CA1105174A - Plasticized reinforced compositions of a polyphenylene ether resin - Google Patents
Plasticized reinforced compositions of a polyphenylene ether resinInfo
- Publication number
- CA1105174A CA1105174A CA293,116A CA293116A CA1105174A CA 1105174 A CA1105174 A CA 1105174A CA 293116 A CA293116 A CA 293116A CA 1105174 A CA1105174 A CA 1105174A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- styrene
- reinforcing agent
- impact modifier
- mineral reinforcing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/42—Constructional features of converters
- C21C5/46—Details or accessories
- C21C5/4653—Tapholes; Opening or plugging thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/42—Constructional features of converters
- C21C5/44—Refractory linings
- C21C5/445—Lining or repairing the taphole
Abstract
ABSTRACT OF THE DISCLOSURE
There are provided plasticized thermoplastic compositions useful for molding which comprise a polyphenylene ether resin, a plasticizer, a mineral reinforcing agent, e.g., aluminum silicate, titanium dioxide, zinc oxide, antimony oxide, and the like, and optionally, an impact modifier. The compositions possess improved stiffness properties with unexpectedly significant retention of ductility in comparison with corresponding compositions which do not contain the mineral reinforcing agent.
There are provided plasticized thermoplastic compositions useful for molding which comprise a polyphenylene ether resin, a plasticizer, a mineral reinforcing agent, e.g., aluminum silicate, titanium dioxide, zinc oxide, antimony oxide, and the like, and optionally, an impact modifier. The compositions possess improved stiffness properties with unexpectedly significant retention of ductility in comparison with corresponding compositions which do not contain the mineral reinforcing agent.
Description
~ CH-2~24 This invention relates to mineral reinforced, plasticized polyphenylene ether compositions. ~ore particularly, it relates to -thermoplastic molding compositions comprising a polyphenylene ether resin with or withou-t an impact modifier, a plasticizing amount of a plasticizer, and a mineral reinforcing agent which provides improved stif~ness with unexpectedly signiEicant retention of ~uctility.
The polyphenylene ether resins are well known in the art as a class of thermoplastics which possess a number of outstan~ing physical properties. They can be prepared, in general, by oxidative and non-oxidative methods, such as are disclosed, for example, in Hay, U.SO 3,306,874 dated ; February 28, 1967 and 3,306,875 dated February 28, 1967 and Stamatoff, U.S. 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966.
: It is known that the polyphenylene ether resins can be combined with impact modifiers to obtain improved impact resistance and other mechanical properties. Suitable impact modifiers for polyphenylene ether resins are disclosed in Cizek, U.S. Patent 3,383,435 dated May 14, 1968.
` As employed herein the term "plasticized" is .~ used to describe compositions having a sufficient amount of plasticizer to reduce the temperature of optimum extrusion by at least about 25F., and normally from about 25 t~
about 100~.
It has now been surprisingly discovered that plasticized polyphenylene ether compositions comprising a mineral reinforcing agent, possess enhanced stiffness, as measured by flexural modulus and flexural strength, in ~ .
' ' ~ ' . ' ' ' L~ f~ ~CH-24~
comparison with corresponding compositions withou-t said agent. Moreover, it was unexpected tha-t the improvements in stiffness properties were to be obtained along with a significant retention of ducti.lity, as measured by tensile elongation and impact resistance.
In its broadest aspects, the present invention comprises reinforced, plasticized thermoplastic compositions suitable for molding or shaping, .i..e., by cornpression molding, extrusion, calendering, and the li.ke, which posses enhanced stiffness in comparison with the corresponding unreinforced compositions, the compositions comprising:
(a) a polyphenylene ether resin alone or in combination with an impact modifier;
(b) a plasticizer therefor in an amount at least sufficient to raduce the temperature of optimum extrusion at least about 25F.; and (c) a mineral reinforcing agent in an amount at least sufficient to provide enhanced stiffness in comparison with a corresponding unreinforced composition.
In general, the polyphenylene ether resins of the compositions are of the family having structural units of the formula:
\~ ~\Q /~
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive .. : , ~ , . :- :
:. ~ - . ., . . .:
~ 8 CH 2~24 integer and is at least 50, and each Q is a monovalent subs-tituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
Preferably, the polyphenylene ether resins are selected from those of the above formula wherein each Q is alkyl, most preferably having from 1 to 4 carbon atoms.
Illustratively, members of this class include (poly(2,6-dimethyl-1,4-phenylene) ether; poly(2,6-diethyl-1, 4-phenylene)ether; poly(2-methyl-6-ethyl-1,4-phenylene)ether;
poly(2-methyl-6~propyl-1,4-phenylene)ether; poly(2,6-dipropyl-1,4-phenylene)ether; poly(2-ethyl-6propyl-1,4-phenylene)ether;
and the like.
Especially preferred is poly(2,6-dimethyl-1,4-phenylene)ether, preferably having an intrinsic viscosity of about 0.45 deciliters per gram (dl./g.) as measured in chloroform at 30C.
The preparation of polyphenylene ether resins corresponding to the above formula is described in the above-mentioned patents of Hay and Stamatoff.
The choice of a plasticizer is not critical and any of the conventional materials used for this purpose can be employed. Preferably, component (b) will be selected from among phthalate and phosphate plasticizing materials, and especially phosphate plasticizers.
The phosphate plasticizer is preferably a compound of the formula:
~ CH-2~24 OR P - ~R
OR
wherein Rl, R2 and R3 are the same or dif~erent and are alkyl, haloalkyl, cycloalkyl, halocycloalkyl, aryl, haloaryl, alkyl substituted aryl, haloalkyl substituted aryl, aryl substituted alkyl, haloaryl substituted alkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkaryl, halogen and hydrogen.
Examples include cresyl diphenyl phosphate, 2-ethyl-hexyl diphenyl phosphate, tricresyl phosphate, triiosopropyl-phenyl phosphate, triphenyl phosphate, triethyl phosphate, di-butyl phenyl phosphate, diethyl phosphate, cresyl diphenyl phosphate, isooctyl diphenyl phosphate, tributyl phosphate,
The polyphenylene ether resins are well known in the art as a class of thermoplastics which possess a number of outstan~ing physical properties. They can be prepared, in general, by oxidative and non-oxidative methods, such as are disclosed, for example, in Hay, U.SO 3,306,874 dated ; February 28, 1967 and 3,306,875 dated February 28, 1967 and Stamatoff, U.S. 3,257,357 dated June 21, 1966 and 3,257,358 dated June 21, 1966.
: It is known that the polyphenylene ether resins can be combined with impact modifiers to obtain improved impact resistance and other mechanical properties. Suitable impact modifiers for polyphenylene ether resins are disclosed in Cizek, U.S. Patent 3,383,435 dated May 14, 1968.
` As employed herein the term "plasticized" is .~ used to describe compositions having a sufficient amount of plasticizer to reduce the temperature of optimum extrusion by at least about 25F., and normally from about 25 t~
about 100~.
It has now been surprisingly discovered that plasticized polyphenylene ether compositions comprising a mineral reinforcing agent, possess enhanced stiffness, as measured by flexural modulus and flexural strength, in ~ .
' ' ~ ' . ' ' ' L~ f~ ~CH-24~
comparison with corresponding compositions withou-t said agent. Moreover, it was unexpected tha-t the improvements in stiffness properties were to be obtained along with a significant retention of ducti.lity, as measured by tensile elongation and impact resistance.
In its broadest aspects, the present invention comprises reinforced, plasticized thermoplastic compositions suitable for molding or shaping, .i..e., by cornpression molding, extrusion, calendering, and the li.ke, which posses enhanced stiffness in comparison with the corresponding unreinforced compositions, the compositions comprising:
(a) a polyphenylene ether resin alone or in combination with an impact modifier;
(b) a plasticizer therefor in an amount at least sufficient to raduce the temperature of optimum extrusion at least about 25F.; and (c) a mineral reinforcing agent in an amount at least sufficient to provide enhanced stiffness in comparison with a corresponding unreinforced composition.
In general, the polyphenylene ether resins of the compositions are of the family having structural units of the formula:
\~ ~\Q /~
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive .. : , ~ , . :- :
:. ~ - . ., . . .:
~ 8 CH 2~24 integer and is at least 50, and each Q is a monovalent subs-tituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
Preferably, the polyphenylene ether resins are selected from those of the above formula wherein each Q is alkyl, most preferably having from 1 to 4 carbon atoms.
Illustratively, members of this class include (poly(2,6-dimethyl-1,4-phenylene) ether; poly(2,6-diethyl-1, 4-phenylene)ether; poly(2-methyl-6-ethyl-1,4-phenylene)ether;
poly(2-methyl-6~propyl-1,4-phenylene)ether; poly(2,6-dipropyl-1,4-phenylene)ether; poly(2-ethyl-6propyl-1,4-phenylene)ether;
and the like.
Especially preferred is poly(2,6-dimethyl-1,4-phenylene)ether, preferably having an intrinsic viscosity of about 0.45 deciliters per gram (dl./g.) as measured in chloroform at 30C.
The preparation of polyphenylene ether resins corresponding to the above formula is described in the above-mentioned patents of Hay and Stamatoff.
The choice of a plasticizer is not critical and any of the conventional materials used for this purpose can be employed. Preferably, component (b) will be selected from among phthalate and phosphate plasticizing materials, and especially phosphate plasticizers.
The phosphate plasticizer is preferably a compound of the formula:
~ CH-2~24 OR P - ~R
OR
wherein Rl, R2 and R3 are the same or dif~erent and are alkyl, haloalkyl, cycloalkyl, halocycloalkyl, aryl, haloaryl, alkyl substituted aryl, haloalkyl substituted aryl, aryl substituted alkyl, haloaryl substituted alkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkaryl, halogen and hydrogen.
Examples include cresyl diphenyl phosphate, 2-ethyl-hexyl diphenyl phosphate, tricresyl phosphate, triiosopropyl-phenyl phosphate, triphenyl phosphate, triethyl phosphate, di-butyl phenyl phosphate, diethyl phosphate, cresyl diphenyl phosphate, isooctyl diphenyl phosphate, tributyl phosphate,
2-ethylhexyl diphenyl phosphate, isodecyl diph~nyl phosphate, isodecyl dicresyl phosphate, didecyl cresyl phosphate, tri-n-hexyl phosphate, di-_-octyl phenyl phosphate, di-2-ethyl-hexyl phenyl and tri-2-ethylhexyl phosphate or mixtures thereof.
Especially preferred are aromatic phQsphates, e.g., triphenyl phosphate.
Examples of phthalate plasticizers include dibenzyl phthalate, phenyl cresyl phthalate, diethyl phthalate, dimethyl 2~ phthalate, phenyl benzyl phthalate, butyl benzyl phthalate, butyl cyclohexyl phthalate, dibutyl phthalate, octyl cresyl -phthalate, diphenyl phthalate, di-_hexyl phthalate, disohexyl phthalate, butyl octyl phthalate, butyl decyl phthalate, di-isooctyl phthalate~ di-2-ethylhexyl phthalatey di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-propyl heptyl phthalate, di-_-nonyl phthalate, di-n-decyl phthalate and d:itridecyl phthalate.
The pLasticizer (b) is added in amounts which will . .~l - - , - .
~ CH 2~24 be sufficient -to provide a plasticized composition within the meaning of the term described above. In general, the plasticizer is present in amounts ranging from at leas-t about 5 parts per hundred par-ts of resinous components combined, preferably from about 5 to about 100 parts per hundred parts of resin.
Illustratively, the mineral reinforcement is selected from among talcs, aluminum silicate, e.g., clay, hydrated, anhydrous or calcined clay, zinc oxide, titanium dioxide, antimony oxide, barium sulfate, precipitated or natural calcium carbonate, zinc sulfide, and the like, Especially preferred is hydrated aluminum silicate.
Amounts of the mineral reinforcing agent will vary depending on the formulation and needs of the particular composition. In preferred compositions, however, the mineral reinforcement will be present in at least about 5 parts per hundred parts of resins combined. E~pecially preferred embodiments will comprise anywhere from about 5 to about 150 parts of mineral reinforcement per hundred parts of resin plus plasticizer.
The nature of the impact modifiers for the poly-phenylene ether or polyphenylene ether/polystyrene resin is not critical and any of the elastomeric polymers and copoly-mers which are conventionally employed to improve impact properties in thermoplastic compositions can be used.
Illustratively, the impact modifiers can be selected from among elastomeric A B-Al block copolymers wherein terminal blocks A and Al are the same or different and are derived from a vinyl aromatic compound, e.g., styrene, ~ -methyl styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, and the like, and center block B is derived from a conjugated diene, e.g., butadlene, isoprene, 1,3-pentadiene, 2,3-dimethyl ::
butadiene, and the like.
These can be made by an organometallic initiated polymeri2ation process using, for example, sodium or l:ithium metal or an organic derivative thereof. The diene monomers can be polymerized with a monofunc-tional or difunctional initiator, as is described in Kennedy et al, Interscience Publishers, Vol. 23, Part II (lg69), pages 553-559. Other methods of preparation are described in Zelinski, U.S.
Especially preferred are aromatic phQsphates, e.g., triphenyl phosphate.
Examples of phthalate plasticizers include dibenzyl phthalate, phenyl cresyl phthalate, diethyl phthalate, dimethyl 2~ phthalate, phenyl benzyl phthalate, butyl benzyl phthalate, butyl cyclohexyl phthalate, dibutyl phthalate, octyl cresyl -phthalate, diphenyl phthalate, di-_hexyl phthalate, disohexyl phthalate, butyl octyl phthalate, butyl decyl phthalate, di-isooctyl phthalate~ di-2-ethylhexyl phthalatey di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, di-2-propyl heptyl phthalate, di-_-nonyl phthalate, di-n-decyl phthalate and d:itridecyl phthalate.
The pLasticizer (b) is added in amounts which will . .~l - - , - .
~ CH 2~24 be sufficient -to provide a plasticized composition within the meaning of the term described above. In general, the plasticizer is present in amounts ranging from at leas-t about 5 parts per hundred par-ts of resinous components combined, preferably from about 5 to about 100 parts per hundred parts of resin.
Illustratively, the mineral reinforcement is selected from among talcs, aluminum silicate, e.g., clay, hydrated, anhydrous or calcined clay, zinc oxide, titanium dioxide, antimony oxide, barium sulfate, precipitated or natural calcium carbonate, zinc sulfide, and the like, Especially preferred is hydrated aluminum silicate.
Amounts of the mineral reinforcing agent will vary depending on the formulation and needs of the particular composition. In preferred compositions, however, the mineral reinforcement will be present in at least about 5 parts per hundred parts of resins combined. E~pecially preferred embodiments will comprise anywhere from about 5 to about 150 parts of mineral reinforcement per hundred parts of resin plus plasticizer.
The nature of the impact modifiers for the poly-phenylene ether or polyphenylene ether/polystyrene resin is not critical and any of the elastomeric polymers and copoly-mers which are conventionally employed to improve impact properties in thermoplastic compositions can be used.
Illustratively, the impact modifiers can be selected from among elastomeric A B-Al block copolymers wherein terminal blocks A and Al are the same or different and are derived from a vinyl aromatic compound, e.g., styrene, ~ -methyl styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, and the like, and center block B is derived from a conjugated diene, e.g., butadlene, isoprene, 1,3-pentadiene, 2,3-dimethyl ::
butadiene, and the like.
These can be made by an organometallic initiated polymeri2ation process using, for example, sodium or l:ithium metal or an organic derivative thereof. The diene monomers can be polymerized with a monofunc-tional or difunctional initiator, as is described in Kennedy et al, Interscience Publishers, Vol. 23, Part II (lg69), pages 553-559. Other methods of preparation are described in Zelinski, U.S.
3,~51,905 dated May 17, 1966 and Flolden et al, U.S.
3,231,635 dated January ~5, 1966.
The relative ratios of the polymer units in the A-B-A block copolymers can vary broadly. It is preferred that the center block B have a molecular weight greater than that of the combined terminal blocks, however, to obtain optimum impact strength and solvent resistance. In general, the molecular weight of each of the respective terminal blocks will range from about 2,000 to about 100,000 and the molecular weight of the center block will range from about 65,000 to about 1,000,000.
20 A Examples include the Kraton~resins, commercially available from Shell Chemical Co., Polymers Division, e.g., K-1101 (polystyrene-polybutadiene-polystyrene), K-110~ (poly styrene-polybutadiene-polystyrene), and K-1107 (polystyrene-polyisoprene~polystyrene).
The hydrogenated A-B-Al block copolymers are also well known. In general, these are block copolymers of the A-B-Al type in which terminal blocks A and Al are the same or different and, prior to hydrogenation, comprise homopolymers or copolymers derived from vinyl aromatic hydrocarbons and, especially, vinyl aromatics wherein the aromatic moiety can be either monocyclic or polycyclic.
Examples of the monomers are styrene, ~ - methyl styrene, .
~ 3~ CH-242~
vinyl xylene, e-thyl vinyl xylene, vinyl naphthalene, and the like. Center block B will always be derived from a conjugated diene, e.g., butadiene, isoprene, 1,3-pentadiene, and the like. Preferably, center block B wil be comprised of polybutadiene or polyisoprene.
The preparation of hydrogenated A-B-A1 block copoly-mers is described in Jones, U.S. Patent 3,431,323 dated March 4, 1969.
Examples include the Kraton GTM resins, commercially available from Shell Chemical Co., Polymers Division, e.g., G-GXT-0650, ~-GXT-0772, G-GXT-0782 and G-6521.
Radial teleblock copolymers of a vinyl aromatic comound, a conjugated diene and a coupling are also suitable impact modifiers for the compositions of this invention.
These are branched polymers having segments, or blocks, ; comprised of a conjugated diene polymer, and a vinyl aromatic polymer, together with a coupling agent, wherein in the copolymer structure chains of the diene polymer radiate outwards from a coupling agent, each chain terminating at its other end with a block of the vinyl aromatic polymer.
The radial teleblock copolymers are known in the art. They are described in ADHESIVES AGE, December, 1971, pages 15-20 and RUBBER WORLD, ~anuary, 1973, pages 27-32.
The preparation of these copolymers is described in Zelinski et al, U.S. Patent 3,281,383 dated October 25, 1966.
~xamples of commercially available radial teleblock copolymers are t:he SolpreneTM resins of Phillips Petroleum Company designat:ed as Solprene 406 (containing about 60 parts by welght of but:adiene units and about 40 parts by weight of styrene unit~;), Solprene 411 (containing about 70 parts by weight~ of butadiene units and about 30 parts by weight of ,~ ~ J
~ 5~ 8 C~ 2~2~
styrene units), Solprene ~14 (con-talning about 60 parts by weight oE butadiene units and about 40 parts by weight of styrene units), Solprene 417 (containing about 20 parts by weight of butadiene units and about 80 parts by weight of styrene units), and S411P (containing about 70 parts by weight of butadiene units and about 30 parts by weight of styrene units). These materials also include a relatively minor amount of coupling agent, e.g., less than 1 part by weight of coupling agent per 100 parts of polymer.
Also included are hydrogenated radial teleblock copolymers of a vinyl aromatic compound, a conjugated diene and a coupling agent, such as Solprene 512, commercially available from Phillips Petroleum Co.
The impact modifier can also be selected from acrylic resin modified diene rubber containing resins.
Preferably, these will be of the group consisting of a resinous composition of a poly(alkylene methacrylate) grafted on to a butadiene-styrene copolymer backbone or an acrylonitrile-butadiene-styrene terpolymer backbone, or a resinous composition of a mixture of a poly(alklmethacrylate) and a butadiene-styrene copolymer or an acrylonitrile-butadiene-styrene terpolymer.
A preferred commercially available impact modifier A of this type is Acryloid KM611, sold by Rohm and Haas Co., which is an acrylic/styrene/styrene-butadiene terpolymer.
: The aforementioned acrylic resin modified elastomers can be prepared by well known techniques, such as those described in U.S. 2,943,074 dated June 28, 1960 and U.S. 2,857,360 dated October 21, 1958.
The impact modifier can also be a graft .:
copolymer of a vinyl aromatic compound and a diene, prefer-ably comprising from about 75 to about 10~ by weight of a : -' ~ 8 CH 2424 vinyl aromatic monomer and from about 25 to about 90%
by weight o-f a conjugated diene. By way of illustration, the aromatic monomer can be selected from among styrene, . ~3 -methyl styrene, vinyl toluene, vinyl xylene, and the likQ, and the diene can be selected from among butadiene, iso~rene, and the like. Graft copolymers of styrene and styrene-butadiene are preferred.
An example of a preferred commercially available ~ graft copolymer is Blendex 525, sold by Marbon Chemical Co.
The compositions of this invention can be prepared by conventional methods. Preferably, each of the ingredients is added as part of a blend premix, and the blend is passed through an extruder at an extrusion temperature of from about 500 to about 625F., dependent on the needs of the particular composition~ The strands emerging from the extruder may be cooled, chopped into pellets, and molded or other wise worked to any desired shape.
The following examples are illustrative of the compositions of this invention. They are not to be construed as limiting the invention to the particular embodiments shown therein. All parts are by weight.
Units for the properties shown in the following Examples are as follows, unless otherwise indicated:
Tensile yield, psi - Tensile break, psi Tensile elongation, %
Flexural modulus, psi Flexural strength, psi Melt viscosity, at 540 F., 1500 sec , poise Gloss, 45 surface gloss, dimensionless units ~UL-94- Underwriters Laboratories Bulletin ~94, sec/sec.
_ g _ ~ 8 C~I 2424 Izod Impact strength, ft.lbs./in.n.
Gardner Impact strength, in.lbs.
Heat distortion tempe:rature, F.
Coefficient of Linear Thermal Expansion (CLTE), in/in F., measured f:rom -30C. to 65C.
EXM~PLES 1 - 4 Self-extinguishing, plasticized blends of 78 parts of poly(2,6-dimethyl-1,4-phenylene ether) resin, intrinsic viscosity about 0.45 deciliters/gram as measured in chloroform at 30C., 22 parts of triphenyl phosphate flame retardant plasticizer, 5 parts of styrene-butadiene-styrene block copolymer (Kraton 1101, Shell Chemical Co., Polymers Division), 1.5 parts of poly-ethylene and 20 parts of various mineral reinforcing agents, as shown, are compounded and extruded at a temperature of 580F. The extrudate is .
chopped into pellets, molded into test bars at a temperature of about 520 F., and evaluated for mechanical and flame resistance properties. For purposes of comparison, a blend of the same ingredients in the same amounts is prepared, but without a filler. The mineral reinforcements and test results are shown in Table 1.
' ~ .
~ o ~ s~
I ~ ~ I I o ~ ~ . I
:~ ~ ,-U CO~
o U~
U
C~
U o o ~ o o ~ ,~
~1 ~ ~ ~1 hU~
Xtl~ O . O
L~ ~ O o 00 1 1 ~
O C~l O
~1 , S~C~
~ C~
H~1 ~ 0~
N O ~I t~ 1 ~1 C
~3 ~ o O ~D ~ U~ r~ , ....
O
,o, C) o ~ rl O O
a ~ o E~ ~ ~
5~ h ~ U O O
a) .
; E~ ~ r~ t ~ ~5 n tJ
~ . ~
~ ~ ~ ' ~
;
~5~
` 8 C~ 2~24 Self-extinguish:ing, plasti.cized compositons of 78 parts of poly(2,6-dimethyl-1,4-phenylene ether), 22 parts of triphenyl phosphate flame retardant plasticizer, 5 parts of styrene-butadiene-styrene block copolymer (Shell's Kraton 1101), 1.'; parts of polyethylene and a clay ~iller (Al-Sil Ate NCF, Freeport Kaolin CoO) in the amounts shown are prepared and molded as in Examples 1-4. The _ 10 physical properties are summarized in Table 2.
', .
,~ -.: . .
. ~.-` .
: .
: I
: i .~j ' .
. . . :: . .
: . : .. -- - ' :
.- - - - .
- , . . . -: . :
, . . . , : . . :, . :
-. , , .:, - :
. . .: . . ,.
,.,,. .:: . - . .. :: . .. :: . : .: .
C) o C~ o ,~
X X I X I I ~C
~) o ~ o~ ~o I~
. ~ o U~
n ~D ~ I~ ~J r~
. ~
o o o ~ o o o o o o o o )J O ~D ~ ~ 0 ~a u~ ~ u~
~:1 ~
:~ o o o o o o o o o o o o ro o C~ o o o o o C`J ~ ~ r~
O G~ I` ~ ~ h 1:: N
al , ,,, .c u C~ O
U~ C~l O ~U~ U) ~ ~ U~
N C`l C`l r I
V C~) r~
~ ~ .' ~ ~J OU~ ~ ~ 1` 0 1~ N O 1~C~ o 1 3 H r-l ~
C~
c o ul ~ o ct~ ~ oo c`l o E~ ri ~ ~
w v) ,~ h c ~) o o o C~ o o o U~
u~ Q) ~ C~
c ~ ~ ~ a~ o c~
E-~ r~ r-l ~:1 X
C ~
:: ~ O O ~ O O O O C r-l r-J O O O O O O O ~U
a~ ~ I r-l t~1 1~ C~ 4 0~ t:~ O O r-l C~ 00 r-l r-l r~ 5:
' ~E-~
r~ ~
U ~d ~o~
rl ~ ~ ~ U~ ~
~ ~ ~ 0 01.'~ C O ^ ~- ~
: ~: ,~ ~ u~ ~ h o ,~ ' U~ ` o ~;~, ):4 ~ ~ D O U~ QJ :
_ r~ r~
~ r-l rl ~1 U
~ ~ ~ : C O ~ r~ :
~ C 4 : ~:
~ : ~ O ~r~ O
~ , . u~ ~ r~ cx:) cr~ o ¢
:~: ~ r-l r~
: ~ ` . .. -. .: - . ` : ' :
It is shown that even with amounts of reinforcement as high as 67 phr (40%), in Example 9, a signi~icant amount of ductility, as measured by tensile elongation and impact strength, is retained as compared with the unreinforced control (lOA ).
EXAMPLES~ 13 Blends of poly(2,6~di:methyl-1,4 phenylene ether) resin, mineral oil, styrene-butadiene-styrene block copolymer (Kraton 1101), polyethylene and a clay reinforcing ~iller are compounded, extruded and molded as in Examples 1-4. The formulations and physical properties are summarized in Table 3.
EXAMPLE 11 ll_* 12 13 13A*
Ingredients (parts by weight) poly(2,6-dimethyl-1,4-phenylene ether) 78 78 78 85 85 mineral oil (Kaydol) 22 22 22 15 15 styrene-butadiene-styrene block copolymer (Kraton 1101) 5 5 5 5 5 ' '' polyethylene 1.5 1.5 1.5 1.5 1.5 ~ clay reinforcing agent : (NCF, Freeport Kaolin) 25 -- 43 43 --~ -- _______ ____ ________ ,~ * control ~ EXAMPLE 11 llA* 12 13 13A*
'~ Proper'ties Tensile yield 8,500 9,100 8,500 11,400 10,900 Tensile strength at break ~ 8,400 8,000 8,400 11,400 9,700 Tensile elongation 39 52 24 71 60 3a Izod impact : 3.5 7.4 2.4 2.0 5.8 ' Gardner impact 163 282 I22 42 272 ' ~ : 14 .~
, . .
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TABLE 3 continued EXMAPLE 11 llA* 12 13 13A*
Flexural modulus 457l000 312,000 547,000 608,000 350,000 Flexural strength 13l600 12,50014,30018,00014,700 Heat Distortion Temp. 232 230 241 267 253 _ _ * control .
Blends of 78 parts of poly(2,6-dimethyl-1,4-phenylene ether) resin, 22 parts of triphenyl phosphate flame retardant plasticizer, 1.5 parts of polyethylene, 0.5 parts of tridecyl phosphite, 0.15 parts of ~inc sulfide, 0.15 parts of zinc oxide, 43 parts of a clay reinforcing filler (NCF, Freeport Kaolin) and various impact modifiers and amounts, as shown, - ~ I are compounded, extruded and molded as in Examples 1-4.
The physical properties are_summarized in Table 4.
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EX~MPLES 20 - 38 Blends of 78 parts of poly (2,6-dimethyl-1,
3,231,635 dated January ~5, 1966.
The relative ratios of the polymer units in the A-B-A block copolymers can vary broadly. It is preferred that the center block B have a molecular weight greater than that of the combined terminal blocks, however, to obtain optimum impact strength and solvent resistance. In general, the molecular weight of each of the respective terminal blocks will range from about 2,000 to about 100,000 and the molecular weight of the center block will range from about 65,000 to about 1,000,000.
20 A Examples include the Kraton~resins, commercially available from Shell Chemical Co., Polymers Division, e.g., K-1101 (polystyrene-polybutadiene-polystyrene), K-110~ (poly styrene-polybutadiene-polystyrene), and K-1107 (polystyrene-polyisoprene~polystyrene).
The hydrogenated A-B-Al block copolymers are also well known. In general, these are block copolymers of the A-B-Al type in which terminal blocks A and Al are the same or different and, prior to hydrogenation, comprise homopolymers or copolymers derived from vinyl aromatic hydrocarbons and, especially, vinyl aromatics wherein the aromatic moiety can be either monocyclic or polycyclic.
Examples of the monomers are styrene, ~ - methyl styrene, .
~ 3~ CH-242~
vinyl xylene, e-thyl vinyl xylene, vinyl naphthalene, and the like. Center block B will always be derived from a conjugated diene, e.g., butadiene, isoprene, 1,3-pentadiene, and the like. Preferably, center block B wil be comprised of polybutadiene or polyisoprene.
The preparation of hydrogenated A-B-A1 block copoly-mers is described in Jones, U.S. Patent 3,431,323 dated March 4, 1969.
Examples include the Kraton GTM resins, commercially available from Shell Chemical Co., Polymers Division, e.g., G-GXT-0650, ~-GXT-0772, G-GXT-0782 and G-6521.
Radial teleblock copolymers of a vinyl aromatic comound, a conjugated diene and a coupling are also suitable impact modifiers for the compositions of this invention.
These are branched polymers having segments, or blocks, ; comprised of a conjugated diene polymer, and a vinyl aromatic polymer, together with a coupling agent, wherein in the copolymer structure chains of the diene polymer radiate outwards from a coupling agent, each chain terminating at its other end with a block of the vinyl aromatic polymer.
The radial teleblock copolymers are known in the art. They are described in ADHESIVES AGE, December, 1971, pages 15-20 and RUBBER WORLD, ~anuary, 1973, pages 27-32.
The preparation of these copolymers is described in Zelinski et al, U.S. Patent 3,281,383 dated October 25, 1966.
~xamples of commercially available radial teleblock copolymers are t:he SolpreneTM resins of Phillips Petroleum Company designat:ed as Solprene 406 (containing about 60 parts by welght of but:adiene units and about 40 parts by weight of styrene unit~;), Solprene 411 (containing about 70 parts by weight~ of butadiene units and about 30 parts by weight of ,~ ~ J
~ 5~ 8 C~ 2~2~
styrene units), Solprene ~14 (con-talning about 60 parts by weight oE butadiene units and about 40 parts by weight of styrene units), Solprene 417 (containing about 20 parts by weight of butadiene units and about 80 parts by weight of styrene units), and S411P (containing about 70 parts by weight of butadiene units and about 30 parts by weight of styrene units). These materials also include a relatively minor amount of coupling agent, e.g., less than 1 part by weight of coupling agent per 100 parts of polymer.
Also included are hydrogenated radial teleblock copolymers of a vinyl aromatic compound, a conjugated diene and a coupling agent, such as Solprene 512, commercially available from Phillips Petroleum Co.
The impact modifier can also be selected from acrylic resin modified diene rubber containing resins.
Preferably, these will be of the group consisting of a resinous composition of a poly(alkylene methacrylate) grafted on to a butadiene-styrene copolymer backbone or an acrylonitrile-butadiene-styrene terpolymer backbone, or a resinous composition of a mixture of a poly(alklmethacrylate) and a butadiene-styrene copolymer or an acrylonitrile-butadiene-styrene terpolymer.
A preferred commercially available impact modifier A of this type is Acryloid KM611, sold by Rohm and Haas Co., which is an acrylic/styrene/styrene-butadiene terpolymer.
: The aforementioned acrylic resin modified elastomers can be prepared by well known techniques, such as those described in U.S. 2,943,074 dated June 28, 1960 and U.S. 2,857,360 dated October 21, 1958.
The impact modifier can also be a graft .:
copolymer of a vinyl aromatic compound and a diene, prefer-ably comprising from about 75 to about 10~ by weight of a : -' ~ 8 CH 2424 vinyl aromatic monomer and from about 25 to about 90%
by weight o-f a conjugated diene. By way of illustration, the aromatic monomer can be selected from among styrene, . ~3 -methyl styrene, vinyl toluene, vinyl xylene, and the likQ, and the diene can be selected from among butadiene, iso~rene, and the like. Graft copolymers of styrene and styrene-butadiene are preferred.
An example of a preferred commercially available ~ graft copolymer is Blendex 525, sold by Marbon Chemical Co.
The compositions of this invention can be prepared by conventional methods. Preferably, each of the ingredients is added as part of a blend premix, and the blend is passed through an extruder at an extrusion temperature of from about 500 to about 625F., dependent on the needs of the particular composition~ The strands emerging from the extruder may be cooled, chopped into pellets, and molded or other wise worked to any desired shape.
The following examples are illustrative of the compositions of this invention. They are not to be construed as limiting the invention to the particular embodiments shown therein. All parts are by weight.
Units for the properties shown in the following Examples are as follows, unless otherwise indicated:
Tensile yield, psi - Tensile break, psi Tensile elongation, %
Flexural modulus, psi Flexural strength, psi Melt viscosity, at 540 F., 1500 sec , poise Gloss, 45 surface gloss, dimensionless units ~UL-94- Underwriters Laboratories Bulletin ~94, sec/sec.
_ g _ ~ 8 C~I 2424 Izod Impact strength, ft.lbs./in.n.
Gardner Impact strength, in.lbs.
Heat distortion tempe:rature, F.
Coefficient of Linear Thermal Expansion (CLTE), in/in F., measured f:rom -30C. to 65C.
EXM~PLES 1 - 4 Self-extinguishing, plasticized blends of 78 parts of poly(2,6-dimethyl-1,4-phenylene ether) resin, intrinsic viscosity about 0.45 deciliters/gram as measured in chloroform at 30C., 22 parts of triphenyl phosphate flame retardant plasticizer, 5 parts of styrene-butadiene-styrene block copolymer (Kraton 1101, Shell Chemical Co., Polymers Division), 1.5 parts of poly-ethylene and 20 parts of various mineral reinforcing agents, as shown, are compounded and extruded at a temperature of 580F. The extrudate is .
chopped into pellets, molded into test bars at a temperature of about 520 F., and evaluated for mechanical and flame resistance properties. For purposes of comparison, a blend of the same ingredients in the same amounts is prepared, but without a filler. The mineral reinforcements and test results are shown in Table 1.
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` 8 C~ 2~24 Self-extinguish:ing, plasti.cized compositons of 78 parts of poly(2,6-dimethyl-1,4-phenylene ether), 22 parts of triphenyl phosphate flame retardant plasticizer, 5 parts of styrene-butadiene-styrene block copolymer (Shell's Kraton 1101), 1.'; parts of polyethylene and a clay ~iller (Al-Sil Ate NCF, Freeport Kaolin CoO) in the amounts shown are prepared and molded as in Examples 1-4. The _ 10 physical properties are summarized in Table 2.
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It is shown that even with amounts of reinforcement as high as 67 phr (40%), in Example 9, a signi~icant amount of ductility, as measured by tensile elongation and impact strength, is retained as compared with the unreinforced control (lOA ).
EXAMPLES~ 13 Blends of poly(2,6~di:methyl-1,4 phenylene ether) resin, mineral oil, styrene-butadiene-styrene block copolymer (Kraton 1101), polyethylene and a clay reinforcing ~iller are compounded, extruded and molded as in Examples 1-4. The formulations and physical properties are summarized in Table 3.
EXAMPLE 11 ll_* 12 13 13A*
Ingredients (parts by weight) poly(2,6-dimethyl-1,4-phenylene ether) 78 78 78 85 85 mineral oil (Kaydol) 22 22 22 15 15 styrene-butadiene-styrene block copolymer (Kraton 1101) 5 5 5 5 5 ' '' polyethylene 1.5 1.5 1.5 1.5 1.5 ~ clay reinforcing agent : (NCF, Freeport Kaolin) 25 -- 43 43 --~ -- _______ ____ ________ ,~ * control ~ EXAMPLE 11 llA* 12 13 13A*
'~ Proper'ties Tensile yield 8,500 9,100 8,500 11,400 10,900 Tensile strength at break ~ 8,400 8,000 8,400 11,400 9,700 Tensile elongation 39 52 24 71 60 3a Izod impact : 3.5 7.4 2.4 2.0 5.8 ' Gardner impact 163 282 I22 42 272 ' ~ : 14 .~
, . .
. . : . . :. . - :
TABLE 3 continued EXMAPLE 11 llA* 12 13 13A*
Flexural modulus 457l000 312,000 547,000 608,000 350,000 Flexural strength 13l600 12,50014,30018,00014,700 Heat Distortion Temp. 232 230 241 267 253 _ _ * control .
Blends of 78 parts of poly(2,6-dimethyl-1,4-phenylene ether) resin, 22 parts of triphenyl phosphate flame retardant plasticizer, 1.5 parts of polyethylene, 0.5 parts of tridecyl phosphite, 0.15 parts of ~inc sulfide, 0.15 parts of zinc oxide, 43 parts of a clay reinforcing filler (NCF, Freeport Kaolin) and various impact modifiers and amounts, as shown, - ~ I are compounded, extruded and molded as in Examples 1-4.
The physical properties are_summarized in Table 4.
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EX~MPLES 20 - 38 Blends of 78 parts of poly (2,6-dimethyl-1,
4-phenylene ether), 22 parts of triphenyl phosphate, 5 parts of acrylic-styrene-styrene-butadiene terpolymer (Acryloid KM 611, Rohm & ~aas Co.), 1.5 parts of - polyethylene, 0.5 parts of tridecyl phosphite, 0.15 parts of zinc sulfide, 0.15 parts of zinc oxide and 43 parts of various mineral reinforcin.g agents are compounded, extruded . and molded as in Examples 1-4. The mineral reinforcements and test results are summarized in Tables 5, 5A and 5B.
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The formulations and physical properties are shown in Tables 7 and 7A, respectively.
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EXAMPLE _ 5 Ingredients (parts by weight) poly(2,6-dimethyl-1,4-phenylene ether) 55 67 triphenyl phosphate 15 13 styrene-butadiene-styrene,~
block copolymer (B~e~/~ilOl) 5 5 t~ra~
~ clay 30 20 polyethylene 1.5 1.5 tridecyl phosphate 0.5 0.5 zinc sulfide 0.15 0.15 zinc oxide 0.15 0.15 :
- ~ 4 8 CH 2424 TABLE 8A. Initial Physical Properties Properties Tensile yield, psi 73 F 9,360 9,120 150F. 6,770 6,370 Elongation, ~73 F. 41 68 150 F. 39 58 Flexural Strength, psi73 F. 13,900 12,700 150F. 8,400 8,200 Flexural Modulus, psi73 F. 558,900 419,600 150 F.446,000 353,000 Notched Izod impact, O
ft.lbs./in. 73 F. 3.3 8.6 -40 F. 0.8 1.1 Gardner impact, in.lbs. 73F. 83 252 -40 F~ 10 45 ~ - 28 -_ _ _ __ o ~ ~ ~ ~r ~; ~n ~r o . ~ ~ ~ I CO ~D CO 0 ~ O
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The formulations and physical properties are shown in Tables 7 and 7A, respectively.
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EXAMPLE _ 5 Ingredients (parts by weight) poly(2,6-dimethyl-1,4-phenylene ether) 55 67 triphenyl phosphate 15 13 styrene-butadiene-styrene,~
block copolymer (B~e~/~ilOl) 5 5 t~ra~
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- ~ 4 8 CH 2424 TABLE 8A. Initial Physical Properties Properties Tensile yield, psi 73 F 9,360 9,120 150F. 6,770 6,370 Elongation, ~73 F. 41 68 150 F. 39 58 Flexural Strength, psi73 F. 13,900 12,700 150F. 8,400 8,200 Flexural Modulus, psi73 F. 558,900 419,600 150 F.446,000 353,000 Notched Izod impact, O
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Claims (35)
1. A reinforced, plasticized thermoplastic composition having enhanced stiffness properties, said composition comprising:
(a) a polyphenylene ether resin alone or in combination with an impact modifier;
(b) a plasticizer therefor in an amount at least sufficient to reduce the temperature of optimum extrusion at least about 25°F.;
and (c) a mineral reinforcing agent in an amount at least sufficient to provide enhanced stiffness in comparison with a corresponding unfilled composition.
(a) a polyphenylene ether resin alone or in combination with an impact modifier;
(b) a plasticizer therefor in an amount at least sufficient to reduce the temperature of optimum extrusion at least about 25°F.;
and (c) a mineral reinforcing agent in an amount at least sufficient to provide enhanced stiffness in comparison with a corresponding unfilled composition.
2. A composition as defined in Claim 1 wherein the plasticizer (b) is present in an amount of at least about 5 parts per hundred parts by weight of resin.
3. A composition as defined in Claim 2 wherein the plasticizer is present in an amount of from about 5 to about 100 parts per hundred parts by weight of resin.
4. A composition as defined in Claim 1 wherein the mineral reinforcing agent (c) is present in an amount of at least about 5 parts per hundred parts of resin.
5. A composition as defined in Claim 4 wherein the mineral reinforcing agent is present in an amount of from about 5 to about 150 parts per hundred parts of resin plus plasticizer.
6. A composition as defined in Claim 1 wherein the mineral reinforcing agent is an aluminum silicate.
7. A composition as defined in Claim 6 wherein said mineral reinforcing agent is a hydrated aluminum silicate.
8. A composition as defined in Claim 1 wherein the polyphenylene ether resin (a) comprises repeating structural units of the formula:
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n is a positive integer and is at least 50, and each Q is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydrocarbon radicals free of a tertiary alpha-carbon atom, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
9. A composition as defined in Claim 8 wherein in said polyphenylene ether resin each Q is alkyl having from 1 to 4 carbon atoms.
10. A composition as defined in Claim 8 wherein said polyphenylene ether resin is poly(2,6-dimethyl-1, 4-phenylene)ether.
11. A composition as defined in Claim 1 which includes an impact modifier.
12. A composition as defined in Claim 11 wherein the impact modifier is an elastomeric A-B-A1 block copolymer.
13. A composition as defined in claim 12 wherein the impact modifier is a block copolymer of styrene and butadiene.
14. A composition as defined in claim 12 wherein the impact modifier is a block copolymer of styrene and isoprene.
15. A composition as defined in claim 11 wherein the impact modifier is an hydrogenated A-B-A1 block copolymer.
16. A composition as defined in claim 15 wherein the impact modifier is an hydrogenated block copolymer of styrene and butadiene.
17. A composition as defined in claim 15 wherein the impact modifier is an hydrogenated block copolymer of styrene and isoprene.
18. A composition as defined in claim 11 wherein the impact modifier is a radial teleblock copolymer of a vinyl aromatic compound, a conjugated diene and a coupling agent.
19. A composition as defined in claim 11 wherein the impact modifier is an acrylic resin modified diene rubber containing resin.
20. A composition as defined in claim 19 wherein said acrylic resin modified diene rubber-containing resin is selected from the group consisting of a resinous composition consisting essentially of a poly(alkyl methacrylate) grafted onto a butadiene-styrene backbone or an acrylonitrile-butadiene-styrene backbone or a resinous composition consisting essentially of a mixture of a poly(alkyl methacrylate) and a butadiene styrene copolymer or an acrylonitrile-butadiene-styrene terpolymer.
21. A composition as defined in claim 11 wherein the impact modifier is a graft copolymer of a vinyl aromatic compound and a diene compound.
22. A composition as defined in claim 21 wherein the impact modifier is a graft copolymer of styrene and styrene-butadiene.
23. A composition as defined in claim 1 wherein the plasticizer (b) is a compound of the formula:
wherein R1, R2 and R3 are the same or different and are alkyl, haloalkyl, cycloalkyl, halocycloalkyl, aryl, haloaryl, alkyl substituted aryl, haloalkyl substituted aryl, aryl substituted alkyl, haloaryl substituted alkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkaryl, halogen and hydrogen.
wherein R1, R2 and R3 are the same or different and are alkyl, haloalkyl, cycloalkyl, halocycloalkyl, aryl, haloaryl, alkyl substituted aryl, haloalkyl substituted aryl, aryl substituted alkyl, haloaryl substituted alkyl, hydroxyalkyl, hydroxyaryl, hydroxyalkaryl, halogen and hydrogen.
24. A composition as defined in claim 23 wherein said plasticizer (b) is an aromatic phosphate plasticizer.
25. A composition as defined in claim 24 wherein said aromatic phosphate is triphenyl phosphate.
26. A composition as defined in claim 1 which includes a flame retardant amount of a flame retardant agent.
27. A composition as defined in claim 1 in which the plasticizer (b) is a flame retardant agent and is present in a flame retardant amount,
28, A composition as defined in claim 1 in which the mineral reinforcing agent is anhydrous aluminum silicate.
29. A composition as defined in claim 1 wherein the mineral reinforcing agent is talc.
30. A composition as defined in claim 1 wherein the mineral reinforcing agent is zinc oxide.
31. A composition as defined in claim 1 wherein the mineral reinforcing agent is titanium dioxide.
32. A composition as defined in claim 1 wherein the mineral reinforcing agent is antimony oxide.
33. A composition as defined in claim 1 wherein the mineral reinforcing agent is barium sulfate.
34. A composition as defined in claim 1 wherein the mineral reinforcing agent is calcium carbonate.
35. A composition as defined in claim 1 wherein the mineral reinforcing agent is zinc sulfide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75502576A | 1976-12-28 | 1976-12-28 | |
| US755,025 | 1985-07-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1105174A true CA1105174A (en) | 1981-07-14 |
Family
ID=25037395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA293,116A Expired CA1105174A (en) | 1976-12-28 | 1977-12-15 | Plasticized reinforced compositions of a polyphenylene ether resin |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5384049A (en) |
| AU (2) | AU516435B2 (en) |
| BR (1) | BR7708515A (en) |
| CA (1) | CA1105174A (en) |
| DD (1) | DD133964A5 (en) |
| DE (1) | DE2752383A1 (en) |
| FR (1) | FR2376185A1 (en) |
| GB (1) | GB1563768A (en) |
| IT (1) | IT1089348B (en) |
| MX (1) | MX146639A (en) |
| NL (1) | NL7713769A (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298514A (en) * | 1976-03-29 | 1981-11-03 | General Electric Company | Flame retardant thermoplastic polyphenylene ether resin compositions |
| US4166812A (en) * | 1977-09-30 | 1979-09-04 | General Electric Company | Filled compositions of a polyphenylene ether resin and rubber-modified alkenyl aromatic resins |
| BR8105866A (en) * | 1980-01-14 | 1981-11-24 | Gen Electric | PERFECTED POLYPHENYLENE PLASTICING MIXTURES |
| US4315084A (en) * | 1980-01-14 | 1982-02-09 | General Electric Company | Polyphenylene ether molding compositions that include an alkenyl aromatic resin and EPDM rubber |
| US4313864A (en) * | 1980-01-21 | 1982-02-02 | General Electric Company | Polyphenylene oxide/plasticizer/hydrogenated radial teleblock copolymer blends |
| US4373045A (en) * | 1980-04-15 | 1983-02-08 | General Electric Company | Polyphenylene ether molding compositions that include an alkenyl aromatic resin, an ethylene propylene rubber and a triaryl phosphate |
| US4318836B1 (en) * | 1980-11-24 | 1995-10-31 | Gen Electric | Titanium dioxide filled polyphenylene ether compositions |
| US4317761A (en) * | 1980-11-24 | 1982-03-02 | General Electric Company | Clay filled polyphenylene ether compositions |
| EP0054845A3 (en) * | 1980-12-18 | 1982-09-22 | General Electric Company | Mineral filled polyphenylene ether compositions having improved properties |
| WO1982002208A1 (en) * | 1980-12-23 | 1982-07-08 | Gen Electric | Composition of polyphenylene ethers with core-shell rubber-modified polystyrene |
| JPS57108153A (en) * | 1980-12-25 | 1982-07-06 | Sumitomo Chem Co Ltd | Resin composition |
| US4373052A (en) * | 1981-09-23 | 1983-02-08 | General Electric Company | Polyphenylene ether compositions |
| AU1044483A (en) * | 1982-11-12 | 1984-06-04 | Babcock & Wilcox Co., The | Thermal energy storage and recovery apparatus and method for a fossil fuel-fired vapor generator |
| US4478970A (en) * | 1983-12-21 | 1984-10-23 | General Electric Company | Polyphenylene ether resin blends reinforced with finely divided particulate clay of narrow size distribution |
| GB8530023D0 (en) * | 1985-12-05 | 1986-01-15 | Ici Plc | Polymer composition |
| US5710206A (en) * | 1986-07-18 | 1998-01-20 | Raychem Limited | Gels comprising block copolymers |
| EP0284385A3 (en) * | 1987-03-26 | 1989-02-22 | MITSUI TOATSU CHEMICALS, Inc. | Aralkylphenolic resin molding material |
| JPH01169889U (en) * | 1988-05-20 | 1989-11-30 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3833688A (en) * | 1971-10-14 | 1974-09-03 | Gen Electric | Composition of a polyphenylene ether and an acrylic resin in combination with a diene rubber-containing resin |
| DE2434848C2 (en) * | 1973-08-13 | 1986-09-04 | General Electric Co., Schenectady, N.Y. | Thermoplastic mass |
| US4118348A (en) * | 1973-10-01 | 1978-10-03 | General Electric Company | Method for preparing blends of rubber, a polyphenylene ether resin and an alkenyl aromatic addition polymer |
| AU507885B2 (en) * | 1976-03-29 | 1980-02-28 | General Electric Company | Polyphenylene ether resin compositions |
| DE2750467A1 (en) * | 1976-12-13 | 1978-06-15 | Gen Electric | FLAME RETARDANT, IMPACT-RESISTANT POLYPHENYLENE ETHER COMPOSITIONS |
| DE2751496C2 (en) * | 1976-12-21 | 1994-09-22 | Gen Electric | Flame retardant, flexible polyphenylene ether compositions |
-
1977
- 1977-11-24 DE DE19772752383 patent/DE2752383A1/en not_active Ceased
- 1977-12-13 NL NL7713769A patent/NL7713769A/en not_active Application Discontinuation
- 1977-12-15 CA CA293,116A patent/CA1105174A/en not_active Expired
- 1977-12-19 FR FR7738244A patent/FR2376185A1/en active Granted
- 1977-12-20 BR BR7708515A patent/BR7708515A/en unknown
- 1977-12-20 GB GB52895/77A patent/GB1563768A/en not_active Expired
- 1977-12-21 IT IT31028/77A patent/IT1089348B/en active
- 1977-12-22 DD DD77202891A patent/DD133964A5/en unknown
- 1977-12-26 JP JP15871777A patent/JPS5384049A/en active Granted
- 1977-12-29 AU AU32049/77A patent/AU516435B2/en not_active Expired
-
1978
- 1978-01-02 MX MX171903A patent/MX146639A/en unknown
-
1982
- 1982-01-22 AU AU79738/82A patent/AU546435B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU3204977A (en) | 1979-07-05 |
| FR2376185A1 (en) | 1978-07-28 |
| AU516435B2 (en) | 1981-06-04 |
| FR2376185B1 (en) | 1984-09-14 |
| DE2752383A1 (en) | 1978-06-29 |
| IT1089348B (en) | 1985-06-18 |
| DD133964A5 (en) | 1979-01-31 |
| AU546435B2 (en) | 1981-06-04 |
| JPS5384049A (en) | 1978-07-25 |
| JPS6326142B2 (en) | 1988-05-28 |
| MX146639A (en) | 1982-07-21 |
| AU7973882A (en) | 1982-08-12 |
| NL7713769A (en) | 1978-06-30 |
| BR7708515A (en) | 1978-08-22 |
| GB1563768A (en) | 1980-04-02 |
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| MKEX | Expiry |