide) and the rubber. The temperature was raised to the stated temperature for a period of 3 hours. The polystyrene was separated from tl~e composition by extraction with methylene chloride according to the method of Factor U.S. patent No.
3,644,227 dated February 22, 1972. The I.V. of the polystyrene was measured in toluene at 30C.
RunReaction Temperature I.V. dl/g 1 145C 0.62 2 138C 0.58
4 120C 0.51 COMPARATIVE TEST A
The effect of peroxide initiated polymerization was studied using the apparatus described in Example 1. The compositions contained the same proportion of the same materials.
The polymerization was initiated with the stated amount of dicumyl peroxide and the polystyrene was isolated according to the method of Example 1:
RunReaction Temperature Amt. of Peroxide I.V. dl/g 145C 1.6g. 0.22 6 138C 1.6g. 0.26 7 130C 1.6g. 0.27 . 25 8 120C 1.6g. 0.34 - 9 145C 0.8g. 0.38 ~176~ 8CH-205~
138C Q.8g. 0.41 11 130C 0.8g. 0.40 12 120C 0.8g. 0.42 13 145C 0.4g. 0.50 14 138C 0.4g. 0.52 130C 0.4g. 0.49 16 120C 0.4g. 0.42 17 145C 0.2g. 0.53 18 138C 0.2g. 0.48 19 130 C 0.3g. 0 r 46 120C 0.2g. 0.39 21 145C O.lg. 0.55 22 138C O.lg. 0.53 23 130C O.lg. 0.48 24 120C O.lg. 0.43 These data shown an overall improvement in I.V. of the type polystyrene produced as one goes to lower amounts of peroxide. When high levels of peroxide are employed, higher I.V. is obtained at lower reaction temperatures. At low peroxide levels, higher I.V. is attained at higher reaction temperatures. The reactions were cut short of maximum attainable I.V. so that the polymers could be removed from the pot without undue difficulty. The best results are obtained with a purely thermal polymerization. Under peroxide-free conditions one also has a more controllable and re-producible reaction.
The procedure of Example 1 was repreated to show the effect of reaction time and inclusion of an impact 1~765~2 modifier on the I.V. of the polystyrene. Runs 25 30 include 360g of styrene, 195g of poly(2,6-dimethyl-1,4-phenylene oxide~ and 45g of rubber of the same type that was employed in Example 1.
Run TimeTemperature I.V. of Polystyrene 1 hour 145C 0.42 dl/g 26 2 hours145C 0.45 dl/g 27 3 hours145C 0.57 dl~g Control (No Rubber) Run TimeTemperature I.V. of Polystyrene 28 1 hour 145C 0.63 dl/g 29 2 hours145C 0.63 dl/g - 30 3 hours145C 0.63 dl/g This example shows that one should let the reaction proceed as long as is practicable.
The composition of Example 1, Run 1 was cut up and extruded through a vacuum vented twin screw extruder at 15-20 RPM with a temperature of 100C at the feed port and 220C at the die. The extruder strand was pelleti~ed and was determined to have 96-98% recoverable solids. The recoverable solids were determined as the weight percent of polymer precipitated from a lO.Og resin sample that was dissolved in 250 ml toluene in a Waring blender. Precipitation was effected by addition of an equal volume of methanol to the agitated solution in a Waring ~ 8CH-2054 blender. The precipitated polymer was dried to constant weight at 75C to determine the percent of recoverable solids. The recoverable solids for the material of Example 1 was 75-85%.
The grafting of polystyrene on the poly(2,6-dimethyl-1,4-phenylene) oxide was estimated to be 3% and the I.V. of the polystyrene - was 0.55. A standard ASTM test bar had a Notched Izod strength of 3.9 ft. lb/in and an HDT temperature of 214C at 264 psi. The procedure of Example 3 was repeated except that dicumyl peroxide was added to the composition prior to extrusion.
COMPARATIVE TEST B
Grafted Izod HDT I.V. of Run Dicumyl Peroxide Polystyrene ft lb/in 265 psi Polystyrene ; 31 0.25~ 7% 3.6 218~C 0.49 dl/g 32 0.50% 18% 3.4 216C 0.43 dl/g - 15 33 0.75% 21% 3.5 220C 0.41 dl/g 34 1.0% 29% 3.3 221C 0.38 dl/g Using the procedure of Example 1, 450g of styrene monomer, 195 g. of poly(2,6-dimethyl-1,4-phenylene oxide)* and 45g. of styrene butadiene rubber** were thermally polymerized.
The resin thus obtained was dissolved in toluene to remove unreacted styrene and recovered by methanol precipitation.
* as in Example 1 ** as in Example 1 The dried powder was extruded, pelletized and molded into test bars. Infra red analysis showed that the dried powder contained 45% by weight of poly(2,6-dimethyl-1,4-phenylene oxide) 50% by weight polystyrene and 5% by weight of the rubber. A portion of the separated polystyrene contained 8% by weight of grafted poly (2,6-dimethyl-1,4-phenylene oxide and had an I.V. of 0.63 dl/g.
The molded bars had an Izod impact (notched) of 3.64 ft lb/in and an HDT of 229F/264 psi.
The procedure of Example 1 was repeated using different rubbery materials. Each composition was extruded using 0.5% by weight of dicumyl peroxide as an additive to the extruder. The compositions was evaluated to determine the I.V.
of the polystyrene and the impact and heat distortion temperature of test bars.
Rubber Modifier I.V. of Polystyrene Notched Izod HDT 264 psi Philprene 1502 0.50 dl/g 4.15 ft lb/in 230C
Solprene 408 0.37 dl/g - _ _ _ _ _ _ 1. Philprene 1502 -an emulsion polymerized SB~ rubber containing about 23.5% bound polystyrene.
2. Solprene 408-a solution polymerized styrene butadiene rubber of 30 parts styrene and 70 part butadiene.
~ 8C~-2054 Rubber Modifier I.V. of Polystyrene Notched Izod HDT 264 psi Solprene 201 0.43 dl/g 3.76 ft lb/in 230F
Butyl Rubber 365 0.41 dl/g 0.44 ft lb/in - - -Vistalon 2504 0.53 dl/g 2.53 ft lb/in - - -Kraton 1101 0.52 dl/g 3.84 ft lb/in 242F
COMPARATIVE TEST C
The following test was done with material prepared according to the procedure of Comparative Test A Run 7 followed by extrusion according to Example 5.
Rubber Modifier I.V. of Polystyrene Notched Izod ~DT 264 psi Solprene 300 0.37 dl/g - - - - - _ _ _ 3. Solprene 201- a solution polymerized butadiene rubber.
4. Butyl Rubber 365- isobutylene-isoprene copolymer containing about 4.5% isoprene.
The effect of peroxide initiated polymerization was studied using the apparatus described in Example 1. The compositions contained the same proportion of the same materials.
The polymerization was initiated with the stated amount of dicumyl peroxide and the polystyrene was isolated according to the method of Example 1:
RunReaction Temperature Amt. of Peroxide I.V. dl/g 145C 1.6g. 0.22 6 138C 1.6g. 0.26 7 130C 1.6g. 0.27 . 25 8 120C 1.6g. 0.34 - 9 145C 0.8g. 0.38 ~176~ 8CH-205~
138C Q.8g. 0.41 11 130C 0.8g. 0.40 12 120C 0.8g. 0.42 13 145C 0.4g. 0.50 14 138C 0.4g. 0.52 130C 0.4g. 0.49 16 120C 0.4g. 0.42 17 145C 0.2g. 0.53 18 138C 0.2g. 0.48 19 130 C 0.3g. 0 r 46 120C 0.2g. 0.39 21 145C O.lg. 0.55 22 138C O.lg. 0.53 23 130C O.lg. 0.48 24 120C O.lg. 0.43 These data shown an overall improvement in I.V. of the type polystyrene produced as one goes to lower amounts of peroxide. When high levels of peroxide are employed, higher I.V. is obtained at lower reaction temperatures. At low peroxide levels, higher I.V. is attained at higher reaction temperatures. The reactions were cut short of maximum attainable I.V. so that the polymers could be removed from the pot without undue difficulty. The best results are obtained with a purely thermal polymerization. Under peroxide-free conditions one also has a more controllable and re-producible reaction.
The procedure of Example 1 was repreated to show the effect of reaction time and inclusion of an impact 1~765~2 modifier on the I.V. of the polystyrene. Runs 25 30 include 360g of styrene, 195g of poly(2,6-dimethyl-1,4-phenylene oxide~ and 45g of rubber of the same type that was employed in Example 1.
Run TimeTemperature I.V. of Polystyrene 1 hour 145C 0.42 dl/g 26 2 hours145C 0.45 dl/g 27 3 hours145C 0.57 dl~g Control (No Rubber) Run TimeTemperature I.V. of Polystyrene 28 1 hour 145C 0.63 dl/g 29 2 hours145C 0.63 dl/g - 30 3 hours145C 0.63 dl/g This example shows that one should let the reaction proceed as long as is practicable.
The composition of Example 1, Run 1 was cut up and extruded through a vacuum vented twin screw extruder at 15-20 RPM with a temperature of 100C at the feed port and 220C at the die. The extruder strand was pelleti~ed and was determined to have 96-98% recoverable solids. The recoverable solids were determined as the weight percent of polymer precipitated from a lO.Og resin sample that was dissolved in 250 ml toluene in a Waring blender. Precipitation was effected by addition of an equal volume of methanol to the agitated solution in a Waring ~ 8CH-2054 blender. The precipitated polymer was dried to constant weight at 75C to determine the percent of recoverable solids. The recoverable solids for the material of Example 1 was 75-85%.
The grafting of polystyrene on the poly(2,6-dimethyl-1,4-phenylene) oxide was estimated to be 3% and the I.V. of the polystyrene - was 0.55. A standard ASTM test bar had a Notched Izod strength of 3.9 ft. lb/in and an HDT temperature of 214C at 264 psi. The procedure of Example 3 was repeated except that dicumyl peroxide was added to the composition prior to extrusion.
COMPARATIVE TEST B
Grafted Izod HDT I.V. of Run Dicumyl Peroxide Polystyrene ft lb/in 265 psi Polystyrene ; 31 0.25~ 7% 3.6 218~C 0.49 dl/g 32 0.50% 18% 3.4 216C 0.43 dl/g - 15 33 0.75% 21% 3.5 220C 0.41 dl/g 34 1.0% 29% 3.3 221C 0.38 dl/g Using the procedure of Example 1, 450g of styrene monomer, 195 g. of poly(2,6-dimethyl-1,4-phenylene oxide)* and 45g. of styrene butadiene rubber** were thermally polymerized.
The resin thus obtained was dissolved in toluene to remove unreacted styrene and recovered by methanol precipitation.
* as in Example 1 ** as in Example 1 The dried powder was extruded, pelletized and molded into test bars. Infra red analysis showed that the dried powder contained 45% by weight of poly(2,6-dimethyl-1,4-phenylene oxide) 50% by weight polystyrene and 5% by weight of the rubber. A portion of the separated polystyrene contained 8% by weight of grafted poly (2,6-dimethyl-1,4-phenylene oxide and had an I.V. of 0.63 dl/g.
The molded bars had an Izod impact (notched) of 3.64 ft lb/in and an HDT of 229F/264 psi.
The procedure of Example 1 was repeated using different rubbery materials. Each composition was extruded using 0.5% by weight of dicumyl peroxide as an additive to the extruder. The compositions was evaluated to determine the I.V.
of the polystyrene and the impact and heat distortion temperature of test bars.
Rubber Modifier I.V. of Polystyrene Notched Izod HDT 264 psi Philprene 1502 0.50 dl/g 4.15 ft lb/in 230C
Solprene 408 0.37 dl/g - _ _ _ _ _ _ 1. Philprene 1502 -an emulsion polymerized SB~ rubber containing about 23.5% bound polystyrene.
2. Solprene 408-a solution polymerized styrene butadiene rubber of 30 parts styrene and 70 part butadiene.
~ 8C~-2054 Rubber Modifier I.V. of Polystyrene Notched Izod HDT 264 psi Solprene 201 0.43 dl/g 3.76 ft lb/in 230F
Butyl Rubber 365 0.41 dl/g 0.44 ft lb/in - - -Vistalon 2504 0.53 dl/g 2.53 ft lb/in - - -Kraton 1101 0.52 dl/g 3.84 ft lb/in 242F
COMPARATIVE TEST C
The following test was done with material prepared according to the procedure of Comparative Test A Run 7 followed by extrusion according to Example 5.
Rubber Modifier I.V. of Polystyrene Notched Izod ~DT 264 psi Solprene 300 0.37 dl/g - - - - - _ _ _ 3. Solprene 201- a solution polymerized butadiene rubber.
4. Butyl Rubber 365- isobutylene-isoprene copolymer containing about 4.5% isoprene.
5. Vistalon 2504 - an EPDM rubber containlng 63% by weight of ethylene
6. Kraton 1101 - Shell Chemical Co., low mol. styrene-butadiene-styrene block copolymer.
7. Solprene 300 a solution polymerized styrene-butadiene rubber of 50 parts styrene and 50 parts butadiene.
Obviously, other modifications and variations of the present invention are possible in light of the above teachings.
It is, therefore, to be understood that changes may be made in the particular embodiments of the invention described which are within the full intended scope of the invention as defined by the appended claims.
,~
Obviously, other modifications and variations of the present invention are possible in light of the above teachings.
It is, therefore, to be understood that changes may be made in the particular embodiments of the invention described which are within the full intended scope of the invention as defined by the appended claims.
,~
Claims (14)
1. A process for the preparation of a composition which comprises:
(a) a polyphenylene oxide resin;
(b) an alkenyl aromatic resin; and (c) a rubbery impact modifier; said process comprising forming a mixture which consists essentially of a poly-phenylene oxide resin and the rubbery impact modifier in an alkenyl aromatic monomer and thereafter heating said mixture to form said composition.
(a) a polyphenylene oxide resin;
(b) an alkenyl aromatic resin; and (c) a rubbery impact modifier; said process comprising forming a mixture which consists essentially of a poly-phenylene oxide resin and the rubbery impact modifier in an alkenyl aromatic monomer and thereafter heating said mixture to form said composition.
2. A process as defined in claim 1 wherein the polyphenylene oxide is derived from a monomer of the formula:
wherein X is a substituent selected from the group consisting of hydrogen, chlorine, bromine and iodine, Q
is a monovalent substituent selected from the group consisting of hydrocarbon radicals, hydrocarbonoxy readicals, halohydrocarbon-oxy radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; and Q' and Q" are the same as Q and in addition may be halogen, with the proviso that Q, Q' and Q" are all free of a tertiary alpha-carbon atom.
wherein X is a substituent selected from the group consisting of hydrogen, chlorine, bromine and iodine, Q
is a monovalent substituent selected from the group consisting of hydrocarbon radicals, hydrocarbonoxy readicals, halohydrocarbon-oxy radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus; and Q' and Q" are the same as Q and in addition may be halogen, with the proviso that Q, Q' and Q" are all free of a tertiary alpha-carbon atom.
3. A process as defined in claim 2 wherein the alkenyl aromatic monomer is selected from the compounds of the formula:
wherein R1 and R2 are selected from the group consisting of lower alkyl or alkenyl groups of from 1 to 6 carbon atoms and hydrogen; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen and lower alkyl of from 1 to 6 carbon atoms; R5 and R6 are selected from the group consisting of hydrogen and lower alkyl and alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group, said compounds being free of any substituent that has a tertiary carbon atom.
wherein R1 and R2 are selected from the group consisting of lower alkyl or alkenyl groups of from 1 to 6 carbon atoms and hydrogen; R3 and R4 are selected from the group consisting of chloro, bromo, hydrogen and lower alkyl of from 1 to 6 carbon atoms; R5 and R6 are selected from the group consisting of hydrogen and lower alkyl and alkenyl groups of from 1 to 6 carbon atoms or R5 and R6 may be concatenated together with hydrocarbyl groups to form a naphthyl group, said compounds being free of any substituent that has a tertiary carbon atom.
4. A process as defined in claim 3 wherein the rubbery impact modifier is selected from the group consisting of polybutadiene rubber, styrene-butadiene rubber, natural rubber, neoprene, butyl rubber, ethylene propylene copolymers, EPDM
rubbers, acrylonitrile rubbers, A-B block copolymers and A-B-A
block copolymers.
rubbers, acrylonitrile rubbers, A-B block copolymers and A-B-A
block copolymers.
5. A process as defined in claim 4 wherein the composition comprises from 10-90 parts by weight of the polypheny-lene oxide; from 90-20 parts by weight of alkenyl aromatic resin and from 1 to 20 parts by weight of rubbery impact modifier.
6. A process as defined in claim 5 wherein the composition includes a reinforcing amount of a reinforcing filler.
7. A process as defined in claim 1 wherein the mixture is thermally polymerized at a temperature of from 105-175°C.
8. A process for the preparation of a composition which comprises:
(a) 10-90 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide) resin;
(b) 90-20 parts by weight of polystyrene resin; and (c) 1-20 parts by weight of a rubbery impact modifier;
said process comprising forming a mixture which consists of a polyphenylene oxide resin and the rubbery impact modifier in styrene monomer and thereafter heating said mixture to form said composition.
(a) 10-90 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide) resin;
(b) 90-20 parts by weight of polystyrene resin; and (c) 1-20 parts by weight of a rubbery impact modifier;
said process comprising forming a mixture which consists of a polyphenylene oxide resin and the rubbery impact modifier in styrene monomer and thereafter heating said mixture to form said composition.
9. A process as defined in claim 8 wherein the rubbery impact modifier is styrene-butadiene rubber.
10. A process as defined in claim 9 wherein the composition includes from 5-40% by weight based on the total weight of the composition of a reinforcing fibrous glass filler.
11. A process as defined in claim 1 including the additional step of passing the composition of the polyphenylene oxide and the alkenyl aromatic resin through a vacuum vented devolatilizing extruder to cause any residual alkenyl aromatic monomer to polymerize.
12. A process as defined in claim 1 wherein said composition is extruded with from 0.l to 2.5% by weight of a peroxide compound.
13. A process as defined in claim 11 wherein the peroxide compound is selected from the group consisting of benzoyl peroxide, lauroyl, peroxide, octanoyl paroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di-t-butyl peroxy-3,5,5-trimethyl cyclohexane and dicumyl peroxide.
14. A process as defined in claim 7 wherein a temperature of about 40-60°C is used to dissolve the polyphenylene oxide and the rubber impact modifier in the alkenyl aromatic monomer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86367177A | 1977-12-23 | 1977-12-23 | |
| US863,671 | 1977-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117692A true CA1117692A (en) | 1982-02-02 |
Family
ID=25341550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000314472A Expired CA1117692A (en) | 1977-12-23 | 1978-10-27 | Process for the preparation of polyphenylene oxide compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1117692A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223577A (en) * | 1990-06-01 | 1993-06-29 | Basf Aktiengesellschaft | Abs molding materials |
-
1978
- 1978-10-27 CA CA000314472A patent/CA1117692A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223577A (en) * | 1990-06-01 | 1993-06-29 | Basf Aktiengesellschaft | Abs molding materials |
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