CA1089150A - Foamable thermoplastic resin composition - Google Patents
Foamable thermoplastic resin compositionInfo
- Publication number
- CA1089150A CA1089150A CA276,327A CA276327A CA1089150A CA 1089150 A CA1089150 A CA 1089150A CA 276327 A CA276327 A CA 276327A CA 1089150 A CA1089150 A CA 1089150A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- weight
- alkyl
- foamable thermoplastic
- aryl
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a foamable resin com-posi??on which is based on an alkenyl aromatic resin, an organic phosphate and a sulfonyl semicarbazide. The pre-ferred compositions will include a polyphenylene ether resin.
The present invention provides a foamable resin com-posi??on which is based on an alkenyl aromatic resin, an organic phosphate and a sulfonyl semicarbazide. The pre-ferred compositions will include a polyphenylene ether resin.
Description
lSO
Novel foamable resin compositions are disclosed that include an alkenyl aromatic resin, an organic phosphate and a sulfonyl semicarbazide. These compositions preferably include a polyphenylene ether resin.
The polyphenylene ether resins are a well known family of engineering thermoplastics that are well known to the polymer art. These polymers may be made by a variety of catalytic and non-catalytic processes from the correspond-ing phenols or reactive derivatives thereof. By way of ~-illustration, certain of the polyphenylene ethers are dis-closed in Hay, U.S. patent No. 3,306,874 dated February 28, 1967 and U.S. patent No. 3,306,875 dated February 28,1971, and in Stamatoff, U. S. 3,257,357 dated June 21, 1966 and U.S. patent No. 3,257,358 dated June 21, 1966. In the Hay patents, the polyphenylene ethers are prepared by an oxida- -tive 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 ether resins, including ;~-graft copolymers of polyphenylene ethers with styrene type compounds, are found in Fox, U.S. patent No. 3,356,761 ~-dated December 5, 1967 - Sumitomo, U.K. 1,291,609 dated November 23, 1965; Bussink et al, U.S. patent No.3,337,499 i ~ :
dated August 22, 1967; Blanchard et al U.S. patent No. :
3,219,626 dated November 23, 1965; Laakso et al, U.S. `~ ;~
patent No. 3,342,892 dated September 19, 1969; Borman U.S.
patent No. 3,344,166 dated September 26,1967; Hori et al U.S. patent 3,384,619 dated May 21, 1968; Faurote et al U.S. `~
3,440,217 dated April 22, 1969 and disclosures relating to ;
metal based catalysts which do not include amines, are known from patents such as Wieden et al, U.S. patent No.
3,442,885 dated May 6, 1969 (copper-amidines); Nakashio lOl~lrjO
et al, U. S. Patent ~o. 3,573,257 dated March 30, 1971 (metal-alcoholate or -phenolate); Kobayashi et al, U.S.
3,455,880 dated July 15, 1965 (cobalt chelates); and the like. In the Stamatoff patents, the polyphenylene ethers are produced by reacting the corresponding phenolate ion with an initiator, such as 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, silver oxide, etc., are described in Price et al, U.S. patent No.
3,382,212 dated May 7, 1968. Cizek, U.S. patent No.3,383,435 dated May 14, 1968 discloses polyphenylene etherstyrene resin compositions.
One of the outstanding properties of the polyphenylene ether resins is the property of high-heat resistance which makes possible the use of this resin in applications where many thermoplastics would fail. This exceptional property, while desirable in a finished article, causes problems when melt blending is used to form compositions that in-clude the polyphenylene ether resins. One problem isrelated to the fact that the high temperatures required for the processing of the polyphenylene ethers approach the temperatures at which additives begin to degrade. This problem is especially serious when compositions are for-mulated which include chemical blowing agents that are added to a foamable thermoplastic composition as the tem-peratures at which the polyphenylene ethers are processed are sufficient to activate most thermolabile blowing agents. -It has now been found that sulfonyl semicarbazides may be blended with polyphenylene ether resin compositions that include an organic phosphate compound and an alkenyl -aromatic compound, at temperatures that are low enough to : .
:, .
., .
10~3i~0 8CH-2194 prevent the activation of the flowing agent. These compositions may be prepared by first preparing a concentrated preblend of the polyphenylene ether, the alkenyl aromatic resin, the organic phosphate and the sulfonyl semicarbazide.
Optionally, the concentrated preblend may be prepared without any polyphenylene ether. The preblend may be combined with either a polyphenylene ether resin or a blend of a polyphenylene ether resin, an alkenyl aromatic resin, ~ -an organic phosphate in addition to conventional additives such as tri-decylphosphite, zinc oxide, titanium dioxide ;
and zinc sulfide.
Accordingly, it is a primary object of this invention to provide novel foamable thermoplastic compositions that include a polyphenylene ether resin.
It is also an object of this invention to provide novel preblended compositions of an alkenyl aromatic resin, an -organic phosphate and a sulfonyl semicarbazide.
,~ : .
U.S. Patent No. 3,639,506 dated February 1, 1972 discloses compositions that include polyphenylene ethers, styrene resins and a phosphate. This reference does not -disclose foamed polyphenylene ether resin compositions.
The present invention provides novel foamable ^
thermoplastic compositions which comprise~
(a) from 0-90 parts by weight of a polyphenylene ~ether resin; -(b) from 5-95 parts by weight of an alkenyl aromatic resin; ~
:~.
B
(c) from 5-40 parts by weight of a phosphate compound;
and (d) from 0.05-30 parts by weight of a sulfonyl semi-carbazide of the formula:
where R is alkyl, aryl or alkyl substituted aryl.
The polyphenylene ethers are preferably of the formula:
o n .
Q :
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; n is the degree of polymerization; and each Q is a monovalent substituent selected from hydrogen, halogen, hydrocarbon radicals, hal-ohydrocarbon radiclas having at least two carbon atoms the halogen atom and the phenyl nucleus. ~
20The preferred polyphenylene ether resin is poly(2,6- :~`
dimethyl-1,4-phenylene ether) resin having an intrinsic : :~
viscosity of about 0.5 as measured in chloroform at 25C
The alkenyl aromatic resin should have at least 25% ~:
of its units derived from a monomer of the formula~
R5 CRl = CHR2 ~: R6 ~ R4 . :
. .:
wherein R and R2 are selected from the group consisting of 30lower 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 l I :~
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. -- .
Materials that may be copolymerized with the alkenyl aromatic monomer include those having the general formula~
R8 . ,` ~ -(II) R - C(H) - - - C _ _ _ (CH2)m ~ R9 wherein the dotted lines represent a single or a double --.
carbon to carbon bond, R7 and R8 taken together represents a :~
11 9 ~ ' '' ~' C- O - C linkage, R is selected from the group consisting of hydrogen, vinyl, alkyl of from 1-12 carbon atoms, alkenyl of from 1-12 carbon atoms, alklcarboxylic of from 1-12 carbon atoms or alkenylcarboxylic of from 1-12 carbon ~:
:~ atoms, n is 1 or 2, depending on the position of the carbon- .. ~.
carbon double bond, and m is an integer of from 0 to about 10. Examples include maleic anhydride, citraconic anhydride, .
itaconic anhydride, aconitic anhydride, and the like. :.
The general formulas set forth above include by way of example, homopolymers such as homopolystyrene and monoch-loropolystyrene, the modified polystyrenes, such as rubber- ~:-modified, high-impact polystyrene and the styrene-contain-ing copolymers, such as the styrene acrylonitrile- ~ alkyl styrene copolymers, styrene-acrylonitrile copolymers,styrene ~ ~
butadiene copolymers, styrene-acrylonitrile butadiene co- ~ ~-, , ,~., .. . .. ., ... , . ~ . . - , . :
. :~. - . : ~. .. - . - .. . .. :
,.. ~:- ~ . :
.,. :- : . .
lOl~iSO
B polymers, poly - d -methylstyrene, copolymers of ethylvin-ylbenzene, divinylbenzene and styrene maleic anhydride co-polymers and block copolymers of styrene butadiene and styrene-butadiene styrene.
The styrene-maleic anhydride copolymers are described in U. S. Patent No. 3,971,939 dated July 27, 1976, U.S.
Patent No 3,336,267 dated August 15, 1967 and U.S. patent No. 2,769,804 dated November 6, 1956.
The rubber-modified, high-impact styrene resins are preferred and these may be made by well-known procedures with rubbers such as nitrile rubbers, polybutadiene rubber, `
styrenebutadiene rubber, polysulfide rubber, ethylene pro-pylene copolymers, propylene oxide and EPDM. These materials are well known and many are commercially available. A
preferred rubber-modified, high-impact styrene resin is commercially available as FG-834. This product contains `
about 8% polybutadiene.
The phosphate compound may be selected from compounds ~ -of the formula:
~ "~
QO P oQ
I
where each Q represents the same or different radicals that are selected from the group consisting of alkyl, such as straight and branched chain alkyl of from 1 to 10 carbon atoms such as methyl, propyl, n-butyl, hexyl, heptyl and the like; cycloalkyl such as those cycloalkyl radicals having from 1 to 8 carbon atoms such as cyclopropyl;, cyclobutyl, cyclohexyl and the like; aryl such as those aryl ,~................................................................... .
. . :
r 10~"3i~iO
radicals having from 6 to 14 carbon atoms such as phenyl and naphthyl; alkyl substituted aryl such as those radicals having from 1 to 5 straight or branched chain alkyl radicals having from 1 to 10 carbon atoms on a phenyl or naphthyl nucleus, e.g., 2-methylphenyl, 4-n-butylphenyl, 2- ethyl-phenyl and the like, aryl substituted alkyl such as phenyl or naphthyl substituted straight or branched chain alkyl radicals having from 1 to 10 carbon atoms such as benzyl, phenethyl, phenpropyl and the like; hydroxy alkyl having ~ ~
from 1 to 10 carbon atoms such as 2-hydroxyethyl, 4-hydroxy- ~ -heyl and the like; hydroxyaryl such as hydroxyphenyl or .~
hydroxynaphthyl, e.g., 4-hydroxyphenyl and the like;
hydroxyalkaryl such as cresyl, 4-ethyl-2-hydroxyphenyl and the like; halogen such as chloro, bromo or fluoro; and -~
hydrogen.
The phosphates may be selected from cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, triiosopropylphenyl phosphate, triphenyl phosp-hate, triethyl phosphate, dibutyl phenyl phosphate, die-thyl phosphate, cresyl diphenyl phosphate, isooctyl dip-henyl phosphate, tributyl phosphate, 2-ethlhexyl diphenyl phosphate, isodecyl diphenyl phosphate, isodecyl dicresyl phosphate, didecyl cresyl phosphate, tri-n-hexyl phosphate, -~
di-n-octyl phényl phosphate, di-2-ethylhexyl phosphate or mixtures thereof. ~ ~
'~. ';
;~ The preferred compositions will have from 5-50 parts~ ~ ;
by weight of a polyphenylene ether resin; from 20-95 parts by weight of an alkenyl aromatic resin; from 5-40 -~
~; parts by weight of the organic phosphate and 1-30 parts by weight of the sulfonyl semicarbazide.
For convenience, concentrated compositions may be prepared that have high concentrations of the sulfonyl .,,.~,.-. i, . . .. . . .
10~9iS0 semicarbazide. These compositions may be blended with blends of polyphenylene ether and styrene resin to prepare the actual composition that is foamed. The concentrated com-positions may include from 5-50 parts by weight of a polyp-henylene ether resin; from S0-90 parts by weight of an alkenyl aromatic resin; from 10-30 parts by weight of an organic phosphate compound; and from 2-25 parts by weight of the sulfonyl semicarbazide.
The sulfonyl semicarbazides are commerically available and the individual members of this group may be prepared by reacting the corresponding sulfonyl hydrazides with an alkali cyanate in an acidic medium in accordance with standard techniques.
The compositions of the invention may also include rein- -forcing amounts of reinforcing fillers. If a reinforcing filler is added, it may comprise from 10-40 parts by weight ~-of the composition. If a concentrated composition is pre- ~ -pared, it should be formulated without a reinforcement to ;
facilitate blending.
The reinforcing fillers may be selected from rein-forcing fillers such as aluminum, iron or nickel, and the like, and non-metals, such as carbon filaments, silicates such as acicular calcium silicate, asbestos, titanium dioxide, potassium titanate and titanate whiskers, woll-astonite, glass flakes and fibers. It is also to be understood that, unless the filler adds to the strength and stiffness of the composition, it is only a filler and not a reinforcing filler.
In particular, the preferred reinforcing fillers are of glass, and it is preferred to employ fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass.
lV~ tj~
However, other glasses are useful where electrical pro-perties are not so important, e.g., the low soda glass known as "C" glass. The filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechinical pulling. The preferred filament diameters range from about 0.000112 to 0.00075 inch, but this is not critical to the present invention.
The length of glass filaments are not critical to the invention. However, it is convenient to use the filamen-tous glass in the form of chopped strands of from about 1/8 inch to about 1 inch long, preferably less than 1/4 ~-inch long. The best properties are usually encountered when the filament lengths lie between about 0.000005 inch and 0.125 (1/8) inch.
The foamable compositions may be used for the pre- -paration of molded parts of business machines, applicance parts, electrical boxes and the like. For certain ap-plications, it is desirable to employ a composition having a low amount of a foaming agent to eliminate "sink" in ~ ~ -molded articles. The low amounts are in the order of 0.1-2 parts by weight. Generally the density of the foamed articles will be less that 1 and preferably about 0.75 to 0.9. The compositions may be molded under con-ditions that are generally employed for standard poly-phenylene ether resin compositions, except that usually "short shooting" is employed, or in other words, only a minimum amount of molding composition to fill the mold is used when the foamable compositions of the invention are molded.
The alkyl, aryl and alkyl substituted aryl substituents of the sulfonyl semicarbazides may be selected from methyl, ethyl, propyl, n-butyl, n-hexyl, decyl etc.; phenyl and _ g _ - 10~9150 naphthyl; and 4-methylphenyl; 3-methylphenyl; 2-methyl-phenyl; 4-ethylphenyl; 4-butylphenyl; etc.
If desired, other additives may be employed in the disclosed compositions for stabilization, flame retardancy and the like.
The following blend was prepared on a Werner Pfleiderer twin-screw extruder with the zone temperatures set at 180/250/330/330/350F. at zones 1-5:
Parts by weight poly(2,6-dimethyl-1,4-phenylene ether)*10 ~ ;
rubber-modified, high-impact polystyrene** 70 tri-phenyl phosphate 20 p-toluene sulfonyl semicarbazide*** 10 The melt temperature was 330F. and the torque was 400 -~
inch-pounds. The composition was easily stranded and pelletized.
* PPO, General Electric Co. having an IV of about 0.5 as measured in chloroform at 25C. -~
,, ~: .
** FG-834 ;~
*** Celogenl RA ~.. :" ;~
The following blend was prepared by the method and --materials prepared in Example 1:
Parts by weight poly(2,6-dimethyl-1,4-phenylene ether) 15 rubber-modified, high-impact polystyrene 65 . . .
tri-phenyl phosphate 30 : -~
p-toluene sulfonyl semicarbazide 10 The melt temperature was 340F. and the torque was 400 inch-pounds. The composition was easily stranded and pelletized. ~-The following blend was prepared by the method and materials of Example 1:
. . .
1 Trade Mark B -lo- ~ ~
10~'-31S0 Par~ by weight poly(2,6-dimethyl-1,4-phenylene ether) 15 rubber-modified, high-impact polystyrene 65 tri-phenyl phosphate 30 p-toluene sulfonyl semicarbazide 30 The melt temperature was 345F. and the torque was ~
400 inch-pounds. The composition was easily stranded and - -pelletized.
The following blend was prepared according to the methods and materials of Example 1 without any poly(2,6-dimethyl-1,4-phenylene ether).
Parts by weight ~
rubber-modified, high-impact polystyrene 80 ~ ;
tri-phenyl phosphate 20 p-toluene sulfonyl semicarbazide lO
The melt temperature was 340F. and the torque was 250 inch-pounds. The composition was easily stranded and pelletized. ~ ;
The preparation of the following blend illustrates the higher melt temperatures and extruder torque that are re-quired when the phosphate compound is eliminated from the -~
blend~
Parts by weight rubber-modified, high-impact polystyrene 100 p-toluene sulfonyl semicarbazide lO
The melt temperature was 380F, and the torque was 700 inch-pounds. The extruder composition showed immediate and gross decomposition of the chemical blowing agent and could not be stranded.
The preparation of the following blend also ill-ustrates the higher melt temperatures and extruder torque that are required when the phosphate compound is eliminated ~ O 8CH-2194 from the blend:
Parts by weight poly(2,6-dimethyl-1,4-phenylene ether) 10 rubber-modified, high-impact polystyrene 90 p-toluene sulfonyl semicarbazide 10 The melt temperature was 360F and the torque was 750 inch-pounds. The extruder composition showed immediate and gross decomposition of the chemical blowing agent and could not be stranded. -Athough the above examples have shown various modifica~
tions of the present invention, other variations are possible in light of the above teachings. It is, therefore, to be understood that changes may be made in the particular em-bodiments of the invention which are within the full intended ;
scope of the invention as defined by the appended claims.
~,
Novel foamable resin compositions are disclosed that include an alkenyl aromatic resin, an organic phosphate and a sulfonyl semicarbazide. These compositions preferably include a polyphenylene ether resin.
The polyphenylene ether resins are a well known family of engineering thermoplastics that are well known to the polymer art. These polymers may be made by a variety of catalytic and non-catalytic processes from the correspond-ing phenols or reactive derivatives thereof. By way of ~-illustration, certain of the polyphenylene ethers are dis-closed in Hay, U.S. patent No. 3,306,874 dated February 28, 1967 and U.S. patent No. 3,306,875 dated February 28,1971, and in Stamatoff, U. S. 3,257,357 dated June 21, 1966 and U.S. patent No. 3,257,358 dated June 21, 1966. In the Hay patents, the polyphenylene ethers are prepared by an oxida- -tive 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 ether resins, including ;~-graft copolymers of polyphenylene ethers with styrene type compounds, are found in Fox, U.S. patent No. 3,356,761 ~-dated December 5, 1967 - Sumitomo, U.K. 1,291,609 dated November 23, 1965; Bussink et al, U.S. patent No.3,337,499 i ~ :
dated August 22, 1967; Blanchard et al U.S. patent No. :
3,219,626 dated November 23, 1965; Laakso et al, U.S. `~ ;~
patent No. 3,342,892 dated September 19, 1969; Borman U.S.
patent No. 3,344,166 dated September 26,1967; Hori et al U.S. patent 3,384,619 dated May 21, 1968; Faurote et al U.S. `~
3,440,217 dated April 22, 1969 and disclosures relating to ;
metal based catalysts which do not include amines, are known from patents such as Wieden et al, U.S. patent No.
3,442,885 dated May 6, 1969 (copper-amidines); Nakashio lOl~lrjO
et al, U. S. Patent ~o. 3,573,257 dated March 30, 1971 (metal-alcoholate or -phenolate); Kobayashi et al, U.S.
3,455,880 dated July 15, 1965 (cobalt chelates); and the like. In the Stamatoff patents, the polyphenylene ethers are produced by reacting the corresponding phenolate ion with an initiator, such as 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, silver oxide, etc., are described in Price et al, U.S. patent No.
3,382,212 dated May 7, 1968. Cizek, U.S. patent No.3,383,435 dated May 14, 1968 discloses polyphenylene etherstyrene resin compositions.
One of the outstanding properties of the polyphenylene ether resins is the property of high-heat resistance which makes possible the use of this resin in applications where many thermoplastics would fail. This exceptional property, while desirable in a finished article, causes problems when melt blending is used to form compositions that in-clude the polyphenylene ether resins. One problem isrelated to the fact that the high temperatures required for the processing of the polyphenylene ethers approach the temperatures at which additives begin to degrade. This problem is especially serious when compositions are for-mulated which include chemical blowing agents that are added to a foamable thermoplastic composition as the tem-peratures at which the polyphenylene ethers are processed are sufficient to activate most thermolabile blowing agents. -It has now been found that sulfonyl semicarbazides may be blended with polyphenylene ether resin compositions that include an organic phosphate compound and an alkenyl -aromatic compound, at temperatures that are low enough to : .
:, .
., .
10~3i~0 8CH-2194 prevent the activation of the flowing agent. These compositions may be prepared by first preparing a concentrated preblend of the polyphenylene ether, the alkenyl aromatic resin, the organic phosphate and the sulfonyl semicarbazide.
Optionally, the concentrated preblend may be prepared without any polyphenylene ether. The preblend may be combined with either a polyphenylene ether resin or a blend of a polyphenylene ether resin, an alkenyl aromatic resin, ~ -an organic phosphate in addition to conventional additives such as tri-decylphosphite, zinc oxide, titanium dioxide ;
and zinc sulfide.
Accordingly, it is a primary object of this invention to provide novel foamable thermoplastic compositions that include a polyphenylene ether resin.
It is also an object of this invention to provide novel preblended compositions of an alkenyl aromatic resin, an -organic phosphate and a sulfonyl semicarbazide.
,~ : .
U.S. Patent No. 3,639,506 dated February 1, 1972 discloses compositions that include polyphenylene ethers, styrene resins and a phosphate. This reference does not -disclose foamed polyphenylene ether resin compositions.
The present invention provides novel foamable ^
thermoplastic compositions which comprise~
(a) from 0-90 parts by weight of a polyphenylene ~ether resin; -(b) from 5-95 parts by weight of an alkenyl aromatic resin; ~
:~.
B
(c) from 5-40 parts by weight of a phosphate compound;
and (d) from 0.05-30 parts by weight of a sulfonyl semi-carbazide of the formula:
where R is alkyl, aryl or alkyl substituted aryl.
The polyphenylene ethers are preferably of the formula:
o n .
Q :
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; n is the degree of polymerization; and each Q is a monovalent substituent selected from hydrogen, halogen, hydrocarbon radicals, hal-ohydrocarbon radiclas having at least two carbon atoms the halogen atom and the phenyl nucleus. ~
20The preferred polyphenylene ether resin is poly(2,6- :~`
dimethyl-1,4-phenylene ether) resin having an intrinsic : :~
viscosity of about 0.5 as measured in chloroform at 25C
The alkenyl aromatic resin should have at least 25% ~:
of its units derived from a monomer of the formula~
R5 CRl = CHR2 ~: R6 ~ R4 . :
. .:
wherein R and R2 are selected from the group consisting of 30lower 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 l I :~
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. -- .
Materials that may be copolymerized with the alkenyl aromatic monomer include those having the general formula~
R8 . ,` ~ -(II) R - C(H) - - - C _ _ _ (CH2)m ~ R9 wherein the dotted lines represent a single or a double --.
carbon to carbon bond, R7 and R8 taken together represents a :~
11 9 ~ ' '' ~' C- O - C linkage, R is selected from the group consisting of hydrogen, vinyl, alkyl of from 1-12 carbon atoms, alkenyl of from 1-12 carbon atoms, alklcarboxylic of from 1-12 carbon atoms or alkenylcarboxylic of from 1-12 carbon ~:
:~ atoms, n is 1 or 2, depending on the position of the carbon- .. ~.
carbon double bond, and m is an integer of from 0 to about 10. Examples include maleic anhydride, citraconic anhydride, .
itaconic anhydride, aconitic anhydride, and the like. :.
The general formulas set forth above include by way of example, homopolymers such as homopolystyrene and monoch-loropolystyrene, the modified polystyrenes, such as rubber- ~:-modified, high-impact polystyrene and the styrene-contain-ing copolymers, such as the styrene acrylonitrile- ~ alkyl styrene copolymers, styrene-acrylonitrile copolymers,styrene ~ ~
butadiene copolymers, styrene-acrylonitrile butadiene co- ~ ~-, , ,~., .. . .. ., ... , . ~ . . - , . :
. :~. - . : ~. .. - . - .. . .. :
,.. ~:- ~ . :
.,. :- : . .
lOl~iSO
B polymers, poly - d -methylstyrene, copolymers of ethylvin-ylbenzene, divinylbenzene and styrene maleic anhydride co-polymers and block copolymers of styrene butadiene and styrene-butadiene styrene.
The styrene-maleic anhydride copolymers are described in U. S. Patent No. 3,971,939 dated July 27, 1976, U.S.
Patent No 3,336,267 dated August 15, 1967 and U.S. patent No. 2,769,804 dated November 6, 1956.
The rubber-modified, high-impact styrene resins are preferred and these may be made by well-known procedures with rubbers such as nitrile rubbers, polybutadiene rubber, `
styrenebutadiene rubber, polysulfide rubber, ethylene pro-pylene copolymers, propylene oxide and EPDM. These materials are well known and many are commercially available. A
preferred rubber-modified, high-impact styrene resin is commercially available as FG-834. This product contains `
about 8% polybutadiene.
The phosphate compound may be selected from compounds ~ -of the formula:
~ "~
QO P oQ
I
where each Q represents the same or different radicals that are selected from the group consisting of alkyl, such as straight and branched chain alkyl of from 1 to 10 carbon atoms such as methyl, propyl, n-butyl, hexyl, heptyl and the like; cycloalkyl such as those cycloalkyl radicals having from 1 to 8 carbon atoms such as cyclopropyl;, cyclobutyl, cyclohexyl and the like; aryl such as those aryl ,~................................................................... .
. . :
r 10~"3i~iO
radicals having from 6 to 14 carbon atoms such as phenyl and naphthyl; alkyl substituted aryl such as those radicals having from 1 to 5 straight or branched chain alkyl radicals having from 1 to 10 carbon atoms on a phenyl or naphthyl nucleus, e.g., 2-methylphenyl, 4-n-butylphenyl, 2- ethyl-phenyl and the like, aryl substituted alkyl such as phenyl or naphthyl substituted straight or branched chain alkyl radicals having from 1 to 10 carbon atoms such as benzyl, phenethyl, phenpropyl and the like; hydroxy alkyl having ~ ~
from 1 to 10 carbon atoms such as 2-hydroxyethyl, 4-hydroxy- ~ -heyl and the like; hydroxyaryl such as hydroxyphenyl or .~
hydroxynaphthyl, e.g., 4-hydroxyphenyl and the like;
hydroxyalkaryl such as cresyl, 4-ethyl-2-hydroxyphenyl and the like; halogen such as chloro, bromo or fluoro; and -~
hydrogen.
The phosphates may be selected from cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, triiosopropylphenyl phosphate, triphenyl phosp-hate, triethyl phosphate, dibutyl phenyl phosphate, die-thyl phosphate, cresyl diphenyl phosphate, isooctyl dip-henyl phosphate, tributyl phosphate, 2-ethlhexyl diphenyl phosphate, isodecyl diphenyl phosphate, isodecyl dicresyl phosphate, didecyl cresyl phosphate, tri-n-hexyl phosphate, -~
di-n-octyl phényl phosphate, di-2-ethylhexyl phosphate or mixtures thereof. ~ ~
'~. ';
;~ The preferred compositions will have from 5-50 parts~ ~ ;
by weight of a polyphenylene ether resin; from 20-95 parts by weight of an alkenyl aromatic resin; from 5-40 -~
~; parts by weight of the organic phosphate and 1-30 parts by weight of the sulfonyl semicarbazide.
For convenience, concentrated compositions may be prepared that have high concentrations of the sulfonyl .,,.~,.-. i, . . .. . . .
10~9iS0 semicarbazide. These compositions may be blended with blends of polyphenylene ether and styrene resin to prepare the actual composition that is foamed. The concentrated com-positions may include from 5-50 parts by weight of a polyp-henylene ether resin; from S0-90 parts by weight of an alkenyl aromatic resin; from 10-30 parts by weight of an organic phosphate compound; and from 2-25 parts by weight of the sulfonyl semicarbazide.
The sulfonyl semicarbazides are commerically available and the individual members of this group may be prepared by reacting the corresponding sulfonyl hydrazides with an alkali cyanate in an acidic medium in accordance with standard techniques.
The compositions of the invention may also include rein- -forcing amounts of reinforcing fillers. If a reinforcing filler is added, it may comprise from 10-40 parts by weight ~-of the composition. If a concentrated composition is pre- ~ -pared, it should be formulated without a reinforcement to ;
facilitate blending.
The reinforcing fillers may be selected from rein-forcing fillers such as aluminum, iron or nickel, and the like, and non-metals, such as carbon filaments, silicates such as acicular calcium silicate, asbestos, titanium dioxide, potassium titanate and titanate whiskers, woll-astonite, glass flakes and fibers. It is also to be understood that, unless the filler adds to the strength and stiffness of the composition, it is only a filler and not a reinforcing filler.
In particular, the preferred reinforcing fillers are of glass, and it is preferred to employ fibrous glass filaments comprised of lime-aluminum borosilicate glass that is relatively soda free. This is known as "E" glass.
lV~ tj~
However, other glasses are useful where electrical pro-perties are not so important, e.g., the low soda glass known as "C" glass. The filaments are made by standard processes, e.g., by steam or air blowing, flame blowing and mechinical pulling. The preferred filament diameters range from about 0.000112 to 0.00075 inch, but this is not critical to the present invention.
The length of glass filaments are not critical to the invention. However, it is convenient to use the filamen-tous glass in the form of chopped strands of from about 1/8 inch to about 1 inch long, preferably less than 1/4 ~-inch long. The best properties are usually encountered when the filament lengths lie between about 0.000005 inch and 0.125 (1/8) inch.
The foamable compositions may be used for the pre- -paration of molded parts of business machines, applicance parts, electrical boxes and the like. For certain ap-plications, it is desirable to employ a composition having a low amount of a foaming agent to eliminate "sink" in ~ ~ -molded articles. The low amounts are in the order of 0.1-2 parts by weight. Generally the density of the foamed articles will be less that 1 and preferably about 0.75 to 0.9. The compositions may be molded under con-ditions that are generally employed for standard poly-phenylene ether resin compositions, except that usually "short shooting" is employed, or in other words, only a minimum amount of molding composition to fill the mold is used when the foamable compositions of the invention are molded.
The alkyl, aryl and alkyl substituted aryl substituents of the sulfonyl semicarbazides may be selected from methyl, ethyl, propyl, n-butyl, n-hexyl, decyl etc.; phenyl and _ g _ - 10~9150 naphthyl; and 4-methylphenyl; 3-methylphenyl; 2-methyl-phenyl; 4-ethylphenyl; 4-butylphenyl; etc.
If desired, other additives may be employed in the disclosed compositions for stabilization, flame retardancy and the like.
The following blend was prepared on a Werner Pfleiderer twin-screw extruder with the zone temperatures set at 180/250/330/330/350F. at zones 1-5:
Parts by weight poly(2,6-dimethyl-1,4-phenylene ether)*10 ~ ;
rubber-modified, high-impact polystyrene** 70 tri-phenyl phosphate 20 p-toluene sulfonyl semicarbazide*** 10 The melt temperature was 330F. and the torque was 400 -~
inch-pounds. The composition was easily stranded and pelletized.
* PPO, General Electric Co. having an IV of about 0.5 as measured in chloroform at 25C. -~
,, ~: .
** FG-834 ;~
*** Celogenl RA ~.. :" ;~
The following blend was prepared by the method and --materials prepared in Example 1:
Parts by weight poly(2,6-dimethyl-1,4-phenylene ether) 15 rubber-modified, high-impact polystyrene 65 . . .
tri-phenyl phosphate 30 : -~
p-toluene sulfonyl semicarbazide 10 The melt temperature was 340F. and the torque was 400 inch-pounds. The composition was easily stranded and pelletized. ~-The following blend was prepared by the method and materials of Example 1:
. . .
1 Trade Mark B -lo- ~ ~
10~'-31S0 Par~ by weight poly(2,6-dimethyl-1,4-phenylene ether) 15 rubber-modified, high-impact polystyrene 65 tri-phenyl phosphate 30 p-toluene sulfonyl semicarbazide 30 The melt temperature was 345F. and the torque was ~
400 inch-pounds. The composition was easily stranded and - -pelletized.
The following blend was prepared according to the methods and materials of Example 1 without any poly(2,6-dimethyl-1,4-phenylene ether).
Parts by weight ~
rubber-modified, high-impact polystyrene 80 ~ ;
tri-phenyl phosphate 20 p-toluene sulfonyl semicarbazide lO
The melt temperature was 340F. and the torque was 250 inch-pounds. The composition was easily stranded and pelletized. ~ ;
The preparation of the following blend illustrates the higher melt temperatures and extruder torque that are re-quired when the phosphate compound is eliminated from the -~
blend~
Parts by weight rubber-modified, high-impact polystyrene 100 p-toluene sulfonyl semicarbazide lO
The melt temperature was 380F, and the torque was 700 inch-pounds. The extruder composition showed immediate and gross decomposition of the chemical blowing agent and could not be stranded.
The preparation of the following blend also ill-ustrates the higher melt temperatures and extruder torque that are required when the phosphate compound is eliminated ~ O 8CH-2194 from the blend:
Parts by weight poly(2,6-dimethyl-1,4-phenylene ether) 10 rubber-modified, high-impact polystyrene 90 p-toluene sulfonyl semicarbazide 10 The melt temperature was 360F and the torque was 750 inch-pounds. The extruder composition showed immediate and gross decomposition of the chemical blowing agent and could not be stranded. -Athough the above examples have shown various modifica~
tions of the present invention, other variations are possible in light of the above teachings. It is, therefore, to be understood that changes may be made in the particular em-bodiments of the invention which are within the full intended ;
scope of the invention as defined by the appended claims.
~,
Claims (13)
1. A foamable thermoplastic resin composition which comprises:
(a) from 0-90 parts by weight of a polyphenylene ether resin;
(b) from 5-95 parts by weight of a alkenyl aromatic resin;
(c) from 5-40 parts by weight of a phosphate com-pound; and (d) from 0.05-30 parts by weight of a sulfonyl semicarbazide of the formula:
wherein R is alkyl, aryl or alkyl substituted aryl.
(a) from 0-90 parts by weight of a polyphenylene ether resin;
(b) from 5-95 parts by weight of a alkenyl aromatic resin;
(c) from 5-40 parts by weight of a phosphate com-pound; and (d) from 0.05-30 parts by weight of a sulfonyl semicarbazide of the formula:
wherein R is alkyl, aryl or alkyl substituted aryl.
2. A foamable thermoplastic resin composition as de-fined in claim 1 wherein the polyphenylene ether resin is of the formula:
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; n is the degree of polymerization; and each Q is a monovalent substituent selected from hydrogen, halogen, hydrocarbon radicals, halohydrocarbon 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 the degree of polymerization; and each Q is a monovalent substituent selected from hydrogen, halogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus.
3. A foamable thermoplastic resin composition as de-fined in claim 2 wherein at least 25% of the units of the alkenyl aromatic resin are derived from a monomer 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 connected 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 connected together with hydrocarbyl groups to form a naphthyl group, said compounds being free of any substituent that has a tertiary carbon atom.
4. A foamable thermoplastic resin composition as de-fined in claim 3 wherein the phosphate compound is of the formula:
wherein each Q represents the same or different radicals that are selected from the group consisting of alkyl, aryl, alkyl substituted aryl, aryl substituted alkyl, hydroxyalkyl, hydroxyaryl and hydroxyalkaryl.
wherein each Q represents the same or different radicals that are selected from the group consisting of alkyl, aryl, alkyl substituted aryl, aryl substituted alkyl, hydroxyalkyl, hydroxyaryl and hydroxyalkaryl.
5. A foamable thermoplastic resin composition as defined in claim 2 which includes from 5-50 parts of the polypheny-lene ether resin.
6. A foamable thermoplastic resin composition which comprises:
(a) 5-50 parts by weight of a polyphenylene ether resin of the formula:
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; n is the degree of polymerization; and each Q is a monovalent substituent selected from hydrogen, halogen hydrocarbon radicals, halo-hydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus;
(b) from 20-95 parts by weight of a rubber-modified, high-impact polystyrene resin;
(c) from 5-40 parts by weight of a phosphate com-pound; and (d) from 1-30 parts by weight of a sulfonyl semi-carbazide of the formula:
wherein R is alkyl, aryl or alkyl substituted aryl.
(a) 5-50 parts by weight of a polyphenylene ether resin of the formula:
wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; n is the degree of polymerization; and each Q is a monovalent substituent selected from hydrogen, halogen hydrocarbon radicals, halo-hydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenyl nucleus;
(b) from 20-95 parts by weight of a rubber-modified, high-impact polystyrene resin;
(c) from 5-40 parts by weight of a phosphate com-pound; and (d) from 1-30 parts by weight of a sulfonyl semi-carbazide of the formula:
wherein R is alkyl, aryl or alkyl substituted aryl.
7. A foamable thermoplastic composition as defined in claim 5 wherein the phosphate compound is of the formula:
wherein each Q represents the same or different radicals that are selected from the group consisting of alkyl, aryl alkyl substituted aryl, aryl substituted alkyl, hydroxy-alkyl, hydroxyaryl and hydroxyalkaryl.
wherein each Q represents the same or different radicals that are selected from the group consisting of alkyl, aryl alkyl substituted aryl, aryl substituted alkyl, hydroxy-alkyl, hydroxyaryl and hydroxyalkaryl.
8. A foamable thermoplastic composition as defined in claim 6 which includes:
(a) from 5-50 parts by weight of the polyphenylene ether resin;
(b) from 50 to 90 parts by weight of rubber-modified, high-impact polystyrene;
(c) from 10 to 30 parts by weight of the organic phosphate compound; and (d) from 2 to 25 parts by weight of a sulfonyl semi-carbazide of the formula:
wherein R is alkyl, aryl or alkyl substituted aryl.
(a) from 5-50 parts by weight of the polyphenylene ether resin;
(b) from 50 to 90 parts by weight of rubber-modified, high-impact polystyrene;
(c) from 10 to 30 parts by weight of the organic phosphate compound; and (d) from 2 to 25 parts by weight of a sulfonyl semi-carbazide of the formula:
wherein R is alkyl, aryl or alkyl substituted aryl.
9. A foamable thermoplastic composition as defined in claim 7 wherein the polyphenylene ether resin is poly(2,6-dimethyl-1,4,-phenylene ether).
10. A foamable thermoplastic composition as defined in claim 9 wherein the organic phosphate compound is tri-phenyl phosphate.
11. A foamable thermoplastic composition as defined in claim 10 wherein the sulfonyl semicarbazide is p-toluene sulfonyl semicarbazide.
12. A foamable thermoplastic composition as defined in claim 1 which includes a reinforcing amount of a reinforcing filler.
13. A foamable thermoplastic composition as defined in claim 12 wherein the reinforcing agent is filamentous glass.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67726076A | 1976-04-15 | 1976-04-15 | |
| US677,260 | 1976-04-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089150A true CA1089150A (en) | 1980-11-04 |
Family
ID=24717973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA276,327A Expired CA1089150A (en) | 1976-04-15 | 1977-04-07 | Foamable thermoplastic resin composition |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS52127969A (en) |
| AU (1) | AU2424777A (en) |
| BR (1) | BR7702464A (en) |
| CA (1) | CA1089150A (en) |
| DE (1) | DE2716273A1 (en) |
| FR (1) | FR2348241A1 (en) |
| GB (1) | GB1558524A (en) |
| NL (1) | NL7704120A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55118735U (en) * | 1979-02-15 | 1980-08-22 | ||
| JPH0686566B2 (en) * | 1984-12-17 | 1994-11-02 | 三菱瓦斯化学株式会社 | Polyphenylene ether resin composition |
| US4661302A (en) * | 1986-04-07 | 1987-04-28 | The Dow Chemical Company | Expandable polymeric composition and method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1276620A (en) * | 1959-12-31 | 1961-11-17 | Us Rubber Co | Sulfonyl semi-carbazides as blowing agents |
| US3235519A (en) * | 1959-12-31 | 1966-02-15 | Us Rubber Co | Sulfonyl semicarbazides as blowing agents for polymeric materials |
| US3639506A (en) * | 1969-05-21 | 1972-02-01 | Gen Electric | Flame retardant composition of polyphenylene ether styrene resin aromatic phosphate and aromatic halogen compound |
| IT950777B (en) * | 1971-04-09 | 1973-06-20 | Dart Ind Inc | COMPOSITIONS OF THERMOPLASTIC EXPANDABLE MATERIAL REINFORCED WITH FI BRE AND PROCEDURE FOR THEIR PRODUCTION |
| CH598301A5 (en) * | 1975-07-10 | 1978-04-28 | Ciba Geigy Ag |
-
1977
- 1977-04-04 GB GB1407777A patent/GB1558524A/en not_active Expired
- 1977-04-07 CA CA276,327A patent/CA1089150A/en not_active Expired
- 1977-04-13 DE DE19772716273 patent/DE2716273A1/en not_active Withdrawn
- 1977-04-13 JP JP4311377A patent/JPS52127969A/en active Pending
- 1977-04-14 AU AU24247/77A patent/AU2424777A/en not_active Expired
- 1977-04-14 FR FR7711251A patent/FR2348241A1/en not_active Withdrawn
- 1977-04-14 NL NL7704120A patent/NL7704120A/en not_active Application Discontinuation
- 1977-04-15 BR BR7702464A patent/BR7702464A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR7702464A (en) | 1977-11-08 |
| GB1558524A (en) | 1980-01-03 |
| FR2348241A1 (en) | 1977-11-10 |
| JPS52127969A (en) | 1977-10-27 |
| NL7704120A (en) | 1977-10-18 |
| DE2716273A1 (en) | 1977-10-27 |
| AU2424777A (en) | 1978-10-19 |
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